Two phase photochemical synthesis of silver nanoparticles and their impact on the chlorophylls

Abstract

We have designed an experimental study dedicated to silver nanotoxicity using a suspension of citrate-silver nanoparticles, obtained by photochemical reduction. Fine granularity of generally symmetrical shape nanoparticles were evidenced by tansmission electron microscopy. The localized surface plasmon resonance spectral band revealed the intensification of silver nanoparticle formation under UV exposure. The nanotoxicity of silver nanoparticles was tested on cereal sprouts by measuring the concentrations of chlorophylls and carotenes in the green tissue. The differences between control samples, supplied with distilled water and test samples, loaded with different volumes of silver nanoparticles suspension were analyzed statistically, and compared with literature reports.     

Influence of heat treatment on the colour of Au and Ag glasses produced by the sol-gel pathway

In this work, coloured glasses were produced based on the synthesis of gold and silver nanoparticles by the sol-gel process having in mind their application in art works. Gold and silver were used separately or as a mixture by varying the mole fractions in order to get a range of colours from yellow to red. The gold and silver nanoparticles were prepared by the reduction of tetrachloroauric acid and silver nitrate with sodium citrate in aqueous solutions which were further introduced in the sol-gel system. Attention was focused on the thermal treatment of the sol-gel samples. Different temperatures were used in order to determine their influence on the obtained colour. The glasses were characterized by UV-Vis absorption spectroscopy and the size of the nanoparticles was examined by transmission electron microscopy (TEM).The range of colours mentioned above is obtained either by preparing nanoparticles of each metal and mixing them or by preparing nanoparticles from solutions containing initially ions of both metals. In the former case, two surface plasmon resonance (SPR) bands were observed for temperatures below 200 °C while higher temperatures promote the formation of alloys between the Ag and Au nanoparticles. In the latter case, only one SPR band is observed and the nanoparticle size distribution is narrower. The results were explained by nanoparticle aggregation promoted by temperature. Glasses containing only Ag did not present the typical yellow colour above 300 °C but it was shown that the colour could be stabilized if Au was added in small amounts (Au/Ag molar ratio 0.1).     

Ag diffusion in amorphous As50Se50 films studied by XPS

X-ray photoelectron spectroscopy and depth profile analysis were used to investigate the X-ray-induced silver photodiffusion into an amorphous As₅₀Se₅₀ thin film. At the initial stages of irradiation an induction period was observed while core level spectra analysis revealed the existence of a mixed As–Se–Ag interlayer between the metal and the chalcogenide matrix. It was found that during the induction period this interlayer is enriched in silver and the existing As–Se–Ag intermediate species are transformed to Ag–Se–Ag that form the metal source for the effective silver photodiffusion. With further irradiation photodiffusion proceeds by the disruption of Ag–Se bonds and the recombination of As atoms with Se to stable As–Se units. Ultimately, silver concentration reaches a plateau when the diffusion stops. A separated Ag₂Se phase on the film’s surface is identified at this stage. Depth profile analysis shows that silver has been homogenously diffused into the chalcogenide matrix and the Ag₂Se phase exists only at the top surface layers probably in the form of quasi-crystalline clusters that prohibit further Ag diffusion.     

Preparation and optical properties of silver nanoparticles induced by a femtosecond laser irradiation

Silver nanoparticles were prepared by a focused femtosecond laser irradiation in a 5 mM AgNO₃ solution in the presence of TiO₂ sol. TEM analysis revealed that the size of silver nanoparticles was less than 20 nm. A mechanism for the precipitation of silver nanoparticles was proposed. Nonlinear absorptions and optical limiting properties of silver nanoparticles contained solution were also measured. It is observed that the composite material showed strong self-focused effect and significant optical limiting property.     

Determination of the size and phase composition of silver nanoparticles in a gel film of bacterial cellulose by small-angle X-ray scattering,electron diffraction,and electron microscopy

The nanoscale structural features in a composite (gel film of Acetobacter Xylinum cellulose with adsorbed silver nanoparticles, stabilized by N-polyvinylpyrrolidone) have been investigated by small-angle X-ray scattering. The size distributions of inhomogeneities in the porous structure of the cellulose matrix and the size distributions of silver nanoparticles in the composite have been determined. It is shown that the sizes of synthesized nanoparticles correlate with the sizes of inhomogeneities in the gel film. Particles of larger size (with radii up to 100 nm) have also been found. Electron microscopy of thin cross sections of a dried composite layer showed that large particles are located on the cellulose layer surface. Electron diffraction revealed a crystal structure of silver nanoparticles in the composite.     

Internal structure of silver crystallites: going beyond nanostructure using novel processing technique

Using novel processing of TEM image to investigate nanoparticles of metallic solutions is exemplified in the case of silver nano‐crystals. The results show for the first time that the real internal structure of silver crystallites consists of nuclei and multi‐layers. The multi‐layers of the crystals are arranged symmetrically around their nuclei. The dimensions of nuclei lie in the range of atomic‐scale. The shape of nuclei determined the final shape of the crystals. The mechanisms of formation and growth for both silver crystallites and silver nanoparticles are demonstrated. This technique will give birth to the ongoing revolution in nano‐technology. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

New chiral metal-mesogenic nanosystems “silver - thiocholesterol” and their adsorption properties

ABSTRACT

New chiral matrices for thin film chromatography were obtained using hybrid metal-mesogenic nanosystems «silver – thiocholesterol» with different metal to ligand ratio, immobilized on silica gel particles. It was shown, that heteroatomic derivative of cholesterol – thiocholesterol and its composition with small silver nanoparticles formed in the system by the chemical reduction of silver ions possess liquid crystalline cholesteric mesophase. Molar ratio between thiocholesterol ligand molecules (L) and silver (Ag) insignificantly influenced on the size of silver nanoparticles formed in the system: for molar ratio Ag : L = 1:5 the main diameter of nanoparticles was equal to (2,7 ± 0,4) nm, for molar ratio Ag : L = 1:2 – (2, 2 ± 0,4) nm, for molar ratio Ag : L = 1:0,5 – (2,1 ± 0,6) nm. The new chiral matrices for thin film chromatography possess enantioselectivity related to optical isomers of 2,2′-diamino-1,1′-binaphtol (DABN) and trifluoroantranylethanol (TFAE). We have succeeded to select optical isomers of TFAE with selecting factor equal to 1,56.     

Preparation of core–shell nanospheres of silica–silver: SiO2@Ag

We prepared SiO₂@Ag core–shell nanospheres: silver nanoparticles (～4 ± 2 nm in diameter) coated silica nanospheres (～50 ± 10 nm in diameter). The preparation route is a modification of the Stöber method, and involves the preparation of homogeneous silica spheres at room temperature, combined with the deposition of silver nanoparticles from Ag⁺ in solution, by using water/ethanol mixtures, tetraethyl-orthosilicate as Si source and silver nitrate as Ag source in a single-pot wet chemical route without an added coupling agent or surface modification, which leads to the formation of core@shell homogeneous nanospheres. We present the preparation and characterization of the SiO₂@Ag core–shell nanospheres and also of bare silica spheres in the absence of silver, and propose a reaction mechanism for the formation of the core–shell structure.     

Experimental and theoretical study of the transport of silver nanoparticles at their prolonged administration into a mammal organism

The transport of silver nanoparticles in the organism of laboratory animals has been investigated. A mathematical model of the biokinetics of prolonged administration of nonmetabolizable and nonaglomerating pharmaceutical preparations is proposed, and its analytical solution is found. Based on the experimental data on the prolonged introduction and excretion of colloidal silver nanoparticles and the numerical approximation of the solutions to the equations for the proposed model, time dependences of the silver mass content in brain and blood are obtained and some other important biokinetic parameters are determined. It is concluded that both chronic¹ and subchronic² peroral application of these nanoparticles as an biologically active additive or antiseptic is potentially dangerous.     

In situ fabrication of waveguide-compatible glass-embedded silver nanoparticle patterns by masked ion-exchange process

We report a study on the properties of silver nanoparticles formed in glass using a masked silver–sodium ion-exchange technique, a process that has been used to fabricate patterned optical waveguides. Characterizations reveal that spherical nanoparticles with a diameter of 5–10 nm are concentrated below the mask edge at a depth of 50–100 nm from the surface. The amount of nanoparticles and the wavelength of the associated localized surface plasmon resonance can be controlled by the spacing between adjacent mask openings. After gentle etching, the surface morphology of the sample shows well-defined nanoparticle patterns. These closely packed nanoparticles embedded in the glass surface have a potential to be used for high-sensitivity surface enhanced spectroscopy, in a glass waveguide device.     

Dielectric Study on the Alignment or Orientation of N(4-n-heptyloxy benzylidene)4´-n-butylaniline and the Anomalous Dielectric Behavior in the Smectic G Phase

The present article reports on the alignment or orientation of a particular compound N(4-n-heptyloxy benzylidene)4´-n-butylaniline through dielectric study. The effect of using two different alignment layers (for homogenous alignment) and doping silver nanoparticles (0.25% by weight) on the behavior in dielectric property with varying temperature and biasing electric field was studied in terms of liquid crystal alignment or orientation using the mechanism proposed by earlier workers. The study includes the anomalous dielectric behavior in SmG phase by presenting a technique for the analysis of the absorption process, which exists only in SmG phase at fixed frequency while varying temperature, is also presented.     

One-step fabrication of Fe2O3/Ag core-shell composite nanoparticles at low temperature

The Fe₂O₃/Ag core-shell composite nanoparticles were successfully prepared via a simple method at low temperature. X-ray diffraction data revealed the formation of core-shell composite nanoparticles, with Fe₂O₃ as the core and silver as the shell. The results from the transmission electron microscopy and scan electron microscopy further indicated that the composite nanoparticles were spherical with a core diameter and shell thickness of 26.0 nm and 13.5 nm, respectively. Magnetic measurements showed that the composite nanoparticles exhibited a typical ferromagnetic behavior, a specific saturation magnetization of 0.95 emu/g and an intrinsic coercivity of 104.0 Oe at room temperature. For a standard two-probe analysis at room temperature, the composite nanoparticles showed a typical conductive behavior and its conductivity was about 3.41 S/m. Moreover, this present synthesis method of Fe₂O₃/Ag core-shell composite nanoparticles shows an easy processing and does not need high-temperature calcining to attain the final product, which can be applied in a variety of areas, including catalysis, medicine, photonics, and new functional device assemblies.     

Localized surface plasmon enhanced microcrystalline–silicon solar cells

A novel type of substrate named “Ag–SP substrate”, in which silver nanoparticles are incorporated, is introduced and utilized as a back reflector for hydrogenated microcrystalline-silicon solar cell in a substrate-type (n-i-p) configuration. Optical and morphological analyses of Ag–SP substrates fabricated with various sizes of silver nanoparticles are systematically performed. It is shown that silver nanoparticles in Ag–SP substrate structure can lead to significant scattering of light when their diameter increases up to 300 nm. Furthermore, the photocurrent of the solar cell fabricated on an Ag–SP substrate with RMS roughness as small as 16.5 nm and a proper lateral diameter (approximately 300 nm) of silver nanoparticles is improved as compared to that of the solar cell prepared on reference textured substrate with RMS roughness of 25.3 nm, owing to strong scattering of light by silver nanoparticles in the red-infrared region.     

Growth of spindle‐shaped silver nanoparticles in SDS solutions

Spindle‐shaped silver nanoparticles were successfully prepared in high yield by a simple wet chemical approach using citric acid (CA) as reducant in the presence of sodium dodecyl sulfate (SDS) at room temperature. Transmission electron microscopy (TEM), UV‐vis absorption spectroscopy and X‐ray diffraction (XRD) have been used to characterize the obtained products. It is found that the spindle‐shaped architecture of siver nanoparticles is drastically influenced by the mass ratio of SDS to CA and the concentration of silver nitrate (AgNO₃). It is revealed that SDS is not as a template but as a capping agent. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low-temperature electron paramagnetic resonance in silver-iron oxide nanoparticles

Water in oil microemulsion technique has been used to obtain silver nanoparticles with a mean size of 7 nm surrounded by a matrix of 2 nm γ-Fe₂O₃ nanoparticles. Magnetic measurements of the sample exhibit a cusp in the ZFC curve at 50 K, which corresponds to the blocking temperature. A detailed study of the thermal evolution of EPR spectra has been performed in the samples. It has been shown that the linewidth, the resonance field and the intensity of the EPR line show different behaviour near the blocking temperature.     

Studies on a possible growth mechanism of silver nanoparticles loaded on TiO2 thin films by photoinduced deposition method

The TiO₂ thin films loaded with silver nanoparticles were prepared on soda-lime glass substrates by a photoinduced deposition method. The TiO₂ films immersed in AgNO₃ solution were vertically irradiated by UV light with center wavelength of 365 nm for 60 h. The as-produced films were characterized by X-ray diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The studies show that the film after UV excitation is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. A possible growth mechanism of silver nanoparticles on TiO₂ thin films under UV irradiation was proposed. The charge carriers of TiO₂ semiconductor are generated by photoexcitation. Owing to the conduction band position of TiO₂ which is above the standard potential of Ag⁺/Ag, the generated electrons could transfer from the conduction band to Ag⁺ adsorbed on the surface of the TiO₂ films. Therefore, the Ag⁺ was finally reduced into a Ag atom, which could preferentially localize in the grain boundaries of TiO₂ particles due to high surface free energy there. With the irradiation time extended, silver nanoparticles were shaped into certain morphologies on the surface of the TiO₂ films.     

Stability of ruthenium nanoparticles synthesized by solvothermal method

One of the major obstacles to the synthesis of nanoparticles and nanocatalyst is the stability of particles. In the present study, polymer stabilized ruthenium nanoparticles were synthesized by solvothermal method using solutions of ruthenium chloride in ethylene glycol in presence of poly(N ‐vinyl‐2‐pyrrolidone) (PVP) as a stabilizing agent. Stability of nanoparticles was studied by varying different parameters e.g. PVP/RuCl₃ molar raio, RuCl₃ concentration, reaction temperature and time and expressed in terms of particle size and size distribution. Transmission electron microscope (TEM) analysis revealed the presence of metallic clusters with a uniform size of about 20‐65 nm. Dispersion destabilisation of colloidal nanoparticles was detected by Turbiscan. Polymer stabilized ruthenium nanoparticles were dispersed on γ‐alumina to prepare uniformly disperse Ru/γ‐Al₂O₃ catalyst by mechanical strirring and sonication. Inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), X‐Ray powder diffraction (XRD), Transmission electron microscopy (TEM) and Thermo gravimetric analysis (TGA) were used to characterize the supported catalyst. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Grain size dependence of physico-optical properties of nanometallic silver in silica aerogel matrix

Synthesis of silver nanoparticles in silica aerogel matrix by sub-critical drying technique is reported in the present article. Physical characterization of silver/silica aerogel nanocomposites with 1, 5 and 25 wt% of silver has been discussed. Physico-optical properties of the composites have been evaluated as a function of the silver particle size crystallized within the silica matrix. The maximum size of the silver grains that could be accommodated in the amorphous matrix was observed to be 25 nm. Silver particles of diameter larger than 25 nm were found segregated out of the silica matrix; such silver particles were single crystalline with dendritic morphology. Optical absorption analysis confirmed the presence of both the oligomeric and nanometallic silver in the samples heat-treated up to 500 °C. With decreasing silver particle size, the surface plasmon resonance was found first to shift towards blue followed then by a red shift. The blue shift is attributed to the chemisorption occurring between the metallic core and the silica matrix. With larger grain size of 25-80 nm in 25 wt% Ag-silica aerogel sample, the diffuseness of electron cloud outside the potential well was observed to cause a red shift in the surface plasmon resonance.     

Investigation of structural and compositional changes in silver-doped GeO2 thin films

The processes going on in silver-doped GeO₂ films during air-heating were investigated by XPS, TEM, IR and UV-visible spectroscopy methods. Silver was shown to interact with the GeO₂ matrix at 500-600 °C to give silver germanate which was decomposed on further heating to form GeO₂ and silver nanoparticles, 10-35 nm in size, absorbing in the plasmon resonance region (λ_max = 415 nm). The silver nanoparticles are located deep in the films and encapsulated by oxide particles.     

Nucleation time lag at nano-sizes

A rapidly convergent exact expression for the time lag (also, ‘induction time’) of transient nucleation obtained by Shneidman and Weinberg [J. Chem. Phys. 97 (1992) 3629] is used to evaluate the lag for clusters with up to 10⁸ monomers. Asymptotic approximations to the exact expression are further advanced to provide explicit elementary expressions for the time lag in the Turnbull-Fisher (TF) nucleation model in various domains of parameters. The difference between the TF time lag and the one of Zeldovich-Frenkel nucleation equation is examined in detail. Transient nucleation flux and the number of nuclei are also discussed, and analytical results appear to be in very good agreement with numerical solutions of the TF equations at large sizes, as reported by Granasy and James [J. Chem. Phys. 113 (2000) 9810].