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Bio-functionalized Silver Nanoparticles: A

Versatile Candidate for the Ceramic


Industry

Vaibhavkumar N. Mehta, Juhi B. Raval, Samarth R. Patel,


Vimalkumar S. Prajapati, and Rameshchandra M. Patel

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

V. N. Mehta (*) · V. S. Prajapati · R. M. Patel


Division of Microbial and Environmental Biotechnology, ASPEE Shakilam Biotechnology
Institute, Navsari Agricultural University, Surat, India
e-mail: vaibhavmehta@nau.in; vimalprajapati@nau.in; gabi@nau.in
J. B. Raval
Ashok and Rita Patel Institute of Integrated Study and Research in Biotechnology and Allied
Science (ARIBAS), Vitthal Udyognagar, Anand, India
S. R. Patel
Department of Plant Molecular Biology and Biotechnology, N. M. College of Agriculture, Navsari
Agricultural University, Navsari, India

© Springer Nature Switzerland AG 2021 1


C. M. Hussain, S. Thomas (eds.), Handbook of Polymer and Ceramic Nanotechnology,
https://doi.org/10.1007/978-3-030-10614-0_52-1
2 V. N. Mehta et al.

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

The definition of the nanotechnology is the engineering of functional systems with


the study of the controlling matter on an atomic and molecular scale. It includes
different materials ranging from extensions conventional device to completely based
upon the molecular self-assembly. The bio-functionalization of nanoparticles with
the functional groups have opened up the broad spectral range of their applications in
various sectors like agriculture, textiles, medicines, photonics, ceramic, etc.
(Ravindran et al. 2013). Among all nanomaterials, metallic nanoparticles have
gained much more attention due to its size, shape, and ease of functionalization
with desired surface groups. In metallic nanoparticles, silver nanoparticles have
consumed the entire market due to its antimicrobial and antifungal effects for the
long time (Brabazon et al. 2018). Ag NPs have broad range of applications in
cosmetics, deodorants, toothpaste, fabrics, food packaging, filters for water purifi-
cation, and many new products are rapidly appearing in the day-to-day life. Further-
more, the Ag NPs also exhibit the valuable property such as a negative zeta potential,
tensile ductility, and higher toughness which would greatly control the surface
charge properties of ceramic membranes (Zou et al. 2020). Ag NPs are one of the
most essential, widely studied, and fascinating nanomaterials among several metallic
nanoparticles that are involved in various ceramic industrial applications. Although
there are several noble metals that have been exploited for several purposes, Ag NPs
have been focused on potential applications in ceramic industry due to its unique
properties like optoelectronic, anti-inflammatory, and antimicrobial activity opens
Bio-functionalized Silver Nanoparticles: A Versatile Candidate for the. . . 3

Methods for the Ag NPs synthesis

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

Fig. 1 Schematic illustration of various routes for the of Ag NPs

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.

Reduction of materials and


Silver salt + ligand, synthesis of silver
nanoparticles through
antibody, herbal extract
bottum up and top down
approach

Silver nanoparticles are Homogeneous synthesis


analyzed using UV- Visible and high yield of silver
spectroscopy to confirm nanoparticles are
synthesis and fabrication of synthesized under optimum
nanoparticles conditions

Characterization of
nanoparticles through
various techniques

Fig. 2 Flow-chart for biological synthesis of Ag NPs

up” methods include chemical reduction, electrochemical methods, and sono-decom-


position. Different physical, chemical, and biological methods used for the synthesis of
Ag NPs are illustrated in Fig. 1.
The preparation through physical methods includes evaporation – condensation
by tube furnace at given atmospheric pressure, spark discharging, pyrolysis, etc.
These methods are conventional though have certain advantages which include
speed, radiation used as reducing agents, and no risk of hazardous chemicals
(Fathian et al. 2017). The disadvantages of these methods include low yield, high
energy consumption, lack of uniform distribution, and solvent contamination. On the
contrary, chemical methods use water or organic solvents to prepare the Ag NPs. The
chemical methods incorporate three main components, such as metal precursors,
reducing agents, and stabilizing agents. The reduction of silver salts is done in the
two stages which include (1) nucleation; and (2) subsequent growth. The upside of
chemical methods includes good yield, as compared to physical methods. The
downside of chemical methods includes that they are not environment friendly as the
Bio-functionalized Silver Nanoparticles: A Versatile Candidate for the. . . 5

Table 1 Biomedical applications of bio-functionalized Ag NPs


Sr.
no. Discipline Applications References
1. Cancer Synthesis of Ag NPs (Ag NPs) using leaf extract of Bethu et al.
diagnosis Rhynchosia suaveolens for anticancer properties (2018)
2. Dentistry Ag-chitosan nanoparticle had a profound inhibitory Divakar et al.
effect on the growth of two major dental pathogens (2018)
S. mutans and P. gingivalis and also inhibits biofilm
formation and is nontoxic to cells
3. Diagnostics The triangular plate-shaped Ag NPs of varying Yen et al. (2015)
sizes conjugated to monoclonal antibodies (mAb)
that bind to specific biomarkers, and thus use for
the diagnosis of several diseases
4. Drug delivery Amphiphilic chitosan-grafted-(cetyl alcohol- Amarnath
maleic anhydride-pyrazinamide) (CS-g-(CA-MA- Praphakar et al.
PZA)) was synthesized by multistep reactions, (2018)
amphiphilic polymeric micelles exhibit outstanding
features, and the system is a promising strategy for
immediate therapeutically effects for alveolar
macrophages
5. Imaging Multimodal imaging approach incorporating dark- Sekine et al.
field light microscopy, high-resolution electron (2017)
microscopy and nanoscale secondary ion mass
spectrometry is an effective approach to
complement dose-response studies in nano-(eco)-
toxicological investigations
6. Gene delivery Green synthesis of polyethylene glycol (PEG) Sarkar et al.
stabilized chitosan-g-polyacrylamide modified Ag (2015)
NPs used for gene delivery
7. Orthopedics The bio-functionalized Ag NPs-doped titanium Li et al. (2016)
specimens, with improved antibacterial activity
while maintaining healthy osteoblast cellular
activity, used in orthopedics, dentistry, and other
biomedical devices
8. Pharmaceutics Ag NPs mediated Selaginella myosurus could be Kedi et al. (2018)
considered as a potential source for anti-
inflammatory drugs

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.

Table 2 Applications of Ag NPs conjugated with the ceramic materials


Sr.
no. Material Mode of application References
1. Ag NPs + ceramic The Ag NPs were coated on the filter on Oyanedel-Craver
filters the outer side for removal of and Smith (2008)
microorganisms and water treatment
2. Ag NPs + silica beads They were conjugated for the Quang et al. (2013)
application in water disinfection
3. Ag The porous ceramic material tablets Ehdaie, Krause,
nanopatches + ceramic were incorporated with silver and Smith Ehdaie
tablets nanopatches used for water purification et al. (2014)
having low cost
4. Ag NPs + ceramic This combination was used to purify Praveena and Aris
material water. The Ag NPs worked as an (2015)
antibacterial agent

widely exploited chemical method which includes chemical reduction of variety of


organic and inorganic reducing agents, radiolysis, physiochemical reduction, elec-
trochemical techniques are generally utilized for the generation of Ag NPs
(Calderón-jiménez et al. 2017).

Green Synthesis of Ag NPs

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

The functional aspects of the nanoparticles are determined by characterization


studies. It is utmost important to characterize the prepared nanoparticles before
application which significantly affect the physico-chemical and biological properties
of the Ag NPs. The necessary feature of nanomaterials, such as size, shape, size
distribution, surface area, shape, solubility, aggregation, and clusters, need to be
evaluated before assessing toxicity or biocompatibility. To identify the synthesized
nanomaterials, different analytical techniques have been used, including ultraviolet
visible spectroscopy (UV-Visible spectroscopy), X-ray diffractometry (XRD), Fou-
rier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy
(XPS), dynamic light scattering (DLS), scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM), and atomic force microscopy (AFM) (Lee and
Jun 2019). The synthesis of Ag NPs in uniform size, morphology, and functions is
essential for use in various applications of medical and other industry.

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.

mainly due to chemical or biological coatings on the nanoparticle. Ag NPs surface


charges could determine the toxicity effect in cells (Siddiqi et al. 2018).

Bio-functionalization of Ag NPs

The action or process of attaching molecules or nanoparticles made from biological


origin to the surface of a material in order to alter its physical or chemical properties
or to increase its therapeutic effects is termed as bio-functionalization. The Ag NPs
possess strong antimicrobial property, good catalytic activity, and enhanced reactiv-
ity via bio-functionalization. The shape and size of Ag NPs plays a crucial role in the
biological applications. Silver can be combined with many different types of reduc-
ing agents for the synthesis of different shape and size of nanoparticles. The colloidal
solution of Ag NPs exhibits the good optical and biological properties but for some
important practical application the aggregates of nanoparticles or thin sheets of
particles are needed. Surface modification with certain biomolecules helps in self-
assembly and also do not affect the application mechanism of the materials.
According to the past studies, silver colloid formed by the reduction of silver iodide
using sodium borohydride in the presence of HSCH2COOH as stabilizer was
transferred from the collide to a quartz substrate coated with positively charged
poly(diallyldimethyl ammonium chloride) (PDDA). The particles were held on the
surface via electrostatic attraction between the negatively charged particle surface
and positively charged quartz substrate, and this forms a good stable lattice structure
of the Ag NPs (Wang and Vermerris 2016). The Ag NPs were also synthesized using
eukaryotic organisms such as fungi via extracellularly and intracellularly by Fusar-
ium oxysporum and Verticillium fungal cells, respectively (Shankar et al. 2003). The
fungal cells undergo reduction of the metal ions for the formation of Ag NPs. The
study further confirmed that the reduction takes place with the help of the enzymes
present in the cell membrane. The fungal cells continue to multiply confirming that
the Ag NPs are non-toxic and biocompatible. The feasibility of developing Ag NPs
in solution using fungi (Fusarium oxysporum) forms extremely stable hydrosol. The
Ag NPs formed by the enzymatic process were in the range of 5–15 nm in
dimensions and are stabilized in aqueous solution by proteins secreted by the fungus.
Past studies also confirm the synthesis of Ag NPs using bacteria. The Ag NPs were
also produced using mushrooms (Pleurotus florida) was conjugated to produce bio-
functionalized Ag NPs as this mushroom is known for its medicinal property as an
antioxidant and antitumor agent (Bhat et al. 2011). The bio-functionalized Ag NPs
were also produced by using bacterial and viral cells (Gaikwad et al. 2013). The Ag
NPs have a larger surface area and higher reactivity than bulk silver. The stable sus-
pensions of zero-valent silver particles (colloidal silver) can be generated by the
aqueous phase reduction of silver nitrate by ascorbic acid (Gomaa 2017). Various
bio-medical applications of bio-functionalized Ag NPs are discuused in Table 1.
Bio-functionalized Silver Nanoparticles: A Versatile Candidate for the. . . 9

Methods for the Preparation of Ag NPs Conjugated Ceramic


Structures

Another interesting application of ceramics includes bio-glasses incorporated with


Ag NPs by sol-gel routes, melting, or ion exchange method. Out of all the methods
used for the manufacturing of this conjugate, there are some disadvantages like melt-
derived method needs high temperature for the synthesis of material, whereas ion-
exchange methods suffer from surface compositions. The sol-gel method overcomes
this limitation as it does not need any high temperature, and it also helps in
homogeneous construction of nanostructures with enhanced physico-chemical prop-
erties. The advantage of this method is low processing temperature and mixing at
molecular level to get the better physico-chemical properties (Mariappan and Ranga
2016). There are number of Ag NPs based ceramic filters which have varied
application in water disinfection and purification. Ag NPs can be conjugated with
the ceramic filters by coating the filter with Ag NPs or by impregnating method in
which the filters are dipped in the solution of Ag NPs where there is no modification
or no functional groups attached. Therefore, Ag NPs can be washed out leading to
the toxicity of water and also results in decreases in the bactericidal efficiency of the
filters which ultimately increases the maintenance cost. To overcome the rapid loss
of Ag NPs due to the weak forces present between the Ag NPs and ceramic filter
material and maintain the antimicrobial property of silver particles, there are two
different methods for the manufacturing of these materials which include the two
major points.

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

Ag NPs Conjugated with the Ceramic Filters

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).

Ag NPs Conjugated with Ceramic Fibers

Ag NPs were successfully synthesized in-situ on a paper matrix composed of


ceramic fibers as the main framework and zinc oxide (ZnO) whiskers as a selective
support for Ag NPs. Paper-like ceramic fiber/ZnO whisker composites were
manufactured using a high-speed, low-cost technique of papermaking, and these
papers are then dipped into aqueous solution of silver nitrate. Ag NPs of particle size
5–20 nm were synthesized on the ZnO whiskers by selective ion-exchange mecha-
nism between Ag and Zn species, and simultaneous ZnO-mediated photo-reduction
under natural light irradiation. As Ag NPs conjugated ZnO paper was subjected to
antibacterial assay by the disk diffusion method using Escherichia coli, it shows that
the conjugate exhibited excellent antibacterial activity and durability for repeated
use, as compared with paper composites containing either ionic Ag components or
commercial crystalline Ag microparticles. This method is handy as synthesis of Ag
NPs on a paper-like matrix is different approach for the immobilization of active Ag
12 V. N. Mehta et al.

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).

Ag NPs Conjugated with Bio-glass Ceramics

Another application includes nano-sized calcium phosphosilicate bio-glass ceramics


doped with different concentration of Ag2O. The conjugate consisted good struc-
tural, dielectric, biocompatibility, and antibacterial properties. The conjugate was
synthesized using sol-gel processes with silver-embedded nano-sized glass ceramic
particles (Kritikaki and Tsetsekou 2009). UV–visible absorption spectra revealed the
silver embedment as Ag+/Ag° form in the glass matrix. Nano-size of the glass
ceramics and Ag NPs embedment in glass matrix was confirmed by HR-TEM
analysis. Dielectric spectra of samples revealed non-Debye relaxation processes.
The dielectric constant of the synthesized conjugate at first decreased and then
increased with Ag2O content. The antibacterial properties of these bio-ceramics
were tested with different bacteria using an agar well diffusion method. Silver-
doped samples show good antibacterial effects without compromising the formation
of hydroxyapatites. The dielectric constant of the bio-glass ceramics is correlated to
their antibacterial performance, with low dielectric constants giving higher anti-
bacterial activity (Vale et al. 2019).

Ag NPs Conjugated with Ceramic Tablets

In the form of silver-embedded ceramic tablet, it showed great performance with


high antibacterial efficiency and sustainable silver release in batch-wise tests. Silver-
embedded ceramic filter disk was tried with flow test exhibiting a good antibacterial
ability, and silver release is lower than Ag NPs-painted ceramic filter. These two
methods for Ag NPs conjugated ceramic filter production have proved the potential
to lessen silver leaching, suggesting a promising way to fabricate a sustainable silver
ceramic pot for water disinfection. Regardless of method to introduce silver, ceramic
filter is usually prepared from clay and filler that comprises of one or a mixture of
organic components. To embed silver into ceramic structure, silver nitrate can be
added into filler prior to mixing with ceramic precursors or directly mix with ceramic
precursors and molded into desirable shapes. The certain fillers are added for proper
binding which at the time of firing are burned off and leaves space and creates pores
resulted in the porous material; this calcination process contributes to form porosity
in the ceramic material which is its important property (Kallman et al. 2011).
Bio-functionalized Silver Nanoparticles: A Versatile Candidate for the. . . 13

Ag NPs Conjugated with Ceramic Materials for Drinking Water


Treatment

The other important application of ceramic conjugated nanoparticles is in drinking


water treatment to remove the biofilm or prevent the formation of biofilm by
microorganisms where Ag NPs based ceramic materials to be proved as new hotspot
of research. Refractory oxides like alumina, titania, and zirconia are usually used to
make porous ceramics structures. The ceramic structure possesses good chemical,
thermal, and pH stability with high porosity. The ceramic nanoparticles possess good
benefits as compared to conventional methods; the ceramic structure does not distort
during operation; longevity, resistance to high temperature, pressure, and corrosive
solutions make them a very effective water treatment material. The bio-film is a
conjugate of many cells, and it is therefore difficult to remove a bio-film by the
ordinary methods that are typically used to treat individual cells grown in suspen-
sion. To compensate this drawback the Ag NPs that possess antimicrobial property
are coated on the ceramic materials and work as excellent antimicrobial agent (Bapat
et al. 2018).

Ag NPs Conjugated Ceramic Materials as Antibacterial Agents

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.

temperatures provides a novel route to non-oxide ceramics with predefined compo-


sition and near net shape. Compared to the classical sintering (Kim et al. 2003), this
route is either an alternative, a complement, or even the only possibility when it
comes to ceramic coatings and fibers (Singh et al. 2019).

Conclusions and Future Perspective

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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