Silver nanoparticle-doped polyvinyl alcohol coating as a medium for surface-enhanced Raman scattering analysis

A simple polymer substrate for inducing Surface-Enhanced Raman Scattering (SERS) has been investigated. This SERS substrate consists of a solid support, such as a glass slide covered with polyvinyl alcohol (PVA) impregnated with fine silver nanoparticles. The preparation simply involves mixing aqueous PVA polymer with solid AgNO3 to produce a solution that can be easily spin coated on the glass substrate and dried to obtain a hard translucent coating. Aqueous solution of FeSO4.7H2O was used to reduce Ag+ ions to silver nanoparticles. The effects of various experimental conditions of sample preparation were investigated in order to improve the Raman enhancement efficiency of the substrate. The overall substrate performance was evaluated with the use of biologically important compounds: benzoic acid, p-amino benzoic acid, pyridine and dopamine. The spectral features of these compounds closely matched with those reported in literature. The use of the polymer matrix made the SERS substrate resistant to scratching, therefore, improving it to be more suitable for field applications. The hydrophilic nature of the polymer provides additional advantages for probing biological samples. The shelf-life of the dried, unreduced substrates is at least one month.     

Polyelectrolyte assisted silver nanoparticles synthesis and thin film formation

Silver nanoparticles were prepared by the reduction of silver salts with sodium borohydride and capped with a copolymer of styrene sulfonate and maleic monomers. The synthesized nanoparticles were then deposited on a glass substrate using the layer-by-layer deposition technique in alternance with polycationic poly(diallyl-dimethylammonium chloride) PDADMAC. The synthesis of the silver nanoparticles as well as the layer-by-layer deposition with PDADMAC was easily monitored by UV–Vis spectroscopy due to the strong plasmon absorbance at 400 nm of the silver nanoparticles. Our study shows that increasing the concentration ration between the co-polyelectrolyte and silver nitrate has a negative effect on the size distribution of the resulting silver nanoparticles. For the layer-by-layer assembly, the PSS-co-Maleic was found to be a good capping agent since it allows later the formation of uniform thin films when deposited with PDADMAC. A linear increase in absorbance as a function of the number of deposited layers was observed.     

Deposition of silver nanoparticles on montmorillonite platelets by chemical plating

A method for directional deposition of silver nanoparticles on montmorillonite platelets was developed. In order to utilize the elemental layer sheets of montmorillonite as substrate for chemical plating, the clay was modified with dodecyl benzyl dimethyl ammonium chloride, and then exfoliated in toluene with the aid of ultrasonic. Silver deposition in dimethyl formamide with PVP as stabilizer was nucleated at the montmorillonite surface and in the solution. Directional deposition was successful through sensitization with stannous isooctoate and reduction of silver nitrate with Tin(II) ions.     

Fluorescence enhancement using silver nanotriangle arrays

We describe the fabrication of silver nanotriangle array using angle resolved nanosphere lithography and utilizing the same for enhancing fluorescence. The well established nanosphere lithography is modified by changing the angle of deposition between the nanosphere mask and the beam of silver being deposited resulting in nanotriangles of varying surface area and density. The 470 nm plasmon resonance wavelength of the substrate was determined using minimum reflectivity method which closely matches with excitation wavelength of the fluorophore. Ten times enhancement in fluorescence emission intensity is obtained from fluorescein isothiocyanate coated on top of silver nanotriangle array separated by a spacer layer of poly vinyl alcohol as compared to glass. The enhanced fluorescence emission is attributed to the increase in local field enhancement.     

Antibacterial performance of polydopamine-modified polymer surfaces containing passive and active components

A growing number of device-related nosocomial infections, elevated hospitalization costs, and patient morbidity necessitate the development of novel antibacterial strategies for clinical devices. We have previously demonstrated a simple, aqueous polydopamine dip-coating method to functionalize surfaces for a wide variety of uses. Here, we extend this strategy with the goal of imparting antifouling and antimicrobial properties to substrates, exploiting the ability of polydopamine to immobilize polymers and induce metal nanoparticle formation. Polydopamine was deposited as a thin adherent film of 4 nm thickness from alkaline aqueous solution onto polycarbonate substrates, followed by grafting of antifouling polymer polyethylene glycol and in situ deposition of silver nanoparticles onto the polydopamine coated polycarbonate substrates. Elemental and morphological surface analyses confirmed successful grafting of polyethylene glycol brushes onto polydopamine-coated substrates, as well as spontaneous silver nanoparticle formation for polydopamine-coated substrates incubated in silver-nitrate solutions. Sustained silver release was observed over at least 7 days from silver-coated substrates, and the release kinetics could be modulated via additional polydopamine overlayers. In vitro functional assays employing gram negative and positive strains demonstrated dual fouling resistance and antibacterial properties of the coatings due to the fouling resistance of grafted polyethylene glycol and antibacterial effect of silver, respectively. Polycarbonate substrates coated only with silver using a method similar to existing commercial coatings provided an antibacterial effect but failed to inhibit bacterial attachment. Taking into account the previously demonstrated substrate versatility of polydopamine coatings, our findings suggest that this strategy could be implemented on a variety of substrate materials to simultaneously improve antifouling and antimicrobial performance.     

聚多巴胺修饰钛表面纳米载银及其抗菌和细胞相容性

通过多巴胺自聚合在钛表面构建了仿生聚多巴胺(PDA)膜层, 有利于类骨羟基磷灰石在钛表面的沉积, 体现了良好的生物活性。利用聚多巴胺的螯合效应及还原性, 将纳米银颗粒载入聚多巴胺修饰钛表面; 利用场发射扫描电镜(FE-SEM)、X射线光电子能谱(XPS)、显微激光拉曼光谱(Raman)和石墨炉原子吸收光谱(GF-AA5)对聚多巴胺/纳米银修饰钛表面的银粒径、含量及离子释放进行表征。采用杀菌率和表面细菌粘附对聚多巴胺/纳米银修饰钛表面的体外抗菌性能进行检测, 研究结果表明: 纳米银对金黄色葡萄球菌具有较强的杀菌能力, 且MC3T3-E1细胞早期粘附和增殖结果证实本研究得到的聚多巴胺/纳米银修饰钛表面具有良好的体外细胞相容性。     

Silver nanoparticles deposited on porous silicon as a surface-enhanced Raman scattering (SERS) active substrate

Silver nanoparticles were deposited spontaneously from their aqueous solution on a porous silicon (PS) layer. The PS acts both as a reducing agent and as the substrate on which the nanoparticles nucleate. At higher silver ion concentrations, layers of nanoparticle aggregates were formed on the PS surface. The morphology of the metallic layers and their SERS activity were influenced by the concentrations of the silver ion solutions used for deposition. Raman measurements of rhodamine 6G (R6G) and crystal violet (CV) adsorbed on these surfaces showed remarkable enhancement of up to about 10 orders of magnitude.     

Parameters controlling silver nanoparticle growth in sol-gel silica coatings

Silica based sol-gel coatings doped with different silver amounts have been prepared. Apart from silver concentration, other experimental parameters such as thermal densification conditions, presence of other co-dopants and the nature of the substrate have been varied in order to determine their influence on the final microstructure and properties. Characterisation of the materials prepared was carried out by optical spectroscopy (photoluminescence and absorption), secondary ion mass spectroscopy (SIMS) and transmission electron microscopy (TEM). The study was oriented to determine the parameters governing the nucleation and growth of silver nanoparticles. The results showed that formation of silver nanoparticles was promoted when one or more of the following conditions were achieved: silver concentration in the initial sol over 5%, thermal densification under reducing atmosphere and use of pure silica substrate (in general, glass substrates without modifier ions and, therefore, with few non-bridging oxygen positions).     

Layer-by-layer deposition of green synthesised silver nanoparticles on polyester air filters and its antimicrobial activity

Silver nanoparticles stabilised with anionic polymeric polyelectrolytes were successfully synthesised by high-energy UV reduction. Three types of polyelectrolytes were used including poly(methacrylic acid) (PMA), poly(acrylic acid) (PAA) and poly(4-styrenesulphonic acid-co-maleic acid) (CoPSS). The formation of the prepared solutions exhibited surface plasmon resonance at the wavelength of 475, 730 and 408 nm by using PMA, PAA and CoPSS as the stabilising agents. UV–visible spectrophotometer, transmission electron microscope (TEM) and zeta potential analyser were employed to characterise the formation of the prepared solutions. The silver nanoparticles stabilised with anionic polyelectrolytes were immobilised on polyester air filters using a layer-by-layer technique. This is the sequential dipping of polyester air filters in a dilute solution of cationic poly(diallyldimethylammonium chloride) and anionic polymeric polyelectrolytes capped silver. The surface topography of the polyester air filters were measured by field emission scanning electron microscope. Results showed that silver nanoparticles had the highest surface coverage on the polyester air filters probably because it is a good bonding candidate and insures strong film growth. The multilayers polyester air filters coated silver nanoparticles were tested against the gram positive pathogen Staphylococcus aureus. The deposition of silver nanoparticles onto the polyester air filters resulted in 92.18%, 84.32% and 71.19% of bacteria removal using PMA, PAA and CoPSS as the stabilising agent.     

Mechanism of immersion deposition of Ni-P films on Si(100) in an aqueous alkaline solution containing sodium hypophosphite

The immersion deposition of Ni-P films on Si(100) surface without prior activation by metallic catalytic was carried out in an aqueous alkaline solution containing sodium hypophosphite. The deposition mechanism was investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Two stages of deposition were observed when the Si substrate was immersed in the deposition solution at an appropriate pH value. In the first stage, crystalline Ni nanoparticles were formed through a galvanic displacement reaction, which accompanied the oxidation of Si substrate without involving the reducing agent, NaH₂PO₂. Experimental results indicate that the oxidation states of Si⁴⁺ and Si³⁺ exist in the oxide layer. The amount of suboxide, Si³⁺, increased with deposition time, and the oxide layer became activated. In the second stage, amorphous Ni-P was deposited on this activation oxide layer in a process involving the reducing agent. The microscopic structure of the deposition film, observed by TEM cross-sectional analysis, verifies the mechanism of deposition suggested in this study.     

染料包覆胶态银纳米粒子掺杂的有机复合膜的制备与光吸收特性

为避免传统的湿化学法制备纳米掺杂复合材料中热处理给材料性能带来的负面影响,提出了一种简易可行的工艺方法:通过胶体化学法制备出稳定的胶态银纳米粒子分散系,以它为纳米粒子来源,使有机染料罗丹名6G(R6G)分子包覆到银纳米胶粒表面,将该胶体分散系均匀掺杂到明胶溶液中,制备出染料包覆胶态银纳米粒子掺杂的有机复合膜.本工作成功地制备出无机/有机活性基元掺杂的三元系复合膜,实现了染料分子对金属纳米粒子完全意义上包覆的设想和对活性基元的室温包埋工艺.电镜(TEM)观测了复合膜的显微结构,对复合膜的UV-Vis吸收光谱进行了测量.给出了一种包覆掺杂的结构模型,并用该模型成功地解释了实验结果.     

Surface-enhanced infrared spectroscopic studies of the catalytic behavior of silver nanoparticles on a germanium substrate

The catalytic activity of silver nanoparticles (AgNPs) on a germanium substrate is reported. Para-nitrothiophenol (pNTP) that had been adsorbed on this substrate is converted to p-aminothiophenol (pATP) under very mild reaction conditions, such as simply soaking in water. The AgNPs may be formed either by physical vapor deposition or by electroless deposition from a solution of silver nitrate. Analogous reactions were not observed on copper nanoparticles on germanium or AgNPs on silicon or zinc selenide even though very slow conversion of pNTP to pATP was observed with Au nanoparticles (AuNPs) on Ge under controlled reaction conditions. The effects of factors that could influence the catalytic reaction were examined; these included the particle size of the AgNPs, reaction temperature, concentration and chemical nature of other ions present in the solution, the pH of the water, and the nature of the substrate. The reaction rate was approximately independent of the particle size for AgNPs between 50 and 150 nm in diameter. Increasing the temperature accelerates the reaction significantly; at temperatures above 40 °C, the adsorbed pNTP is completely converted by water within five minutes. Not surprisingly, the reaction rate was increased as the pH of the solution was decreased, as the reduction of each nitro group to an amino group requires six protons. The presence of Br(-) and I(-) ions accelerated the reaction to the point that even at 4 °C, the conversion of the nitro group was still observable, while solutions containing chloride ions had to be heated to 40 °C before their effect became apparent. Apparently, Br(-) and I(-) ions remove the oxide layer from the surface of the germanium substrate, facilitating transfer of electrons from the germanium to the nitro group of the pNTP.     

A facial microwave-assisted polyol activation process for fabrication of Ni@PMMA microspheres

A simple and efficient activation process was conducted by deposition of palladium (Pd) nanoparticles on PMMA surface using a microwave-assisted polyol method with ethanol used as the reductant. The newly synthesized Pd nanoparticles were utilized as an activator for electroless nickel deposition. TEM images revealed that Pd nanoparticles of size 4-6 nm are formed evenly over the PMMA surface. A tight, smooth and continuous Ni plating layer was coated on these Pd nanoparticle activated PMMA microspheres. In contrast, a rough and discontinuous Ni film was obtained for the sample activated with a conventional sensitization/activation procedure.     

Silver sulfide nanoparticle assembly obtained by reacting an assembled silver nanoparticle template with hydrogen sulfide gas

A fast, simple procedure is described for obtaining an assembly of silver sulfide nanoparticles (Ag(2)S NPs) on a glass substrate through reaction of a template of an assembled layer of silver nanoparticles (Ag NPs) with hydrogen sulfide (H(2)S) gas. The Ag NP template was prepared by assembling a monolayer of spherical Ag NPs (mean diameter of 7.4?nm) on a polyethylenimine-treated glass substrate. Exposure to pure H(2)S for 10?min converted the Ag NPs of the template to Ag(2)S NPs. The resulting Ag(2)S NP assembly, which retains the template nanostructure and particle distribution, was characterized by optical absorption spectroscopy, atomic force microscopy, transmission electron microscopy (TEM), scanning high resolution TEM, energy dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy. The Ag(2)S NPs have a crystal structure of monoclinic acanthite, and while they retained the spherical shape of the original Ag NPs, their mean particle size increased to 8.4?nm due to changes to the crystal structure when the Ag NPs are converted into Ag(2)S NPs. The measured optical absorption edge of the Ag(2)S NP assembly indicated an indirect interband transition with a band gap energy of 1.71?eV. The Ag(2)S NP assembly absorbed light with wavelengths below 725?nm, and the absorbance increased monotonically toward the UV region.     

Single particle model of SnO2 deposition on silver nanoparticles

Silver nanoparticles coated with almost uniform, thin shell of tin oxide are synthesized via a simple colloid chemistry technique, where the reduction of Ag⁴⁺ to Ag⁰ followed by the encapsulation of oxide takes place. The as prepared dispersions of tin oxide coated silver nanocomposite particles display a surface plasmon band, which is significantly red shifted with respect to that of bare Ag. Morphology of the composite nanoparticles was investigated by TEM. Presence of SnO₂ shell on the silver nanoparticles was also supported by XPS results. A theoretical single particle model has been proposed for the formation of tin oxide shell on the silver nanoparticles.     

Preparation of low-crystalline apatite nanoparticles and their coating onto quartz substrates

We prepared low-crystalline apatite nanoparticles and coated them onto a surface of a Au/Cr-plated quartz substrate by the electrophoretic deposition (EPD) method or by using a self-assembled monolayer of 11-mercaptoundecanoic acid (SAM method). Low-crystalline apatite nanoparticles around 10?nm in size with extremely low contents of undesirable residual products were obtained by adding (NH(4))(2)HPO(4) aqueous droplets into a modified synthetic body fluid solution that contained Ca(CH(3)COO)(2). The apatite nanoparticles were successfully coated by either the EPD method or the SAM method; the nanoparticle coating achieved by the SAM method was more uniform than that achieved by the EPD method. The present SAM method is expected to be a promising technique for obtaining a quartz substrate coated with apatite nanoparticles, which can be used as a quartz crystal microbalance device.     

Separation of nanoparticles by gel electrophoresis according to size and shape

We demonstrate the separation of gold and silver nanoparticles according to their size and shape by agarose gel electrophoresis after coating them with a charged polymer layer. The separation is monitored optically using the size- and shape-dependent plasmon resonance of noble metal particles and confirmed by transmission electron microscopy (TEM). Electrophoretic mobilities are quantitatively explained by a model based on the Henry formula, providing a theoretical framework for predicting gel mobilities of polymer coated nanoparticles.     

Fabrication of nanoscaled silica layer on the surfaces of submicron SiO2-Ag core-shell spheres

A two-step silica deposition process, including prefunctionalization with poly(vinylpyrrolidone) and the following silica deposition, has been used to fabricate silica layer on the surface of nanoscaled silver shell. The influencing parameters of silica coating process were optimized to prevent the precoated silver nanoparticles from desquamating from silica spheres, finally to obtain mono-dispersed silica spheres with silver and silica multilayer films. The resulted silica layer was dense and uniform, its thickness was controllable in the range of 20–50 nm. Such coated silica layer can provide improved thermal stability of the SiO₂-Ag core-shell structural spheres.     

Direct printing of silver nanoparticles by an agarose stamp on planar and patterned substrates

In this study, we have used an agarose stamp to conduct direct printing of silver nanoparticles, nanowires and nanoplates on both planar and structured substrates. Nanoparticle solution could be first coated on an agarose stamp, and then transferred to a planar substrate. Micro-patterns comprising metal nanoparticles could be printed on planar substrates without the formation of residual layers. Thus a three-dimensional metal microstructure could be easily fabricated. The patterning of electrodes by printing Ag nanowires directly on TiO(2) was also demonstrated to fabricate resistive random access memory (RRAM) devices by all-solution-processing methods. By using a flat agarose stamp, the patterns printed on the microstructured substrates were quite different from those on the nanostructured substrates. On the microstructured substrates, direct printing could print silver nanoparticles onto the protrusion surface, and could print silver layers as thick as several microns, useful for high conductivity electrodes. On the substrates with nanostructures such as photonic crystals or nano-gratings, direct printing could transfer nanoparticles into the grooves or cavities only due to the contact of the agarose stamp with the groove or concavity surface. A new approach to fabricate metal wire grid polarizers was further demonstrated. A nanoporous agarose stamp has a good potential for printing using nanoparticle suspension.     

ZnO/Al_2O_3复合纳米颗粒的制备与表征

为研究ZnO/Al2O3复合纳米颗粒在涂料、化妆品等领域的应用,采用直接沉淀法制备了纳米ZnO,用硫酸铝水解生成的Al2O3对纳米ZnO进行了表面改性。采用IR、TEM、SEM、XRD等手段对改性前后的粉体进行表征。分析结果表明,改性后粉体颗粒的团聚现象减轻。粉体的光催化降解甲基橙的实验研究表明,改性后ZnO粉体的光催化活性明显下降,进一步证明纳米ZnO颗粒表面存在Al2O3的包覆层。