Advances in Colloid and Interface Science

Advances in Colloid and Interface Science 284 (2020) 102246
Contents lists available at ScienceDirect
Advances in Colloid and Interface Science
journal homepage: www.elsevier.com/locate/cis
Historical Perspective
Silver nanoparticles: Synthesis, investigation techniques, and properties

Oleksandra Pryshchepa a,b, Paweł Pomastowski a, Bogusław Buszewski a,b,⁎
a
Centre for Modern Interdisciplinary Technologies, Nicolaus Copernicus University in Torun, Wileńska 4, 87-100 Torun, Poland
b
Department of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Nicolaus Copernicus University in Torun, Gagarina 7, 87-100 Torun, Poland
a r t i c l e i n f o a b s t r a c t
Article history: The unique silver properties, especially in the form of nanoparticles (NPs), allow to utilize them in numerous ap-
15 August 2020 plications. For instance, Ag NPs can be utilized for the production of electronic and solar energy harvesting de-
Available online 26 August 2020 vices, in advanced analytical techniques (NALDI, SERS), catalysis and photocatalysis. Moreover, the Ag NPs can
be useful in medicine for bioimaging, biosensing as well as in antibacterial and anticancer therapies. The Ag
Keywords:
NPs utilization requires comprehensive knowledge about their features regarding the synthesis approaches as
Silver nanoparticles
Synthesis methods
well as exploitation conditions. Unfortunately, a large number of scientific articles provide only restricted infor-
Analytical techniques mation according to the objects under investigation. Additionally, the results could be affected by artifacts intro-
Biological activity duced with exploited equipment, the utilized technique or sample preparation stages. However, it is rather
Toxic mechanism difficult to get information about problems, which may occur during the studies. Thus, the review provides infor-
mation about novel trends in the Ag NPs synthesis, among which the physical, chemical, and biological ap-
proaches can be found. Basic information about approaches for the control of critical parameters of NPs, i.e.
size and shape, was also revealed. It was shown, that the reducing agent, stabilizer, the synthesis environment,
including trace ions, have a direct impact on the Ag NPs properties. Further, the capabilities of modern analytical
techniques for Ag NPs and nanocomposites investigations were shown, among other microscopic (optical, TEM,
SEM, STEM, AFM), spectroscopic (UV-Vis, IR, Raman, NMR, electron spectroscopy, XRD), spectrometric (MALDI-
TOF MS, SIMS, ICP-MS), and separation (CE, FFF, gel electrophoresis) techniques were described. The limitations
and possible artifacts of the techniques were mentioned. A large number of presented techniques is a
distinguishing feature, which makes the review different from others. Finally, the physicochemical and biological
properties of Ag NPs were demonstrated. It was shown, that Ag NPs features are dependent on their basic param-
eters, such as size, shape, chemical composition, etc. At the end of the review, the modern theories of the Ag NPs
toxic mechanism were shown in a way that has never been presented before. The review should be helpful for
scientists in their own studies, as it can help to prepare experiments more carefully.
© 2020 Published by Elsevier B.V.
Abbreviations: AES, Auger Electron Spectroscopy; AF4, Asymetric flow field flow fractionation; AFM, Atomic Force Microscopy; BSA, Bovine Serum Albumin; BSE, Backscattered electrons;
CE, Capillary Electrophoresis; CP-MAS NMR, Cross-Polarization Magic Angle Spinning Nuclear Magnetic Resonanse Spectroscopy; Cryo-TEM, Cryogenic Transmission Electron Microscopy;
CTAB, Cetrimonium Bromide; CTEM, Conventional Transmission Electron Microscopy; DLS, Dynamic Light Scattering; DNA, Deoxyribonucleic acid; DSC, Differential scanning calorimetry;
EDX or EDS, Energy Dispersive X-ray Spectroscopy; EELS, Electron Energy Loss Spectroscopy; EG, Ethylene glycol; ESEM, Environmental Scanning Electron Microscopy; FFF, Field Flow
Fractionation; FTIR, Fourier Transform Infrared Spectroscopy; G4-DNA, G-rich Deoxyribonucleic acid quadruplex structure; HEPES, 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid;
HPIV-3, Human parainfluenza virus type 3; HR-MAS-NMR, High-Resolution Magic Angle Nuclear Magnetic Resonanse Spectroscopy; HRTEM, High-Resolution Transmission Electron
Microscopy; HSV-1, Herpes simplex virus type 1; IC50, Half-maximal inhibitory concentration; ICP-MS, Iductively Coupled Plasma Mass Spectrometry; IFE, Inner Filter Efect; LOH, Loss Of
Heterozygosity; LP-TEM, Liquid-Phase Transmission Electron Microscopy; LSPR, Localized Surface Plasmone; MALDI-TOF-MS, Matix Assisted Laser Desorption/Ionization Time Of Flight
Mass Spectrometry; MALS, Multi Angel Light Scattering; MHB, Mueller-Hinton Broth; MIR, Mid-Infrared Range; NALDI, Nanoassisted Laser Desorption/Ionization; NIR, Near-Infrared
Range; NMR, Nuclear Magnetic Resonance; NP/NPs, Nanoparticle/Nanoparticles; NSOM, Near-field Scanning Optical Microscopy; PVP, Polyvinylpirrolidone; QDs, Quantum Dots; SAED,
Selected Area Electron Diffraction; SE, Secondarry Electron; SEM, Scannig Electron Microscopy; SERS, Surface Enhanced Raman Spectroscopy; SIMS, Secondary Ion Mass Spectrometry; SP-
ICP-MS, Single-Particle Inductively Coupled Plasma Mass Spectrometry; SPM, Scanning Probe Microscopy; STEM, Scanning Transmission Electron Microscopy; TEM, Transmission Electron
Microscopy; TEOS, Tetraethyl orthosilicate; TGA, Thermograviametric analysis; TOF-SIMS, Time Of Flight Secondary Ion Mass Spectrometry; UPS, Ultraviolet Photoelectron Spectroscopy;
UV-Vis, Ultraviolet and Visible light range; XPS, X-ray Photoelectron Spectroscopy; XRD, X-ray Diffraction Spectroscopy.
⁎ Corresponding author at: Department of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100 Toruń, Poland.
E-mail address: bbusz@chem.umk.pl (B. Buszewski).
https://doi.org/10.1016/j.cis.2020.102246
0001-8686/© 2020 Published by Elsevier B.V.
O. Pryshchepa, P. Pomastowski and B. Buszewski Advances in Colloid and Interface Science 284 (2020) 102246
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Physical approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Chemical synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Biological methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.4. Size and shape control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Investigation techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1. Optical imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2. Electron microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.3. Scanning probe microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4. Dynamic light scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.5. UV-Vis and fluorescence spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.6. Infrared and Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.7. Nuclear magnetic resonance spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.8. Electron spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.9. XRD and SAED investigations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.10. Mass spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.11. Separation techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.12. Thermal analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4. Physicochemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5. Biological activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.1. Mechanism of Ag NPs biological toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
6. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1. Introduction ion-desorption efficiency of analyte in comparison to Au, Pd, and Pt

NPs [8]. Additionally, the Au and Pt NPs nearly a hundred times more
Over the past few decades, nanotechnology has reached an unprece- expensive than Ag NPs, while Cu NPs utilization is much more compli-
dented scale. Thus, the increased interest of researchers in the field is not cated due to high susceptibility to oxidation and very few known nano-
a surprise. Nanotechnology can be described as the field in science and structures [21]. Lately, more attention is paid for the utilization of metal
technology involved in the engineering, production, and utilization of oxide NPs in the antibacterial applications, such as ZnO or ZrO2 [22],
nanomaterials [1]. Nanoscale or nanometer objects, as defined by the pre- which potentially can be a substitute for Ag NPs. However, long-time
fix “nano” meaning 10−9, in general, should fall within the limits of history of successful silver utilization in medicine as an antibacterial
1–1000 nm. However, according to the European Commission recommen- agent as well as the fact that till now it has been reported only one bac-
dations, to nanomaterials can be accounted any material of natural, inci- teria, P. stutceri (its natural habitat is silver mines), which completely re-
dental or engineered origin, which comprises at least 50% of the particles sistant to Ag+ [23], indicate that silver preparations, including in the
(in unbound or aggregated form) possessing one or more external dimen- form of NPs, is hardly can be replaced completely. Thus, Ag NPs still is
sions in the range from 1 to 100 nm [2]. However, the objects that exceed the “hot topic” of numerous investigations.
the designated limits are often considered by researchers as NPs [3]. One of the most important issues in nanotechnology is the possibil-
The NPs made from coinage metals attract attention due to their ity to engineer the NPs with desired properties for corresponding appli-
unique optical properties coming from the specific behavior under cations. The desired results can be achieved only in case of
light irradiation, namely the appearance of Localized Surface Plasmon comprehensive knowledge about the NPs features regarding the syn-
Resonance (LSPR). Among all “noble” metals, silver as a bulk material thesis approaches as well as exploitation conditions. A simple search
exhibits the highest electrical and thermal conductivities, the lowest in scientific publication databases reveals the hundreds of thousands
melting and boiling points. Moreover, silver is the most reactive of the of results on keywords like “Ag nanoparticles” or “silver nanoparticles”.
“noble” metals, and its cations exert toxic effects against various micro- Unfortunately, a significant amount of the publications comprise highly
organisms [4]. Silver in form of NPs revealed even more unique proper- restricted information regarding the Ag NPs properties, and how they
ties, which enables them to be utilized in the multiple fields of are affected by the synthesis conditions. For instance, in the work by
technique and medicine: solar energy harvesting [5], electronic devices E.-Y. Ahn et al., among thirty utilized plant extracts only seven showed
[6], advanced analytical techniques, e.g. SERS (Surface Enhanced Raman the capability to reduce Ag+, the comparative characterization of the
Spectroscopy) [7] and NALDI (Nanoassisted Laser Desorption/Ioniza- mentioned extracts or NPs surface functional groups were not per-
tion) [8,9], catalysis and photocatalysis [10,11], environmental applica- formed [24]. Moreover, no correlation between NPs primary features
tions [12], bioimaging [13] and bioanalysis [14,15], as antibacterial (i.e. size, shape, surface charge, hydrodynamic radii) and biological ac-
agent [16–18] or agent in anticancer therapies [19,20]. tivity could be derived. The authors attributed the toxicity of the synthe-
The utilization of Cu, Au, Pt, or Pd NPs for plasmonic applications is sized Ag NPs to the extensively accepted theory of Reactive Oxygen
also considered. However, all the mentioned NPs cannot completely re- Species (ROS) formation by released Ag+. However, the Ag NPs show
place Ag NPs, since they have the highest quality factor in the plasmonic a much wider spectrum of possible toxic routs [25] and the surface
ability and exhibit the plasmonic band in a wide range of wavelengths chemistry strictly influences the NPs interaction with cells [26,27].
(from near ultraviolet to near infrared spectrum), which is provided Hence, researchers should consider the possibility of a more compre-
by numerous known nanostructures [21]. Moreover, in NALDI applica- hensive study of each individual investigated system, rather than to dis-
tion the Ag NPs prepared by metal sputtering have shown the highest sipate their resources.
2
Another subject that has poorly been covered in the literature is the bottom-up. Top-down methods imply the creating of nanoscale struc-
influence of different analytical techniques on the obtained results dur- tures starting from bulk material by reducing their size through “cut-
ing the study of Ag NPs. Still, some information can be derived from the ting” to required values. Instead, bottom-up approaches are the
scientists' reports, so it can be concluded that depending on the instru- variety of synthetic techniques, which utilize the molecular, atomic, or
mental technique the studied features of Ag NPs can differ significantly ionic components to produce the more complex nanoscaled assemblies
[28]. Moreover, the results can be affected by artifacts introduced by the [36]. Further, synthesis techniques can be categorized according to the
employed equipment, the utilized technique or sample preparation processes had been used, i.e. physical, chemical, biological methods
stages [29,30]. Even though the progress in the technologies allows us (Fig. 1). The selection of an appropriate synthesis method is a major
to eliminate a significant number of artifacts that can be introduced by issue for engineered NPs production, as it affects their properties. For in-
the apparatus, it is rather impossible to consider or remove all the fac- stance, galactose and mannose-capped Ag NPs possess lower toxicity
tors that influence the objects under investigation. Besides, the majority against hepatocytes and neuronal-like cell lines in comparison to NPs
of the techniques have notable limitations and cannot provide exhaus- stabilized with citrate [37], so they can be recognized as more biocom-
tive knowledge about the examined objects. Thus, researchers should patible and therefore are more suitable for exploitation in medical ap-
carefully prepare their experiments and not avoid to perform additional plications. Instead, for NPs utilization in catalytic applications the size,
analysis, as even simple chemical test may result in useful corroborative shape, the unique dopants are more important than bioavailability
information. [38]. Hence, the selection of synthesis rout usually is determined by de-
The influence of Ag NPs on biological systems is also a sensitive issue, sired NPs utilization features.
which induces numerous discussions in scientific society. Different ef-
fects, induced by Ag NPs in the prokaryotic and eukaryotic cells have
been described in the literature [25]. Despite, the scientists' numerous 2.1. Physical approaches
attempts to distinguish separately the effects of each agent related to
Ag NPs (stabilizer [31], Ag+ [32], or the NP itself [33]), it is still impossi- Physical approaches include the exploitation of the physical agents,
ble to perform completely, especially in terms of a time-resolved man- such as heat [39], electrical discharge [40], plasma [41], or electromag-
ner [34]. Moreover, the majority of the investigations are performed netic irradiation [11]. The advantages of physical methods are their
in vitro, which cannot reproduce the conditions of real biological sys- speed and minimal chemicals consumption. However, physical synthe-
tems. It was shown, that plasma proteins adsorption on Ag NPs surface sis approaches have drawbacks to which the high energy of the process,
[27,34] and Ag+ chelation [17] change the NPs interaction with cells as the wide particle size distribution and low yield can be included [42].
well as their toxicity in general. Thus, the exact mechanism of AgNPs bi- Actually, the top-down approach is entirely based on physical synthesis
ological activity is still under consideration and is a challenge for future methods. The arc discharge is frequently utilized for bulk silver atomiza-
investigations. tion with subsequent Ag NPs formation, as in general, it considered as a
Due to high interest in nanotechnology and in particularly in Ag NPs fast and simple technique [43]. What is interesting, M. Miranzadeh with
engineering and utilization in last decades a multiple studies have been M. Z. Kassaee has shown that in the process the Ag NPs morphology and
performed, which in consequence was a reason for publication of sev- size can be controlled by utilization of different synthesis media [40].
eral review articles. However, the issue of Ag NPs synthesis, properties, However, authors have also claimed that synthesis medium influences
investigation techniques, the action mechanisms and application is so not only NPs morphology but also their purity, the size distribution, sta-
huge so it cannot be fit in the edges of one review. To give an example, bility against aggregation, and oxidation. Laser ablation is also well-
M. Oćwieja et al. review is focused on the formation of layered structure known for NPs synthesis. The primary features (e.g. size, chemical com-
of Ag NPs on different substrates [35]. In the article the basic approaches position) in the method can be influenced by the synthesis environment
for the Ag NPs synthesis and characterization was shown. However, the as well as laser parameters. The laser ablation in the water environment
main deliverable of the work is the excellent presentation of NPs depo- is a well-known technique for the production of ultrapure, monodis-
sition process on different substrates, including the adsorption kinetic of perse, and ultrafine Ag NPs [11]. The production of Ag NPs in the open
monolayers formation and its stability. In Rycenga et al. article the for- air was also revealed [44]. However, the presence of the oxygen may
mation of Ag NPs structures for plasmonic applications has been re- lead to the undesirable formation of Ag2O instead of metallic NPs,
vealed [21]. The authors, among others, have paid big attention to the even with the utilization of Ar jet at the interaction zone. Moreover,
plasmon phenomenon and possible ways to investigate it. P. Dubey the Ag NPs can be produced by thermal bulk silver evaporation/conden-
with colleagues in their work has reviewed the Ag NPs cytotoxicity sation. L. S. Kibis et al. have shown that within the method the final
[25]. The review presents the information about numerous effects product properties can be changed by synthesis conditions [39]. For in-
caused by Ag NPs to different cells. Moreover, the issues related to the stance, the thermal silver evaporation with the simultaneous transfer in
Ag NPs properties and applications is developed continuously and hun- the convective gas flow of oxygen led to the formation of oxidized Ag2O
dreds of new research articles appears annually. NPs. The same product was obtained with the silver sputtering by radio-
Thus, the purpose of the present study was to show the trends and frequency discharge in an oxygen atmosphere. By the changes of the ox-
achievements of the last years in Ag NPs synthesis and characterization. ygen to helium for the first method and to argon in the second case, it
The latest development in the field of instrumental techniques offers was possible to obtain metallic Ag NPs. The features of synthesized
new possibilities in materials science investigations. Hence, the manu- NPs by thermal evaporation were also affected by the position of the
script was prepared with the main focus on the capabilities of modern substrate relative to an evaporation device. Instead, the Ag NPs proper-
instrumental techniques in line with NPs and nanocomposites investi- ties produced by sputtering can be partially controlled by the sputtering
gations as well as their limitations. Finally, at the end of the review, time. Another route was introduced by O. Kylian et al., they have pro-
the attempt to consider the toxic mechanism of Ag NPs on the molecular duced polymer@Ag NPs deposited on the nylon 6,6 target by plasma
level was presented in a way that to the best of our knowledge has during gas-phase synthesis [41]. Finally, for the production of Ag
never been shown before. nanosized structures, the lithography can be utilized. The lithography
is a technique, which offers precise control over the shape, size, and
2. Synthesis placement of the synthesized nano-assemblies, which is very desirable
in plasmonic applications [36]. However, it should be mentioned that li-
Since the beginning of the nanotechnology, various routes for Ag NPs thography is highly labor-extensive, making the utilization of obtained
synthesis were introduced. The abundance of existing methods can be products very expensive. Some other physical, as well as chemical or bi-
divided into two basic synthesis approaches, namely top-down and ological approaches for Ag NPs synthesis can be seen in the Table 1.
3
Fig. 1. The principles of Ag NPs synthesis.
2.2. Chemical synthesis different shapes and sizes, such as spherical, rod-like, triangle, and
even coupled “cookie-like” from the same set of the reagents [54]. How-
Chemical synthesis implies the NPs production through chemical ever, the uniform colloid was possible to obtain only for spherical NPs,
transformations of the starting materials. The process requires the pres- while rod-like and triangle together with spherical NPs occurred in so-
ence of three main components, namely metal precursor, reducing lution as a mixture of different molar ratios. The silver mirror reaction
agent, and stabilizing/capping agents [42]. The fourth important com- involves the utilization of Tollen's reagent, Ag(NH3)2OH as a precursor,
ponent for NPs synthesis is a solvent, as the majority of the chemically and the aldehyde-group containing reducing agent (which may be
and biologically conducted Ag NPs fabrication performed in the solu- sugars) for Ag NPs fabrications. The Tollen's reagent is not as popular
tion. However, in W. H. Eisa et al. the solid-state production of Ag NPs in Ag NPs synthesis as AgNO3, but in some cases provides additional
was performed by milling of Zingiber officianale powder with silver ni- possibilities for different valuable synthesis routes. To give an example,
trate salt in desktop vibrating mill machine [45]. The distilled water P. Yang with colleagues has shown the fascinating approach for tuning
and ethanol were utilized only at the end of the process for obtained Ag@resorcinol-formaldehyde resin core-shell NPs to inverse
NPs purification from unreacted species. The majority of chemically resorcinol-formaldehyde-core@Ag shell NPs through the formation of
synthesized Ag NPs are made by four chemical reactions: citrate Tollen's reagent by the mixture of NH3/O2 gases [10]. Moreover, J. Yoo
(Turkevich) method [46,47], borohydride reduction [48–51], Tollens et al. have produced the Ag NPs via hydrazine reduction of Tollen's re-
(silver mirror) reaction [10], polyol process [52,53]. Turkevich method agent obtained from the dissolution of AgCl in ammonium hydroxide
involves the utilization of AgNO3 as the metal precursor and trisodium solution [57]. Insoluble nature of AgCl makes difficult to utilize it as a
citrate both as a capping and stabilizing agent [46]. Even though the cit- precursor in synthesis, but with the transformation to Tollen's reagent,
rate method was one of the very first proposed for Ag NPs synthesis, it is it becomes possible to produce Ag NPs. In turn, the AgCl is one of the
still extensively utilized by researchers. The method is cost-effective and products that can be retrieved by recycling of silver-containing scrap.
does not require advanced manipulation, so it is often utilized for NPs The utilization of polyols for Ag NPs synthesis is related to the possibility
behavior investigations [47]. The borohydride reduction implies the uti- to engineer NPs with desired properties. By changes in the reaction con-
lization of NaBH4 as a reducing agent. The borohydride exploitation for ditions, such as temperature, reagent concentration, variations of polyol
NPs synthesis seems to be the most popular among other chemical been used, or the presence of trace ions, the high degree of shape and
methods [48–51]. The popularity of NaBH4 for Ag NPs production size control can be achieved [52,53]. What is interesting, in the process
comes from the fact that it has higher reducing capability than citrate, polyol serves both as a reducing agent and the solvent. Some other syn-
and therefore it can be utilized for more precise size and shape control thesis approaches can be utilized, for instance Y. Tian et al. have pre-
in Ag NPs synthesis [54,55]. To give an example, the utilization of pared the flower-looked Ag NPs by reducing AgNO3 in the presence of
NaBH4 for the reduction of Ag2O has provided the possibility to form ascorbic acid and citrate ions as reducing and capping agents respec-
hollowed Ag NPs [56]. Instead, the utilization of less active reducing tively [58]. Besides, the chemical transformation of precursor can be in-
agents led either to the formation of a hollowed structure with lower ef- duced by different physical agents, such as heat or electromagnetic
ficiency in case of hydrazine or even did not resulted in hollowed mor- irradiation, so this group of methods can be defined as physicochemical
phologies at all, as it was shown for ascorbic acid. Moreover, the precise approaches. To give an example, H. Le Trong et al. have synthesized Ag
utilization of NaBH4 as a reducing agent allows to synthesize NPs with NPs by thermal decomposition of silver oxalate [59]. However, long
4
Table 1
Methods of AgNPs synthesis.
Method Precursor Synthesis conditions Stabilization Product Ref.

system
Physical Ag 99.9% Ar ion beam sputtering, Ag target (Ø 54 mm, 0,1 mm Deposited on Ag NPs 1.7–3.1 nm on glass coverslips [8]
thickness), metal-support distance 80 mm, current 4 mA, glass support
t = 4 s, chamber flushed with argon, synthesis
P = .04–.05 mbar
Ag 99.9% Thermal evaporation, Ag target (10 × 10 mm,0.2 mm in Gold foil Ag NPs with 3–9 nm, mean 6 nm [39]
thickness) rolled into cylinder, placed in chromel wire helix (99.9%) Ag2O NPs 1–5 nm/twinned 8–10 nm
(previously annealed in O2 atmosphere at 1000 °C), heated support (crystallite 2–3 nm)
to 700 °C in He (10 Pa) and O2 (1 kPa) environment
Ag 99.9% Radio-frequency discharge sputtering, silver electrode Ø Tantalum Ag2O/AgO NPs ≈ 4.5 nm [39]
2 mm in O2 (25 Pa), support was preoxidazed in O2 (99,9%) foil
(100 Pa) at 300 °C, 30 min
Ag 99.9% Target substrate distance 0.5–1.5 cm, Nd:YVO4 laser, Deposited on Ag/Ag2O NPs from 8 to 40 nm, with mean diameter [79]
moving speed 100 mm/s, λ = 532 nm, 50 ns pulse, 20 kHz glass support 14.7 nm
average output 6 W, irradiance of 100 MW/cm2, open air, in
jet of Ar
Ag 99.9% Ag target (Ø 20 mm, 4 mm thickness), polished by – Average size Ag NPs depending on pulse energies [11]
sandpaper, washed with water and ethanol, immersed in 3.2 nm, 6.0 nm, 9.1 nm
deionized water, treated with pulsed laser ablation, Nd:YAG
laser, λ = 1064 nm, 10 ns pulse, 10 Hz frequency, single
pulse energy 435, 406 and 365 mJ/pulse
Ag 99.9% Wires Ø1 mm used as electrodes, submerged in deionized – Ag NPs with average sizes of 10 nm and 100 nm [43]
water at 25 °C, arch discharged initial voltage of 135 V, 6,4 A
peak current, on-pulse and off-pulse duration - 50 μs
Ag 99.9% Ag electrodes (Ø 2 mm, length 40 mm), exposed in different – Ag NPs 35 to 100 nm, shape, depending on [40]
media (glucose/distilled water 10% and 25% w/w, medium: rice shape, spheres, beads, grapes,
glycerin/distilled water 10% and 25% w/w, phenol/distilled platelets, balls, sponge particles, green bean
water 5% w/w, Mg(NO3)2•6H2O/distilled water 0.01% w/w shaped, cloudy leaflets, stacked plates, seeds
and 0,05% w/w, xylene, ethylene glycol, ethyl acetate, and
phenol/toluene 5% w/w) with pulses of 5–10 A/cm2, the
cathode-anode gap was ≈ 1 mm, the NPs were separated by
centrifugation and dried at 70 °C for 24 h
Chemical AgNO3 Twelve similar mixtures with sodium citrate, PVP and H2O2 Citrate Triangle, sphere, rod-like and cookie-like Ag NPs Ø [54]
were added to AgNO3 solution under stirring. Different from 3 to 30 nm, different aspect ratios
amounts of NaBH4 solution were utilized for each mixture,
stirred for 3 h, then filtered through 0.2 μmmembrane filter
AgNO3 HAuCl4 HAuCl4 solution was added to heated AgNO3 solution, after Citrate 50 ± 9 nm Au0.5Ag0.5 NPs with Ag prevalence in [47]
mixture started to boil sodium citrate was added, keeped the shell
boiling for 30 min
AgNO3 AgNO3 was added to 0.4 mM Cetyltrimethylammonium CTAB Triangular Ag NPs with different edge length [50]
bromide (CTAB) solution under stirring, then NaBH4 (the smallest 46 nm and 14 nm thickness)
solution was added, obtained seeds kept in dark (1 h), then
seeds were added to freshly prepared solution of AgNO3,
ascorbic acid and 10 mM CTAB
AgNO3 AgNO3 solution, NaCl and sodium citrate premixed together, Citrate 23 nm Ag NPs seeds [3]
quickly added to boiling water, reducing agent - ascorbic
acid, heated and stirred for 1 h
[Ag(NH3)2]+ Different amount of AgNPs seeds were added into water at Citrate 40–300 nm Ag NPs, depending on amount of Ag [3]
room temperature, then ammonia complex solution and NPs seeds
ascorbic acid was added, stirred for 1 h, the AgNPs separated
by centrifugation and redispersed in sodium citrate solution
[Ag(NH3)2]+ Mesoporous silica was mixed with [Ag(NH3)2]+, sonicated Embedded in Silica‑silver nanocomposite [12]
for 2 h, placed in dark at ambient temperature overnight, silica
then dried at 60 °C in an air-circulated oven
AgNO3 AgNO3 with PVP mixed in ethylene glycol, heated at 120 °C Silica 65–90 nm Ag@SiO2@Agseed NPs with surface seeds [13]
for 1 h, cooled solution added to ethanol/water mixture, ≈ 5 nm
then TEOS and ammonia were added, stirred for 1 h at room 70–100 nm Ag@SiO2@Ag NPs with surface
temperature. Further, to induce AgNPs growth on surface Ag NPs ≈ 12 nm
the NaBH4 was added to mixture, stirred for 1 h
AgNO3 The 1:15:15 M ratio of DNA:Ag+:NaBH4 was utilized. DNA DNA-harbored Ag clusters with ≈ 4 nm size [15]
Previously the DNA assembly with specific sequences was
prepared in phosphate buffer saline in 37 °C for 2 h, then
Ag+ ions were added and kept in dark at 4 °C for 1 h,
subsequently NaBH4 was added, the reaction maintained for
5 h in dark at 4 °C
AgNO3 AgNO3 and glutathione (molar ratio 4:3) was added to the Glutathione 2–10 nm Ag2S NPs, depending on reaction time [14]
flask under nitrogen flow with heated (120 °C) ethylene
glycol, kept at 120 °C for 1 min to form colorless solution,
then the temperature increased 165 °C with heating rate
20 °C/min. The reaction mixture cooled in ice-water bath in
different time points (11, 13, 15, 16, 22, 28 min)
AgNO3 AgNO3 solution and glutathione was added to ice cold water, Glutathione 1. Hollow Ag NPs, 2. ordinary Ag NPs, 3. hollow in [56]
pH raised to 12 by NaOH solution the formation of Ag2O-NPs part Ag NPs, 4. hollow Ag2S NPs, 5. hollow AgBr/Ag
was observed. To the obtained Ag2O nanocrystals separately NPs
the 1. NaBH4 solution, 2. ascorbic acid, 3. hydrazine, 4.
sodium sulfide or 5. sodium bromide was added at once
(continued on next page)

Table 1 (continued)

system
CF3-CO2Ag Ag trifluoroacetat was dissolved in isoamyl ether/oleic acid Oleic acid Hydrophobic Ag NPs ≈ 5.2 nm [80]
mixture at 160 °C under N2 atmosphere, then precipitation
was performed with sonication in ehtanol and subsequent
centrifugation (3000 rpm)
AgNO3 NaBH4 and citrate mixture heated to 60 °C for 30 min, then Citrate Ag NPs with size 5–100 nm, depending on Ag+ [55]
AgNO3 was added drop-wise and temperature was raised to amount
90 °C, then the pH was adjusted to 10.5, the reagent excess
was removed by centrifugation (12,000 rpm) and washing
with deionized water
AgNO3 AgCl Ethylene glycol (EG) was heated to 140 °C, subsequently the PVP 1. Irregular/polydisperse Ag NPs, 2. truncated [52]
HCl/EG, the AgNO3/EG and PVP/EG solutions were octahedra; 3. nanowires, nanocubes and irregular,
simultaneously introduced, after 8 h the mixture removed 4. nanocubes, 5. cuboctahedra and truncated cubes,
from heat, the vial was kept loosely capped for 20 h and 6. nanocubes, 7. nanocubes
then tightened. The tests with addition of different amount
of HCl, NaCl and HNO3 were performed: 1. pure EG (with no
HCl), 2. with addition of HNO3 (no HCl), 3. with NaCl (no
HCl), 4. standard procedure, 5. HNO3 and NaCl (no HCl), 6.
HNO3 and HCl, 7. AgCl and HNO3
AgNO3 PVP/EG solution was heated to 160 °C, then NaBr/EG PVP Ag nanowires, ≈ 20 nm diameter [53]
solution was added, subsequently dropwise AgNO3 was
introduced, kept for 35 min and then transferred to
ice-water bath, the product crushed by acetone, separated
(2000 rpm) and washed by water
AgNO3 The synthesis in microfluidic device, where to the first inlet Citrate Triangular Ag NPs [81]
the mixture solution of AgNO3, trisodium citrate and H2O2
and to the second inlet solution of NaBH4 were introduced
To the first inlet the triangular nanoparticles with TEOS and SiO2 shell Triangular Ag@SiO2 NPs
to the second inlet the ammonia in ethanol were introduced
Physico-chemical AgNO3 Laser ablation of 99.9% purity silicon target immersed in Silica Ag@SiO2 NPs, with 11 ± 4 nm core and 1–2 nm [82]
AgNO3 solution, Nd:YAG laser, λ = 355 nm, pulses <40 ns shell
frequency 5 Hz, power density per pulse <40 J/cm2
Ag2C2O4 Silver oxalate decomposition at 125 °C for 100 h – Ag NPs 5–20 nm [59]
AgNO3 Dipped platinum anode and stainless-steel capillary tube Fructose Polydisperse irregular Ag NPs [63]
utilized as cathode immersed in solution of AgNO3 with
fructose
AgNO3 99.9% titanium anode and cathode Ø 2 mm were immersed Citrate Ag NPs ≈ 18 nm [62]
in AgNO3 solution, 15 A current and 3 V voltage
Biological AgNO3 Flavone, chrysin, galangin, 3-hydroxyflavone, kaempferol, Flavonoids Ag NPs 12–39 nm size, which depends on flavonoid [7]
quercetin, myricetin, apigenin, luteolin, tricetin mixed with been used and synthesis temperature
the AgNO3 solution, pH adjusted to different values from 7.2
to 10.1, depending on flavonoid been used, the reaction
carried at 23, 40, 70 °C
AgNO3 Different amount of beetroot extract were mixed with Betanin Ag NPs spherical, triangular and truncated [75]
AgNO3, reaction maintained overnight triangular ≈ 15 nm
AgNO3 Lactoferrin, suspended in 0.09% NaCl, pH = 6, then AgNO3 Lactoferrin Lactoferrin-conjugated Ag NPs with sizes 8–18 nm [16]
basic solution was added, the nanocomplex was separated
by centrifugation 15,000 rpm, at 4 °C
AgNO3 Casein suspension in 0.05 M ammonium bicarbonate Casein Casein-conjugated Ag NPs in size range 4–100 nm [83]
solution was mixed with AgNO3 solution incubated at room
temperature for 24 h, the nanocomplex was separated by
centrifugation max speed for 8 min
AgNO3 Essential oil of orange peel was mixed with AgNO3 solution, Compounds of Ag NPs ≈ 3 nm [66]
stirred at 70 °C for 48 h essential oil
AgNO3 Solid state synthesis by milling of Z. officinale powder with Compounds of Ag NPs with average size 11, 16, 20 and 24 nm, [45]
0,05–0,5 g of AgNO3 salt, in hardened chromium steel jar Z. officinale depending on AgNO3 amount
with zirconia balls Ø 3 mm, 50 rpm, 30 min, balls:reacting powder
powder was 15:1 w/w
AgNO3 Aqueous plant extract was mixed with aqueous AgNO3 Compounds of Coated Ag NPs with size in range 40–80 nm [20]
solution, kept in ambient temperature for 4 h S. chinensis L.
extract
AgNO3 To chitosan (50–190 kDa) dissolved in 0,5% acetic acid at Embedded in Ag NPs - chitosan films <5 nm, (Ag 0.1–0.5%) and [17]
40 °C, cooled to room temperature, the AgNO3 solution (to chitosan Ag NPs
corresponding concentration 0.1, 0.2, 0.5, 1.0 and 1.5%) was 5–10 nm, (Ag content 1–1.5%)
added, then mixture was kept protecting from light to
complete dissolution, films were formed on polystyrene
plates and dried at 37 °C for 48 h
AgNO3 Bacillus licheniformis biomass was mixed with AgNO3 Compounds of 40–50 nm Ag NPs [19]
solution, then kept on shaker (200 rpm) at 37 °C for 24 h, Bacillus
then the biomass was removed by sonication and licheniformis
centrifugation (4000 ×g, 10 min), Ag NPs was purified by biomass
dialysis with 12,000 Da cut-off and by ultracentrifugation
(200,000 ×g at 4 °C for 16 h) from HEPES buffer with
sucrose gradient
6
Table 1 (continued)

system
AgNO3 L. lactis isolated from milk was incubated for 5 d at 26 °C in Compounds of Biocomposite with Ag NPs ≈ 19 nm [84]
Mueller-Hinton broth, culture was centrifuged (9000 rpm), L. lactis
supernatant was combined with AgNO3 solution, kept at supernatant
26 °C for 7 d, biocomposite separated by centrifugation
(14,000 rpm) for 30 min
AgNO3 O. limnetica homogenate in phosphate buffer pH 7 mixed Compounds of Quasi-spherical Ag NPs with 3–18 nm size [85]
with AgNO3 solution, kept at 35 °C under illumination for O. limnetica
48 h homogenate
AgNO3 Fungal cell filtrate of 1. Alternaria species, 2. F. oxysporum, Compounds of Ag NPs of 1. 7–20 nm, 2. 4–13 nm, 3. 5–23 nm, [86]
3. Curvularia species, 4. C. indicum, and 5. Phoma grown on fungal cell 4. 10–31, 5. 7–20 nm
potato dextrose broth at 28 °C for 72 h, mixed with AgNO3 filtrate
solution
heating caused metal sintering, which led to the formation of bigger approaches, only the reducing and capping agents involved in the reac-
NPs. Moreover, B. B. Bokhonov with coauthors has shown that thermal tions should be of biological origin.
decomposition of silver salts of fatty acids led to the formation of self- The “hot topic” in the biological synthesis of Ag NPs is the utilization
assembled Ag NPs [60]. The authors have also observed the NPs of plants [45], fruits [20], plant seeds [67], or their extracts [68,69].
sintering with an increase in temperature above 260 °C. It was sug- Moreover, the Ag NPs production with mushroom extract [70], marine
gested that fatty acids stabilize the Ag NPs assemblies, but the elevation algae [71] and even propolis [72] have been shown. To the active com-
of the temperature led to the desorption of carboxylic acids and subse- pounds, that can be involved in the Ag+ reduction, and therefore NPs
quent aggregation. Y. Cai with colleagues has performed the deposition formation, the sugars [67], terpenes [66], amino acids [73], flavonoids
of uniform Ag NPs on stainless steel plates by AgNO3 decomposition [7], and other phenolic compounds [74] can be include. To give an ex-
with laser irradiation [61]. They proposed the NPs formation mecha- ample, R. K. Tomas et al. have produced Ag NPs with chlorogenic acid,
nism, which comprises the AgNO3 decomposition through Ag2O forma- which served both as a reducing and capping agent [74]. M. Svecova
tion with subsequent reduction to Ag under laser heating. However, the with coauthors has performed the Ag NPs synthesis with different flavo-
authors claim that the laser power should be controlled precisely. It was noids for SERS applications [7]. H. Veisi with colleagues has utilized the
shown that low laser power was not sufficient to perform high efficient orange peel essential oil, composed mostly from limonene, to produce
synthesis, while very high laser power led to overheating and to Ag NPs Ag NPs [66]. Moreover, the natural plant-derived pigments such as
evaporation and sputtering. Additionally, even though, in general, arc betanin [75] and curcumin [76] have also shown to be effective in the
discharge usually is utilized for the atomization of the bulk metal in Ag NPs synthesis. What is interesting, the curcumin-based Ag NPs
NPs synthesis, it can also be utilized for AgNO3 transformation to Ag have revealed the synergistic antibacterial effect against E. coli and
NPs [62]. Moreover, the H. M. Yasin with coauthors has revealed the B. subtilis. Finally, in S. Shankar and J.-W. Rhim work the amino acid me-
possibility to utilize micro-plasma for Ag+ reduction in the solution to diated Ag NPs formation was shown [73]. The authors have also utilized
form fructose-coated Ag NPs [63]. The arc discharge as well as micro- agar for the production of novel functionalized nanomaterials, which
plasma are the source of the fast electrons, which take part in the Ag+ supposed to be useful in biodegradable packaging films formation.
reduction. It is obvious that the amount of produced electrons plays a The polysaccharide utilization for nanocomposites production in
crucial role in the reduction process, thus providing an opportunity to general is very popular in line with their medical applications. The Ag
control the synthesis. Moreover, the Ag NPs basic parameters can be NPs-containing hydrogels and other polymer films are of the big inter-
controlled with the amount of utilized precursor and capping agent. It est for wound healing scaffolds and bandages production. Y. Jiang
was shown, that a lower ratio of stabilizer to precursor led to the forma- et al. have investigated the antibacterial and cytotoxic properties of Ag
tion of bigger NPs with higher polydispersity, which can be explained by NPs-containing hydrogel based on konjac glucomannan and chitosan
the increased contribution of aggregation in the NPs growth [63]. The [77]. S. Ul-Islam et al. [78] as well as G. Lopez-Carballo et al. [17] have
electrolysis has also been used for Ag+ reduction, where the mechanism also utilized chitosan for production of new functional materials. In-
of NPs formation is similar to that one with the utilization of micro- stead, A. K Kodoth et al. have revealed a possibility to utilize pectin for
plasma [64]. Finally, the synthesis mediated by UV-Vis irradiation al- the synthesis of transdermal drug-delivery Ag-containing films [87].
lows to change NPs shape [65]. It was suggested that UV-Vis irradiation J. H. Lee with coauthors has also exploit pectin and pullulan for antimi-
increases the energy of small Ag nanoseeds, which then caused aggrega- crobial films formation [88]. Proteins and nucleic acids are another bio-
tion with the formation of Ag NPs of different shapes. polymers that show beneficial features in Ag NPs production. Recently,
in our group, the synthesis of Ag NPs-containing nanocomposites based
2.3. Biological methods on whey proteins was performed [16,83]. Moreover, the Ag NPs forma-
tion through lysozyme [89], trypsin [90], and cytochrome C [91] was re-
Recently, more attention is paid for the impact of the technologies on vealed. Finally, the self-assembled Ag NPs formation with G4-DNA has
the environment. Thus, the so-called “green chemistry” becomes more been shown by I. Libitz and A. Kotlyar [92].
popular. Regarding Ag NPs, the biological synthesis methods are consid- Lately, it has become more popular to create Ag NPs via microorgan-
ered to be eco-friendly, as for their production the harmful chemicals ism synthesis. It was shown that bacteria [19,84,93,94], fungi [86],
are not involved. Moreover, the biologically synthesized NPs in general cyanobacteria [85] and even viruses [95] can be utilized for NPs synthe-
exhibit lower toxicity to eukaryotic cells, so they provide a possibility for sis. The viruses capsid predominantly comprise proteins, so it can be
their exploitation in biomedical applications. The lower toxicity of bio- considered as protein-mediated Ag NPs synthesis. Instead, the Ag NPs
logically synthesized NPs is attributed to the fact, that the capping synthesized by cellular organisms can be performed in several different
agent is formed with the compounds such as proteins [16], terpenes ways, namely intracellular and by utilization of culture supernatant,
[66], flavonoids [7], which naturally can be found in an organism. Bio- bacterial biomass, or cell-free extract [96]. The components of the syn-
logical synthesis is based on the same principles as for chemical thesis mixture act both as a reducing agent and the stabilizer, forming
7
Fig. 2. The structure of AgNPs with organic deposits on the surface.
the organic deposits on the surface of the NPs (Fig. 2). Unfortunately, the the metal precursor in general leads to bigger NPs formation [68]. In-
exact mechanism and substances that are involved in the Ag NPs forma- stead, the high reaction rate at the beginning of the process makes it
tion are still unclear. Moreover, S. M. Mehta et al. have revealed the pos- possible to produce a bigger amount of NPs with a lower size. Thus, it
sibility to exploit tryptone, the component of various culture media, for can be derived that the reduction potential and utilized amount of re-
Ag NPs synthesis, which makes the interpretation much more compli- ducing agent, which influences the reaction speed, is one of the major
cated [97]. Additionally, a lot of culture media for microorganisms factors. The redox potential of Ag+ can also be influenced by pH value.
growth comprise casein hydrolysate, and investigations of our group Obviously, the reaction can be affected by changes in temperature
have shown that casein is able to reduce Ag+ without any additional [3,56,68].
conditions [83]. The aggregation plays an essential role in the NPs formation (Fig. 1).
However, it should also be mentioned that with the utilization of the The widely accepted theory implies NPs growth through the aggrega-
biological synthesis, the control of NPs basic parameters is less precise. tion of the crystal nuclei [68,99]. Moreover, the liquid-cell TEM have re-
Hence, the utilization of biologically synthesized Ag NPs is rather revealed the formation of sub-10-nm Ag nanorods through smaller quasi-
stricted in different devices or in advanced analytical techniques, spherical particles aggregation, which can be considered as the evidence
where the desired optical features of the NPs are obtained by the of previously accepted theories [100]. However, uncontrollable aggre-
changes in shape and size. Moreover, the biological systems may in- gation can lead to the formation of more massive structures, that no lon-
clude some contaminants that disturb the synthesis. To one of such con- ger possess the unique features of NPs. Thus, sufficient stabilization is an
taminants the Cl− can be include, which forms the insoluble AgCl, thus indispensable part of NPs synthesis and storage. Still, in A. Suresh et al.
tending to form non-metalic AgCl NPs [71]. Generally, the production of work the synthesized uncoated Ag NPs unexpectedly revealed zeta po-
pure metallic NPs is a challenge in biological approaches, which attracts tential −42.5 mV in deionized water, which is considered to be enough
big attention of the scientists. The Cl− is an integral part of culture for NPs stabilization through electrostatic mechanism [101]. The effect
media for microorganisms growth. Thus the utilization of microorgan- was attributed to the adsorbed nitrate ions on the NPs surface. The H.
isms for Ag NPs synthesis often leads to the formation of undesirable Kang et al. in their review have shown the variety of approaches in-
AgCl or composed Ag/AgCl NPs. The main question, which appears dur- volved in the stabilization of plasmonic NPs [102]. Besides the ap-
ing such a synthesis process is which kind of the product has been ob- proaches that already have been shown above (i.e. citrate, PVP,
tained. In some cases, the scientists make erroneous statements by flavonoids, proteins, DNA, polysaccharides, etc.) the utilization of inor-
incorrect interpretation of obtained data. N. Duran et al. have reviewed ganic shells induces high interest among the researchers. Silica coatings
the articles focused on biogenic Ag and AgCl NPs synthesis and they no- have shown beneficial properties during metallic NPs utilization [103].
ticed, that in some cases the researchers claim the production of metal- To silica virtue, the high stability to the water environment, various
lic Ag NPs, while the XRD (X-ray Diffraction) for such products exhibited chemicals, and elevated temperatures can be include. Moreover, silica
only the formation of AgCl [98]. is transparent for electromagnetic irradiation in the wavelength range
from 300 to 800 nm, which makes it possible to utilize in the synthesis
2.4. Size and shape control of different nanocomposites for optical applications. The different silica-
containing structures can be easily produced through a highly-
One of the major issues in the NPs production is a size control, as size controllable Stöber process. More synthesis details and properties of
determines NPs physical and biological properties. The NPs formation is silica-containing structures can be found in B. J. Jankewicz et al. work
the complex process, which in general can be divided into several main [104]. It should be noted, that besides the stabilization of the NPs
parts: nucleation, growth through Me0 incorporation, and the aggrega- the capping agent also determines the surface charge of the NPs,
tion. The nuclei formation is a thermodynamically dependent process which in general is a reason for electrosteric stabilization mechanism.
[99]. The surface free energy always being positive, meaning that nuclei To give an example, A. Suresh et al. have synthesized Ag NPs with
appearance is a thermodynamically disadvantageous process. Instead, different capping agents [101]. The Ag NPs stabilized with poly
crystal growth leads to a decrease in system energy. Thus, the growth (diallyldimethylammonium) have a positive surface charge of +45 ±
process mainly depends on the possibility of mass exchange between 3.1 mV, biologically synthesized NPs have a negative charge of
NPs seeds and the solution as well as from the capability to aggregate. −12 ± 2 mV, finally, the NPs capped with oleate revealed the negative
T. K. Nguyen et al. in their excellent review have revealed the theoretical charge of −45.8 ± 4.4 mV. However, the authors have investigated the
details of the NPs nucleation and growth mechanisms in a solution [99]. cytotoxicity of as synthesized NPs, and it was shown that positively
It can be derived that Ag NPs size and size distribution are strictly de- charged Ag NPs have revealed the highest cytotoxicity against both
pendent on the time-resolved Ag0 concentration in the solution, macrophage cells and lung epithelial cells. What is interesting, the bio-
which in turn depends on the amount of metal precursor, that have genic Ag NPs, which supposed to be more biocompatible also have re-
been used as well as the reaction rate of Ag+ reduction. The excess of vealed higher cytotoxic properties than uncoated and oleate-coated
8
Ag NPs. The reason for such behavior partially can be explained by the transformation under heating or light irradiation [65]. C. -M. Tsai et al.
same mechanism as for NPs stabilization, namely electrostatic interac- have also shown the AgNPs prisms conversion by KSCN, which was de-
tions between charged objects. T. Silva et al., which also have synthe- pendent on the reagent concentration [114]. The effect can be explained
sized the positively charged NPs with the utilization of the branched by NPs partial dissolution with subsequent structure rearrangement,
polyethyleneimine as a stabilizer, claim that possible higher toxic be- namely the recrystallization process [115].
havior is due to the interaction of such NPs with negatively charged
cell wall [31]. In the case of biogenic Ag NPs, probably the relatively 3. Investigation techniques
low surface charge was not able to prevent interaction with cell walls,
thus causing a higher toxic effect. The properly planned experiment is a milestone in all investigations.
Another approach for size control is the limitation of the NPs forma- Advances in science and technique have introduced numerous sophisti-
tion volume, which implies the utilization of templates. D. J. Lipomi et al. cated devices, which can be utilized for nanomaterials study. The accu-
work can illustrate the approach in the simplest way [61]. Authors have rately chosen set of techniques can provide comprehensive information
produced the Au and Ag nanostructures by creating of protecting epoxy about the object under investigation. However, the received results can
masks on the substrate and subsequent deposition of metallic thin films. be affected by drawbacks and artifacts of utilized methods, and in con-
The epoxy masks then were etched from the surface, leaving the highly sequence, can lead to false conclusions. Thus, the scientist should con-
structured plasmonic nanoarrays. Generally, the formation of NPs layers sider all possible problems during their investigations. Table 2
on the substrates is of high interest for multiple applications in tech- presents the scope of the techniques and approaches for AgNPs and
nique and science. Therefore this issue is extensively investigated and their composites study, the more detailed description for them can be
shown in different articles. To give an example, in K.-M. Ng et al. work found below.
the NALDI plates were prepared by argon ion sputtering of Ag plates
with subsequent NPs deposition on the glass substrate [8]. In T. 3.1. Optical imaging
Nakamura et al. the Ag NPs were deposited on the hydrogen-
terminated silica by vaporization of Ag disk [105]. However, the pre- Conventional optical microscope due to diffraction barrier is re-
sented processes is highly labor-extensive, moreover in L.S. Kibis work stricted in the ability to distinguish between two points separated by a
it was shown that the presence of the oxygen in synthesis zone may lateral distance less than half the wavelength of visible light
provide to formation of undesirable Ag2O NPs [39]. Thus, the high inter- (≈200 nm), which in general makes difficult the direct investigation of
est attracts the possibility to form layered structures by deposition of Ag nano-objects. However, T. Huang with X.-H. N. Xu in their work showed
NPs prepared by chemical synthesis. M. Oćwieja with colleagues in their that the dark-field optical microscope (DFM) can be useful for single-NPs
excellent review work have revealed different methods for the AgNPs plasmonic microscope investigations [54]. The technique allowed to
layers deposition on the substrates together with the kinetics of the pro- study Ag NPs LSPR properties in solution depending on their size and
cess as well as the stability of formed structures [35]. At the end of the shape since NPs under DFM appeared as bright shining and colored
work authors have revealed the possible applications of the obtained spots. However, the dark-field optical microscopy and spectroscopy
materials. allow to study only the scattered light, therefore obtained single-NP
However, a more simple way is to use naturally formed templates LSPR represents the scattering of single NP, but not the absorption. Still,
for NPs size control. For instance, the polymers can be utilized for NPs dark-field microscopy was useful for single Ag NPs oxidative dissolution
synthesis, where inter-chain spaces serve as a reaction cavities for NPs monitoring [116]. The changes in the light intensity and color of the NPs
formation [106]. Moreover, I. Moglia et al. have synthesized AgNPs in over time clearly indicated the electrochemical dissolution process de-
the human ferritin cavity [107]. T. W. Giessen and P. A. Silver have also pendence from the applied potential. However, the technique usually re-
utilized a bioengineered protein compartment (bacterial encapsulin quires an intense light source and long exposing time (up to several
system) derived from T. maritima for uniform and stable AgNPs synthe- seconds) in order to collect spectra with satisfactory signal-to-noise
sis [108]. The highly structured frustules of diatoms can also be utilized ratio, so the fast dynamic observations can be impeded [151].
as a template for NPs synthesis [109]. Moreover, the viruses capside can Fluorescent and confocal microscopy are frequently utilized for in-
be considered as nanoreactor for NPs production [110]. Still, the utiliza- vestigation of the Ag NPs toxicity and antibacterial properties. To give
tion of microfluidic devices in line with their possibility in NPs size and an example, in T. Liu with colleagues work fluorescence microscope
shape control were reported [18]. Moreover, the microemulsion have been utilized for investigation of the surface-attached bacteria
method, where the micelles serve as a microreactors, has also shown and the influence of Ag NPs on bacteria capability to adhere [51]. Addi-
to be efficient for size control in AgNPs synthesis [111]. tionally, M. Assis et al. have studied the apoptosis and necrosis caused to
The second important Ag NPs feature that should be controlled dur- MB49 and BALB/3 T3 cells by Ag NPs/α-Ag2WO4 composite [119]. C. G.
ing synthesis is their shape, as it affected the NPs optical properties. The Castro-Gonzalez with coauthors has observed the migration and accu-
possibility to control Ag NPs shape is highly desired in plasmonic appli- mulation of Ag NPs in Stevia rebaudiana B. leafs by multiphoton fluores-
cations (surface-enhanced Raman spectroscopy, light energy harvest- cence microscopy, which allowed to identify preferable places of NPs
ing, photocatalysis, etc). As it was mentioned above, the NP formation accumulation [120]. The virtue of the fluorescent microscopy is that
begins from the nuclei or NP seed formation, then it goes through a the cellular components may be labeled through specific molecules,
metastable fluctuating state where the primary structure can be formed. allowing to observe the structures inside a live sample in real-time.
In the end, the particle obtained its final shape, which depends on mul- However, the conventional fluorescent microscope is limited by low
tiple factors: temperature, the concentration as well as the type of re- spatial resolution, which is near 200–300 nm in the lateral direction
agents that have been used, the presence of trace ions [48,52]. To give and 500–700 nm in the axial direction [152]. Lately, new possibilities
an example, T. Huang with X.-H. N. Xu has performed the Ag NPs syn- were implemented with such techniques as stimulated emission deple-
thesis with various shapes by changes in the amounts of NaBH4 added tion microscopy and super-resolution fluorescent microscopy per-
to the reaction mixture [54]. J. Wu et al. have shown that in DNA- formed with single molecule imaging, so the resolution can be
mediated Ag NPs synthesis the nucleotide sequence can affect the enhanced to ≈ 30–40 nm in an axial direction [152]. Still, it should be
final morphology [112]. I. Chakraborty with colleagues has also shown noted that for NPs tracking in different parts of an organism the fluores-
that synthesis with different proteins, i.e. lysozyme, apotransferrin, avi- cent labeling by different ligands is often utilized. However, in C. Kastner
din, β-lactoglobulin, BSA (bovine serum albumin), hemoglobin, ovalbu- et al. work it was shown that the low stability of such complexes may
min, and catalase, led to the formation of AgNPs with different shapes lead to false results, as enhanced fluorescence may be due to free ligand
[113]. Moreover, the NPs shape can be changed by post-synthesis but not the complex [153]. They showed that tyrosine may provide
9
Table 2
Instrumental techniques for study of Ag-containing NPs and NCs.
Technique Study purpose Information Artifacts/problems Ref.
Dark-field Ag NPs features Single-NP scattering LSPR for NPs with different shapes Low sensitivity, which requires intense light source and [54]
microscopy were defined long exposing time (up to several seconds)
Ag NPs dissolution Changes in the NPs color and scattering LSPR intensity, [116]
kinetics which were dependent from applied potential were
revealed
The influence of The red-shifts in Ag NPs LSPR were observed with [117]
surrounding media on increasing in refractive index of surrounding media
LSPR
Ag NPs interaction with The light scattering enhancement from the algae cells [118]
green algae treated with Ag NPs was observed in comparison to
control sample
Fluorescent Attached bacteria on the The results have shown the lower quantity of attached Low spatial resolution, low affinity of labeling molecules [51]
microscopy surface bacteria on the surfaces doped with Ag NPs to NPs can lead to misinterpreta-tion
The Ag NPs/α- Ag2WO4 MB49 and BALB/3 T3 cells stained with acridine [119]
toxic activity to cells orange/ethidium bromide revealed the changes in the
color intensity and uniformity, indicating the apoptosis
and necrosis
NPs migration in leafs Multiphoton fluorescent microscopy revealed the places [120]
of NPs distribution in stem and leafs of Stevia
rebaudiana B.
SEM Ag NPs morphology SEM images revealed predominantly spherical Ag NPs Non-conductive samples surface charging, sample [57,66]
shape damage and transformation (i.e. reduction), artifacts
Surface morphology Images revealed the formation of Ag NPs shell on silica from sample preparation (aggregation, size reduction, [78,121,122]
changes rods and spheres, Ag NPs deposition on polyester and shape change, sample cracking)
linen fibers
Ag NPs biological activity SEM revealed damage caused to bacterial cells B. subtilis, [76,123,124]
E. coli, S. aureus. The epidermal fissuring in C. elegans was
shown
Ultrathin surface The images of the surface morphology of R. subcapitata [118]
morphology exposed to Ag NPs were made by more sensitive SE
electrons
Ag NPs uptake by The presence of 3138 ± 722 Ag NPs within one [125]
FIB/SEM macrophage was revealed, mostly agglomerated, the
distribution inside cell organelles cannot be
discriminated
TEM Ag NPs features Ag NPs size and size distribution were defined Non-conductive samples surface charging, sample [48,126]
Ag NPs shape and structure were defined damage and transformation (i.e. reduction), aggregation [54,127]
The lattice spacing in crystals was measured during sample preparation, the technique requires [16,90]
Ag NPs growth LP-TEM revealed the formation of Ag-nanorod through ultra-high vacuum, thin sample < 100 nm [100]
small spherical NPs aggregation
Cryo-TEM Ag NPs assemblies The formation of chain-like Ag NPs aggregates mediated [128]
by 2,2′-bipyridine decorated peptoids was defined
+
Ag remediation The adsorption of Ag+ and distribution all over the [129]
bacterial cell surface with subsequent Ag NPs formation
was revealed (made by EDX mapping)
AFM Ag NPs size The measured size for 100 NPs ≈ 20 ± 8 nm, while Electrostatic charging, which can change the movements [130]
measured by TEM were 22 ± 6 nm of cantilever
Surface morphology Spherical Ag NPs formed by glucose were in size 10.3 nm [131]
and uniformly distributed on the support surface, while
formed with dialdehyde nanofibrillated cellulose were
with diameter of 19–37 nm and deposited along the fiber
position
NSOM Ag NPs The LSPR for Ag NPs was performed, which revealed the The interference of emitted by tip light with scattered, [132]
red shift in comparison to UV-Vis due to coupling effect coupling effect with conducting tip
The NPs spherical shape and topography was defined
DLS Ag NPs size Measured size was 79 ± 0.5 nm in water, 71 ± 0.2 nm Aggregation, measurements are highly dependent from [125]
in cell culture medium the surrounding media (the concentration of NPs, ions,
Ag NPs aggregation, ζ-potential of citrate-capped was −27.7 ± 5 with proteins and other molecules, pH, viscosity, etc.) [49]
ζ-potential hydrodynamic radii 27.8 nm (TEM - 10.1 ± 1.8 nm),
prepared with green tea extract −36.2 ± 5 with
hydrodynamic radii 87.7 nm (TEM - 8.3 ± 3.6 nm). The
Ag NPs prepared with green tea extract showed higher
aggregation stability in solutions with different content
of NaCl, glucose, glutamine, cell culture component and
different pH
UV-Vis Ag NPs LSPR Au@Ag nanocuboids longitudial band ≈552 nm, and The sample should be clear with no dust and bubbles [133]
transverse ≈461 nm
Spherical Au0.5Ag0.5 NPs band ≈ 470 nm [47]
Hollow Ag NPs LSPR band ≈ 480 nm [56]
Triangular Ag NPs, out-of-plane quadrupole band [50]
339 nm, out-of-plane dipolar band 414 nm, in-plane
dipolar resonance 523–585 nm
Ag NPs stability The freshly synthesized NPs LSPR ≈ 400 nm, the NPs [130]
exposed to sunlight for 25 days get another bands (470,
600 nm)
10
Table 2 (continued)
Fluorescence Pb2+ quantification 1.45 ± 0.3 nm Ag NPs capped with polymethacrylic acid Inner Filter Effect (IFE I and II), absorbance by impurities [134]
revealed linear fluorescent enchantment depending on and quencher in fluorescent band, the presence of
Pb2+ concentration in range from 0.0 to 1.0 μM fluorescent impurities
Dopamine quantification Fluorescent AgNPs ≈ 10 nm capped with 4-mercapto [135]
phenylboronic acid and 40-aminobenzo-18-crown-6
revealed linear quenching depending on dopamine
content (0.001–0.1 mM) due to NPs aggregation
FTIR Ag NPs formation and 1214.5 cm−1, 3072.4 cm−1 bands appearance, increase The specific bands hardly can by discriminated due to [136]
functionaliza-tion in 1455.7 cm−1, shift 1635.7 cm−1 → 1627 cm−1 after overlapping and significant shifts depending on
ampicillin binding molecular structure
Presence of 1694 cm−1 stretching band of C_O group [137]
and 734 cm−1 of weak S\ \S vibration revealed
alpha-lipoic acid binding
The AgNPs formation and binding to lactoferrin affected [16]
the infrared spectra in range 1650–1400 cm−1
Raman Ag NPs functionaliza-tion The vibration between Ag(0) surface and pyridine Fluorescence of sample and impurities as well as [128]
study nitrogen was revealed by appearance of 241 cm−1 on adsorption by matrix can burdened the study, heating
spectra may damage the sample and can cause blackbody
SERS study All SERS spectra of Ag NPs with lyzozyme, BSA, thermal emission [89]
cytochrome-C and hemoglobin has band ≈ 240 cm−1
attributed to Ag\\N and Ag\ \S, band ≈ 1630 cm−1, which
replaces the amide I band at 1655 cm−1, the shifts near
1375 cm−1 in cytochrome and hemoglobine can be
assigned to hem bands
NMR Mechanism of Ag NPs The hydride intermediates ([Ag7(H){Se2P(OiPr)2}6] and Considerably low sensitivity, requires the core digestion [138]
formation [Ag7(H){S2P(OEt)2}6]) formation was revealed by of big NPs, 107/109Ag has low gyromagnetic ratio and big
appearance of doublets 1125. ppm (d, JAgH = 39.7 Hz) T1 value, which requires special devices and long term
and 1116.7 ppm (d, JAgH = 41.1 Hz) at 298 K as well as analysis
octet at 3.50 ppm (1JH−Ag = 39.4 Hz) at 293 K and
broad peak 5.65 ppm, (1JH−Ag = 39.6 Hz) at 223 K
Ag NPs effect on cell The glutathione signals in the range 2.51–2.55 ppm have [139]
glutathione content disappeared after Ag NPs treatment, revealing its
complete depletion
Role of stabilizer and Significant changes in chemical shifts of sodium dodecyl [140]
reducing agent in Ag NPs sulfate protons 4.086 ppm → 4.037 ppm,
formation 1.360 ppm → 1.320 ppm, 0.952 ppm → 0.900 ppm after
Ag NPs formation in the mixture with trisodium citrate,
the decreased intensities of signals from trisodium citrate
protons
XPS Quantitative binding ≈2% of Ag as in unbound (elemental) state, Ag\ \O, Ag\\N Sample charging, the sample transformation (i.e. [141]
affinity of taurine and Ag\ \S bounds were found to be ~71%, 11% and 16%, reduction), sample can be examined only on 2 nm depth,
respectively, which revealed the sulphonate group requires ultra-high vacuum
binding to Ag
UPS Photoelectron emission Doped with ≈ 4.5 nm Ag NPs hydrogen-terminated Si [105]
yield (111) show the photoelectron yield with p-polarization:
2.8•106, while that without Ag NPs has 1.4•104
AES The morphology of Ag The data showed that Ag gas atoms adsorbed on Fe3O4 Sample charging, small examination depth, requires [142]
growing on Fe3O4 according to hemispherical cap model, which revealed ultra-high vacuum, the sample transformation and
the formation of separated Ag NPs but not the Ag layer damage
Ag NPs formation The technique revealed that small (5 nm) particles [143]
comprised from Ag have formed on bismuth silicate
EELS LSPR modes for Ag NPs LSPR evolves depending on electron dose from Sample charging, requires ultra-high vacuum, the sample [144]
embedded in SiO2 2.1•106e−Å−2 to 18.7 •106e−Å−2, under lowest dose no transformation and damage
LSPR shift was observed, with increasing of electron dose
blue-shifts were observed from 2.8 to 3.2 eV (for
NP ≈ 7 nm)
Elements distribution In the middle of the NPs the electron energy losses [89]
over the NPs corresponding to Ag atoms was observed, on the edges
the presence of C, N and Ca was shown
XRD in situ annealing For NPs heated in air the 2θ signals at ≈29°, 31.5°, 38°, Preferred orientation of non-spherical NPs, low signal [145]
behavior of Ag2S NPs 41°, corresponding to monoclinic acanthine α-Ag2S intensity for NPs below 10 nm, 2% sensitivity limit for
disappeared, and the 2θ signals 39° and 43° of pure silver composites
appeared. For NPs heated in argon, the XRD pattern
changed to more complex, which may be attributed to
monoclinic non-stochiometric acanthine α-Ag1.95–1.98S
SAED Ag NPs crystalline phase Measured d-spacing (nm) were 0.233, 0.203, 0.141, 0.121 Sample charging and damage, requires ultra-high [79]
examination which are in good correspondence with Ag(0) hkl (nm) vacuum
0.236, 0.204, 0.145, 0.123, and AgO hkl (nm) 0.237 and
0.143
ICP-MS Changes in Ag, Fe, N and With changes of Ag NPs concentration in culture media Atomic (Cd) and polyatomic interferences, samples [120]
Mg content in Stevia from 0 to 200 mg/L the changes in N (38,067.3 ± 45.3 to usually requires mineralization
rebaudiana B. treated 55,339.7 ± 31.1 μg/g), Mg (882.4 ± 9.5 to 1292.6
with Ag NPs ± 11.2 μg/g), Fe (289.3 ± 4.5 to 143.3 ± 0.7 μg/g) and
Ag (0.13 ± 0.0 to 188.2 ± 1.6 μg/g) content (calculated
on dried weigh) were observed
(continued on next page)
11
Table 2 (continued)
SP-ICP-MS Ag NPs callular uptake by Cells treated with 2 μg/mL of Ag NPs with sizes 50 and Aggregation, lower size limit (20 nm), impossible to [146]
Neuro-2a cells 75 nm revealed the uptake of 1662 and 605 number/cell distinguish different Ag form
respectively, while treated with 10 μg/mL of Ag NPs
revealed the uptake 1989 and 1740 number/cell
TOF-SIMS Ag NPs interactions and In positive mode silver-amine ions were observed Spatial resolution is limited by diameter of primary ion [147]
transformations in AgC2H6NO+, AgC3H4NO+, AgC4NO2H+ 3 at 167, 177, 203.9 beam, which is often bigger than NPs size
municipal wastewater mass and Ag bonded with sulfur AgSC2H3N+, AgSC3H6N+
at 179.90 and 194.93, mass. In negative mode
AgCOOHCNH2−, C3H2NO2Ag−, C5N3O2Ag− at 179.91, 192,
241 and AgC2H3SN−, C3H2SNAg−, C3H7SNO2Ag− at
179.89, 190.89, and 227.92 mass were observed
MALDI-TOF NALDI analysis of With changes in laser fluence from 15 to 80 mJ/cm2 the NPs aggregation, analyte fragmentation [8]
MS benzpyridi-nium normalized total ion intensities for Ag NPs were from 5 to
35 •104 count/mm2, while for Au NPs from 0 to 21•104
count/mm2
AF4 Ag NPs determination in 1. the recoveries of PVP-capped NPs with sizes 30, 60 and Membrane fouling by irreversibly bonded NPs, [148]
environmental samples 90 nm were shown to be 90.2, 78.6, 69.4 and 55.6% for NPs aggregation, non-selective upon size detectors
tap water, river water, effluent and influent of (UV-Vis/MALS)
wastewater treatment plant respectively; 2. the better
resolution was shown to be in order effluent > river
water > influent > tap water (based on UV-Vis detector);
3. the better consistency between measured and original
sizes was observed in tap water and effluent (based on
DLS detector); 4. ICP-MS detector showed the good
separation only in tap water
CE Ag NPs separation 1. migration time in single standard analysis for 40 nm Aggregation, NPs sticking to capillary walls, [149]
capped with branched polyethylenimine, PVP, citrate and low selectivity
polyethylene glycol were 958 ± 21 s, 1048 ± 15 s,
1275 ± 115 s and 958 ± 32 s respectively; 2. four
component mixture was not possible to separate; 3.
citrate capped was possible separate from PVP and
polyethyleneglicol capped in two-component mixture
DSC TiO2-Ag NPs doped Glass transition values by DSC were 59.52, 51.77, 52.19, Heating rate is crucial [150]
gelatin films stability 51.8 and 52.61 °C for films with 0, 1, 2, 3 and 4% of
TiO2-Ag respectively
unreliable results, since it desorbs from the Ag NPs surface very fast, Instead, positive surface charging transforms the sample to an electron
while fluorescent-marked BSA showed satisfactory Ag NPs-ligand trap [156]. An environmental scanning electron microscope (ESEM) is
stability. one of the techniques that can deal with the charging effect due to the
presence of water vapor in the microscope chamber. What more, wet
3.2. Electron microscopy mode prevents samples from dehydration, which can introduce addi-
tional artifacts such as size reduction, shape change, and cracking, so it
The very first techniques that should be utilized for NPs characteri- is extremely useful for biological systems examination [155,157]. For in-
zation are SEM (Scanning Electron Microscope) and TEM (Transmission stance, ESEM was utilized to investigate the changes that occurred in
Electron Microscope) since they give invaluable information about earthworms after Ag NPs exposure [158]. Finally, to SEM drawbacks
structure and surface morphology of the materials. SEM is an imaging the low signal-to-noise ratio and spatial resolution, in comparison to
technique which in general deals with backscattered electrons (BSE) TEM, can also be included [154].
[154] and allows to investigate surface morphology of NPs [57,66], fur- TEM is one of the most common techniques for NPs structural features
ther the interactions of NPs with different systems can be studied. The study. It provides information about size, shape, arrangement, and NPs
Ag NPs deposition on silica spheres and rods [121], on polyester fibers structure. TEM exist in several different forms to which CTEM (Conven-
[122] or on linen [78] and the investigation of the damage caused by tional TEM), HRTEM (High-resolution TEM), and STEM (Scanning TEM)
Ag NPs to microorganisms [76,123] and nematodes [124] was observed can be include. The image in CTEM is formed with an appropriate detecting
by SEM micrographs. However, some other signals such as secondary system by transmitted through sample electrons. Adhikari et al. use TEM
electrons (SE) can also be obtained within this technique. images to determine size and size distribution of synthesized Ag NPs
SE show higher sensitivity to surface morphology therefore can pro- [126]. However, they noted that in some cases NPs sizes could not be reli-
vide images with better quality [118]. In SEM incident beam electrons ably determined due to disproportionate aggregation during sample prep-
with energy in range 1 keV–30 keV are utilized, which can provide a aration for analysis. Polte J. with colleagues were also unable to distinguish
complementary information, as depending on the electron energy sam- the Ag NPs sizes due to large aggregation caused by simple drying [48].
ple can be scanned on the different depth (up to 100 nm for SE and Generally, the NPs aggregation is one of the main problems in Electron mi-
500 nm for BSE) [118,154,155]. Further extension of the technique can croscopy (EM) investigations. Donald A. et al. have observed the transfor-
be made by combination with a focused ion beam (FIB), typically Ga+, mation of AgNPs to a core@shell and hollow Ag@Ag2SNPs, TEM images
to make sample cross-sections and imaging by SEM [125]. The clearly indicate the changes in structure [127]. Still, TEM-images have
non-conducting sample charging is one of the most significant SEM 2D-character, so 3D-images made by SEM can provide more details re-
problems that influence the image quality and therefore its interpreta- garding the morphology of the NPs [58,123]. HRTEM technique is based
tion. The negative charged surface can produce undesirable SE and on observation of interference of the electron beam by the sample. This al-
influence on landing energy of the incident electrons, which lead to lows to obtain high phase-contrast images, that show details finer than
field enhancement between the surface and the electron detector. 0,2 nm. In particularly HRTEM provides direct images of the atomic
12
structure of the samples [159]. By HRTEM it was possible to distinguish the map of the surface in the atomic-resolution scale. Among other SPMs,
protein coating of different protein-conjugated Ag nanocomposites [89,90] an atomic force microscope (AFM) is one of the most employed tech-
and the lattice spacing between neighboring fringes as it was made niques for surface topography determination and is also common for
for trypsin-Ag conjugates [90]. Still, TEM has its drawbacks to which nanostructures investigation. In AFM the moving probe across the sur-
labor-intensive sample preparation can be include, as the sample should face changes its vertical position depending on roughness and electric
be very thin, so it can allow passing electrons through the sample properties of the sample, which in most cases is detected by the
(not more than 100 nm if possible). In some cases for HRTEM samples position-sensitive photodetector. The AFM has been utilized for investi-
should be as thin as 10 nm (generally 50 nm). Additionally, TEM gation of Ag NPs deposition on dialdehyde nanofibrillated cellulose. It
handles with high-voltage electrons (80–300 keV) that may damage the was possible to determine the Ag NPs sizes distribution, which was in
sample [159]. the range between 19.0 and 37.0 nm with an average size 28.14 nm
In STEM instruments the principles of the SEM and TEM are com- [131]. I. Romer et al. also investigate the Ag NPs by various techniques,
bined, where the sample is scanned across by sub-nanometer diameter the average size of citrate capped AgNPs was measured as 20 ± 8 nm
probe, and the image is formed through transmitted electrons. Micros- by AFM, while TEM showed the NPs size as 22 ± 6 nm [130]. It should
copy and spectroscopy techniques are shown to be complementary be noted that AFM measurements can be burdened with unwanted ar-
techniques, and the utilization of both can help to avoid inadequate tifacts and signals including the motion of the macroscopic body of can-
characterization of material [154]. STEM instrument in comparison to tilever due to electrostatic effects between the cantilever body and the
CTEM can be employed to spectroscopic analysis, as within the tech- sample, which can lead to misinterpretation of obtained results [161].
nique some additional valuable signals can be measured, such as SE, Near-field scanning optical microscopy (NSOM) is another scanning
BSE, characteristic X-rays, and electron energy loss, so it provides infor- technique, that can be assumed as an improved version of the conven-
mation with much better resolution about sample structure and is also tional optical microscope. In NSOM the properties of evanescent
suitable for chemical composition determination [159]. Energy disper- waves are utilized, which implies that scanning probe during the analy-
sive X-ray spectroscopy (EDX or EDS) is a technique, usually coupled sis is located not further away than aperture diameter. Thus, it is possi-
with electron microscopy, where the characteristic X-ray radiation ble to overcome the resolution limit and obtain information about the
from excited atoms is measured. Within the technique, it is possible to optical properties of the sample. Within the technique both the image
estimate both the compositional information of the whole sample as and the relevant spectra can be obtained [162]. M. Beleites et al. have
well as the location of individual elements across the surface. In performed the NSOM topographical investigation of the Ag NPs. They
Pomastowski et al. work by EDX detector the prevalence of Ag ions in also performed transmission mode measurements, which showed that
synthesized NPs was estimated (Fig. 3), but also the presence of C, O, S Ag NP was surrounded with a halo with the increased transmission on
and P confirmed the protein participation in NPs stabilization [16]. the distance up to 200 nm. Such a phenomenon can be explained by in-
Blommaerts et al. conducted an EDX mapping of the Au/Ag NPs. The terference of the light emitted by scanning tip and scattered light from
analysis shows the core-shell structure of the particle, with the preva- NP. Finally, it was shown that the LSPR for Ag NPs measured by trans-
lence of Ag on the surface [47]. EELS (Electron Energy Loss Spectros- mission NSOM exhibit the redshift in comparison to UV-Vis analysis,
copy) combined with STEM was also useful for the chemical which may be explained through the coupling effect with the conduc-
composition determination of lysozyme-Ag nanocomplex [89]. Within tive probe [132].
STEM the Selected Area Electron Diffraction (SAED) can also be con-
ducted. SAED is widely utilized to distinguish crystal structure of 3.4. Dynamic light scattering
AgNPs and it was shown that obtained data is complementary to that
one from XRD analysis [74]. Another extension of the technique is Dynamic light scattering (DLS) is a technique with a short time re-
Cryo-TEM approach. This technique together with liquid cell sample quired for measurements and relatively low cost of the apparatus,
preparation TEM, which also called liquid-phase TEM (LP-TEM), allow therefore it frequently exploits for NPs sizing. For instance, DLS is
to investigate nanoscale materials formation and nano-objects behavior often utilized as the detector during the NPs separation by A4F [148].
in solutions. Both techniques are very labor-extensive but partially can However, in general the particles size values derived by DLS are
fill gaps left by other methods [160]. By LP-TEM in situ particle growth overestimated. In R. Ma work the measured by TEM size for nanostruc-
in detail can be observed, as it was made for Ag nanorods [100]. How- tured Ag NPs was 76.6 ± 20.7 nm, calculated from XRD diameter was
ever, the dynamic nature of LP-TEM processes and the presence of liquid 30.4 nm, while hydrodynamic radius measured in 1 mM NaHCO3 was
decreases the resolution, what more important the incident electron 89.1 ± 1.5. It should be mentioned, that in TEM only the size of the
beam can influence on synthesis process [160]. During Cryo-TEM anal- NPs metallic core can be estimated. Instead, in DLS the hydrodynamic
ysis thin (up to 100 nm) frozen films of sample solutions are examined. radius, which is defined as hypothetical hard sphere that diffuses with
As all processes in the samples are arrested it became possible to per- the same speed as the particle assayed in DLS [30], of the particles is
form X-ray spectroscopic and EELS analysis, what more the 3D structure measured. By XRD the size of crystallite can be calculated, which in
can be outlined. Ahmad et al. studied silver remediation from aqueous case of twinned or poly-crystallite NPs can be several times smaller
solutions by microorganisms. By Cryo-TEM coupled with EDX mapping than whole particle core. In practice, NPs in colloidal dispersion are
the extra- and intracellular Ag NPs formation through silver ion adsorp- the combination of the metal core with solvated corona, which has a dy-
tion and conversion was observed [129]. Moreover, Cryo-TEM tech- namic character and fluctuates depending on the surrounding environ-
nique confirmed the presence of chain-like Ag NPs assemblies, ment. Such a phenomenon was shown in Guehrs et al. work where DLS
mediated by 2,2′-bypiridine decorated peptoids, in solution, as such analysis of commercially produced 75 nm size Ag NPs have been per-
structures could also be introduced through NPs aggregation induced formed, the measured values were 79 ± 0.5 nm and 71 ± 0.2 nm for
by dried sample TEM preparation [128]. Still, the object under investiga- particles dispersed in water and in cell culture media respectively,
tion is highly sensitive to electron beam exposure, which can damage while TEM measurements revealed NPs sizes as 74 ± 8 nm [125].
both the sample and vitrified solvent, so the interpretation of the images Song et al. have also characterized Ag NPs synthesized by silver nitrate
became more complicated [160]. reduction with curcumin, and the measured hydrodynamic radius
ranged from 30 nm to 90 nm [76]. TEM analysis has revealed that as
3.3. Scanning probe microscopy mentioned Ag NPs were of spherical shape with a relatively uniform di-
ameter of 35 ± 5 nm. Generally, the high concentration of different mol-
Scanning probe microscopy (SPM) exploits a very sharp probe tip for ecules in the culture media, especially proteins, through surface
local characterization of materials surface and can provide a structural adsorption can drastically change the hydrodynamic radius of dispersed
13
Fig. 3. TEM image of Ag-Lactoferrin nanocomplexes. Bar: (A) 200 nm, (B) 5 nm, (C) Fast Fourier Transformation, and (D) EDX spectra. Reproduced with permission from ref. [16]. Copyright
2016 American Chemical Society.
NPs. Moreover, adsorption is a complex process, which needs time to the high concentration effects the multiscattering occurrence can be at-
stabilize, so obtained results can change over time. However, the mea- tributed, which results in artificially smaller measured NPs size [30].
surements are also not recommended to perform in deionized water, Changes in pH and electrolytes concentration in solution also influence
as it always leads to size overestimation up to 10 nm, which is due to charge of NPs surface, which commonly expressed in ζ-potential (or
the long-distance interactions between particles in the absence of ions electrokinetic potential) changes. ζ-potential cannot be measured di-
[30]. Additionally, the hydrodynamic radius in DLS is derived from rectly, therefore it can be expressed through electrophoretic mobility
Stokes-Einstein relationship, in which the calculations for spherical deduced from Henry's equation [35]:
shape particles are considered, so for anisotropic particles, it does not
correspond to any of their geometrical dimension and can be accounted
ζ ¼ ημ e =εf κdp ð1Þ
to the DLS drawbacks. Moreover, in DLS the cumulative analysis for av-
erage size estimation is utilized, which is not suitable for polydisperse
systems [35]. However, it should also be mentioned that for NPs the an- where ŋ – solutions viscosity; μe – electrophoretic mobility; ɛ – dielectric
isotropic inelastic Mie scattering is observed that has an angle- constant of the dispersant, f(κdp) – Henry's function of dimensionless
dependent character [30]. Moreover, for smaller NPs the absorption parameter.
cross-section is dominant over scattering cross-section [5,163] thus In case when the electric double layer thickness is much smaller
smaller NPs reveal the lower intensity of scattered light. In some than the radius of the particle in particularly for particles much bigger
older versions of the DLS instruments the backscattered light was than 100 nm, the Henry's equation with some approximation can be
gathered at the angle of 90°, presently detectors are placed at 173°, modified to Smoluchowski equation [30,164]:
which allows to avoid the excess of scattered light and unmask
scattered light of low intensity, thus contributing in the higher resolu-
ζ ¼ ημ e =εr ε0 ð2Þ
tion of measurements [30].
The dependence of measured size from solvent characteristics (re-
fractive index, viscosity) was also revealed, which should be considered where ŋ – solutions viscosity; μe – electrophoretic mobility; ɛ0 – electric
during the investigations [30]. Belteky et al. have investigated the influ- permeability in vacuum, ɛr– dielectric constant of the solution.
ence of different electrolytes and pH on Ag NPs hydrodynamic radius Instead, for NPs dispersed in low salt concentration, when the elec-
and aggregation behavior, which is considered to be the most frequent tric double layer thickness is much bigger than particle radius and
problem in DLS analysis [49]. Besides environmental conditions, the ag- Henry's function of dimensionless parameter is taken as 1 the Hückle
gregation may also appear due to NPs high concentration. Moreover, to equation can be utilized:
14
molecules on the NPs surface) [166], and interactions with other NPs
ζ ¼ 3ημ e =2εr ε0 ð3Þ (including aggregation) [121,167], which alone with NPs size distribu-
tions have an influence on the width of the absorbance band, the shifts
where ŋ – solutions viscosity; μe – electrophoretic mobility; ɛ0 – electric of the resonant wavelength as well as the appearance of the additional
permeability in vacuum, ɛr– dielectric constant of the solution. absorption band [46,166]. For spherical silver NPs the LSPR absorption
However, the Hückle equation is shown to be not applicable for light band normally is near 400 nm, while for triangular Ag nanoplates
aqueous solutions [30]. Thus, most often the Smoluchowski model is the maximum absorption in a range 500 nm - 1000 nm was observed
utilized. However, some scientists claim that Smoluchowski equation [50,168] and aggregation of the NPs, as well as rod-like shape, leads to
should not be utilized for NPs ζ-potential estimation as the measured the appearance of two peaks: one near 400 nm and additional in the
values by this model in general are smaller than real one, which can range from 500 nm to 1000 nm [46,169]. The influence of the NPs size
be obtained only from Henry's model [35]. distribution on the broadening of LSPR band was shown in M. A. Garcia
The electrokinetic potential is often measured within DLS analysis, work [166]. It was calculated that AgNPs with a size of 10 nm and devi-
as it was made in the above-mentioned work of P. Belteky with coau- ation of ±8.5 nm has three time higher full-width-at half maximum of
thors. They have investigated the Ag NPs synthesized with green tea ex- LSPR band than for NPs with the same size but dispersion of ±4.5 nm.
tract in comparison to Ag NPs stabilized with citrate. In consequence, T. Huang and X.-H. N. Xu have also shown significant LSPR band broad-
NPs stabilized with green tea extract had about 8,5 mV lower ening in AgNPs of different shapes and size distributions [54]. The ma-
ζ-potential than citrate capped (−27,8 mV), which caused better stabil- jority of the reports note the appearance of the intense absorption
ity in solutions with different content of NaCl, glucose, glutamine, cell band in UV-Vis range as evidence of NPs production and by the changes
culture component and different pH [49]. Generally, the surface charge in the absorbance intensity explain the completeness of the process
of the NPs determines their electrokinetic stability in the suspension. In [93]. To give an example, J Polte et al. have observed the in-situ intensity
turn, the magnitude and the sign of the surface charge are determined changes in UV-Vis spectra during AgClO4 reduction by NaBH4. However,
by the adsorbed molecules on the surface of NPs, in particular the during the process they noted that the formation of hydrogen bubbles
capping agent. For instance, the Ag NPs stabilized with poly on the cuvette walls disturbs the kinetic study [48]. Some scientists try
(diallyldimethylammonium) have positive surface charge, while un- to exploit LSPR for synthesizing process development and optimization
coated Ag NPs which probably contain adsorbed nitrate ions on the sur- [68,168]. UV-Vis spectra are also suitable for NPs stability investigation
face were negatively charged [101]. According to Derjaguin−Landau [130]. However, experimental data along with mathematical calcula-
−Verway−Overbeek (DLVO) theory, the stability of the NPs suspen- tions indicate that seemingly negligible changes (including those re-
sions against aggregation is a result of interplay of two opposite forces, lated to synthesis) in nanostructures may cause significant changes to
i.e. the attractive van der Waals forces and repulsive Coulombic forces of the optical features of the Ag NPs [144]. Thus, it should be paid more at-
charged particles [102]. It is suggested that absolute ζ-potential values tention to NPs LSPR investigation, as it may have an influence on results
greater than ±25 mV are required for NPs and biocoloids systems sta- during exploitation in different optical applications such as biosensing
bility against rapid aggregation, where the particles would stay in dis- and biolabeling, photocathalysis, different photoelectric devices, etc.
persion for a longer period [16]. In work performed in our group, the The knowledge about potential applications associated with plasmonics
measured ζ-potential of AgNPs was 0 ± 0.5 mV in pH range 2–4, may be extracted only from a complete understanding of LSPR appear-
which in consequence led to the AgNPs aggregation and therefore the ance phenomena, which will contribute in the design of highly specific
measured by DLS sizes varied from 1500 nm to 200 nm [93]. Instead, nanostructures with desired optical properties.
ζ-potential values in pH range 4.5–10 decrease up to – 25 eV, and the The fluorescence spectra of Ag NPs-containing systems usually are
NPs size was estimated as 100 ± 1.5 nm [93]. However, the transfer of measured in line to determine the possibility for different substances
NPs from a synthesis solution to the environment of the investigated quantification in biological or environmental applications. It was re-
systems usually leads to the exchange of the surface adsorbed mole- ported that extremely small Ag NPs, which sometimes also called Ag
cules with dissolved one, which in consequence can change the charge nanoclusters or Ag quantum dots (Ag QDs), exhibit fluorescence emis-
and magnitude of the NPs surface and therefore influence their stability sion. Changes in the closest vicinity to Ag QDs surface can either en-
and interaction behavior [27,34,147]. hance the effect, as it was investigated for Pb2+ ion interaction in
water [134], or decrease in case of dopamine binding [135]. Addition-
3.5. UV-Vis and fluorescence spectroscopy ally, the aggregation of the Ag QDs also lead to the fluorescence
disappearance, which was utilized for anti-digoxigenin antibody immu-
UV-Vis spectroscopy is a fast, simple and sensitive technique, thus it noassay analysis [15]. A.V. Pansare with coauthors exploited Ag QDs
is widely utilized for Ag NPs initial characterization. UV-Vis spectros- synthesized with N. cadamba extract to determine the BSA fluorescence
copy can provide both quantitative and qualitative information about quenching [170]. However, it should be strongly considered the mech-
investigated material [35]. For example, UV-Vis detectors are typical in anism of fluorescence intensity changes during the process, especially
separation techniques, such as CE (capillary electrophoresis) or FFF, for such complex mixtures as in the last example, since some flavonoids,
for Ag NPs quantification and therefore the information about NPs ab- which usually are abundant in the extracts, can exhibit fluorescence
sorption in the UV-Vis range is so valuable [148,165]. However, it should properties [171]. In general fluorescence measurements can be affected
be mentioned that for organic compounds the UV-Vis spectrum is a con- by Inner Filter Effects (IFE), which include IFE I - the absorbance
sequence of the presence of the chromophores, while UV-Vis enormous of exiting energy by impurities and IFE II - the reabsorbance of the emit-
light absorption extinction of metal NPs is connected to LSPR appear- ted light by quencher or other impurities. Finally, the presence of un-
ance. LSPR is a complex process and described as excitation and coher- known fluorescence substances in the mixture can also interfere the
ent oscillation of electrons under the electromagnetic field of incident analysis [29].
light [166]. The main feature of the LSPR in NPs is that the oscillation
of the excited electrons is limited by the volume of the NPs [166]. 3.6. Infrared and Raman spectroscopy
Thus, it plays a dominant role in the excited electrons oscillation fre-
quencies and therefore on the wavelength of the resonant light band. At the early stage of infrared investigations, it was noticed that cer-
Still, the complexity of LSPR phenomenon implies the influence not tain functional groups are associated with specific characteristic absorp-
only the NPs volume but also their composition [133] and structure tion, and after years of painstaking work of many scientists, it became a
[56], shape [50], surrounding media (especially that one that is in the technique for the determination of characteristic groups in the sample
closest vicinity to NPs, in particularly the capping agent/adsorbed [172]. The majority of publications that are focused on Ag NPs usually
15
exploit Fourier Transform Infrared Spectroscopy (FTIR) in MIR (Mid-In- spectra during Ag NPs synthesis by thermal decomposition can be ob-
frared extends from 4000 cm−1 to 400 cm−1) range as a reliable tech- served [178]. The authors also noted the broadening of all signals in
nique for Ag NPs characterization. FTIR is frequently used for surface spectra of silver caprylate in comparison to caprylic acid spectra,
functional group investigations [84], surface functionalization control which they attributed to presence of small amounts of Ag(0) atoms,
[136,137] or for investigation of the possible groups which take part in exhibiting paramagnetic properties and therefore influence on nuclear
Ag NPs formation and/or stabilization by different extracts [45], proteins spin relaxation. Such effect was utilized by L.E. Marbella and colleagues
[16,90], polysaccharides [87], etc. On the flip side, the significant shifts to investigate magnetic susceptibility of AuCo NPs by Evans' method
in the characteristic absorption band due to perturbation emerging [179]. C13 NMR spectra were also useful in the investigation of Ag-
from neighboring groups or the spatial geometry of the molecule to- doped Pt NPs formation. The L. C Jones with coauthors noted that PVP-
gether with the fact that in general more than one functional group ab- Pt NPs C13-NMR spectrum is very similar to only-PVP spectrum, but
sorb in the same region [172], make possible to determinate the after adding of AgNO3 the new shifts at 20 ppm, 46 ppm, and 63 ppm
individual functional groups only in case when FTIR is coupled with appeared and spectrum became more similar to that one from Ag-
other techniques, which can be NMR (Nuclear magnetic resonance) PVP. The differences may indicate the differences in Pt and Ag interac-
[173]. To give an example, while it is relatively easy for simple com- tions with PVP and also it provided an insight into possible intermedi-
pounds as alpha-lipoic acid to discriminate which groups are involved ates that play role in directing the PtxAgyNP shape [180]. What is
in Ag NPs binding [137] it becomes more complicated when we try to interesting, the analysis was performed with the utilization of cross po-
investigate how metal interacts with proteins or polysaccharide-based larization, which is extremely useful for solid-phase NMR, in particular
nanocomposite [16,87], and almost impossible for extracts or propolis, Cross Polarization Magic Angle Spinning NMR (CP-MAS NMR). 31P
which are multicomponent mixtures [66,69,72]. NIR-range (Near-Infra- NMR spectra were also useful for investigation of Ag NPs formation
red extends from 12,500 cm−1 to 4000 cm−1) spectra can serve as an through [Ag7(H){E2P(OR)2}6] (E = Se, S) conversation. The spectra indi-
extension of the technique since it can provide valuable information cated the creation of [Ag8(H)L6]+ as an intermediate prior to the forma-
about different hydrogen-containing groups (the majority of the ab- tion of Ag7H clusters. Moreover, the presence of a hydride within the
sorption bands in the NIR region are due to CH, NH, and OH) [172]. Fur- heptanuclear silver was determined by 1H and 109Ag NMR-analysis
thermore, some Ag NPs exhibit LSPR in NIR absorption region, which [138]. However, the 107/109Ag nuclei suffer from low gyromagnetic
also should not be skipped in the Ag NPs investigations [168,169]. ratio, which decreases the sensitivity and generally requires specialized
In Raman spectroscopy, inelastic scattering of the electromagnetic measurement devices. Moreover, the T1 value of Ag nuclei is on the
waves in the infrared range is measured and information about vibra- order of hours, so the technique is a highly time-consuming [177]. The
tional and rotational modes of the molecules can be gathered. The virtue conventional NMR in general posses considerably low sensitivity, espe-
of the technique is that the groups, which may be weak or inactive cially in comparison to other spectroscopic techniques, e.g. fluorescence
under FTIR analysis can exhibit strong bands in Raman spectra, so it pro- measurements can be performed for single molecule [181]. Still, the
vides complementary information. Raman spectra were utilized to in- signal-to-noise ratio can be enhanced by magnetic field enhancement.
vestigate the binding of the Ag NPs to 2,2′-piridine decorated Additionally, Fourier-transform pulsed NMR allows to more than 100-
peptoids, the presence of the band at 241 cm−1 clearly indicate the ex- fold increase in sensitivity by utilization of short radiofrequency pulses,
istence of Ag(0)-(pyridine)N interaction [128]. Pomastowski et al. have which can cover a wide range of excitation frequencies at the same time.
also observed the changes that occurred in the Raman spectra of Some other approaches for NMR sensitivity enhancement can be found
lactoferrin after Ag-ions uptake [16]. Moreover, in the last decades in J. H. Lee et al. work [181]. However, at the end of the last century, the
metal nanoparticles are widely studied for SERS. S. Reymond-Laruinaz HR-MAS NMR (High-Resolution Magic-Angle Spinning NMR) technique
et al. have observed the enhancement of the signals in Ag- conjugates has been introduced and showed high sensitivity and selectivity in the
with lysozyme, BSA, cytochrome-C, and hemoglobin in comparison to investigation of complex mixtures [182]. Such an approach can be
intact proteins [89]. However, during spectra interpretation, it should used for the identification and quantification of metabolites from bio-
be considered the heating effect of the sample, which may lead to sam- fluids affected with Ag NPs. For instance, M. J. Piao et al. have measured
ple decomposition or baseline increasing due to blackbody thermal by HR-MAS NMR the changes in glutathione quantities in human liver
emission. Additionally, the fluorescence of the sample or the impurities cells treated with Ag NPs [139].
may lead to the appearance of additional bands. Finally, the matrix ef-
fect should be considered as it can absorb the scattered waves and de- 3.8. Electron spectroscopy
crease the signals [174].
Photoelectron or photoemission spectroscopy is a technique, where
3.7. Nuclear magnetic resonance spectroscopy the discrete energy levels (electron orbitals) are studied by measure-
ments of ejected electrons energies from material illuminated with
NMR is a powerful tool for identification and quantification of mo- light of a certain length. Depending on the wavelength of utilized light
lecular species, as it can provide information about the molecular struc- the technique is divided into X-ray Photoelectron Spectroscopy (XPS)
ture of the compounds and the resonance strength is directly and Ultraviolet Photoelectron Spectroscopy (UPS). In XPS the most
proportional to the number of the particular nuclei. The NMR spectra common Mg Kα and Al Kα X-ray sources with energies 1253.6 eV and
can be recorded for atoms that have a non-zero spin number (have an 1486.6 eV are utilized, which allows to investigate the core states of
intrinsic magnetic moment) but the most frequently NMR spectra for the atoms [183]. Taurin interaction with Ag NPs has been studied by
1
H, 13C, 15N, and 31P nuclei are recorded. 1H NMR is widely utilized for XPS as a common technique for chemical composition determination.
surface functional group determination and quantification [175]. Re- The technique allowed to estimate not only the percentage composition
garding Ag NPs it was shown that 1H NMR could be useful for determi- of Ag, O, N, and S elements on the surface, but also the percentage of Ag–
nation how organic compounds are involved in the synthesis process. V. O, Ag–N, and Ag–S bonds [141]. The XPS has also been utilized for chem-
Shah with coauthors suggested the decrease of some signals in 1H NMR ical composition estimation of Pt NPs doped with Ag. ICP-MS quantifica-
spectra was due to tri‑sodium citrate oxidation [140]. What more, 1H tion of such composite showed the lower values of Ag in comparison to
NMR can be utilized for quantitative determination of ligands participa- XPS, which suggested to be due to the limited photoelectron free pass
tion in NPs stabilization [176]. However, quantitative information about (nearly 2 nm), so the differences may be attributed to Ag surface enrich-
adsorbed ligands often requires the NPs core digestion, as they cause ment [180]. The composition of Ag-content formulations was possible
significant signal broadening, especially in case of the NPs with larger to estimate by Ag 3d level shifts measurements, which also were
size [177]. In Pawłowski et al. work the changes in silver caprylate shown to be sensitive to NPs size. T. Radu with colleagues has measured
16
the Ag 3d shift dependence from Ag NPs size embedded into bioglasses that the electrons incident beam influenced both the NPs and
volume [184]. The authors showed that for bioglasses containing Ag NPs surrounded silica structure, which in consequence influenced LSPR
with the average size of 9 ± 0.2 nm the peak position of Ag 3d level on shifts. Initially, the NPs did not exhibit a clear plasmon resonance, as
XPS spectra shifted to lower binding energies by 0.3 eV comparing to the synthesis conditions have led to Ag2O formation. The NPs interface
bioglasses containing Ag NPs with the average size of 7.4 ± 0.2 nm, clearance from oxygen due to reduction caused the plasmon peak ap-
which was assigned to the influence of Ag NPs dimensions. Still, the pearance on EELS spectrum and the matrix damage appeared as shifts
final peak position shift which may be observed on the spectrum is to higher energies. Moreover, they conclude that small Ag NPs size
due to the competition of two phenomena: initial state effects (partial does influence on LSPR shifts, but these are often masked by environ-
electron transmission to the clusters) that implies a tendency to shift mental influences.
the peak to lower binding energies and final state effect, which influ-
ences the relaxation energy of the system with a tendency to shift the 3.9. XRD and SAED investigations
peak to higher binding energies. These two phenomena imply not
only the impact of the NPs size and shape but also the nature of the XRD is based on measurements of the angles and intensities of
supporting substrate [185]. The extension of the technique – near- diffracted X-ray beams. Depending on the wavelength of incident
ambient pressure XPS, which allows to study NPs in suspension. How- X-ray, the wave amplitude can be enhanced due to constructive inter-
ever, the Ag 3d peak under near-ambient XPS showed the shift in ference and detected during the analysis. Such enhancement is ob-
0,7 eV in comparison to Ag NPs studied in the dried sample on Si- served, when Bragg's law is fulfilled, which allows to estimate the
wafer [186]. What more, S. Dahle with colleagues has investigated the relation between the wavelength of the incident electromagnetic radia-
interaction of Ag ions with glucose, and by XPS they observed the unex- tion to the diffraction angle and the lattice spacing in crystalline sample
pected reduction of OH groups, which may be attributed to charging ef- [190]. The XRD analysis is a common technique by which the crystalline
fect on insulators during the study [187]. structure of both single Ag NPs [55] as well as incorporated in nanocom-
UPS utilizes electromagnetic waves with energies in the range from posite [87] can be detected. However, the intensity of signals obtained
3.10 eV to 124 eV, which is suitable for valence and conductive bands in- from Ag NPs embedded in organic films usually are at a very low level,
vestigation [183]. Such information is very valuable since Ag NPs- so it barely could be noticed [17,87] and signals from Ag NPs deposited
containing nanocomposites in the last decades are often investigated on the ZnO were not noticeable at all [191]. Generally, for mixed mate-
for photoelectric conversion in different optoelectronic devices [188]. rials, the detection limit is shown to be approximately 2% [190]. More-
UPS was used for the estimation of photoelectron emission yield for over, within the XRD technique by the Debye−Scherrer equation the
Ag NPs on a hydrogen-terminated Si surface [105]. Still, for all electron NPs size can be estimated as it was made for Ag NPs doped in
spectroscopy techniques, in general, the ultra-high vacuum is essential, dialdehyde nanofibrillated cellulose, the calculated crystallite size was
which can be included to their drawbacks. The necessity of the ultra- in the range from 14,03 to 16,63 nm, while SEM measurements indi-
high vacuum is related to the fact, that the electrons have limited free cated NPs size in the range 20.75 nm - 38.25 nm, which was suggested
path and additional collisions are unacceptable. Moreover, the mole- to the presence of aggregates consisting several crystallites [131]. The
cules presented in the gas phase as well as adsorbed on the surface NPs size estimation by XRD is based on the fact, that the decrease in par-
can lead to the appearance of additional signals. Finally, the high- ticle size leads to peak broadening in XRD patterns. However, for parti-
energy beams can heat the material causing additional changes in cles with sizes from 1 μm to 50 nm the peak broadening is almost
their structure [183]. negligible and mainly caused by instrumental effects. In turn, the signif-
Auger electron spectroscopy (AES) is based on an analysis of elec- icant peak broadening for NPs with sizes less than 10 nm lead to ex-
tron energies emitted from excited atoms through a series of internal tremely low signal intensity and peaks overlap, which in consequence
relaxation events, which also called the Auger effect. Auger electrons hardly can be distinguished. Such the situation burdened both the NPs
are very specific regarding elements from which they were ejected, so size determination as well as crystal characterization [192]. What is in-
the technique is common for surface scanning and imaging. J.C. Sharp teresting, the NPs shape can influence the intensities of the individual
et al. have studied the growth of Ag NPs on Fe3O4 (111), the results in- signals. The cubic or rod-like particles under the drying process or dur-
dicated that Ag formed 3D islands on the surface with a fixed particle ing precipitation tend to orient with flat faces parallel to the substrate,
density of 4 × 1012 particle/cm2 and the average size was ≈ 4 nm which called “the preferred orientation” of the sample. The phenome-
[142]. A. E. Abbass et al. have used Auger spectroscopy to investigate non can provide additional valuable information but generally is unde-
Ag NPs embedded in bismuth silicate [143]. They noted that the study sirable, especially in quantitative XRD analysis [192].
was burdened with sample charging effect, which was overcome by Selective area electron diffraction (SAED) is another technique for
providing good sample contact to rough copper holder. Moreover, materials crystalline structure investigation. The principle is similar to
even though Auger spectroscopy have confirmed the formation of Ag XRD, only instead of X-rays, the diffraction pattern of the electron
NPs smaller than 5 nm, the information about its distribution through beam is obtained. The virtue of the technique is that it can be performed
all the sample was not possible to extract, since AES makes possible to during electron microscopy investigation and that the analysis can be
scan surface only on the depth of few nm. made from a selected area of the sample, which allows obtaining infor-
Electron energy loss spectroscopy is a technique where the differ- mation about the crystalline structure of different parts in composite
ence in energy of electrons in the incident beam with inelastically materials, in particular for individual NPs. To give an example, the
scattered electrons are compared. Depending on the level of energy SAED analysis was made for Ag NPs derived from thermal decomposi-
loss the information about bandgap, plasmon modes, valence, and tion of fatty acids silver salts. Such synthesis allowed to obtain self-
core energy levels can be obtained. EELS in general is integrated in an assembled Ag NPs with a diameter near 4,5 nm (in the temperature
electron microscope and can be used for imaging as well as for estima- range from 230 to 270 °C) and SAED analysis confirmed the long-
tion of spatially resolved information [189]. EELS was utilized for chem- range order structure [60]. G. Shen and D. Chen have synthesized the
ical composition estimation in Ag NP-lysozyme bioconjugates. The ZnO nanowires decorated with Ag NPs and performed the SAED analy-
results clearly indicate the presence of Ag, C, N, O, and Ca at different sis, in which selective character showed the possibility to investigate
measurment points. The presence of Ca at NPs edges provided addi- area corresponded to ZnO nanowire only. The results indicated that
tional confirmation of Ag NPs binding to lysozyme, since it was derived the obtained ZnO nanowires appeared as single crystals with the pre-
from chicken egg white with 90% purity and calcium is a major compo- ferred growth directions alone the [0001] orientation [191]. However,
nent of eggs [89]. A. Campos with coauthors has investigated plasmon in the XRD analysis by the characteristic angles, the inorganic crystal
modes of Ag NPs embedded in silica by STEM-EELS [144]. They noticed compounds can be identified, while SAED gives only information
17
about basic parameters of the materials crystal structure, which often is labor-consuming character. Moreover, as it can be deduced, the chemi-
not enough to distinguish two different compounds. To give an exam- cal composition, as well as the size, were measured not for each partic-
ple, B. Boutinguiza et al. have shown that measured by SAED interplanar ular NP, but for all NPs population. Thus, the obtained data presents the
distances of 0.233 and 0.141 can correspond both to Ag (theoretical average parameters of all quantified NPs and can be applied with high
0.236 and 0.145) as well as to Ag2O (theoretical 0.237 and 0.143) crystal credibility only for spherical, monodisperse, and uniform in terms of
structures, so the discrimination of these Ag forms is complicated. chemical content particles. However, in S. Naasz the size and chemical
composition of Au@Ag core-shell NPs were also determined [196]. The
3.10. Mass spectrometry authors reported that due to restrictions within the SP-ICP-MS coupled
with quadrupole analyzer it is not possible to perform multi-isotope
The widespread employment of Ag NPs in numerous applications re- analysis, thus the determination of Au and Ag content in the NPs was
quires very precise techniques for its investigation, as the influence of performed in two separate runs. Instead, the SP-ICP-MS coupled with
nanomaterials on different systems is huge, while caused by agents in the TOF analyzer was able to distinguish all isotopes simultaneously.
insignificant amounts. Inductively Coupled Plasma Mass Spectrometry Moreover, in the work the determination of the chemical composition
(ICP-MS) has shown to be a powerful tool for accurate trace analysis of more complex multi-component BiVO4 and (Bi0.5Na0.5)TiO3 particles
of Ag content in the samples and possesses excellent detection limit, was performed. It was shown, that in case of Au@Ag NPs the SP-ICP-MS
high resolution power that can reach 10,000. Moreover, the ICP-MS coupled with TOF instrument could simultaneously detect Au and Ag in
can be utilized for multi-elemental investigations as well as for measur- 97% of particles events, while the simultaneous determination of Bi and
ing elemental isotope ratios [193]. Regarding nanosized Ag or its V for BiVO4 as well as Bi and Ti for (Bi0.5Na0.5)TiO3 was possible to per-
composites the ICP-MS is frequently utilized for silver uptake quantifi- form in >90% of all particle events.
cation in different systems. In our group, we have investigated the Ag Secondary ions mass spectrometry (SIMS) is a technique that im-
adsorption by whey proteins lactoferrin [16] and casein [83] during plies the surface sputtering of the sample by focused primary ion
the nanocomposite synthesis. Moreover, C. Tiantian with coauthors beam and the analysis of ejected secondary ions. Such technique is suit-
has utilized ICP-MS for Ag content estimation in silver-silica nanocom- able for surface 3D chemical mapping with detection sensitivity for even
posites [12]. ICP-MS is also suitable for different biological samples in- ppb scale. S. Wagener with colleagues has investigated the textiles func-
vestigation. To give an example, C. G. Castro-Gonzales et al. have tionalized by Ag NPs, and it was shown that TOF-SIMS (Time of flight-
utilized ICP-MS to study the Ag uptake by Stevia rebaudiana B. under ex- SIMS) was able to determine not only the chemical composition of Ag
posure of Ag NPs with different concentrations in the culture media species on the fiber surface but also provided the information about
[120]. Additionally, J. Tang with colleagues has measured the time- its spatial distribution [197]. Additionally, TOF-SIMS allowed to estimate
resolved silver distribution in the different parts of rat organism after changes that occurred on Ag NPs surface after exposure to wastewater.
treatment with Ag NPs and Ag microparticles injections [194]. The Ag The analysis indicated that Ag NPs after 72 h in wastewater in TOF-SIMS
NPs biological activity is frequently attributed to the possibility of Ag+ analysis produce different sulfur-content ions in both negative and pos-
production. Thus, the ICP-MS is commonly utilized for quantification itive mode, which may be attributed to the presence of Ag2S and other
of Ag+ release from different silver-containing nanomaterials, as it silver sulfide species in the sample. Instead, the results from XPS analy-
was made by T. Liu al. [51]. They have investigated the Ag+ release sis was more precise, and it was possible to distinguish the Ag–S–C
from Ag NPs enclosed in superhydrophobic polyelectrolyte films, as a organosulfur bonds, which appeared on the Ag NPs surface [147]. Still,
possible agent of nanocomposite antibacterial properties. However, as SIMS is greatly limited by the diameter of the primary ion beam. The
every ICP-MS investigation, the Ag determination is suffered from nu- size of NPs, in general, is in order or even smaller than the diameter of
merous interferences. The interferences in the quantification of 107Ag primary ion beam, therefore it is rather difficult to investigate the thin
are the 91ZrO+, 90Zr16OH+, and 89Y18O+, while to 109Ag interferences structure of nano-objects [198].
the 93Nb16O+, 92Zr16OH+, and 92Mo16OH+ can be included [193]. Matrix-assisted laser desorption/ionization, that most often coupled
Lately the single-particle ICP-MS (SP-ICP-MS) is frequently utilized with time of flight analyzer mass spectrometry (MALDI-TOF MS), is con-
for Ag NPs behavior investigations in different environmental and bio- sidered to be a soft ionization mass spectrometry technique as in gen-
logical systems. SP-ICP-MS implies the utilization of very diluted NPs eral within it pseudo-molecular ions are produced. It was shown in
suspensions, so it allows to introduce single particle into ICP-MS during S. Dhanya et al. work that small Ag nanocluster with up to 11 atoms
the analysis. Moreover, the measurements in SP-ICP-MS mode are per- could be ionized and analyzed by MALDI-TOF MS directly [199].
formed with very short dwell time, so it allows to estimate both the con- E. Oliveira with coauthors have also investigated the Ag nanoclusters,
centration of the dissolved metal and incorporated in NPs in the sample they were able to distinguish nanoclusters with 21 Ag atoms [200].
at the same time [148]. Thus, the technique is frequently utilized for NPs However, lately, more attention paid to the fact that Ag NPs unique op-
size estimation and quantification. I.-L. Hsiao et al. has investigated the tical properties make possible to use it as a matrix, which contributed to
cellular uptake of TiO2 and Ag NPs for Neuro-2a cells [146]. They utilized the new approach in MS – NALDI. To give an example, K.-M. Ng et al. has
conventional ICP-MS, SP-ICP-MS, and laser ablation ICP-MS. The per- investigated different noble NPs as a possible promoter for
formed analysis showed that the Ag uptake was higher in case with benzylpyridinium ionization [8]. The investigation showed that Ag
cell treatment by bigger NPs but the higher particle number uptake NPs have the biggest ion-desorption efficiency in comparison to Au,
for smaller NPs. However, the sample preparation for conventional Pd, and Pt NPs. However, Ag NPs lead to slight analyte fragmentation
ICP-MS could contribute to a higher quantity of estimated silver uptake, and to metal cluster ion appearance (Ag+ and Ag+ 2 ). M. Yang with coau-
as some of quantified particles may be not due to cell absorption but thors has shown that signals can be enhanced even more in case of de-
adsorbed on the culture media plate. On the other hand, the NPs aggre- position of Ag NPs on zeolite [9]. They suggested that zeolite as a
gation as well as limited size for detection (20 nm for Ag NPs [148]) can supporter can make the distribution of Ag NPs more homogeneous
contribute to SP-ICP-MS analysis results. Moreover, A. Keri with col- and prevent the NPs aggregation, which is one of the widest problems
leagues has performed an SP-ICP-MS analysis of Au/Ag bimetallic NPs in NALDI approaches. Moreover, the active sites on zeolite may influ-
with different structures and was able to estimate NPs size and their el- ence the electronic state of Ag NPs by reducing the excitation energy
emental composition [195]. It was shown that in SP-ICP-MS mode the threshold. What interesting, in MALDI-TOF-MS analysis the enhanced
sequential determination of Au and Ag in the particles with calibration signals may come from compounds directly bounded to NPs, as it was
by different sized monometallic NPs and subsequent mathematical esti- shown in our work, where we observed the greater signal for α-casein
mation was the most precise and accurate for both size and molar ratio (Fig. 4), which we assumed to be due to it prevalence role in Ag NPs
investigation. The drawbacks of the utilized method are its time- and bounding [83]. Finally, it was shown that MALDI-TOF MS is suitable
18
Fig. 4. SEM image of native casein (A); mass spectrum of intact casein (B); SEM image of casein‑silver complexes (C); mass spectrum of casein‑silver complexes (D) and mass spectrum of
intact α- and β-casein standard solutions (E), respectively [83]. Copyright 2019 by the authors. Licensee MDPI, Basel, Switzerland.
for tracking how Ag NPs alone with modification by antibiotics influ- broadening and improves resolution [165]. S.T. Kim with colleagues
ence the protein profiles of bacteria [201]. in their work has shown the possibility for AF4 utilization in stability
study of Ag NPs-protein conjugates, as they performed the investiga-
3.11. Separation techniques tion of the aggregation behavior in different conditions of Cyto-
chrome C - conjugated Ag NPs [91]. K. Loeschner et al. reported the
The physicochemical and biological properties of the NPs are successful utilization of the technique for Ag NPs determination in
strictly dependent on their size. In the above sections of the article, chicken meat [202]. However, they noted that the extracted from
numerous techniques for size determination were presented, but meat Ag NPs have shown the earlier elution in comparison to the
each of them suffers from limitations, especially in the case of poly- pristine Ag NPs suspended in water. As the TEM and SP-ICP MS
disperse samples. Field flow fractionation is frequently mentioned have shown no changes in the NPs size, the difference was attributed
as an effective and low-cost method for NPs sizing. The separation to the presence of enzymes. Moreover, in W.-C. Lee et al. work it has
in the technique occurs due to different mobility of particles under been shown that carrier liquid, as well as capping agent, have an in-
the field applied perpendicularly to the parabolic main flow. The ap- fluence on the obtained results [148]. The analysis of 30 nm, 60 nm,
plied field may be of several different natures: made by cross-flow and 100 nm Ag NPs capped with citrate and PVP has shown that for
and asymmetric cross-flow, centrifugal, gravitational, or thermal NPs capped with PVP suspended in deionized water the highest re-
field. Asymmetric flow field-flow fractionation (AF4) is one of the covery can be obtained. Instead, the fractionation by AF4 could not
most popular variations of the technique and the most typical detec- be efficient for PVP-capped Ag NPs carried in surfactant FL-70 due
tors are UV-Vis, DLS, and MALS (Multi angel light scattering) to interactions between the functional groups of FL-70 and Ag NPs.
[148,165]. However, off-line and on-line ICP-MS can also be utilized. T. K. Mudalige et al. has also reported the process dependence on
In AF4 only one wall of the flow channel makes up of semi-permeable the carrier mixture as well as a stabilizing agent of the NPs [203].
membrane, so it makes possible to perform NPs focusing before frac- They noted that irreversible NPs binding to AF4 membrane at the fo-
tionation. In consequence, the focusing step prevents peak cusing side leads to membrane fouling, which in consequence
19
decreases the NPs recovery. The problem was possible to overcome Moreover, the NPs are often incorporated in different materials in line to
by membrane functionalization and NPs stabilization. give antibacterial properties, so it may alter the thermal stability of such
NPs in aqueous solutions occur with surface charge originated from composites. Thus, thermal analysis is frequently utilized for Ag NPs and
functional groups of stabilizing agents or from adsorption on the NPs sur- Ag-nanocomposites characterization, which can be performed in sev-
face of ions present in the solution. The NPs surface charge makes it pos- eral different ways. S. I Sadovnikov et al. have carried out high-
sible to use electrophoresis for its separation. Electrophoretic separation temperature in situ XRD analysis of nanosized Ag2S, which is a promis-
is based on differences in electrophoretic mobility of the particles, which ing substitute for germanium and silicon-containing semiconductors
in general depends on its charge and size [165]. In CE the separation pro- [145]. The results indicated that in the oxidizing medium the NPs
cess is performed in fused silica capillary, which inner surface can be were in form of α-Ag2S up to 448 K and in the form of β- Ag2S in the
modified on purpose to alter the electroosmotic flow and decrease the temperature range from 453 to 623 K. After the temperature has
analyte adsorption onto capillary walls [204]. H. Qu et al. have performed reached 673 K the formation of metal Ag has begun and in the temper-
the optimization for the separation process of both the Ag NPs an Ag+ by ature range from 723 to 773 K signals only from metal Ag were ob-
CE [205]. They noted that alkaline conditions are more suitable for such served. The thermal annealing of as mentioned NPs has also been
purposes, as it prevents the Ag NPs dissolution and aggregation. Addi- performed under conditions without oxygen and moisture at 393,
tionally, the necessity of chelating agent usage for Ag+ capture as well 423, 453, 493, and 930 K. The analysis showed the appearance of mono-
as non-ionic surfactants was emphasized. Moreover, D. Mozhayeva clinic non-stochiometric acanthine α-Ag1.95–1.98S and the NPs size
with C. Engelhard has shown that CE can separate Ag NPs with the growth at a temperature above 453 K.
same size but different coatings [149]. Still, in the case of a five- Another technique for thermal investigation is thermogravimetric
component mixture, the migration time of 20 nm citrate capped Ag analysis (TGA), where the mass loss of the sample over the temperature
NPs was in the same time window as the migration of 40 nm and dependence is investigated. S. M K. Thiagamani with coauthors has uti-
60 nm PVP-capped particles. The investigation has shown that the Ag lized TGA for cellulose-based hybrid nanocomposites investigation
NPs migration times depend on the mixture, in which they are injected. [209]. It was shown, that nanocomposite comprised from cellulose ma-
Thus, the correct discrimination of different species is possible only in trix, banana peel powder as a filler and incorporated Ag NPs was more
case of combination with other techniques, for example, SP-ICP-MS. Fi- resistant to thermal decomposition in comparison to pure cellulose.
nally, B. Michalke and I. Vinkovic-Vrcek in their work have shown, that This might be due to the higher thermal stability of the banana peel
methods presented in literature not always can be applied for real sam- powder filler. S. Boughriba with colleagues has investigated the changes
ples, which was the liver extract [206]. They have tested six different ap- in thermal stability in Rhinobatos cemiculus gelatin films modified by
proaches to find satisfactory conditions for Ag NPs and Ag+ separation. TiO2-doped Ag NPs [150]. The first three stages for all films were attrib-
The optimized method proposed by authors implies a strong alkaline uted to water (60–100 °C) and glycerol (250 °C) evaporation as well as
condition, usage of tetramethyl-ammonium hydroxide and reverse po- small weight gelatin fraction decomposition. Gelatin films modified
larity. The beneficial influence of tetramethyl-ammonium hydroxide with 2, 3, and 4%of TiO2-Ag NPs showed enhanced stability, so the
was attributed to Ag NPs-sticking prevention. degradation peak at 500 °C was not present in comparison to material
Gel electrophoresis is another separation technique, which com- with less amount of filler. Moreover, the differential scanning calorime-
monly is associated with biopolymers separation and study, i.e. proteins try (DSC) was performed for as-prepared samples. DSC is a thermoan-
or nucleic acids. The principle is the same as for CE, but the process is alytical method, which allows to study phase changes. The technique
performed in the gel. Lately, with progress in nanotechnology gel elec- is based on measurements of the temperature changes depending on
trophoresis become popular for NPs and nanocomposites characteriza- the portion of applied heat. At transition point the heat is spent on the
tion. M. Hanauer with colleagues has shown that metal NPs with changes in the structure, the additional heat portion does not lead to
different shapes and sizes can be separated by gel electrophoresis temperature growth till all samples turn into other phase states [210].
[207]. They noted that different capping agent can influence the separa- Rhinobatos cemiculus gelatin glass transition temperature (Tg) was esti-
tion efficiency. Moreover, they performed a mathematical calculation to mated as 150 °C, while gelatin film Tg value was about 59,5 °C. The TiO2-
explain quantitatively the NPs behavior in the process, which also al- AgNPs incorporation decreases the Tg value up to 52,6 °C for 4%-com-
lows to estimate the packing density of polyethylene glycol absorbed posite. The changes were attributed to a disordered state caused by
on the NPs surface. Gel electrophoresis is also useful for observation of NPs among the gelatin molecule's net-like structure.
NPs interaction with different biomolecules. I. Moglia et al. have investi-
gated Ag NPs formation in recombinant human L- and H-ferritine [107]. 4. Physicochemical properties
Gel electrophoresis allowed to confirm the formation of Ag NPs in L-
ferritine by chemo- and photo-reduction, while chemo-reduction in The first most important property of the Ag-content NPs is their
the H-ferritine did not appear. What is more, the formation of protein chemical composition. Metallic Ag NPs are the central object of the ma-
dimers and higher monomers induced by Ag+ was observed. I. Lubitz jority of publications. However, other forms of nanosized Ag should also
with A. Kotlyar has performed the preparative gel electrophoresis for not be avoided, as they exhibit beneficial features, so they can be uti-
G4-DNA-AgNPs (G-rich DNA-quadruplex structure) conjugates, which lized in different applications. Ag2S NPs have shown to be a promising
they subjected for TEM [92]. During the process, the G4-DNA-Ag NPs biocompatible contrast agent for dual-energy mammography and com-
separation on three different bands was observed. In consequence puter tomography [14]. Ag2O NPs are reported to be a good filler for
nanocomposites from each band showed the different NPs content pastes for the production of printed electrical devices [6]. Additionally,
(from one to three pieces). Finally, gel electrophoresis was useful for the Ag2O NPs the same as Ag NPs showed the antibacterial properties
the observation of changes that take place in cells treated with Ag NPs against various Gram-positive and Gram-negative bacteria [211]. More-
and their composites. For instance, S. Meenakshisundaram with col- over, the metallic Ag NPs can undergo changes through sulfidation,
leagues has observed the expression levels of various anti-apoptotic, chlorination, oxidation, and aggregation, which drastically change
cell cycle regulators and apoptotic genes caused by Ag NPs synthesized their properties: decreasing in bioavailability and bioactivity, poor solu-
with A. muricata leaf extract[208]. bility, etc. S. Karimi et al. have shown that utilization of the marine algae
extract of Chaetomorpha sp for Ag NPs synthesis led to Ag@AgCl NPs
3.12. Thermal analysis formation [71]. Additionally, M. Azodi with coauthors has shown the
metallic AgNPs transformation in the complex mixtures, which
Thermal behavior is a crucial characteristic of Ag NPs, as their utiliza- the wastewater is, through surface oxidation to Ag2O and subsequent
tion in electronics and catalysis implies the elevated thermal conditions. S-content NPs formation [147]. D. Chen et al. have also reported the
20
Ag2S surface formation in presence of S2O2− 3 ions [212]. They empha- with a 16:1 aspect ratio [215]. The second effect may be explained by
sized the crucial role of phenolic groups of the tannic acid, which served the limitations for electron movement inside the metallic NP
as Ag NPs stabilizing agent, in the S2O2− 3 reduction. All these indicate surrounded by an insulator. The electron behavior in the metallic parti-
that the presence of different ions in the synthesis mixture or in the in- cles was explained by M. A. Garcia, where the rod-like shape influence
vestigated systems should be considered, as the formation of different on LSPR was illustrated [166]. The electromagnetic field of the incident
Ag-containing impurities may influence on the obtained results. light causes the electron movement to the NPs surface. Such electron ac-
To the Ag-containing NPs variations can be include several different cumulation on one side of the NP causes the negative charge, whereas
groups: pure Ag NPs, alloys, core-shell, and doped metallic NPs (AgAu other electron-deficient part stays positively charged. The created di-
[47,195], AgPd and AgPt [180], etc.), nanocomposites (Ag/TiO2 [213], pole forces electrons to return to the equilibrium position, causing the
Ag@AgCl [71], SiO2@Ag [122], etc). To the Ag NPs chemical features electron oscillation with a certain frequency, named the plasmonic fre-
the capping agent and/or surface modifier can also be include, as it de- quency or resonant frequency. Larger electron displacement creates
termines NPs physical, chemical, and biological behavior. The capping larger dipole and in consequence larger restoring force altering the res-
agent is directly responsible for the sign and magnitude of the NPs sur- onant frequency. The electron movement along the rod axis in rod-like
face charge, which in turn influences hydrodynamic radii and aggrega- NPs creates greater charge accumulation on the surface, which in conse-
tion stability [49]. Moreover, the metallic NPs LSPR plasmon quence shifts the resonant frequency to a higher wavelength. However,
maximum is strictly dependent on the stabilizer, as it changes the di- the shape-depended NPs properties caused by more complex phenom-
electric constant of the surrounding media near the NPs surface. Finally, ena. Besides the light adsorption, the NPs shape also alters the light scat-
C. D. Walkey et al. have investigated the influence of the surface modi- tering [5]. Moreover, the anisotropic NPs structure changes the energy
fiers on the NPs interaction with serum proteins [26]. It was shown distribution on the surface. In general, the atoms on apexes and edges
that the capping agent has influenced the protein corona composition, possess more energy than atoms on faces, which for example causes
which formed on the NPs surface. Thus, the stabilizer may influence the faster Ag NPs dissolution on the apexes [216]. Additionally, the ad-
the NPs mechanism interaction with cells and therefore can influence sorption, desorption processes as well as adsorbed molecules distribu-
cell regulation routes [27]. tion changes on the NPs with different shapes [217]. The higher
Size is another important feature, which together with chemical surface-to-volume ratio implies the higher adsorption, which in conse-
composition determines the majority of NPs properties. The size- quence changes the surface charge and therefore the behavior in the so-
dependent characteristics of NPs are attributed to the so-called “quan- lution, making possible for example to separate NPs with different
tum size effect”. The properties of bulk material are determined by the shapes by gel electrophoresis [207]. Moreover, R. Vankayala et al. have
average of all the quantum forces affecting all the atoms from which revealed that singlet oxygen formation by Au and Ag NPs greatly
the material is made. By decreasing the size of the objects it can be depended on the NPs shape [218]. The authors noted, that oxygen exists
reached the point, where the averaging no longer works. The distinctive in molecular form only on the Ag(111) plane, and decompose on the
behavior of the atoms or molecules in small clusters in comparison to atomic form on both Ag(100) and Ag(110). Finally, the NPs shape influ-
that one from bulk material is called quantum size effect. Besides, the ences their interaction with cells [219]. S. Dasgupta et al. by calculations
surface energy excess also contributes to specific properties of the nano- of the curvature energies of lipid bilayer membranes combined with a
scale objects, as the specific surface is increased drastically with de- contact adhesion energy for the particle−membrane interaction have
creases in the particles size [214]. However, the size of the NPs can be revealed the complexity of the endocytosis process for non-spherical/
determined by several methods and each of the methods will provide non-ellipsoid NPs [220]. The calculations showed that cellular uptake
controversial data. It was shown, that size measured by DLS, in general, depends not only on global parameters like aspect ratio but also on
is overestimated. R. Ma with coauthors in their study has shown that the local geometrical parameters, like extrema of the local mean curvature.
DLS measured NPs size can be even 20 times bigger, than that one ob- The combination of three abovementioned NPs characteristics deter-
tained by TEM [28]. The hydrodynamic diameter for Ag NPs coated mines other physicochemical and biological NPs properties. To the fea-
with gum arabic was measured as 99.1 ± 1.1 nm by DLS and 5.5 ± tures that differ the Ag behavior in the form of NPs from that one in
1.7 nm by TEM. The effect is attributed to hydrated corona on the NPs the bulk material, the optical, thermal, and catalytic properties can be in-
surface, which behave rather as a hard shell than the liquid causing cluded. The optical properties of Ag NPs are the most emphasized and
the light scattering [30]. Moreover, the NPs aggregation also could result discussed in the literature. As it was mentioned in the other sections of
in higher measured values of NPs size. Even though DLS estimated size the review the LSPR is the major effect of the unique behavior of the me-
is not the exact radii of the NP, it may contribute to the results obtained tallic NP and commonly is related to the light absorption of specific
for desirable NPs characteristics. DLS is a spectroscopic technique oper- wavelengths. The absorbed light depends on the size and shape of the
ating in the visible part of the electromagnetic radiation. Thus, it may in- NPs, and in consequence, determines the NPs color (Fig. 5). T. Huang
dicate the alters in the UV-Vis spectra, conventionally utilized for LSPR with X.-H. N. Xu has synthesized Ag NPs with different colors [54]. The
measurements. B.-J. Liu et al. have shown in their work, that depending color of synthesized colloids was dependent from the shape of the NPs
on the NPs size and shape the scattered and absorbed light contribution and was light yellow for spherical NPs with a diameter of 2.6 ± 0.8 nm
in the overall extinction spectrum may differ significantly [163]. They (λmax = 393 nm) and orange-red for the mixture of predominantly
also noted, that in fact the direct discrimination of the scattered and spherical NPs (91.2%) with a diameter of 9.5 ± 3.2 nm and rod-shaped
absorbed part of the light is cannot be performed with existing mea- NPs (7.9%) with size 13.5 ± 4.2 nm × 10.5 ± 3.9 nm (λmax = 461 nm).
surement tools, therefore only mathematical calculations may slightly The colloids with the purple, purple violet, violet and blue colors (λmax =
shed light on the issue. In the abovementioned work of R. Ma et al. the 536 nm, 552 nm, 572 nm, and 606 nm respectively) were the mixtures of
XRD diameter evaluation was also performed [28]. The crystallite diam- a nearly equal amount of spherical NPs with sizes 16.7–20.3 nm and rod-
eter for uncoated Ag NPs and coated with PVP, in general, have shown shaped NPs with aspect ratios 23–27 nm × 15–19 nm (37–54% of each),
the calculated sizes twice lower than TEM investigations. The obtained and with small amount of triangle NPs (8.8–15.2%). However, the LSPR is
data may be due to the presence of twinned particles, which cannot also significantly modified by surrounding media, in particular, the re-
be distinguished by TEM. fractive index has a big influence on the changes in resonant wavelength
Shape influence on the metallic NPs properties may be assigned to and therefore in the NPs color. J. J. Mock et al. have observed the NPs
several factors. Firstly, the shape factor alters the specific surface area, color changes subjected to dark-field microscope investigation [117]. In
and therefore the thermodynamic characteristics of the NPs. In the sim- their work, the spherical 40–90 nm-sized Ag NPs immobilized on SiO2
plest approximation for two NPs of the same volume, the spherical NP wafer appears in the blue color in the local dielectric interface of air,
will have 2.5 times lower surface in comparison to the rod-like NP while in oil with refractive index 1,44 the color is shifted to green/yellow.
21
the maximum enhancement among all studied Ag NPs. The obtained re-
sults may be due to increased extinction at the excitation wavelength,
which was caused by the formation of a strong longitudinal band, reso-
nant with the excitation band.
The discrete character of the NPs makes them a semiconductor even
though silver as a bulk material has the highest electrical conductivity
among all metals. The NPs behavior as a semiconductor emerges from
the fact that the size of the NPs is in the same order as the exciton Borh
radius, which is a distance between electron and hole of exciton. The
electron-hole pair, called the exciton, is originated from the excited
state of the semiconductor when the electron leaves the hole on the va-
lence band by transferring to the conductive band [1]. The UV-Vis spec-
troscopy usually is exploited for optical band gap determination. The
band gap study, in general, shows the properties of the whole Ag NPs-
containing system rather than Ag NPs alone, as the metallic NPs are
often utilized in order to improve the optoelectronic properties of the
materials. W. L. Wang et al. has investigated the TiO2 nanotubes deco-
rated with AgNPs [225]. It was shown that the band gap of TiO2 nano-
tubes were 3.18 eV and by changes in Ag content from 12.5% to 17.8%
it was possible to adjust the cut-off for band gap from 420 nm
(2.95 eV) to 430 nm (2.88 eV). Instead, S. I. Mogal with coauthors has no-
ticed that the band gap for pure TiO2 particles was 3.08 eV [213], which is
Fig. 5. Study of absorption and scattering plasmonic optical properties of colloidal Ag NPs between the measured values for anatase (3.2 eV) and rutile (3.0 eV)
using UV-Vis absorption spectroscopy: (A) photos of colloids with AgNPs of different [226]. The modification with 0.75% Ag shows two ban gaps 2.99 eV and
shapes, (B) normalized absorbance of UV-Vis absorption spectra of AgNPs colloids
2.35 eV. The further increase of Ag content caused the shifts in band
shown on (A). Reproduced with permission from ref. [54]. Copyright 2010 Royal Society
of Chemistry. gap absorption edges and the disappearance of the visible absorption
band. These indicated the absence of a doping effect for composites
with higher Ag-content. The XPS analysis of as-prepared nanocoposites
A. P. Kulkarni et al. have also investigated the influence of the refractive shows that on the surface of low silver-content NPs predominant silver
index on the LSPR band, they performed the Ag NPs transition from a species were in the form of oxides and increase of the silver content
water environment to polar organic solvents [221]. The transfer of Ag led to Ag0 nanoclusters formation. However, it was shown by N. T.
nanoprisms to methanol, 2-propanol, dimethylformamide, and Tsendzulghul et al. that AgO, depending on deposition condition, had
dimethylsulfoxide have shown that the in-plane LSPR band slightly the band gap in the range between 2.3 eV (539 nm) and 3.1 eV
broadened and redshifted, the relevant shifts were higher in case of (388 nm) [227]. Moreover, as it was shown earlier the XPS analysis of in-
higher refractive indexes. Instead, the change of water media to acetone sulators can cause the surface group reduction due to charging effect,
causes significant in-plane band broadening. which could contribute to results shown by S. I. Mogal et al. Still, K. H.
To LSPR induced effects the formation of so-called “hot electrons” Mahmoud et al. have also noticed the non-linear influence of Ag NPs
(electrons with high kinetic energy) can be included [222]. The hot elec- on band gap of the gelatin [228]. The authors have calculated the optical
trons formation can be utilized in solar energy harvesting. Moreover, band gap changes from 4.60 eV for pure gelatin to 3.85 eV for gelatin
hot electrons can directly interact with molecules adsorbed on the doped with 0.6% of Ag NPs and 4.2 eV for gelatin doped with 1.0% Ag.
metal surface. Thus, Ag NPs exhibit enhanced catalytic properties in The thermodynamic properties of the material can be divided into
photochemical reactions. To give an example, P. Jiang et al. have ob- two constituents: bulk quantity and surface quantity [229]. The signifi-
served the dehalogenation of 4-iodothiophenol, 4-bromothiophenol, cant size reduction leads to considerable magnification of surface com-
and 4-chlorothiophenol by in-situ SERS detection [223]. It was shown, ponent influence on the material properties. The result of the relatively
that dehalogenation reaction rate performed on 80 nm Ag NPs was highly-energetic state of the Ag NPs is a lower melting temperature in
much higher than that one for 40 nm or 80 nm Au NPs. Finally, as it comparison to the bulk material. C.-W. Chiu et al. have investigated
was mentioned earlier, the optical properties of NPs also include fluo- the melting point of Ag NPs synthesized in the interlayer space of syn-
rescence, which was reported for extremely small NPs with diameters thetic fluorinated mica clay [230]. The DSC analysis indicated that
below 10 nm. For example, L. Burratti et al. [134] have investigated 8.1 nm Ag NPs has melting point ≈ 118 °C, while 11.7 nm particles
the fluorescence features of NPs with 1.45 ± 0.26 nm size. C. Li et al. ≈135 °C. R.-X. Dong et al. have also studied the thermal stability of
[15] also reported the fluorescence behavior of 3.9 ± 0.7 nm-sized 26 nm Ag NPs synthesized on bentonite clay, the reported melting
NPs. However, Oliveira with colleagues [200] suggested that the fluores- point was 110 °C [223]. However, the investigation was performed in
cence exhibit only extremely small Ag-clusters containing several silver a different way, namely the Ag NPs after synthesis were subjected for
atoms (up to 4). The fluorescence of larger nanoparticles is a conse- 2 h drying at 110 °C, and then observed under FE-SEM. The coalescence
quence of as mentioned nanoclusters adsorption on the surface of the of as-prepared NPs has been revealed. Such behavior can be explained
particles. Oliveira et al. in their work concluded that the investigation by Hanszen's theory of the pre-melting process, which implies the ap-
of such small objects is impossible due to low stability under the elec- pearance of a quasi-liquid film on the NPs surface before melting,
tron beam of HRTEM. Bigger Ag NPs also can exhibit photoluminescence which can occur even at temperatures lower than the melting point
properties, but the excitation mechanism greatly differs. To force the big and cause the NPs coalescence [231]. Under the pre-melting process,
NPs to emit light the two-photon excitation can be utilized. F. Han with the NPs core can stay solid, while DSC analysis shows the ending point
coauthors has investigated the influence of the Ag NPs size on the two- of the phase transformation process for whole NPs volume.
photon excitation photoluminescence intensity [224]. Moreover, they
have utilized the plasmon coupling, which was reported to be responsi- 5. Biological activity
ble for the enhancement of the phenomenon. The 14-fold enhancement
of two-photon excitation photoluminescence was observed for coupled Biological activity can be defined as direct action (positive or nega-
with poly(diallyldimethylammonium chloride) 50 nm Ag NPs, which is tive) on a living organism, i.e. bacterial, plant, or animal cells [232].
22
The Ag NPs biological activity frequently is associated with their anti- therapeutical concentration (the viability was ≥95% in the presence of
bacterial properties. Indeed, Ag NPs and their composites were reported 78.62, 39.31, 19.65, 9.82, 4.91, and 2.45 μg/mL of NPs). Finally, the Ag
as effective agents for a variety of Gram-positive and Gram-negative NPs in the concentration of 78.67 ± 3.60 μg/mL displayed <3% hemoly-
bacteria's growth inhibiting. The trypsin-conjugated Ag composite was sis, which lies within the biocompatible range in accordance to ISO/TR
able to inhibit the growth of E. coli and S. aureus [90]. Besides, B. Das 7406 [20]. However, Ag NPs can exhibit toxic properties against normal
et al. have demonstrated the effectiveness of Ag NPs synthesized with cell cultures. A. K. Suresh with coauthors has investigated the cytotoxic
Ocimum gratissimum leaf extract in case of a multidrug-resistant form effect of Ag NPs against mouse macrophage and lung epithelial cell lines
of the abovementioned microorganisms [123]. A. Rogowska et al. have [101]. Four different types of Ag NPs were utilized, namely poly
reported the antimicrobial activity of Ag NPs synthesized with (diallyldimethylammonium)-Ag, biogenic-Ag, uncoated-Ag, and
Actinomietes strain CGG11n against Gram-negative K. pneumoniae, oleate-Ag with sizes in the range 4–9 nm. The IC50 concentrations for
E. coli and P. aeruginosa as well as Gram-positive S. aureus and RAW-264.7 cells were found to be 0.1, 0.125, 1.1, and 4.9 μg/mL for
S. epidermidis [136]. Finally, K. Rafińska with colleagues has shown the each of the abovementioned Ag NPs respectively and 0.45, 0.7, 1.6,
susceptibility of B. subtilis to as-mentioned CGG11n-synthesized Ag and 6.3 μg/mL for C10 lung cells. The authors emphasized that the sur-
NPs [201]. Still, Ag+ ions were more effective, as they completely face coatings alone had no toxic effect, but the direct correlation be-
inhibited the B. subtilis growth in the concentration of 12.5 μg/mL, tween the Ag NPs surface charge and toxic effect can be observed.
while the Ag NPs in the concentration of 100 μg/mL inhibited the Moreover, the authors revealed that as-mentioned oleate-coated Ag
growth only by about 13% in comparison to the control. NPs nanoparticles were found to be nontoxic or noninhibitory to pro-
In addition to antibacterial properties, Ag NPs and their nanocompos- karyotic Gram-negative E. coli, S. oneidensis, and Gram-positive
ites were reported as antifungal, antiamoebic, antiviral, antiangiogenic B. subtilis.
agents. S. S. Dakshayani et al. have shown both the antibacterial activity Ag NPs can cause various physiological effects on the cell level and
against E. coli and S. aureus as well as antifungal against A. niger of Ag NPs therefore on an organism in general. The Ag NPs can activate
synthesized with Selaginella plant extract [69]. The Ag NPs conjugated mitochondria-mediated stress. For instance, J. S. Teodoro et al. have re-
with Guanebenz have been shown to be toxic for Acanthamoeba vealed that Ag NPs impaired the oxidative phosphorylation capacity and
castellanii and Naegleria fowleri [233]. S. Gaikwad et al. have synthesized depressed transmembrane potential in isolated rat liver mitochondria
the Ag NPs by different fungi (Alternaria species, Fusarium oxysporum, [235]. Moreover, the authors have shown that mitochondria pre-
Curvularia species, Chaetomium indicum, Phoma specie) and the as- incubated with Ag NPs exhibit increased susceptibility to calcium-
synthesized NPs were subjected to antiviral capability investigations induced permeability transition. P.V. AshaRani with colleagues has
[86]. The Ag NPs produced with Alternaria species and Phoma species re- also investigated the cellular Ca2+ homeostasis and changes in mito-
vealed to be toxic at a concentration of 10 mg/mL, but the viral inhibition chondria permeability of Ag NPs-treated human lung fibroblast [236].
with lower Ag NPs concentrations was on a relatively low level (between However, the perturbation in Ca2+ cellular homeostasis influences not
0% to 40%). Instead, the inhibitory activity against herpes simplex virus only the mitochondria normal functioning, but also injures the cytoskel-
type 1 (HSV-1) and human parainfluenza virus type 3 (HPIV-3) of Ag eton. The cytoskeleton injury blocks the chromosome segregation and
NPs synthesized with F. oxysporum and C. indicum showed the highest cytokinesis. Similarly, in the M. Piao et al. work the Ag NPs treatment in-
scores. The reduction in virus infectivity can be reached up to 80% for fluenced the mitochondrial transmembrane potential and caused the
Ag NPs produced by F. oxysporum against HSV- 1, and 90% for Ag NPs pro- cytochrome C release [139]. The authors have shown, that transmem-
duced by C. indicum against HPIV-3. Ag NPs produced by Curvularia spe- brane potential loss is a result of the down-regulation of Bcl-2 and up-
cies shows the resembling activity as F. oxysporum and C. indicum for regulation of Bax. A. Sachdev et al. have also shown that carbon dots-
HSV-1 virus, however no effect with HPIV-3. Moreover, L. Lu with col- Ag@ZnO nanocomposite down-regulated the Bcl-2 gene, which could
leagues have revealed that compounds with Ag in various oxidation lead to the expression of pro-apoptotic genes [237]. R Zhang et al.
states, such as AgNO3, [AgII(meso-tetraphenylporphyrin)], and [AgIII have revealed that Ag NPs can induce the endoplasmic reticulum medi-
(meso-triphenylcorrole)], had no significant anti-viral activity against ated stress by affecting the PERK/eIF2α signaling pathway, IRE1 phos-
hepatitis B virus (HBV) [234]. phorylation, and ATF6 cleavage [238]. The Ag NPs were also shown to
Ag NPs also exhibit toxic effects against a variety of cancer and nor- alter the ion interplay in the biological fluids, among other the forma-
mal cell cultures. Additionally, the Ag NPs anticancer activity can be tion and accumulation of Ag2Se and Ag2S insoluble salts [239]. More-
attributed to their antiangiogenic properties. S. Gurunathan with col- over, the high Ag+ affinity to S and Se can affect the selenoprotein
leagues has investigated the antiangiogenic properties of Ag NPs syn- synthesis [240] or S-containing peptides, proteins and enzymes activity,
thesized with Bacillus licheniformis [19]. The antiangiogenic properties such as glutathione or dehydratases [241,242]. Besides, glutathione is
for as-prepared NPs were attributed to decreased viability of endothelial considered to be a major cell antioxidant that removes ROS from an or-
cells (up to 50% in the concentration of 500 nM), their reduced migra- ganism and maintains cellular oxidation-reduction homeostasis. How-
tion and altered formation of tubular structures. The Ag NPs synthesized ever, the Ag NPs mediated oxidative stress is connected not only with
with Bacillus spp. were shown to affect the viability of breast cancer cells glutathione elimination. The cells subjected to NPs exposure had the de-
MCF-7 [94]. The cell toxicity was dose-depended and at the concentra- creased activity of antioxidant enzymes [243] and the changes in ex-
tion of 30 μg/mL the cell viability was calculated as 80%, while at the pression of genes connected to oxidative stress regulation [244]. N.
concentration of 50 μg/mL cell viability was substantially decreased as Mei with colleagues has shown that 5 nm Ag NPs induced the expres-
15%. Even though the growth inhibition was not very significant, the sion of 59 from 84 genes related to oxidative stress in mouse lymphoma
Ag NPs treated cells also exhibit decreased adhesion capacity, changes cells [245]. Moreover, they have revealed the mutagenic activity of Ag
in cell shape and size. K. Jadhav et al. have also performed the in vitro NPs. The authors presented the results of LOH (loss of heterozygosity)
investigation of anticancer activity for phytosynthesized 40–80 nm- analysis in dose ranged of 3–6 μg/mL, the mutant formation in cells
sized Ag NPs against a number of cancer cell cultures, among others treated with 5 μg/mL Ag NPs was sevenfold higher than in control. Ag
liver HepG2, lungs L-132, pancreas MIA-Pa-Ca-2, breast MDA-MB-231, NPs can also influence cell proliferation and differentiation. The Ag
oral KB cells, prostate PC-3, and cervical HeLa cancer cell lines [20]. NPs can enter cells in several different ways: autophagy (through mem-
The IC50 value (half-maximal inhibitory concentration) was estimated brane channels), clathrin-mediated or caveolar endocytosis, phagocyto-
as 6.31, 4.002, 5.228, 8.452, 14.37, 7.46, and 6.55 μg/mL for each sis, pinocytosis. In P. Dubey et al. work the routes of NPs in-cell
abovementioned cancer cell cultures respectively. Moreover, the intercalation and distribution are presented in a more detailed way
cytocompatibility assay with normal human fibroblast L929 cell lines in- [25]. Additionally, a more exhaustive description of effects, that Ag
dicated that the as-synthesized NPs have no significant toxicity in NPs can cause to living cells is presented.
23
5.1. Mechanism of Ag NPs biological toxicity concentration and dramatically decreases at a concentration higher
than 0.5 mg/L, which could be the reason for negative results. Further-
The toxic mechanism of metallic NPs is the main issue of a large more, the hydroxyl radical formation in S. epidermidis treated with
number of scientific publications. Even though the numerous effects Ag+ was observed, which could be due to the silver interactions with
can be observed in bacterial and eukaryotic cells treated with Ag NPs enzyme iron‑sulfur clusters [241]. The addition of the Fenton reaction-
the exact molecular mechanism of their action still has no clear elucida- specific quencher, thiourea, which does not consist thiol groups, led to
tion. Fig. 6. graphically presents the scope of the chapter. There is plenty decreased hydroxyl radical occurrence. Even though, the ICP-MS mea-
of publications, which attributed the biological activity of the Ag NPs to surements in S. epidermidis lysates indicated that silver itself is not
their possibility to release Ag+ by oxidation. Such a mechanism, where able to liberate coordinated Fe ions, their role in ROS formation cannot
Ag NPs are considered only as an Ag+ carrier, some researchers called be dismissed completely. F. F. Xu et al. have also investigated the influ-
“Trojan horse” mechanism. The Ag+ was reported to have an affinity ence of Ag+ on [4Fe-4S]+ clusters of dehydratases, in particular fuma-
to phosphate, carboxyl, amino, and thiol groups. The O. Gordon et al. rase [242]. They noticed, that malate (fumarase substrate/product)
have investigated the impact on bactericidal properties of Ag+ ions in can partially prevent the damage, as the malate by the active site occu-
the presence of DNA, phosphate, cysteine, and glutamine amino acids pation make it more difficult for Ag+ reach it.
[241]. The authors concluded, that only the Ag+ interaction with thiol The Ag+ has also reported to electrostatically interact with mem-
groups is the reason for their bactericidal properties, as only the pres- brane phospholipids and proteins, which can cause the depolarization
ence of thiol-containing amino acid abolished the antibacterial activity. and destabilization of cellular membrane and leakage of H+ [248]. The
Further, to confirm the theory, the Ag+ influence on succinate dehydro- Ag+ release from the Ag NPs is a generally accepted fact, as it was con-
genase deactivation was shown, which was possible to avoid by adding firmed by multiple investigations [32,77,249,250]. The Ag+ release
cysteine-containing tripeptide glutathione. Moreover, in C. N. Banti et al. through the oxidative dissolution of the Ag NPs is the main issue in
the lipoxygenase inhibition by Ag+ complexes with anti-inflammatory the assessment of their toxicity and fate in biological systems and the
agents (2-hydroxybenzoic acid, salicylic acid, and aspirin) has been environment. M. Azodi et al. has investigated the dissolution behavior
shown [246]. However, the as-mentioned Ag+ containing complexes of Ag NPs in municipal wastewater [147]. The process was dependent
were also able to interact with DNA. The hypochromism observed in on the amount of dissolved oxygen and the initial concentration of the
the UV spectra for Ag-containing complexes with calf thymus DNA Ag NPs. For deionized water suturated with oxygen the highest dissolu-
was attributed to the intercalated or electrostatic binding mode. Addi- tion rate was revealed, while the presence of the inorganic reduced sul-
tionally, the Ag+ complexes with anti-inflammatory agents caused the fur in the form of HS− in the wastewater may contribute to a lower
DNA fragmentation in leiomyosarcoma cancer cells. dissolution by forming insoluble sulfides. Moreover, the utilization of
The Ag+ is also considered to be responsible for ROS formation. H. J. higher concentration of Ag NPs (1000 ppb over 10 ppb) led to a smaller
Park et al. has shown that Ag+ induced the expression of superoxide- extent particles size reduction, but to a higher Ag+ content in the solu-
sensor protein production, which can indicate the superoxide radical tion. S. Kittler et al. have performed the dialysis study of citrate and PVP-
formation [247]. The authors noticed that earlier studies had shown stabilized Ag NPs, which confirmed the low-rate NPs dissolution even in
the controversial results, but the process is depended on Ag+ the absence of specific oxidizing agents [249]. The authors suggested
Fig. 6. The mechanisms of silver nanoparticles toxic action.
24
the process occurrence due to dissolved oxygen in the solution, but no- The changes in surface compression modulus value C−1 s for Ag NPs/
ticed that observed dissolution kinetic can be explained neither by the lipids mixtures as a function of the surface pressure provided the infor-
possible oxygen diffusion nor by residual solved oxygen, which may in- mation about monolayer in-plane packaging elasticity. The decreased
dicate the more complex process. In R. Ma et al. work the size- C−1
s values for lipid monolayer in the presence of Ag NPs at low and
dependent dissolution of Ag NPs has shown [28]. It was revealed that high pressure were observed, which indicated the higher compressibil-
the solubility of Ag NPs was increased in the case of smaller particles. ity and therefore the more fluidic and expanded character. Thus, the Ag
However, the dependence was not linear in accordance with the surface NPs induce greater disorder at the molecular level of lipid layers. More-
area of the NPs, meaning that the ratio of released Ag+ to the surface over, the Brewster Angle Microscopy was able to distinguish the coexis-
area was not constant for NPs of different sizes. Thus, it can be con- tence of different phases in stratum corneum mimic membrane, which
cluded that surface area alone could not explain the differences in disso- indicated the phase segregation induced by Ag NPs and can be as evi-
lution rate, but the surface tension may provide reasonable information dence of their destructive role on cell membranes.
about Ag NPs solubility in the aqueous solubility. Additionally, the in- The charge influence on the Ag NPs toxicity has been shown in T.
vestigations also showed that the coating type and synthesis method Silva et al. work [31]. The toxicity of positively charged branched
has no significant impact on the Ag NPs dissolution kinetic. Finally, in polyethyleneimine-coated, moderate negatively charged PVP-coated
C. Graf et al. the shape-dependent character of Ag NPs dissolution has and negatively charged citrate-coated Ag NPs were inspected. The pos-
been revealed [216]. The authors observed fast dissolution of the itively charged Ag NPs exhibited higher toxicity both to prokaryotic
nanoprisms' tips, followed by a slowdown of the process when NPs be- (E. coli) and eukaryotic (D. magna) cells, which is attributed, similar to
come spherical, which was attributed to a higher energy on apexes and Ag+, to the possibility for more easy interaction with negatively charged
edges. In general, the oxidative dissolution is a dynamic process, which cell membranes. However, A. Lesniak et al. have compared the
depends on environmental conditions. In B. Tang work it was shown polystyrene-NPs adhesion to human adenocarcinoma alveolar basal ep-
that under light irradiation the Ag NPs can be partially dissolved, ithelial A549 cells, and they noted that protein corona formed on NPs
which in consequence led to changes in NPs shape from nanoprism to surface influenced on their adhesive properties [34]. The cells exposure
nanodisc [251]. The authors have revealed that after removing the to NPs in complete cell culture medium supplemented with 10% fetal
light irradiation, the dissolved Ag+ adsorbed again on the NPs surface, bovine serum indicated lover adhesion rate than that one cultured in
so the final size of the Ag nanodisc was larger than that one which can serum-free medium. Additionally, S. Juling et al. have revealed that
be inscribed in the initial nanoporism. Moreover, it was possible to the metabolic response to the Ag NPs treatment in Caco-2 human intes-
turn nanodisc to nanoprisms again, with addition of extra citrate. How- tinal epithelial cells is dependent on the protein corona formed on the
ever, the newly obtained nanoprisms were of larger size than the initial NPs surface [27]. G. Lopez-Carballo et al. have also noticed the higher an-
one. tibacterial capacity against E. coli and S. aureus of chitosan films, contain-
Still, the Ag+ release only cannot explain the higher biological activ- ing silver nanoparticles, in diluted MHB comparing to normal culture
ity of Ag NPs. A. Ivask et al. have shown that the Ag NPs toxicity in- media [17]. The effect was attributed to the chelating capability of pro-
creased with decreasing in size, and the correlation was observed for teins, that decreased the availability of ions to exert antimicrobial activ-
all investigated organisms: E. coli, P. fluorescence, S. cerevisiae, ity. Hence, even though the primary stabilizer has an influence on the
P. subcapita, D. magna and murine fibroblast line BALB/3 T3 [250]. NPs toxicity, it can be changed significantly depending on the surround-
What is interesting, the highest size-depended difference in toxicity ing environment. The A. Lesniak et al. has also emphasized that in gen-
was observed for D. magna, while the smallest for mammalian fibro- eral the adhesion process as well as NPs uptake is difficult to disentangle
blast. The size-depended toxicity was attributed to the Ag+ release ca- as they occur simultaneously, so the time-resolving toxic mechanism
pability, which correlated for all tested NPs size, except the smallest investigation is the task for future investigations [34].
one (10 nm). The authors suggested that 10 nm Ag NPs have additional The third Ag NPs toxicity mechanism can be attributed to the conse-
not-dissolution driven toxicity. The C. Beer et al. work has also shown quence of plasmon modes and quantum states of the metallic NPs - the
that suspension of Ag NPs with 16–20 nm size revealed higher toxicity unique light propagation, enhanced reactivity of hot electrons, or the re-
against A549 human lung carcinoma cell, than its corresponding super- laxation mechanisms of excited NPs. Thus, it can be denominated as a
natant with Ag+ fraction between 1 and 2.6% [32]. Still, the Ag NPs sus- “Quantum-mechanical” mechanism. As a consequence of such a mech-
pension with higher Ag+ fraction (5.5–6.0%) did not differ in toxicity anism, the photodynamic therapy with metallic NPs can be performed.
from their supernatant. In classical photodynamic therapy, the molecule of the photosensitizer
The Ag NPs itself can disorder the different cell organelles function can receive the long-term excited triplet state by a non-radiative transi-
due to adhesion to their surface. The NPs then can induce changes in tion from the singlet state, which the molecule reached after photon ab-
structure or activate cellular destructive mechanisms, which leads to or- sorption. The photosensitizer triplet state can be decay by energy
ganelles' inappropriate functioning, therefore it can be called “Induc- transfer to surrounding molecules producing radicals, radical ions, or
tive” toxicity mechanism. Ag NPs adhesion can occur in several excited singlet oxygen (1O2) [252]. The LSPR-induced hot electron dy-
different ways, i.e. through electrostatic attraction or weak interaction namics and thermalization is also described in the literature. The hot
forces, where the capping agent has a dominant role. X. Sun with col- electrons in noble NPs can decay through two different actions, namely
leagues has shown that Ag NPs can induce the VE-cadherin (endothe- electron-electron and electron-phonon interactions [253]. The success-
lium specific cell-adherent protein) internalization in human umbilical ful transfer of Ag NPs energy, provided by LSPR, through electron-
vein endothelial cells, while the Ag+ had no effect [33]. The direct evi- electron interactions requires the direct substrate molecules deposition
dence for Ag NPs adhesion on the cell surface was proved by BSE-SEM on NPs surface. R. Vankayala et al. have revealed that Ag NPs were able
imaging and EDX spectra. Moreover, the experiment with direct and in- to promote the formation of 1O2, but only in the lightened conditions,
direct (trough ultrathin 1–2 nm membranes) Ag NPs treatment was car- confirming the LSPR-depended nature of the process. Moreover, the
ried out. The results indicated, that in both cases the total cell VE- sensitization process has shown to be strongly dependent from NPs
cadherin amount in lysates was not affected, but the direct exposure morphology [218]. To give an example, O. Erdogan et al. have investi-
to Ag NPs influenced on a higher amount of internalized VE-cadherin. gated the photo-induced enhanced toxicity of the Ag NPs synthesized
Additionally, M. E. Villanueva et al. have investigated the Ag NPs interac- via Cynara scolymus leaf extract [243]. The as-synthesized NPs alone
tion with model biomembranes [80]. The oleic acid was used as a stabi- had no influence on adenocarcinoma MCF7 cell viability in concentra-
lizer with the aim to provide hydrophobic properties to Ag NPs. The tion 10 μg/mL, but in combination with photodynamic therapy, it
changes in surface pressure-area isotherms of the membrane lipids in- inhibited the cell growth, viability, and migration by 50%. The ROS for-
dicated the Ag NPs incorporation into the films as a non-ideal mixture. mation under the irradiation was confirmed by the decrease in the
25
superoxide dismutase, catalase and glutathione peroxidase activity. In discussed in the literature, however, its exact elucidation is still un-
contrast, the electron-phonon interactions lead to thermal diffusion known, and is the issue of future investigations.
(heat transfer) outside the NPs, which is the basis for photothermal Even though the study of Ag NPs has begun several decades ago
therapy. K. Manivannan et al. have shown that core-shell Ag@SiO2@ there is still a lot of unclear aspects in their properties. The continuous
Agseed NPs can reach 43 °C under visible light irradiation, so it is enough development of more sophisticated techniques brings new knowledge
to get the tumor cell cytotoxicity and tumor vascular tissue destruction, about objects under investigation. The new facts about Ag NPs proper-
which occurs at 41.1 °C and 43 °C respectively [13]. However, for the ties allow to utilize them in a more precise way and provide a possibility
Ag@SiO2@Ag NPs, the visible light was able to induce heat only up to for a more wide range of their applications. In turn, new applications en-
40.5 °C. Moreover, the Ag@SiO2@Agseed NPs exhibited fluorescence courage to develop new routes for Ag NPs synthesis, which will satisfy
properties, so it can be utilized as a bioimaging probe. The utilization the conditions of their utilization. Lately, the NPs utilization in the
of metallic NPs in the photodynamic and photothermal therapies has NALDI technique gained a lot of interest among researches. Still, the
multiple virtues in comparison to conventional photosensitizers. The issue of Ag NPs utilization in solar energy harvesting, bioimaging,
NPs are more stable under irradiation, metallic NPs have significantly SERS, and different medical preparation is not exhausted and needs
higher extinction coefficient due to LSPR, which additionally can be new considerations.
tuned by changes in NPs form and size, so their adsorption band will
be in a biological transparency window (650 to 1300 nm) [218,252].
An additional virtue of NPs is that they can be utilized as a carrier for dif- Declaration of Competing Interest
ferent substances, which can enhance the photodynamic and
photothermal action [254]. In the case of Ag NPs the increased Ag+ pro- The authors declare that they have no known competing financial
duction under irradiation is also considered. G. Fuertes with colleagues interests or personal relationships that could have appeared to influ-
has shown that Ag NPs coated with silica received the antimicrobial ence the work reported in this paper.
properties against E. coli only in case of irradiation with light of LSPR
band [255]. The irradiation with light of 387 nm wavelength caused Acknowledgements
the changes in NPs structure and characteristic “staining” of bacterial
cells, so the NPs toxic properties were assigned to photo-induced Ag+ This work was financially supported in the frame of the project “Ad-
release. vanced Biocomposites for Tomorrow's Economy BIOG-NET”, FNP
POIR.04.04.00-00-1792/18-00, project is carried out within the TEAM-
6. Conclusions and perspectives NET programme of the Foundation for Polish Science co-financed by
the European Union under the European Regional Development Fund.
Ag NPs have shown to be the objects with unique properties that Oleksandra Pryshchepa, Paweł Pomastowski and Bogusław Buszewski
allow to exploit them in multiple applications such as electronic devices are members of Toruń Center of Excellence “Towards Personalized
and solar energy harvesting, advanced analytical techniques, medical Medicine” operating under Excellence Initiative-Research University.
diagnostics and treatment, catalysis and environmental applications.
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Advances in Colloid and Interface Science 284 (2020) 102246

Contents lists available at ScienceDirect

Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Silver nanoparticles: Synthesis, investigation techniques, and properties

1. Introduction ion-desorption efﬁciency of analyte in comparison to Au, Pd, and Pt

Fig. 1. The principles of Ag NPs synthesis.

Method Precursor Synthesis conditions Stabilization Product Ref.

(continued on next page)

Method Precursor Synthesis conditions Stabilization Product Ref.

Method Precursor Synthesis conditions Stabilization Product Ref.

Fig. 2. The structure of AgNPs with organic deposits on the surface.

Technique Study purpose Information Artifacts/problems Ref.

Technique Study purpose Information Artifacts/problems Ref.

(continued on next page)

Technique Study purpose Information Artifacts/problems Ref.

Fig. 6. The mechanisms of silver nanoparticles toxic action.

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