Synthesis of zwitterionic shell cross-linked micelles with pH-dependent hydrophilicity

Synthesis of bi-functional silica particles by a simple wet chemical method is described where the mixture of ultra fine nanoparticles (1-3 nm) of titania and silver were attached on the silica particle surface in a controlled way to form a core-shell structure. The silica surface showed efficient bi-functional activity of photo-catalytically self cleaning and antibacterial activity due to nanotitania and nanosilver mutually benefiting each other's function. The optimum silver concentration was found where extremely small silver nanoparticles are formed and the total composite particle remains white in color. This is an important property in view of certain applications such as antibacterial textiles where the original fabric color has to be retained even after applying the nanosilver on it. The particles were characterized at each step of the synthesis by X-ray photoelectron spectroscopy, UV-visible spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron energy loss spectroscopy. Bi-functional silica particles showed accelerated photocatalytic degradation of methylene blue as well as enhanced antibacterial property when tested as such particles and textiles coated with these bi-functional silica particles even at lower silver concentration.     

Silica–silver core–shell particles for antibacterial textile application

The silica–silver core–shell particles were synthesized by simple one pot chemical method and were employed on the cotton fabric as an antibacterial agent. Extremely small (1–2 nm) silver nanoparticles were attached on silica core particles of average 270 nm size. The optimum density of the nano silver particles was found which was sufficient to show good antibacterial activity as well as the suppression in their surface plasmon resonance responsible for the colour of the core–shell particle for antibacterial textile application. The change in the density and size of the particles in the shell were monitored and confirmed by direct evidence of their transmission electron micrographs and by studying surface plasmon resonance characteristics. The colony counting method of antibacterial activity testing showed excellent results and even the least silver containing core–shell particles showed 100% activity against bacterial concentration of 10⁴ colony counting units (cfu). The bonding between core–shell particles and cotton fabric was examined by X-ray photoelectron spectroscopy. The antibacterial activity test confirmed the firm attachment of core–shell particles to the cotton fabric as a result 10 times washed sample was as good antibacterial as that of unwashed sample. The bacterial growth was inhibited on and beneath the coated fabric, at the same time no zone of inhibition which occurs due to the migration of silver ions into the medium was observed indicating immobilization of silver nanoparticles on silica and core–shell particles on fabric by strong bonding.     

Metal-enhanced fluoroimmunoassay on a silver film by vapor deposition

We studied a fluoroimmunoassay using metal-enhanced fluorescence (MEF) detection on silver film generated by vapor deposition method. The morphology of the silver film was controlled through the thickness of the film. A silica layer was coated on the silver film to protect the film and separate the fluorophore from the metal surface. Rabbit immunoglobulin G (IgG) was adsorbed on the silica by physiosorption and then dye-labeled anti-rabbit IgG was bound to the immobilized rabbit IgG. It was observed that the fluorophore was quenched on a thin silver film (2 nm), enhanced on a thick film (>5 nm), and reached saturation (ca. 10 times enhancement) at 20 nm. The MEF was also dependent on the thickness of the silica with a maximum at 10 nm. The lowest lifetime was observed on the 20 nm silver film, which was consistent with the saturation of MEF. These results showed the properties of a silver film needed for a maximum increase of fluorescence intensity in a fluoroimmunoassay. Dependence of the MEF on the emission wavelength was also studied using different dye-labeled anti-rabbit IgGs.     

单分散金属介电复合粒子制备及表征研究

过去20年纳米材料科学与技术的飞速发展使人们对于这种新材料寄予极大的期望,合成、组装及设计纳米相材料取得了巨大的进步。一方面单纯的纳米线、纳米杆、纳米晶、纳米管、纳米带、纳米球及量子点材料不断的被报道;另一方面,人们也加大了寻找纳米复合材料的步伐。以二氧化硅等胶体球形粒子为基体发展起来的纳米包覆(nanocoating)技术引起人们的极大兴趣犤1犦。这种纳米包覆技术得到的产物常常被称为核壳粒子(core-shellparticles),通常包括作为核的基体球的表面性质改性与其它材料于表面包覆形成壳层。纳米包覆技术实际上也是粒子表面性质…     

Nano silver coated patterned silica thin film by sol–gel based soft lithography technique

We report the fabrication of nano silver coated patterned silica thin film by sol–gel based soft lithography technique. Initially, silica gel film on soda lime silica glass was prepared by dipping technique from a silica sol of moderate silica concentration. A PolydimethylSiloxane elastomeric stamp containing the negative replica of the patterns of commercially available compact disc was used for embossing the film and the embossed film was cured up to 450 °C in pure oxygen atmosphere for oxide film. Finally, a precursor solution of AgNO₃ in water containing polyvinyl alcohol as an organic binder was made and used for coating on the patterned silica film by dipping technique and cured the sample up to 450 °C in reducing gas atmosphere to obtain nano silver layer. The formation of only cubic silver (~4.0 nm) and both cubic silver (~5.2 nm) and silver oxide (~3.6 nm) crystallites at 350 and 450 °C film curing temperatures respectively were confirmed by XRD measurements. The % of nano silver metal and silver oxide were 75.4 and 24.6 respectively. The nano-structured surface feature was visualized by FESEM whereas AFM revealed the high fidelity grating structure of the films. Presence of both spherical and rectangular structure (aspect ratio, 2.37) of nano silver/silver oxide was confirmed by TEM. The films were also characterized by UV–Vis spectral study. The patterned film may find application in chemical sensor devices.     

Preparation and microstructure of sol-gel derived silver-doped silica

Silver-doped silica was prepared by hydrolysis and condensation of tetraethyl orthosilicate (TEOS, Si(OC₂H₅)₄) in the presence of a silver nitrate (AgNO₃) solution by two different synthesis methods. In the first synthesis route, sol-gel mixtures were prepared using an acid catalyst. In the second synthesis route, silver-doped silica gels were formed by two-step acid/base catalysis. For the same concentration of silver dopant [AgNO₃]/[TEOS] = 0.015 acid-catalyzed sol-gel formed a microporous silica with an average pore size of <25 Å whereas the two-step catalyzed silica had an average pore size of 250 Å and exhibited a mesoporous structure when fully dried. The differences in the pore size affected the silver particle formation mechanism and post-calcination silver particle size. After calcination at 800 °C for 2 h the acid-catalyzed silica contained metallic silver particles size with an average particle size of 24 ± 2 nm whereas two-step catalyzed silica with the same concentration of [AgNO₃]/[TEOS] = 0.015 contained silver nanoparticles with an average size of approximately 32 ± 2 nm. Mechanisms for silver particle formation and for silica matrix crystallization with respect to the processing route and calcination temperature are discussed.     

Infrared study of the interaction of charged silica particles with TiO2 particles containing adsorbed cationic and anionic polyelectrolytes

Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy was used to study the adsorption of charged silica particles onto TiO(2) particles coated with anionic sodium polyacrylate (NaPA) or cationic poly(diallyldimethylammonium) chloride (PDADMAC). To the best of our knowledge, this is the first time that IR spectroscopy has been used to study the interaction of a polymer layer on one particle with a second different particle. The results show that, once adsorbed on the TiO(2) particle, the PDADMAC or the NaPA does not transfer to the silica particles. In the case of NaPA coated TiO(2), positively charged silica particles deposit on the TiO(2) and this is accompanied by a change in the relative intensities of the bands due to COOH and COO(-) groups. From this change in band intensity, it is calculated that only approximately 6% of the COO(-) groups located in the loops and tails bind to the silica particle. This shows that the polymer bridges the two particles through an electrostatic interaction with the outer COO(-) groups. Similarly, in the case of the TiO(2) particles coated with PDADMAC, negatively charged silica deposits on the TiO(2) and this is accompanied by an increase in intensity of the symmetric bending mode of the (+)N(CH(3))(3) group. This change in band intensity arises from the binding of these cationic sites of the polymer to the negative surface sites on the silica.     

Amplified light scattering and emission of silver and silver core-silica shell particles

Side versus forward light scattergrams, and fluorescence (488 nm excitation) intensity versus particle count histograms were gathered for bare, R6G-coated, and silica-R6G-coated silver particles of 150-200 nm diameter, one-by-one by flow cytometry. Fluorescence emission intensity of the composite particles monotonically increased and then reached a plateau with greater R6G concentrations, as measured by flow cytometry. Fluorescence amplification factors of up to 3.5x10(3) were estimated by reference to measurements on core-shell particles with silica instead of silver cores. Huge surface enhanced Raman scattering (SERS) intensities, at least 10(14)-fold greater than normal Raman scattering intensities, were observed with 633 nm excitation for molecules such as rhodamine 6G (R6G) on the same single particles of silver. Although routine transmission (TEM) and scanning (SEM) electron microscopies showed gross structures of the bare and coated particles, high-resolution field emission scanning electron microscopy (FE-SEM), revealed Brownian roughness describing quantum size and larger structures on the surface of primary colloidal silver particles. These silver particles were further characterized by extinction spectra and zeta potentials. Structural and light scattering observations that are reported herein were used to tentatively propose a new hierarchical model for the mechanism of SERS.     

Headspace SPME–GC Method for Acetone Analysis and its Biomedical Application

A new method for extraction and analysis of acetone in human urine based on headspace solid phase microextraction using a mixture of activated carbon and zeolite as sorbents in a PVC matrix coated on a silver wire and its application to the determination of ketone bodies is described. Unlike commercial fibers, which are coated on fused silica, the coating adheres strongly to the silver wire and is thermally stable up to 250 °C. After optimization of coating composition and microextraction conditions the fiber was used for the analysis of acetone in human urine.     

Analysis of ethanol and methanol in human body fluids by headspace solid phase microextraction coupled with capillary gas chromatography.

A new method for extraction and analysis of ethanol and methanol in human whole blood, urine and saliva samples based on headspace solid phase microextraction (SPME) using silver sulfide (Ag(2)S) and polyvinyl chloride (PVC) coated on silver wire is described. Unlike commercial fibers, which are coated on fused silica, the proposed fiber has a metallic base to which the coating adheres very strongly. Due to metallic base, this fiber is very durable and is thermally stable up to 250 degrees C. After optimization of coating composition and microextraction conditions, the fiber was used for sampling of methanol and ethanol from human body fluids prior to capillary gas chromatographic analysis. The high recovery (>94%), low detection limits (5.6 mg/L for ethanol and 12.8 mg/L for methanol) and excellent linearity (>0.9900) of calibration graphs made the proposed method suitable for this purpose.     

Dye-labeled silver nanoshell-bright particle

Silica beads with average diameters of 40-600 nm were prepared, and Ru(bpy)3(2+) complexes were incorporated into the beads. These beads were coated by silver layer by layer to generate porous but continuous metal nanoshells. The thicknesses of these metal shells were 5-50 nm. The emission band from the dyes in the silica cores was more narrow and the intensity was enhanced with growth of silver shell thickness due to coupling of the emission light from Ru(bpy)3(2+) in the cores with the metal plasmon from the silver shells. The enhancement of emission intensity was also dependent on the size of the silica core, showing that the enhancement efficiency decreased with an increase in the size of the silica beads. Lifetime measurements support the coupling mechanism between the dye and metal shell. This study can be used to develop novel dye-labeled metal particles with bright and narrow emission bands.     

In situ preparation of polyaniline coated fumed and precipitated silica fillers and their composites with nitrile rubber (Investigation on structure-property relationship)

In situ synthesis of polyaniline (PAni) coated pyrogenic or fumed silica (PCFS) and precipitated silica (PCPS) were carried out by the oxidative polymerization of aniline in presence of fumed silica (FS) and precipitated silica (PS). Both uncoated and PAni coated silica fillers were characterized through scanning electron microscope (SEM), infrared spectroscopy and thermo-gravimetric analysis (TGA) to evaluate particle morphology and physico-chemical character of coated and uncoated silica particles. Semi-conducting composites made from two different types of PAni coated silica fillers with NBR exhibit different trend in the variation of electrical properties under different temperature and pressure. These differences in electrical properties of two types of composites are mainly due to physico-chemical characteristics of filler particles as well as their distribution in the polymer matrix. This type of composites may be used as semi-conducting and ESD (electrostatic discharge) material.     

l‐Cysteine‐modified silver‐functionalized silica‐based material as an efficient solid‐phase extraction adsorbent for the determination of bisphenol A

A new silver‐functionalized silica‐based material with a core–shell structure based on silver nanoparticle‐coated silica spheres was synthesized, and silver nanoparticles were modified using strongly bound l‐ cysteine. l‐ Cysteine‐silver@silica was characterized by scanning electron microscopy and FTIR spectroscopy. Then, a solid‐phase extraction method based on l‐ cysteine‐silver@silica was developed and successfully used for bisphenol A determination prior to HPLC analysis. The results showed that the l‐ cysteine‐silver@silica as an adsorbent exhibited good enrichment capability for bisphenol A, and the maximum adsorption saturation was 20.93 mg/g. Moreover, a short adsorption equilibrium time was obtained due to the presence of silver nanoparticles on the surface of the silica. The extraction efficiencies were then optimized by varying the eluents and pH. Under the optimized conditions, good linearity for bisphenol A was obtained in the range from 0.4 to 4.0 μM (R² > 0.99) with a low limit of detection (1.15 ng/mL). The spiked recoveries from tap water and milk samples were satisfactory (85–102%) with relative standard deviations below 5.2% (n = 3), which indicated that the method was suitable for the analysis of bisphenol A in complex samples.     

Preparation of highly monodispersed hybrid silica spheres using a one-step sol-gel reaction in aqueous solution

The successful one-step preparation method of monodisperse hybrid silica particles was studied using organosilane chemicals in aqueous solution. In general, almost all of the hybrid silica materials were made by a complex method where organic materials were coated on the surface of silica substrate via chemical reaction. However, our novel method can be applied to prepare colloidal hybrid particles without using substrate material. This method has three advantages: (i) this simple method gives the opportunity to prepare hybrid particles with high monodispersity through the self-hydrolysis of various organosilane monomers in aqueous solution, (ii) this efficient method can be applied to load lots of organic functional groups on the surface of silica particles through a one-step preparation method using only organosilane, and (iii) this effective method can be used to control the particle size of the product by changing the experimental conditions such as the concentration of the precursor or the reaction temperature. Detailed characterization of the hybrid particles by scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA) was performed to elucidate the morphologies and properties of the hybrid silica particles.     

Facile synthesis of silver core - silica shell composite nanoparticles

Combining metal nanoparticles and dielectrics (e.g. silica) to produce composite materials with high dielectric constant is motivated by application in energy storage. Control over dielectric properties and their uniformity throughout the composite material is best accomplished if the composite is comprised of metal core - dielectric shell structured nanoparticles with tunable dimensions. We have synthesized silver nanoparticles in the range of 40-100nm average size using low concentration of saccharide simultaneously as the reducing agent and electrostatic stabilizer. Coating these silver particles with silica from tetraalkoxysilanes has different outcomes depending on the alcoholic solvent and the silver particle concentration. A common issue in solution-based synthesis of core-shell particles is heterogeneous nucleation whereupon two populations are formed: the desired core-shell particles and undesired coreless particles of the shell material. We report the formation of Ag@SiO(2) core-shell particles without coreless silica particles as the byproduct in 2-propanol. In ethanol, it depends on the silver surface area available whether homogeneous nucleation of silica on silver is achieved. In methanol and 1-butanol, core-shell particles did not form. This demonstrates the significance of controlling the tetraalkoxysilane hydrolysis rate when growing silica shells on silver nanoparticles.     

Encapsulation of Organic Pigment Particles with Silica via Sol-Gel Process

This paper presented a novel preparation method of silica coated organic pigment. In this approach, the surfaces of the organic pigment were first orderly modified by poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), then coated by silica via sol-gel process of tetraethylorthosilicate (TEOS). The results showed that PVP, pH value, water and TEOS contents had significant influence on the morphology of the silica encapsulated organic pigment. Organic pigments coated silica by this approach could scatter UV ray with wavelength less than 270 nm, and this scattering property increased with more silica coated.     

Fast and facile synthesis of silica coated silver nanoparticles by microwave irradiation

A novel, fast and facile microwave technique has been developed for preparing monodispersed silica coated silver (Ag@SiO(2)) nanoparticles. Without using any other surface coupling agents such as 3-aminopropyltrimethoxysilane (APS) or polymer such as polyvinyl pyrrolidone (PVP), Ag@SiO(2) nanoparticles could be easily prepared by microwave irradiation of a mixture of colloidal silver nanoparticles, tetraethoxysilane (TEOS) and catalyst for only 2 min. The thickness of silica shell could be conveniently controlled in the range of few nanometers (nm) to 80 nm by changing the concentration of TEOS. Transmission electron microscopy (TEM) and UV-visible spectroscopy were employed to characterize the morphology and optical properties of the prepared Ag@SiO(2) nanoparticles, respectively. The prepared Ag@SiO(2) nanoparticles exhibited a change in surface plasmon absorption depending on the silica thickness. Compared to the conventional techniques based on St?ber method, which need 4-24 h for silica coating of Ag nanoparticles, this new technique is capable of synthesizing monodispersed, uniform and single core containing Ag@SiO(2) nanoparticles within very short reaction time. In addition, straightforward surface functionalization of the prepared Ag@SiO(2) nanoparticles with desired functional groups was performed to make the particles useful for many applications. The components of surface functionalized nanoparticles were examined by Fourier transform infrared (FT-IR) spectroscopy, zeta potential measurements and X-ray photoelectron spectroscopy (XPS).     

Correcting for a density distribution: particle size analysis of core-shell nanocomposite particles using disk centrifuge photosedimentometry

Many types of colloidal particles possess a core-shell morphology. In this Article, we show that, if the core and shell densities differ, this morphology leads to an inherent density distribution for particles of finite polydispersity. If the shell is denser than the core, this density distribution implies an artificial narrowing of the particle size distribution as determined by disk centrifuge photosedimentometry (DCP). In the specific case of polystyrene/silica nanocomposite particles, which consist of a polystyrene core coated with a monolayer shell of silica nanoparticles, we demonstrate that the particle density distribution can be determined by analytical ultracentrifugation and introduce a mathematical method to account for this density distribution by reanalyzing the raw DCP data. Using the mean silica packing density calculated from small-angle X-ray scattering, the real particle density can be calculated for each data point. The corrected DCP particle size distribution is both broader and more consistent with particle size distributions reported for the same polystyrene/silica nanocomposite sample using other sizing techniques, such as electron microscopy, laser light diffraction, and dynamic light scattering. Artifactual narrowing of the size distribution is also likely to occur for many other polymer/inorganic nanocomposite particles comprising a low-density core of variable dimensions coated with a high-density shell of constant thickness, or for core-shell latexes where the shell is continuous rather than particulate in nature.     

Microwave-Assisted Self-Organization of Colloidal Particles Inside Water-in-Oil Emulsions

Commercial amidine polystyrene microspheres were self-organized to obtain colloidal microclusters from water-in-oil emulsion droplets as confining geometries. For demulsification process, microwave was irradiated to remove water droplets selectively resulting in the shrinkage of water droplets which induces inward capillary pressure for the particle self-assembly. The amidine polystyrene clusters were coated with silica nanospheres or titania nanoparticles by co-organizing the mixed particle suspensions inside water droplets by microwave heating. Titania-coated polystyrene clusters were calcined to produce hollow macroporous titania powders. Finally, sulfate-coated polystyrene microspheres were self-assembled with silica nanoparticles to generate polystyrene/silica composite clusters by microwave irradiation method.     

Solid Phase Extraction of Neutral Analytes through Silica Gel Coated with Layers of Au Nanoparticles Self‐Assembled with Alkanethiols

In this study, we used Au nanoparticle (NP)‐coated silica gel as a solid phase extraction sorbent for the preconcentration of neutral analytes (steroid drugs). The sorbent was fabricated using two alkanethiol self‐assembly processes: one to deposit the Au NPs onto a 3‐aminopropyltrimethoxysilane‐modified silica gel and the other to functionalize the surfaces of the Au NPs. A large volume of the steroid solution was passed through the silica gel to facilitate adsorption mediated by hydrophobic interactions between the steroids and the hydrophobic moieties on the silica gel surface. Extraction of the steroids was accomplished by flushing the silica gel with a low‐polarity solvent. In this preliminary study, we found that the particle size of the silica gel and the number of layers of Au NPs coated on the silica gel both affected the preconcentration performance for the steroids. When using six layers of Au NPs coated on 5–20‐μm silica gel, the detection limits for steroids were below 80 ng L^?1; the preconcentration efficiency was over 170‐fold higher than that of the original steroid solution. Our findings provide further evidence that nanotechnology has much to benefit analytical science.