Radical-induced generation of small silver particles in SPEEK/PVA polymer films and solutions: UV-Vis, EPR, and FT-IR studies

The present study is centered on the processes involved in the photochemical generation of nanometer-sized Ag particles via illumination at 350 nm of aqueous solutions and cross linked films containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol). Optical and electron paramagnetic resonance experiments, including electron nuclear double resonance data, proved conclusively that the photogenerated chromophore exhibiting a band with lambda(max) = 565 nm is an alpha-hydroxy aromatic (ketyl) radical of the polymeric ketone. This reducing species was produced by illumination of either solutions or films, but the radical lifetime extended from minutes in the fluid phase to hours in the solid. Direct evidence is presented that this long-lived chromophore reduces Ag(I), Cu(II), and Au(III) ions in solution. A rate constant of k = 1.4 x 10(3) M(-)(1) s(-)(1) was obtained for the reduction of Ag(+) by the ketyl radical from the post-irradiation formation of Ag crystallites. FTIR results confirmed that the photoprocess yielding polymeric ketyl radicals involves a reaction between the macromolecules. The photochemical oxidation of the polymeric alcohol, as well as the formation of light-absorbing macromolecular products and polyols, indicates that the sulfonated polyketone experienced transformations similar to those encountered during illumination of the benzophenone/2-propanol system.     

Multifunctional silk fibroin/PVA bio-nanocomposite films containing TEMPO-oxidized bacterial cellulose nanofibers and silver nanoparticles

Cellulose - Silk fibroin (SF) has been intensively studied as a biobased renewable material for biomedical and other applications. However, its relatively low mechanical properties have limited its...     

Photochemical formation of silver nanoparticles in elastomer films

Photochemical deposition of silver nanoparticles in poly(butyl acrylate) and poly(butadiene-styrene) under the action of monochromatic UV light (254 nm) was studied. Changes in the polymer structure in the course of photolysis were revealed and analyzed. A mechanism of formation of silver nanoparticles was suggested. Electron microscopic examination showed that the efficiency of the particle formation is determined by the residual moisture content of the polymer films. Physicomechanical properties (tensile strength and relative elongation) of the elastomer films containing silver nanoparticles were studied.     

Preparation of antibacterial polyimide films containing silver nanoparticles

Polyimide/silver composite films were successfully prepared by in situ polymerization. A precursor, AgNO₃ was used as the source of the silver nanoparticles. The structure and morphology of resulting films were characterized by FTIR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Consequently, the silver nanoparticles were well dispersed in polyimide matrix. Meanwhile, thermal properties from thermal gravimetric analyses (TGA) and mechanical properties from tensile test which confirmed composites were kept good performance as compared to pure polyimide. In addition, the antimicrobial activity of polyimide/silver composite films against three different bacteria, B. subtilis, S. aureus, and E. coil, illustrated excellent activity. This composite is potential useful as antimicrobial material with good thermal performance in a wide variety of biomedical and general use applications.     

Photomediated crosslinking of cinnamated PDMS for in situ direct photopatterning

Polydimethylsiloxane (PDMS) polymers incorporating pendant cinnamate groups have been synthesized and evaluated for their ability to form patterned thin films via photo‐crosslinking. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3482–3487, 2008     

Laser-induced changes in silver metal nanoparticles incorporated in viscous media

The effect of laser pulse irradiation on silver metal nanoparticles in ethylene glycol and glycerol is studied and compared with the parallel processes in aqueous solutions. The influence of 355 nm laser pulse irradiation at the surface plasmon frequency and on the size of the silver nanoparticles is examined by UV-Vis absorption spectroscopy and by transmission electron microscopy. It appears that viscosity of the medium plays a crucial role for the stabilization of the melted particles in the absence of the stabilizer. In ethylene glycol containing PVP, fragmentation of particles was observed. In neat glycerol, similar excitation led to morphological changes as the nanoparticles fused to produce particles of larger size. The changes in reduction of shape and size are considered to occur through melting and vaporization of the silver nanoparticles.     

Chiral nematic assemblies of silver nanoparticles in mesoporous silica thin films

Silver nanoparticles (NPs) have been synthesized inside mesoporous silica films with chiral nematic structure. Circular dichroism measurements of the silver NP-loaded silica films show NP-based optical activity in the vicinity of the surface plasmon resonance. These materials, with an optical response associated with the chiral assembly of metal NPs, may be useful for developing new sensors.     

Green synthesis of antibacterial chitosan films loaded with silver nanoparticles

An eco-friendly chemical reduction method was successfully used for the preparation of chitosan (CTS) composite films loaded with silver nanoparticles (AgNPs) by self assembly method using poly(ethylene glycol) as both reducing and stabilizing agent. UV-Vis spectra of the prepared chitosan loaded silver nanoparticles (CTSLAg) films reveal that full reduction of silver ions to silver nanoparticles takes place at 90 °C. The effect of reaction conditions on the silver nanoparticles formation was investigated using UV-Vis spectrophotometer. The morphology of the films was tested by scanning electron microscopy (SEM). The DSC curves showed that the CTSLAg film had a favorable compatibility and heat stability. AgNPs were confirmed by XRD and UV-Vis spectroscopy. The TEM findings revealed that the silver nanoparticles synthesized were spherical in shape with uniform dispersal, and by increasing CTS:PEG ratio larger silver nanoparticles could be obtained. The results of antibacterial study reveal that the prepared nanocomposite films exhibited potential inhibition.     

TiO2 films loaded with silver nanoparticles: control of multicolor photochromic behavior

Ag-TiO(2) films exhibiting multicolor photochromism were prepared by photoelectrochemical reduction of Ag(+) to Ag nanoparticles in nanoporous TiO(2) films under UV light. Color of the Ag-TiO(2) film, initially brownish-gray, changes under a colored visible light to the color of the light and reverts to brownish-gray under UV light. Their chromogenic properties were improved by simultaneous irradiation for Ag deposition with UV and blue lights to suppress the formation of anisotropic Ag particles. Nonvolatilization of a color image was also achieved by removing Ag(+) that was generated during the irradiation with a colored light. Once nonvolatilized, the image can be reproduced by UV light, even after the image is discolored under white light. This new effect evidenced that nanopores in the TiO(2) film determine the resonance wavelengths of the Ag particles, as their molds. In addition, solvatochromic behavior of the Ag-TiO(2) film proved that nanospaces left around the Ag nanoparticles affect the resonance wavelengths of the Ag particles.     

Hemoglobin/colloidal silver nanoparticles immobilized in titania sol-gel film on glassy carbon electrode: direct electrochemistry and electrocatalysis

By vapor deposition method, both hemoglobin (Hb) and colloidal silver nanoparticles (CSNs) were entrapped in a titania sol-gel matrix on the surface of a glassy carbon electrode (GCE). CSNs could greatly enhance the electron transfer reactivity of Hb and its catalytic ability toward nitrite. Direct fast electron transfer between Hb and the GCE was achieved, and a pair of well-defined, quasi-reversible redox peaks was observed. The anodic and cathodic peak potentials are located at -0.298 V and -0.364 V (vs. Ag/AgCl), respectively. The dependence of the formal potential on solution pH indicated that the direct electron transfer reaction of Hb was a one-electron transfer coupled with a one-proton transfer reaction process. Meanwhile, the catalytic ability of Hb toward the reduction of NO2- was also studied. Accordingly, a NO2- biosensor was prepared, with a linear range from 0.2 mM to 6.0 mM and a detection limit of 34.0 microM. The apparent Michaelis-Menten constant was calculated to be 7.48 mM. Moreover, the biosensor had good long-term stability.     

Synthesis and direct interactions of silver colloidal nanoparticles with pollutant gases

Silver nanoparticles (NPs) were synthesized in organic solvents. Spontaneous reduction of silver salts takes place in N,N′-dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) at room temperature. The formed colloids are not stable without a stabilizing agent, hence rarely used, and inexpensive organic molecules (β-cyclodextrin and cholic acid) were used as surface modifiers in DMF. The stabilization was successful; the Ag NPs remained stable for more than 3 months. Additionally, Ag NPs were prepared using Ag-2-ethylhexanoate and Na-citrate as capping agent in DMSO. The resulting NPs are stable, of 4.4 nm average size, and at the same time reactive for catalytic purposes. The interaction of Ag NPs with pollutant atmospheric gases (NO and SO₂) was studied. UV–visible spectra show the oxidation of silver and the very efficient reduction of NO at room temperature. SO₂ molecules are adsorbed on the NPs surface, causing their aggregation and precipitation.     

Novel antibacterial hybrid materials based on polyvinyl alcohol and mercaptopropyltriethoxysilane with embedded silver nanoparticles (PVA/AgNps/MPTES)

Hybrid materials based on polyvinyl alcohol (PVA) and mercaptopropyltriethoxysilane (MPTES) with embedded silver nanoparticles (AgNps) have been synthesized via a sol–gel method. Silver nanoparticles were obtained via thermal reduction in the presence of PVA as a stabilizer and reducing agent. The formation of silver nanoparticles within the PVA/MPTES matrix was proven by FTIR, XRD, and TEM analysis. The antibacterial activity of PVA/AgNps/MPTES materials was determined against strains belonging to Gram-positive and Gram-negative bacteria by disk diffusion and growth curve methods. The hybrid materials showed high antibacterial activity, which depends on the concentration of the silver nanoparticles.     

Reversible conversion of nanoparticles of metallic silver and silver oxide in ultrathin TiO2 films: a chemical transformation in nano-space

The in-situ interconversion of silver and silver oxide nanoparticles was achieved in ultrathin TiO2 films using hydrogen and oxygen plasmas as dry redox reagents. Absorption spectroscopy and transmission electron microscopy showed that the chemical transformation gave rise to narrowing of size distributions of both silver and silver oxide nanoparticles upon repeated interconversion.     

Structure and properties of biodegradable carboxymethyl cellulose films containing silver nanoparticles

Silver nanoparticles stabilized in a solution of sodium carboxymethyl cellulose with a degree of substitution of 0.85 and a degree of polymerization of 600 have been synthesized. The structuring; physical, chemical, and mechanical properties; and antimicrobial activities of films prepared from sodium carboxymethyl cellulose solutions containing silver nanoparticles have been studied. The shapes, quantities, and sizes of the silver nanoparticles occurring in the sodium carboxymethyl cellulose films were determined with the use of transmission electron microscopy, atomic force microscopy, and UV spectroscopy. It was found that an increase in the concentration of silver nitrate in sodium carboxymethyl cellulose solutions, as well as photoirradiation of the films, leads to the changes in the sizes and shapes of silver nanoparticles. The shapes, sizes, and quantities of silver nanoparticles determine their biological activity. An increase in the quantity of 5- to 25-nm silver nanoparticles was found to enhance the microbicidal activities of the carboxymethyl cellulose films.     

Thermally stimulated processes in Eu-containing oxide films with silver and gold nanoparticles

The influence of the nature of the matrix on the properties of Eu-containing oxide films doped with silver and gold was studied by spectral-luminescent methods, X-ray diffraction, and electron microscopy as depending on the temperature of thermal treatment in air. The nature of the matrix was shown to determine the character of processes that occurred in GeO₂-Eu₂O₃-Ag-Au and Al₂O₃-Eu₂O₃-Ag-Au films and to substantially influence the properties of these films. The Ag⁺-Ag⁰-Au⁰ optical centers formed in films based on GeO₂ at 800°C; these centers effectively sensitized europium ion luminescence. In films based onAl₂O₃, silver was strongly bound by the matrix, and the effectiveness of the sensitization of europium ion luminescence decreased. Original Russian Text ? S.V. Vashchenko, Yu.V. Bokshits, A.P. Stupak, G.P. Shevchenko, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 3, pp. 528–533.     

Photocatalytic synthesis of silver nanoparticles stabilized by TiO2 nanorods: a semiconductor/metal nanocomposite in homogeneous nonpolar solution

A novel colloidal approach toward semiconductor/metal nanocomposites is presented. Organic-soluble anatase TiO(2) nanorods are used for the first time to stabilize Ag nanoparticles in optically clear nonpolar solutions in the absence of specific ligands for silver. Metallic silver is generated upon UV illumination of deaerated TiO(2) solutions containing AgNO(3). The Ag nanoparticles can be obtained in different size-morphological regimes as a function of the irradiation time, due to light-induced photofragmentation and ripening processes. A mechanism for the colloidal stabilization of the silver nanoparticles is tentatively suggested, which regards the TiO(2) nanorods as inorganic stabilizers, thus acting in the same manner as conventional surfactant molecules. The proposed photocatalytic approach offers a convenient method for producing TiO(2)/Ag nanocomposite systems with a certain control over the metal particle size without the use of surfactants and/or additives. Stable colloidal TiO(2)-nanorod-stabilized Ag nanoparticles can be potentially available for a number of applications that require "clean" metal surfaces, such as homogeneous organic catalysis, photocatalysis, and sensing devices.     

Experimental probes of silver metal nanoparticle formation kinetics: Comparing indirect versus more direct methods

The kinetics of noble metal nanoparticle formation in bottom-up syntheses are important for controlling and optimizing these methods. Hence, experimental probes that are easily accessible to most laboratories are also of interest. We collected kinetic curves for the formation of silver nanoparticles in a modified Turkevich method with citrate acting as the reducing and stabilizing agent by (i) measuring the change in silver nanoparticle surface plasmon resonance by UV-visible spectroscopy, a somewhat indirect method, and then also by (ii) measuring the change in silver ion concentration by ion-selective electrode potentiometry and/or atomic absorption spectroscopy, two more direct methods. The resulting sigmoidal kinetic curves were curvefitted with the Finke-Watzky two-step kinetic model of slow, continuous nucleation and fast autocatalytic growth to extract average rate constants. We found that the kinetic curves obtained by following the change in silver ion concentration were apparent mirror images of those constructed by following the change in nanoparticle surface plasmon resonance, and that their respective curvefits displayed the same sigmoidal characteristics. The resultant values of the rate constants for nucleation and growth overlapped within experimental error between the methods and showed similar trends over the range of citrate concentrations studied. The use of multiple probes in this work to follow the kinetics of nanoparticle formation helps fill a need for the comparison and evaluation of different methods available to scientists, particularly those considered easily accessible.     

A direct synthetic approach to vanadium pentoxide nanofibres modified with silver nanoparticles

Small amounts of silver ions have been found to significantly enhance the growth rate of vanadium pentoxide (V(2)O(5)) nanofibres in aqueous solution at room temperature, yielding fibres with lengths of several micrometers within a few days; the V(2)O(5) fibres are decorated with silver nanoparticles with sizes in the range of 5-15 nm, which opens perspectives for applications in chemical sensors.