A novel shape-controlled synthesis of dispersed silver nanoparticles by combined bioaffinity adsorption and TiO2 photocatalysis

Shape-controlled silver nanoparticles (Ag NPs) were prepared in a well-dispersed mode on the active imprinting sites of chitosan-TiO₂ adsorbent (CTA) by means of bioaffinity adsorption and TiO₂ photocatalysis. Nontoxic hydrogen peroxide (H₂O₂) was used as a suitable etching reagent in our production of shape-controlled Ag NPs, since it could regulate the TiO₂ photocatalysis and accelerate the generation of O₂. With the same amount of H₂O₂ addition, silver nanocubes, nanospheres and truncated triangular nanoplates were individually obtained on the surface of CTA under UV irradiation by facilely adjusting the initial Ag⁺ concentration. The FE-SEM, XRD and UV-visible characterizations confirmed single crystal Ag NPs with different shapes loaded on CTA. The mechanism for the formation of shape-controlled Ag NPs was discussed based on a photocatalytic reaction system. As an example of applications of the Ag NPs, we tested the biocidal properties, and silver nanocubes exhibited the highest antibacterial activity. Our research provided a simple synthesis for shape-regulated Ag NPs steadily loaded on CTA. It might moreover be a guide in preparing metal nanocrystals monodispersely immobilized on chemical substrates.     

Preparation and antibacterial activity of polyvinyl alcohol/regenerated silk fibroin composite fibers containing Ag nanoparticles

Polyvinyl alcohol (PVA)/regenerated silk fibroin (SF)/AgNO₃ composite nanofibers were prepared by electrospinning. A large number of nanoparticles containing silver were generated in situ and well‐dispersed nanoparticles were confirmed by transmission electron microscopy (TEM) intuitionally. Ultraviolet (UV)‐visible spectroscopy and X‐ray diffraction (XRD) patterns indicated that nanoparticles containing Ag were present both in blend solution and in composite nanofibers after heat treatment and after subsequent UV irradiation. By annealing the nanofibers, Ag⁺ therein was reduced so as to produce nanoparticles containing silver. By combining heat treatment with UV irradiation, Ag⁺ was transformed into Ag clusters and further oxidized into Ag₃O₄ and Ag₂O₂. Especially size of the nanoparticles increased with heat treatment and subsequent UV irradiation. This indicated that the nanoparticles containing silver could be regulated by heat treatment and UV irradiation. The antimicrobial activity of heat‐treated composite nanofibers was evaluated by Halo test method and the resultant nanofibers showed very strong antimicrobial activity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In situ preparation of Au or Ag nanoparticles in the presence of hyperbranched poly(amidoamine)s with hydrophobic end‐groups as nanoreactors and reductants

Hyperbranched poly(amidoamine)s with methyl ester terminals (HPAMAM‐COOCH₃) were used as nanoreactors and reductants to prepare gold or silver nanoparticles (Au NPs or Ag NPs). HPAMAM‐COOCH₃ could bind AuCl₄ ⁻ (or Ag⁺) and then reduce AuCl₄ ⁻ (or Ag⁺) into Au NPs (or Ag NPs) through their internal amines, while the external methyl ester groups prevented the aggregation of polymers. The formation of Au NPs or Ag NPs was verified using transmission electron microscopy (TEM), ultraviolet‐visible spectroscopy (UV‐Vis), X‐Ray powder diffraction (XRD), Fourier‐transform infrared spectroscopy (FT‐IR), and thermogravimetric analysis (TGA), confirming the formation of Au NPs or Ag NPs with small particle size and low size distribution.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of novel silver/L‐phenylalanine‐based optically active polyacrylate nanocomposite

Novel bioactive and optically active poly(N‐acryloyl‐L ‐phenylalanine) (PAPA) was synthesized by atom transfer radical polymerization. PAPA‐silver (Ag) nanocomposites have been successfully prepared via in situ reducing Ag⁺ ions anchored in the polymer chain using hydrazine hydrate as reducing agent in an aqueous medium. By controlling of the amount of Ag⁺ ions introduced, we have produced an organic/inorganic nanocomposite containing Ag nanoparticles with well controlled size. Nanocomposites were characterized by X‐ray diffraction (XRD), UV–Vis spectrophotometry, transmission electron microscopy, and Fourier transform infrared. XRD pattern showed presence of Ag nanoparticles. The PAPA/Ag nanocomposites with 1 : 10 silver nitrate (AgNO₃) : PAPA ratio revealed the presence of well‐dispersed Ag nanoparticles in the polymer matrix. All of these Ag nanoparticles formed are spherical and more than 80% of them are in the range of 15–25 nm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Degradation characteristic of TiO<Subscript>2</Subscript>-chitosan adsorbent on Rhodamine B and purification of industrial wastewater

Based on biosorption and photodegradation coupling technology, a novel adsorbent, which not only adsorbs the heavy metal ions but also degrades organic compound, was prepared by immobilization of nano-TiO₂ on chitosan matrix. Degradation characteristic of Rhodamine B (Rh.B) was investigated by TiO₂-chitosan adsorbents. The results showed that degradation ratio reached 94.3% by 0.2 g adsorbents under ultraviolet radiation light (UV) at initial Rh.B concentration of 10 mg/L and optimal pH of 9.0. Degradation and adsorption behavior characteristics were discussed in the presence of binary pollutants (Rh.B and Ag⁺). The coexistence of Ag⁺ intensely inhibited the degradation ability of Rh.B. Higher Ag⁺ concentration weakened the degradation ability. However, Rh.B did not affect the adsorption capacity of Ag⁺. Moreover, TiO₂-chitosan adsorbent contributed to a higher degradation ability of organic pollutants in practical wastewater. Degradation capacity of contaminants in paper-making wastewater reached 60.8 mg/g at the initial COD concentration of 2,000 mg/L.     

Silver-doped titanium dioxide nanoparticles encapsulated in chitosan–PVA film for synergistic antimicrobial activity

The objective of the present study performed was to develop and characterize of silver (Ag)-doped titanium dioxide (TiO₂) naoparticles (NPs) encapsulated in chitosan–polyvinyl alcohol (PVA) film for synergistic antimicrobial activity. The acidic solution of chitosan with PVA was used for the reduction of silver ions into silver NPs using their functional groups such as hydroxyl, carboxyl, and amino groups. The chitosan–PVA silver nanoparticle films showed significant antimicrobial and antifungal activity against Staphylococcus aureus, Candida albicans, and Pseudomonas aeruginosa. Therefore, the present study is an alternative for conventional treatment as antimicrobial film showed synergistic, noninvasive, and economic effects.     

Studying the localized deposition of Ag nanoparticles on self-assembled monolayers by scanning electrochemical microscopy (SECM)

The local deposition of Ag nanoparticles (NPs) on ω-mercaptoalkanoic acid, HS(CH₂)_nCO₂H, (n = 2, 10) self-assembled monolayers (SAMs) by scanning electrochemical microscopy (SECM) is reported. We found that the presence of a SAM had a pronounced effect on Ag deposition. Experiments were conducted by applying different potentials to an Au(1 1 1) substrate either in the presence of a constant concentration of Ag⁺ ions in solution (bulk deposition) or by generating a flux of Ag⁺ from an Ag microelectrode that was positioned close to the Au(1 1 1) substrate (SECM deposition). SECM was used for generating a controlled flux of silver ions by anodic dissolution of an Ag microelectrode close to the SAMs modified Au(1 1 1). We found that the shape of the NPs was affected by the length of the carbon-chain of the SAM. Tetrahedral NPs were obtained on bare Au(1 1 1) surfaces while rod like and cubic Ag NPs were deposited onto 3-mercaptopropanoic acid (MPA) and 11-mercaptoundecanoic acid (MUA) SAMs, respectively. The size and shape of the deposited NPs were influenced by the deposition potential.We conclude that the shape and distribution of locally deposited Ag NPs on Au(1 1 1) can be controlled by modification of the substrate with a SAM and through controlling the Ag⁺ flux generated by SECM.     

Selective preparation of Ag species on photoluminescence of Sm3+ in borosilicate glass via Ag+-Na+ ion exchange

Photoluminescence (PL) of rare earth ion-doped glasses could be enhanced by diverse Ag species such as Ag⁺ ions, Ag⁺-Ag⁺ pairs, Ag nano-clusters (NCs), and Ag nanoparticles (NPs). Selective preparation of silver species in rare earth ion-doped glasses is a crucial step to obtain the luminescence enhancement of rare earth ions caused by the different silver species. In this work, Ag⁺ ions and Ag NCs were selectively prepared in the Sm³⁺-doped borosilicate glass via the Ag⁺-Na⁺ ion exchange. The influence of AgNO₃/NaNO₃ ratio in the molten salt on the Ag existing states was investigated. The results demonstrate that the isolated Ag⁺ ions exist in the Sm³⁺-doped borosilicate glass when the ratio of AgNO₃/NaNO₃ is 1/1000. The Ag NCs are formed in the Sm³⁺-doped borosilicate glass when the AgNO₃/NaNO₃ ratio is 1/10. The influence of Ag⁺ ions or Ag NCs on the PL of Sm³⁺ was systematically investigated. The results show that the PL of Sm³⁺ was enhanced by the energy transfer from Ag⁺ ions or Ag NCs to Sm³⁺.     

Preparation and Characterization of Gelatin Nanofibers Containing Silver Nanoparticles

Ag nanoparticles (NPs) were synthesized in formic acid aqueous solutions through chemical reduction. Formic acid was used for a reducing agent of Ag precursor and solvent of gelatin. Silver acetate, silver tetrafluoroborate, silver nitrate, and silver phosphate were used as Ag precursors. Ag⁺ ions were reduced into Ag NPs by formic acid. The formation of Ag NPs was characterized by a UV-Vis spectrophotometer. Ag NPs were quickly generated within a few minutes in silver nitrate (AgNO₃)/formic acid solution. As the water content of formic acid aqueous solution increased, more Ag NPs were generated, at a higher rate and with greater size. When gelatin was added to the AgNO₃/formic acid solution, the Ag NPs were stabilized, resulting in smaller particles. Moreover, gelatin limits further aggregation of Ag NPs, which were effectively dispersed in solution. The amount of Ag NPs formed increased with increasing concentration of AgNO₃ and aging time. Gelatin nanofibers containing Ag NPs were fabricated by electrospinning. The average diameters of gelatin nanofibers were 166.52 ± 32.72 nm, but these decreased with the addition of AgNO₃. The average diameters of the Ag NPs in gelatin nanofibers ranged between 13 and 25 nm, which was confirmed by transmission electron microscopy (TEM).     

TiO<Subscript>2</Subscript> porous ceramic/Ag–AgCl composite for enhanced photocatalytic degradation of dyes under visible light irradiation

TiO₂ porous ceramic/Ag–AgCl composite was prepared by incorporating AgCl nanoparticles within the bulk of TiO₂ porous ceramic followed by reducing Ag⁺ in the AgCl particles to Ag⁰ species under visible light irradiation. The porous TiO₂ ceramic was physically robust and chemically durable, and the porous structure facilitated the implantation of AgCl NPs. Compared with the bare TiO₂ ceramic, TiO₂ porous ceramic/Ag–AgCl composite exhibited higher photocatalytic performance for the degradation of MO and RhB under visible light irradiation. The reaction rate constants k of MO and RhB degradation over TiO₂ porous ceramic/Ag–AgCl composite was respectively 6.25 times and 3.62 times higher than those recorded over the bare TiO₂ porous ceramic. The photocatalytic activity showed virtually no decline after four times cyclic experiments under visible light irradiation. Scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectra and X-ray photoelectron spectroscopy were used to characterize the TiO₂ porous ceramic/Ag–AgCl composite.     

Enhanced the dispersibility and permeability of silver nanoparticles over rGO grafted by positively-charged polyethyleneimine toward broad-spectrum sterilization

Silver nanoparticles (Ag NPs) are used as antimicrobial agents due to their high-efficiency, broad-spectrum disinfection activity. However, the agglomeration and stability problems caused by excessive release of silver ions (Ag⁺) have severely restricted their developments. Herein, a novel silver/polyethyleneimine/reduced graphene oxide (Ag/PEI/rGO) antibacterial material featuring good dispersibility and permeability was rationally designed, thus benefiting for the capture of bacteria due to the introducing of highly-cationic PEI modifier and controllable release of biocidal agents (Ag⁺). Compared with Ag/rGO, the Ag/PEI/rGO has excellent stability and shows a more efficient sterilization efficacy against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) with 100% germicidal efficiency with low orders of dozens of ppm. In addition, the outstanding biocompatibility of this Ag/PEI/rGO antibacterial material endows it with promising potential in sterilization applications, which is expected to solve the infection problem caused by bacterial biofilm formation.     

Highly Efficient Room Temperature Synthesis of Silver‐Doped Zinc Oxide (ZnO:Ag) Nanoparticles: Structural,Optical, and Photocatalytic Properties

Synthesis of silver‐doped zinc oxide (ZnO:Ag) nanoparticles through precipitation method has been reported. The synthesis was conducted at room temperature and no subsequent thermal treatment was applied. ZnO nanoparticles were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), fourier transmission infrared spectroscopy (FTIR), and ultraviolet‐visible (UV–Vis) spectroscopy. Detailed crystallographic investigation was accomplished through Rietveld refinement. The effect of silver content on structural and optical properties of resultant ZnO nanoparticles has been reported. It was found that silver doping results in positional shifts for the XRD peaks and the absorption band edge of ZnO. These were attributed to the substitutional incorporation of Ag⁺ ions into Zn²⁺ sites within the ZnO crystal. In addition, higher silver incorporation resulted in smaller size for ZnO nanoparticles. The photocatalytic activity of the ZnO:Ag nanoparticles was also determined by methylene orange (MO) degradation studies and compared to that of undoped ZnO. Improved photocatalytic activity was obtained for ZnO:Ag nanoparticles. It has been shown that an optimum amount of silver dopant is required to obtain maximum photocatalytic activity.     

Adsorption of Silver Nanoparticles onto Different Surface Structures of Chitin/Chitosan and Correlations with Antimicrobial Activities

Size-controlled spherical silver nanoparticles (Ag NPs) can be simply prepared by autoclaving mixtures of glass powder containing silver with glucose. Moreover, chitins with varying degrees of deacetylation (DDAc < 30%) and chitosan powders and sheets (DDAc > 75%) with varying surface structure properties have been evaluated as Ag NP carriers. Chitin/chitosan-Ag NP composites in powder or sheet form were prepared by mixing Ag NP suspensions with each of the chitin/chitosan-based material at pH 7.3, leading to homogenous dispersion and stable adsorption of Ag NPs onto chitin carriers with nanoscale fiber-like surface structures, and chitosan carriers with nanoscale porous surface structures. Although these chitins exhibited mild antiviral, bactericidal, and antifungal activities, chitin powders with flat/smooth film-like surface structures had limited antimicrobial activities and Ag NP adsorption. The antimicrobial activities of chitin/chitosan-Ag NP composites increased with increasing amounts of adsorbed Ag NPs, suggesting that the surface structures of chitin/chitosan carriers strongly influence adsorption of Ag NPs and antimicrobial activities. These observations indicate that chitin/chitosan-Ag NPs with nanoscale surface structures have potential as antimicrobial biomaterials and anti-infectious wound dressings.     

Ag and Si Codoped Phosphate Glasses: Plasmonic Nanocomposites with Enhanced UV Transparency

The use of silicon powder to produce plasmonic Ag nanocomposite phosphate glasses which also exhibit improved transparency in the ultraviolet (UV) is proposed. Ag₂O/Si codoped glasses were prepared in a barium‐phosphate matrix by a simple melt‐quench method in ambient atmosphere. The as‐prepared glasses exhibit enhanced UV transparency, whereby the surface plasmon resonance of Ag nanoparticles (NPs) is manifested for the glasses with higher Ag₂O contents. ³¹P nuclear magnetic resonance spectroscopy is consistent with the formation of P–O–Si bonds, thus suggesting their possible role on the improved UV light transmission. Consequently, a model was presented accounting for the influence of silicon on the polymerization of the phosphate network concomitant with the creation of highly reactive oxygen species. Further exploiting the proposed reactive species, a real‐time spectroscopic study of the plasmonic response of Ag NPs in Ag/Si codoped glass samples was carried out during an in situ thermal processing. The temperature dependence of the Ag particle precipitation was studied in the 400°C–430°C range, from which an Arrhenius‐type plot allowed for estimating the activation energy of the process at 3.42 (±0.38) eV. Ultimately, the vanishing of the luminescence ascribed to Ag⁺ ions was observed in a heat‐treated sample, consistent with the high reactivity acquired by the glass matrix. Silicon thus appears promising for producing UV transparent glasses for high‐performance optics and for the reduction of Ag⁺ ions to produce Ag nanocomposites valuable for photonic (nanoplasmonic) applications.     

Luminescence Enhancement of CdS Quantum Dots in Glass by Ag+ Ion Exchange

Luminescence of CdS quantum dots (QDs) enhanced by the induction of Ag nanoparticles (NPs) in glasses was investigated. Ag⁺ ions diffused into glasses containing CdS QDs by ion exchange, then formed Ag NPs after subsequent heat treatment. Luminescence intensity of CdS QDs increased approximately three times when the ion‐exchange duration was 1 min, but was severely quenched when the duration was extended to 30 min. Increasing the amount of Ag⁺ ions increased the number of Ag NPs and decreased the average distance between Ag NPs and CdS QDs. This decrease in the average distance induced the changes of luminescence intensity.     

Preparation and characterization of SiO2/polydopamine/Ag nanocomposites with long-term antibacterial activity

Silver nanoparticles (Ag NPs) with diameter of approximately 10 nm were prepared by the reduction of silver nitrate using green synthesis, an eco-friendly approach. The synthesized Ag NPs were homogeneously deposited on silicon dioxide (SiO₂) particles modified with dopamine, leading to the formation of SiO₂/polydopamine (PD)/Ag nanocomposites (NCs) with a core–shell–satellite structure investigated by transmission electron microscopy. The Ag content of SiO₂/PD/Ag NCs determined by inductively coupled plasma optical emission spectrometry was approximately 5.92 wt%. The antibacterial properties of both Ag NPs and SiO₂/PD/Ag NCs against Vibrio natriegens (V. natriegens) and Erythrobacter pelagi sp. nov. (E. pelagi) were investigated by bacterial growth curves and inhibition zone. Compared to Ag NPs, the SiO₂/PD/Ag NCs exhibited superior long-term antibacterial activity, attributed to its controlled release of Ag⁺ ions.     

Enhanced mechanical properties and bactericidal activity of polypropylene nanocomposite with dual‐function silica–silver core‐shell nanoparticles

Dual‐function silica–silver core‐shell (SiO₂@Ag) nanoparticles (NPs) with the core diameter of 17 ± 2 nm and the shell thickness of about 1.5 nm were produced using a green chemistry. The SiO₂@Ag NPs were tested in vitro against gram‐positive Staphylococcus aureus (S. aureus) and gram‐negative Escherichia coli (E. coli), both of which are human pathogens. Minimal inhibitory concentrations of the SiO₂@Ag NPs based on Ag content are 4 and 10 μg mL^?1 against S. aureus and E. coli, respectively. These values are similar to those of Ag NPs. SiO₂@Ag NPs were for the first time incorporated to a commodity polypropylene (PP) polymer. This yielded an advanced multifunctional polymer using current compounding technologies i.e., melt blending by twin‐screw extruder and solvent (toluene) blending. The composite containing 5 wt % SiO₂@Ag NPs (0.05 wt % Ag) exhibited efficient bactericidal activity with over 99.99% reduction in bacterial cell viability and significantly improved the flexural modulus of the PP. Anodic stripping voltammetry, used to investigate the antibacterial mechanism of the composite, indicated that a bactericidal Ag⁺ agent was released from the composite in an aqueous environment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphological and thermal properties of photodegradable biocomposite films

Biocomposites containing ultraviolet (UV) radiation absorbing inorganic nanofillers are of great interest in food packaging applications. The biodegradable polylactide (PLA) composite films were prepared by solvent casting method by incorporating 1 wt % of titanium dioxide (TiO₂) and Ag‐TiO₂ (silver nanoparticles decorated TiO₂) nanoparticles to impart the photodegradable properties. The films were exposed to UV radiation for different time periods and morphology of the composite films before and after UV exposure were investigated. The results showed that homogenous filler distribution was achieved in the case of Ag‐TiO₂ nanoparticles. The thermal properties and thermomechanical stability of the composite film containing Ag‐TiO₂ nanoparticles were found to be much higher than those of neat PLA and PLA/TiO₂ composite films. The scanning electron microscopy and X‐ray diffraction studies revealed that the photodegradability of PLA matrix was significantly improved in the presence of Ag‐TiO₂ nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adsorption of Cd(II), Pb(II), and Ag(I) in aqueous solution on hollow chitosan microspheres

Cross‐linked chitosans synthesized by the inverse emulsion cross‐link method were used to investigate adsorption of three metal ions [Cd(II), Pb(II), and Ag(I)] in an aqueous solution. The chitosan microsphere, was characterized by FTIR and SEM, and adsorption of Cd(II), Pb(II), and Ag(I) ions onto a cross‐linked chitosan was examined through analysis of pH, agitation time, temperature, and initial concentration of the metal. The order of adsorption capacity for the three metal ions was Cd²⁺ > Pb²⁺ > Ag⁺. This method showed that adsorption of the three metal ions in an aqueous solution followed the monolayer coverage of the adsorbents through physical adsorption phenomena and coordination because the amino (? NH₂) and/or hydroxy (? OH) groups on chitosan chains serve as coordination sites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Green Chemical Synthesis of Silver Nanoparticles and its Catalytic Activity

Silver nanoparticles (Ag(0) NPs) were synthesized by the chemical reduction method, in which ceftriaxone (antibiotic) used as reducing (to convert Ag⁺ to Ag(0)) and capping agent. UV–Visible spectroscopy revealed the first indication of formation of Ag(0) NPs. FT-IR spectroscopy showed the interaction of formation of bonding between antibiotic standard and silver. X-ray powder diffraction powder pattern confirmed the crystalline nature of prepared Ag(0) NPs. These Ag(0) NPs were used as catalyst for three organic hazardous chemicals i.e., 4-nitro-1,3-Phenylene diamine, 6-methyl-2-nitroanilline, 4-methyle-2-nitroanilline. The prepared Ag(0) NPs showed good catalytic activity against these compounds.