16 Mehta Et Al., 2021
16 Mehta Et Al., 2021
16 Mehta Et Al., 2021
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Synthesis of Ag NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Green Synthesis of Ag NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Characterization of Ag NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Toxicity of Ag NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Bio-functionalization of Ag NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Methods for the Preparation of Ag NPs Conjugated Ceramic Structures . . . . . . . . . . . . . . . . . . . . . . . 9
Ag NPs Conjugated with the Ceramic Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Ag NPs Conjugated with Ceramic Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Ag NPs Conjugated with Bio-glass Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Ag NPs Conjugated with Ceramic Tablets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Ag NPs Conjugated with Ceramic Materials for Drinking Water Treatment . . . . . . . . . . . . . . . . . . . 13
Ag NPs Conjugated Ceramic Materials as Antibacterial Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Conclusions and Future Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Abstract
The nanotechnology research is an emerging area, having its roots in every field
of science such as physics, chemistry, biology, material science, and medicine.
The unique physico-chemical properties of nanomaterials like size, shape, and
high surface and ease of functionalization make them suitable for various appli-
cations in clinical use, therapeutics, microelectronics, ceramic industries, etc.
There are various nanomaterials such as mettalic nanoparticles, quantum dots,
carbon nanoparticles, polymeric nanoparticles which have been used for large
number of applications but metallic nanoparticles have gained enormous atten-
tion in wide variety of applications. Among metallic nanoparticles, silver nano-
particles (Ag NPs) are widely exploited due to its outstanding optoelectronic,
anti-inflammatory, and antimicrobial properties. Ag NPs can be synthesized by
different physical, chemical, and biological methods. Due to number of draw-
backs faced in physical and chemical method, the research has moved to the green
synthesis of nanoparticles using nontoxic elements as the precursor. This chapter
consists of different methods for the synthesis of Ag NPs, and its characterization.
Furthermore, the different methods of manufacturing of various bio-
functionalized Ag NPs-ceramic conjugated materials and its applications are
also discussed.
Keywords
Ag NPs · Bio-functionalization · Ceramic · Anti-inflammatory · Anti-microbial
properties
Introduction
Bottom-up Top-down
approaches approaches
1. Etching
2. Mechanical milling
3. Electro-explosion
sputtering
4. Laser ablation
5. Melting
Chemical/Physical
Biological methods
methods
1. Spinning
1. Yeast
2. Plasma/Flame spray
2. Plant extracts
pyrolysis
3. Dry algal mass
3. Sol-gel
4. Bacteria cells
4. Laser pyrolysis
5. Mycelial cells
5. Aerosol based approaches
6. Chemical Vapor
Deposition
7. Atomic/Molecular
condensation
8. Ion-exchange
9. Supercritical fluid
wider areas of applications such water filtration, bio-glass, and antibacterial coatings
(Lv et al. 2009; Göl et al. 2020). This chapter will highlight the various synthesis
routes of silver nanoparticles and their characterizations. Moreover, the methods
used to fabricate the efficient ceramic structures conjugated with the Ag NPs and
mechanism involved in synthesis are also highlighted and applications of various Ag
NPs-ceramic conjugates are also briefly discussed.
Synthesis of Ag NPs
The Ag NPs are synthesized using two main approaches that includes top-down and
bottom-up approaches according to the choice of raw materials. The “top-down”
approach includes mechanical grinding of heavy and bulky metals with subsequent
colloidal protecting agents which provides stability to the mixture whereas the “bottom-
4 V. N. Mehta et al.
Characterization of
nanoparticles through
various techniques
materials used for Ag NPs synthesis, such as citrate, borohydride, thio-glycerol, and
2-mercaptoethanol, are toxic and hazardous. Apart from these disadvantages, the
synthesized particles purity is not satisfactory and is sedimented with chemicals.
It is also very difficult to prepare Ag NPs with a well-defined size with the
prevention of particle aggregation. At the time of synthesis process, large numbers
of toxic and hazardous by-products are released out. Chemical methods make use of
techniques such as cryo-chemical synthesis, chemical reduction, photochemical
methods, microwave processing, one pot hydrothermal methods for the controllable
synthesis of Ag NPs. The beneficial side of chemical synthesis of nanoparticles
includes ease of production, minimal cost, and good yield; however, the use of
chemical reducing agents is toxic to living organisms (Zhang and Yu 2016). The
6 V. N. Mehta et al.
Various types of nanoparticles with different size and shape were synthesized from
herbal plants, inorganic metals, biomolecules etc. The biological synthesis of nano-
particles is said to be the most efficient, simple, cost effective, dependable, and
healthy option for environment as compare to the various physical and chemical
methods. The yield produced through these approaches is also quite high as com-
pared to other methods. Various living systems like bacteria, algae, fungi, plant
extracts, biomolecules like amino acids, and vitamins are exploited as a source not
only for the synthesis of Ag NPs but many different nanoparticles. The synthesis of
Ag NPs using eco-friendly method, cost effective, and biocompatible methods
without the use of toxic chemicals in biological methods opens new door for
research. Fig. 2 depict the steps involved in biological synthesis of Ag NPs. In this
green chemistry approach, several bacteria, including Pseudomonas stutzeri AG259
(Agrawal et al. 2018), Lactobacillus strains (Nair and Pradeep 2002), Bacillus
licheniformis (Gomaa 2017), Escherichia coli (E. coli) (Gurunathan et al. 2009),
Brevibacterium casei (Kalishwaralal et al. 2010), fungi including Fusarium
oxysporum (Shankar et al. 2003), Ganoderma neo-japonicum Imazeki (Gurunathan
et al. 2013), plant extracts such as Allophylus cobbe (Gurunathan et al. 2014),
Artemisia princeps (Gurunathan et al. 2015), and Typha angustifolia (Gurunathan
et al. 2015) were successfully utilized for the environmental friendly production of
Ag NPs. In addition to these, several biomolecules, such as biopolymers (Leung et
al. 2010), starch (Kumar et al. 2014), fibrinolytic enzyme (Deepak et al. 2011), and
Bio-functionalized Silver Nanoparticles: A Versatile Candidate for the. . . 7
amino acids (Malik et al. 2015), were used. The biological synthesis of nanoparticles
involves three main factors (a) the solvent; (b) the reducing agent; and (c) the
nontoxic material. The presence of amino acids, proteins, and secondary metabolites
gives an additional advantage and minimizes the step required for the prevention of
particle aggregation. Biological methods synthesized nanoparticles have controlled
particle size and shape, which plays vital role in different sectors for multipurpose
applications. Using bacterial protein or plant extracts as reducing agents, the shape,
size, and monodispersity of the nanoparticles can be controlled. The availability of
different biological resources, less time, high density, better stability, and the faster
solubility of prepared nanoparticles in water are some of the plus points of using
biological methods. The biological activity of Ag NPs depends on the morphology
and structure of Ag NPs, controlled by size and shape of the particles. Compared to
chemical methods, biological methods allow for more ease in the control of shape,
size, and distribution of the produced nanoparticles by optimization of the synthesis
methods, including the amount of precursors, temperature, pH, and the amount of
reducing and stabilizing factors.
Characterization of Ag NPs
Toxicity of Ag NPs
The important factors for determining the cytotoxicity of Ag NPs are surface
chemistry, size, size distribution, shape, particle morphology, particle composition,
coating/capping, agglomeration, dissolution rate, particle reactivity in solution,
efficiency of ion release, cell type, tissue specificity, and finally type of reducing
agents (Bapat et al. 2018). Sometimes the size of the nanoparticle is dependent on the
biological reducing material. It is asserted from past studies that the shape is equally
important for the determination of toxicity as small size particles are more toxic due
to greater surface area as compared to larger molecules. The toxicity of Ag NPs is
8 V. N. Mehta et al.
Bio-functionalization of Ag NPs
1. The Ag NPs are anchored on the surface and pore wall of ceramic material, in this
method the amino functional groups are grafted on surface and pore wall of
ceramic membrane using chemicals like 3-aminoprypyltriethoxysilane as cou-
pling agent and grafting is proceeded via siloxane (Si-O-Si) condensation. The
amino groups anchored on ceramic structure interact with impregnated Ag NPs
through N-Ag coordination, which allows Ag NPs to be fixed on surface and pore
wall of ceramic filter and prevents them from leaching out (Fathian et al. 2017).
2. The Ag NPs are embedded inside the core of ceramic material which involves the
direct embedment of Ag NPs into ceramic structure during ceramic filter fabri-
cation. Silver nitrate and ceramic precursors, which comprise of clay and filler,
are mixed well before molding and firing. Silver ions embedded into ceramic
precursors are then reduced to metallic silver during firing process without the
presence of any external reductant (Agrawal et al. 2018).
The materials used in the formation of filters should be chosen wisely as vapor-
ization begins at 100 °C which combust all the biomass, and the decomposition of
the biomass can also lead to low porosity of ceramic structure. The widely used
materials are charcoal and activated carbon which do not possess any kind of organic
component which can be easily vaporized or broken down so it can generate highly
porous ceramic material and act as potential fillers for the manufacturing of ceramic
structures. Many past studies have shown potential incorporation of activated carbon
10 V. N. Mehta et al.
for the filtration of the water (Kallman et al. 2011). There is another study in which
Ag NPs are embedded inside the ceramic filters through a novel method of in-situ
reduction. Ceramic filters can be constructed using different fillers including saw-
dust, charcoal, and activated carbon; among these, activated carbon proved to be the
best filler which produces ceramic filter with highest porosity. By adding silver
nitrate to activated carbon before mixing with ceramic mixture, silver ions got
reduced to metallic silver to form Ag NPs during the firing process; this is called
an in-situ reduction. For water disinfection, kaolinite and clay mixture prior to
molding is mixed with activated carbon and silver nitrate then mixed with the
ceramic material. The silver metal is reduced to Ag NPs, and ceramic filters
impregnated with Ag NPs can be used for water purification after firing process.
According to the past studies, Ag NPs are formed at 600 °C without the incorpora-
tion of biomass filler, but they are again oxidized back to ionic state at 1000 °C, this
drawback was overcome by addition of biomass, that is, activated carbon which
helps to thermally reduce the silver nitrate into Ag NPs, during the firing process at
1000 °C. This method also helps to synthesize highly porous Ag NPs conjugated
ceramic filters, with uniform distribution of Ag NPs in the whole filters. As the
nanoparticles are dispersed throughout the ceramic filter, it aids in slow release and
its antibacterial efficacy is preserved for long-term filtration. The resulting Ag NPs-
ceramic filter prepared by in-situ reduction was then tested for water filtration and
compared with filters prepared by conventional Ag NPs-coating method in term of
antibacterial efficiency and silver release (Thi et al. 2019). Moreover, by the addition
of Ag NPs, the property of porosity of the activated carbon-ceramic filter is not
affected regardless of the method used, that is, coating or in-situ reduction methods.
The temperature at which the filters are fired, that is, the firing temperature has a
crucial role in the construction of mesoporous ceramic structure; increasing temper-
ature in the range of 1000–1400 °C leads to decrease in the surface area from 3.9 to
0.24 m2/g. Ag NPs conjugated ceramic filters can be prepared by both coating and
in-situ reduction methods and both possess high antibacterial efficacy, but the Ag
NPs-coated filter released silver rapidly resulting in high Ag concentration in the
treated water, which can cause toxicity. Whereas in-situ reduction method produces
Ag NPs which are uniformly distributed throughout the filter structure and allows
silver to slowly release into the filtrate media in a controllable manner resulting in a
slow release of silver which results in low maintenance and low level of silver in
drinking water which benefits human living. This method is similar to the conven-
tional method so it can be easily produced on large scale. Hence, Ag NPs conjugated
ceramic filter can be produced in an cost-effective manner (Jackson and Smith
2018). Table-2 indicates the applications of Ag NPs conjugated with ceramic
materials.
Bio-functionalized Silver Nanoparticles: A Versatile Candidate for the. . . 11
A new method is developed for point-of-use water treatment by using Ag NPs based
porous ceramic filters (Patel et al. 2011). Various types of dense materials are
available but do not contain the same porosity and other properties which tailored
materials exhibit. Therefore, porous materials have numerous applications as end
products and in several technological processes. Porous ceramic materials are more
inert and do not get affected by various bacterial attacks or harsh chemicals or
environment. These ceramic materials are widely used as filters, catalyst matrix,
chemical electrodes, or electronic sensors. To reduce the brittleness of the ceramic
materials, various additives like Poly(methyl methacrylate), poly vinyl alcohol,
starch, etc., are added (Feng et al. 2013). The Ag NPs-ceramic filter disk is prepared
by mixing clay, sawdust, and water and then melded into a pot shape. This filter is
then fired in a kiln, causing the clay to change into a ceramic material and sawdust to
combust. This creates pore channels that allow water to flow after filtration. After
quality of the filter is tested, the filter is painted with a Ag NPs solution, where the
silver acts as an antimicrobial agent without changing the taste, color, or odor of
treated water which is safe for the human consumption (Agrawal et al. 2018). There
are various methods like sol-gel processing, ion exchange, and surface modifications
through which many silver-doped antibacterial inorganics like Ag-hydrogen titanate
nanobelt sheets and Ag-incorporated tetraethyl orthosilicate thin silica films are
produced (Zhang and Oyanedel-Craver 2013). Despite such various approaches,
enormous amount of research is focused for the preparation of many different
immobilization techniques to produce a more facile way which maintains the
original properties of silver and develops other bioactive functionality which can
be exploited for further wide variety of applications (Jackson and Smith 2018).
Many different immobilization techniques on familiar support materials like
ceramics have been developed for increased application of Ag NPs (Thi et al. 2019).
NPs onto easy-to-handle support materials. The Ag NPs conjugated ZnO paper is
expected to be a promising bioactive material having both antibacterial function and
paper-like utility (Kitaoka et al. 2009).
The ceramic materials that contain silver species are excellent antibacterial agents,
also it can be prepared with various shapes and size, and the amount of silver
material incorporated can be varied according to the function or the application of
the ceramic structure (Li et al. 2008). The release of silver metal can also be
controlled according to the requirement by changing the porosity of the material.
As discussed above the nanoparticles bind through weak Van der Waals interaction,
so they can easily be removed by impulse flow of water, and therefore an amino-
silane coupling agent is used for imobilization of Ag NPs on the interior walls of
ceramic structure. One end of the amino-silane molecule is connected to the interior
surface of the channel through a Si–O–Si bond, and the other end is connected to the
silver atoms on the surface of the nanoparticles through an N–Ag coordination bond.
This kind of connection ensures that the Ag NPs remain tightly fixed to the interior
channel walls of the porous ceramic so that they can release a sufficient quantity of
silver ions for antibiosis. Such Ag NPs–porous ceramic composites have paved their
way in drinking water purification (Bakumov et al. 2007). Antibacterial ceramics are
predominantly prepared through many different routes which include sol-gel
method, in-situ reduction, melting, ion exchange method, etc. However, iron and
zinc have also been used as antibacterial ferrite ceramic materials for suppressing
bacterial growth in water tanks. Among these active ingredients, Ag NPs is most
promising and can be exploited for various applications such as bone replacement
and wastewater treatment due to its nontoxicity and biocompatibility.Various wet
chemical methods have also been developed for reduction of the material from micro
to nano scale to explore and utilize the unique physico-chemical effects such as
quantum confinement. Pyrolysis of inorganic polymers at relatively low
14 V. N. Mehta et al.
It is well established that Ag NPs can be effectively combined with the ceramic
nanoparticles for wide variety of applications in various fields especially in water
purification. The conjugation of Ag NPs with the ceramic materials increases the
effectiveness of the conjugate and also can be exploited for many different applica-
tions. Due to the extensive research in the synthesis routes of Ag NPs, biological
methods have come up with the most fascinating method due to its minimal
detrimental effects. This chapter has summarized the different routes of bio-
functionalization of Ag NPs by using various natural non-toxic reducing agents.
The conjugation of Ag NPs with the ceramic nanoparticles could be achieved via
surface functionalization or incorporating Ag NPs into the ceramic structure and can
be utilized in the various applications like drinking water treatment, ceramic tablets,
as antimicrobial agents, in ceramic fibers, bio-glass ceramics. Moreover, Ag NPs
conjugated ceramic materials are considered as versatile candidate for commercially
used products in various industries. All these recent studies open the doors for the
future research in the field of materials nanotechnology based on the Ag NPs based
ceramic materials. Therefore, more studies can be explored for Ag NPs based
ceramic composites for biomedical applications with excellent biocompatibility in
near future. Furthermore, the long-term health effects of Ag NPs generating the
bacterial resistance are also major concern for the scientist for the future study.
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