Polymeric coatings on silver nanoparticles hinder autoaggregation but enhance attachment to uncoated surfaces

The propensity of silver nanoparticles (AgNPs) having two different polymer coatings (poly(vinylpyrrolidone), PVP, or gum arabic, GA) to aggregate, or to deposit to a reference surface (silica), was explored as a basis for differentiating the effect of surface coating on the stability of nanoparticles in aggregation and in deposition. Surface polymeric coatings stabilize nanoparticles against aggregation as shown by either an increased critical coagulation concentration as for PVP-coated AgNPs (AgPVP) or the absence of observable aggregation even at a high ionic strength as for GA-coated AgNPs (AgGA). In experiments of AgNPs deposition in a silica porous medium, dissimilar surfaces favored deposition, such as the case where polymer coatings were present on the AgNPs but were absent on the porous medium. The increased affinity of the AgNPs for the porous medium in this case may be explained by a shifted contact frontier where electrical double layer interaction is weaker. When coating polymers were introduced to the porous medium and allowed to preadsorb to the silica surfaces, the attachment efficiencies for both the AgPVP and AgGA were reduced due to steric and electrosteric stabilization, respectively. The results suggest that polymeric coatings that are usually deemed as stabilizers (as they indeed are in the case of autoaggregation) might not necessarily stabilize nanoparticles against deposition unless the collector surfaces are also coated with polymer.     

Electrospun nanofiber pyropolymer electrodes for fuel cells on polybenzimidazole membranes

After the deposition of Pt on their surface, the carbon nanofiber materials synthesized by sequential oxidation and pyrolysis of electrospun nanofiber mats based on polyacrylonitrile are used as the gas-diffusion electrodes for high-temperature hydrogen–air fuel cells on a polybenzimidazole (PBI) proton-conducting membranes. In contrast to the traditional methods of electrode preparation in which the catalyst (Pt) nanoparticles are localized on the surface of carbon black which is applied as “ink” on the conducting support (carbon paper or tissue), in this study the Pt nanoparticles are being deposited and developed on the surface carbon nanofibers to form a combined gas-diffusion material. In the tests, the resulting electrodes demonstrate good efficiency within hydrogen-air fuel cells on the PBI membrane.     

Characterization of poly(methyl methacrylate) nanofiber mats by electrospinning process

In this study, the aim is to describe the influence of electrospinning parameters on the morphology, the water wetting property and dye adsorption property of poly(methyl methacrylate) nanofiber mats. Specifically, the effects of solution concentration, solvent type, applied voltage, distance between the electrodes and particulate reinforcement on the diameter and shape of the nanofibers were investigated. All poly(methyl methacrylate) nanofiber mats contained beaded nanofiber structures. With increasing the polymer solution concentration, the average fiber diameter also increased. Poly(methyl methacrylate) nanofiber mat electrospun from dimethylformamide solution resulted in thicker fibers when compared with the mat electrospun from acetone solution. Increasing the electric potential difference between the collector and the syringe tip did not increase the average fiber diameter. Besides increasing the distance between the electrodes resulted in a decrease in the average fiber diameter. When compared with PMMA nanofiber mat, thicker fibers were obtained with silica nanoparticles reinforced nanofiber mat. According to the water contact angle measurements, all poly(methyl methacrylate) nanofiber mats revealed hydrophobic surface property. PMMA nanofiber mat with the highest water contact angle gave rise to the highest dye adsorption capacity.     

Highly transparent superhydrophobic thin film with low refractive index prepared by one-step coating of modified silica nanoparticles

An easy and effective method to prepare superhydrophobic thin film has been developed. The film with optically transparent and low refractive index was composed by one-step coating with modified silica nanoparticles. The silica nanoparticles were prepared by sol–gel process of hydrolysis and condensation of alkoxysilane compounds and then surface modification silica nanoparticles, 50 ± 10 nm, were accomplished using methoxytrimethylsilane (MOTMS). Water contact angle of film increased with the weight of MOTMS of silica sol. When the weight of MOTMS was optimized, the water contact angle and sliding angle of film were 152.8° and less than 10°, respectively. The transmittance of film was also increased as compared to the un-coated microscope glass slide, from 91 to 93.5 %. The refractive index of the film was approximately 1.09 as measured by ellipsometer. The superhydrphobic thin film was also successfully made by using spray coating and the water contact angle of this film was more than 160°. Surface morphology of difference coating methods, dip and spray, were studied. Our result suggests that the film can be applied for superhydrophobicity and optical applications.     

Probing colloidal forces between a Si3N4 AFM tip and single nanoparticles of silica and alumina

The atomic force microscope (AFM) has been used to measure surface forces between silicon nitride AFM tips and individual nanoparticles deposited on substrates in 10(-4) and 10(-2) M KCl solutions. Silica nanoparticles (10 nm diameter) were deposited on an alumina substrate and alumina particles (5 to 80 nm diameter) were deposited on a mica substrate using aqueous suspensions. Ionic concentrations and pH were used to manage attractive substrate-particle electrostatic forces. The AFM tip was located on deposited nanoparticles using an operator controlled offset to achieve stepwise tip movements. Nanoparticles were found to have a negligible effect on long-range tip-substrate interactions, however, the forces between the tip and nanoparticle were detectable at small separations. Exponentially increasing short-range repulsive forces, attributed to the hydration forces, were observed for silica nanoparticles. The effective range of hydration forces was found to be 2-3 nm with the decay length of 0.8-1.3 nm. These parameters are in a good agreement with the results reported for macroscopic surfaces of silica obtained using the surface force apparatus suggesting that hydration forces for the silica nanoparticles are similar to those for flat silica surfaces. Hydration forces were not observed for either alumina substrates or alumina nanoparticles in both 10(-4) M KCl solution at pH 6.5 and 10(-2) M KCl at pH 10.2. Instead, strong attractive forces between the silicon nitride tip and the alumina (nanoparticles and substrate) were observed.     

Polymer coatings for sensitive analysis of colloidal silica nanoparticles in water

A new analytical approach has been developed for the sensitive detection of trace nanomaterials in water using silica as model inorganic nanoparticles. Our novel approach is based on coating of the nanoparticles with a polymer to make them larger in size for better ultraviolet (UV) light absorption. These polymer-coated nanoparticles can be separated from the monomer and polymer by capillary electrophoresis (CE) due to differences in their ionic charge, size, and surface functionality. Controlled polymerization of 2-hydroxypropyl methacrylate (HPMA) on silica nanoparticles increased their UV detection sensitivity by 5–7-fold. A second coating with polydopamine produced an extra 2-fold increase of the UV detection sensitivity. With both polyhydroxypropyl methacrylate and polydopamine coatings, a significant total enhancement of 10–14-fold in detection sensitivity was attained. Alternatively, addition of bisphenol A or polyvinyl alcohol to the HPMA polymerization mixture resulted in 9–10-fold increase of SiO₂ detection sensitivity due to additional absorption of the UV detector light.     

Preparation of ultrathin coating layers using surface modified silica nanoparticles

Silica nanoparticles are used in various applications including catalysts, paints and coatings. To reach an optimal performance via stability and functionality, in most cases, the surface properties of the particles are altered using complex procedures. Here we describe a simple method for surface modification of silica nanoparticles (SNP) using sequential adsorption of oppositely charged components. First, the SNPs were made cationic by adsorption of a cationic polyelectrolyte. Poly(allylamine hydrochloride) (PAH) and polyethyleneimine (PEI) were chosen as polycations to investigate the difference between a linear and a branched polyelectrolyte. Next, the dispersion of cationic SNPs was combined with an anionic alkyl ketene dimer (AKD) emulsion. Using this approach cationic, hydrophobic silica particle dispersions were produced. Dynamic light scattering, contact angle measurements and atomic force microscopy (AFM) were used for analyzing the particle and coating layer properties. The chosen polyelectrolyte affected the structure of the dispersion. The layer build-up was studied in detail using a quartz crystal microbalance with dissipation monitoring (QCM-D). The adsorption and layer properties of the cationic polyelectrolytes adsorbed on silica as well as the affinity of AKD to this layer were explored. The application possibilities of the modified particle dispersions were demonstrated by preparing paper and silica surfaces with tailored properties, such as elevated surface hydrophobicity, using an ultrathin coating layer.     

Solution Blowing of Poly（dimethylsiloxane）/Nylon 6 Nanofiber Mats for Protective Applications

A new strategy was developed to fabricate superhydrophobic nylon 6 nanofibers, in which the blend solutions of poly(dimethylsiloxane)(PDMS) prepolymer and nylon 6 was spun using an innovative solution blowing process, and then the PDMS prepolymer contianning nanofibers were cured to obtain PDMS/nylon 6 nanofiber mats. Morphology, surface composition, non-wetting property and protective performance were investigated. The results showed that the addition of PDMS prepolymer improved the spinnability of the spinning solutions, and the PDMS/nylon 6 nanofibers had smooth surfaces and diameters from 100 nm to 350 nm. The presence of PDMS effectively enhanced the hydrophobicity of the nanofiber mats, showing water contact angles of 132° to 161° for PDMS contents of 1 wt% to 3 wt%. The PDMS/nylon 6 mats also possessed excellent protective and transport properties. The results indicated the potential application of the novel nanofiber mats in protective clothing.     

Silica coating of nanoparticles by the sonogel process

A modified aqueous sol-gel route was developed using ultrasonic power for the silica coating of indium tin oxide (ITO) nanoparticles. In this approach, organosilane with an amino functional group was first used to cover the surface of as-received nanoparticles. Subsequent silica coating was initiated and sustained under power ultrasound irradiation in an aqueous mixture of surface-treated particles and epoxy silane. This process resulted in a thin but homogeneous coverage of silica on the particle surface. Particles coated with a layer of silica show better dispersability in aqueous and organic media compared with the untreated powder. Samples were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and the zeta potential.     

Silane-based poly(ethylene glycol) as a primer for surface modification of nonhydrolytically synthesized nanoparticles using the Stöber method

This paper describes the use of methoxy-poly(ethylene glycol) silane (MPEG-sil) as a linker molecule for the synthesis of silica-coated nanoparticles by the St?ber method. While short alkane chain-based siloxanes including (acryloxypropyl)trimethoxysilane and 3-methacryloxypropyl-trimethoxysilane are popular molecules used in surface modification, they are not efficient for the silica coating of nanoparticles synthesized from organic solvents containing long carbon chain carboxylic acids or amines as capping agents. Here, we report the utilization of MPEG-sil to bridge this gap. Our approach is based on a two-phase system, in which ligand exchange takes place in a hydrophobic environment and the surface modification with silica is conducted in an ethanol-water mixture. Our results show that this two-phased approach was effective to coat monodisperse Fe2O3 nanoparticles capped with oleic acid and Ag nanoparticles capped with oleylamine with uniform SiO2 shells. The process was also demonstrated for double-shell nanostructures to produce SiO2-coated Pt@Fe2O3 core-shell nanoparticles. The results described in this work represent a new approach for the surface modification with silica coating of monodisperse nanoparticles synthesized from nonhydrolytic solutions and can potentially have a broad ramification in the development of water-dispersible nanoparticles for biological applications.     

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).     

Biochemically functionalized silica nanoparticles

In this report, we demonstrate the biochemical modification of silica based nanoparticles. Both pure and dye-doped silica nanoparticles were prepared, and their surfaces were modified with enzymes and biocompatible chemical reagents that allow them to function as biosensors and biomarkers. The nanoparticles produced in this work are uniform in size with a 1.6% relative standard deviation. They have a pure silica surface and can thus be modified easily with many biomolecules for added biochemical functionality. Specifically, we have modified the nanoparticle surfaces with enzyme molecules (glutamate dehydrogenase (GDH) and lactate dehydrogenase (LDH)) and a biocompatible reagent for cell membrane staining. Experimental results show that the silica nanoparticles are a good biocompatible solid support for enzyme immobilization. The immobilized enzyme molecules on the nanoparticle surface have shown excellent enzymatic activity in their respective enzymatic reactions. The nanoparticle surface biochemical functionalization demonstrates the feasibility of using nanoparticles for biosensing and biomarking applications.     

二氧化硅@聚合物同轴纳米纤维

The preparation and formation mechamsm ot silica/polyvinylpyrrolidone(PAN) coaxial nanofibers were presented in this paper. The PVP-PAN composite nanofibers were obtained via an electrospinning technique, while SiO2 nanoparticles were prepared according to a Stoeher method. The measurements of water contact angle(WCA), the compared results of silica coating PVPPAN composite nanofibers with PAN nanofibers indicate that much PVP resided on the composite nanofiber surface, which resuks in the occurrence of SiO2@polymer coaxial nanofibers due to the formation of hydrogen bonding between silica and composite nanofibers and subsequent adsorption of silica on the fiber surface.     

Two layered silica protective film made by a spray-and-dip coating method on 304 stainless steel

The silica coating has attracted much attention because of its superior corrosion resistance with almost no harm to human health and to the environment. In this study, a two layered silica film was tried to get an enhanced corrosion resistance. The silica film was prepared on the hairline finish 304 stainless steel surfaces by-a-spray- and subsequent-dip-coating process. The spray coating solution was prepared by mixing sodium silicate solution, silica colloid, tetraethyl orthosilicate (TEOS), methyltriethoxysilane (MTES), ethanol, and distilled water. Then the solution was sprayed onto the stainless steel surface, and was dried and heat treated. The dip coating solution was prepared by a simple mixing of TEOS and acidic water into ethanol, and the prior spray coated sample was dipped into the solution. The outer dip coated layer was intended to cover spray coated rough and porous layer and hence to enhance the corrosion resistance. A homogeneous and crack free surface was successfully obtained after the dip coating. The prepared silica film was characterized using scanning electron microscopy, potentiodynamic polarization scan, and electrochemical impedance spectroscopy. The two layered film showed an enhanced corrosion resistance. The enhancement was attributed to a protecting effect of the dip coated layer where the diffusion of ionic species was successfully impeded.     

A general method for the controlled embedding of nanoparticles in silica colloids

A novel method for the controlled embedding of multiple nanoparticles of various materials, such as gold nanoparticles, quantum dots, and magnetic nanoparticles, in silica colloids is presented. After adsorption of the amphiphilic polymer poly(vinylpyrrolidone) on hydrophobic or hydrophilic stabilized nanoparticles, these are adsorbed on silica spheres and covered by variable-thickness silica shells. This silica coating protects the embedded nanoparticles against chemical transformations, which is of crucial importance for the biocompatibility of particles containing toxic elements. Moreover, it is found that the optical properties of the nanoparticles are retained. Possible applications of multicore particles are briefly discussed.     

One-step coating of fluoro-containing silica nanoparticles for universal generation of surface superhydrophobicity

Stable superhydrophobic surfaces with water contact angles over 170 degrees and sliding angles below 7 degrees were produced by simply coating a particulate silica sol solution of co-hydrolysed TEOS/fluorinated alkyl silane with NH(3).H(2)O on various substrates, including textile fabrics (e.g. polyester, wool and cotton), electrospun nanofibre mats, filter papers, glass slides, and silicon wafers.     

Reverse microemulsion-mediated synthesis of silica-coated gold and silver nanoparticles

A reverse microemulsion method is reported for preparing monodispersed silica-coated gold (or silver) nanoparticles without the use of a silane coupling agent or polymer as the surface primer. This method enables a fine control of the silica shell thickness with nanometer precision. As compared to the St?ber method reported for direct silica coating, which can only coat large gold particles ( approximately 50 nm in diameter) at low concentrations (<1.5 x 10(10) particles/mL), this new approach is capable of coating gold particles of a wide range of sizes (from 10 to 50 nm) at a much higher concentration ( approximately 1.5 x 10(13) particles/mL). Moreover, it enables straightforward surface functionalization via co-condensation between tetraethyl orthosilicate and another silane with the desired functional groups. The functional groups introduced by this method are readily accessible and thus useful for various applications.     

A novel route for immobilization of oligonucleotides onto modified silica nanoparticles

A novel approach for immobilization of probe oligonucleotides that uses zirconium phosphate modified silica nanoparticles is proposed. The surface modification of nanoparticles was carried out in two stages. Initially binding of Zr4+ to the surface of silica nanoparticles and later treated with phosphoric acid for terminal phosphate groups. Oligonucleotide probes modified with amine group at 5'-end were strongly binds to the phosphate terminated silica nanoparticles with imidazole in presence of 0.1 mol L(-1) EDC [N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide], as phosphate groups are more reactive towards amine group. Various studies, i.e., synthesis of silica nanoparticles, their surface modification, probe immobilization, measurement of hybridization and effect of bovine serum albumin (BSA) were carried out during optimization of reaction conditions. The significant reduction in the background signal was observed by treating the probe modified silica nanoparticles with bovine serum albumin prior to hybridization. The probe modified silica nanoparticles were retained their properties and the hybridization was induced by exposure of single-stranded DNA (ssDNA) containing silica nanoparticles to the complementary DNA in solution. The decrease in the fluorescence signal for one mismatch and three mismatch was observed upon hybridization of probe with target DNAs, while there was no response for the random target ssDNA under the same experimental conditions. The intensity of fluorescence signal was linear to the concentration of target DNA ranging from 3.9 x 10(-9) to 3.0 x 10(-6)mol L(-1). A detection limit of 1.22 x 10(-9) mol L(-1) of oligonucleotides can be estimated. The proposed hybridization assay is simple and possesses good analytical characteristics and it can provide an effective and efficient route in the development of DNA biosensors and biochips.     

Zwitteration as an alternative to PEGylation

A direct, head-to-head comparison of the efficacy of a zwitterionic versus a poly(ethylene glycol), PEG, coating in preventing protein adsorption to silica and aggregation of silica nanoparticles is presented. The same siloxane coupling chemistry was employed to yield surfaces with similar coverages of both types of ligand. Nanoparticle and planar surfaces were challenged with salt, serum, lysozyme, and serum albumin at 25 and 37 °C. While both types of surface modification are highly effective in preventing protein adsorption and nanoparticle aggregation, the zwitterion provided monolayer-type coverage with minimal thickness, whereas the PEG appeared to yield a more three-dimensional coating. The mechanism for adsorption resistance is thought to be based on preventing ion pairing between protein and surface charges, which releases counterions and water molecules, an entropic driving force enough to overcome a disfavored enthalpy of adsorption.