Surface-modified Silica Nanoparticles Research Articles

Preparation of transparent silica–PMMA nanocomposite hard coatings

The preparation of silica–PMMA nanocomposite was reported. The surface modified-silica nanoparticles can be well dispersed in organic solvent and incorporated into the polymer resin. The nanocomposite showed improved mechanical property and can be applied on different acrylic functional materials. DSC analysis showed that the glass transition temperature of the hybrids was increased with increasing content of silica. Good transparency (>90%) and hardness grade (>5H) is observed in nanocomposite with 10 wt% silica content.

Effect of particle size on surface modification of silica nanoparticles by using silane coupling agents and their dispersion stability in methylethylketone

The effect of particle size on the reactivity of hexyltrimethoxysilane (C6S) with the particle surface was studied by using silica nanoparticles (SNPs) with different diameters (30 or 200 nm). In case of 30-nm SNPs, a large amount of isolated silanol was observed. On the other hand, in the case of 200-nm SNPs, the amount of hydrogen bonded silanol and hydrogen bonded water molecules at the surface of the SNPs increased. Since the hydrogen bonded silanol and the hydrogen bonded water enhanced the reaction of C6S with SNPs, the chemisorbed C6S on 200-nm SNPs was larger than that on 30-nm SNPs. Furthermore, the effects of surface modification on the dispersion stability in MEK were studied using viscosity measurements and surface force measurements by the AFM colloid probe method. The viscosity of the dilute SNPs/MEK suspension did not change by the chemisorptions of C6S; however, the viscosity of dense suspension reduced effectively by surface modification. It was estimated that the suspension viscosity reduced effectively when the mean particle surface distance in the suspension was near to the distance where the repulsive force appeared by the surface force measurements using the colloid probe AFM.

Surface modification of silica nanoparticles to reduce aggregation and nonspecific binding.

In this article, a systematic study of the design and development of surface-modification schemes for silica nanoparticles is presented. The nanoparticle surface design involves an optimum balance of the use of inert and active surface functional groups to achieve minimal nanoparticle aggregation and reduce nanoparticle nonspecific binding. Silica nanoparticles were prepared in a water-in-oil microemulsion and subsequently surface modified via cohydrolysis with tetraethyl orthosilicate (TEOS) and various organosilane reagents. Nanoparticles with different functional groups, including carboxylate, amine, amine/phosphonate, poly(ethylene glycol), octadecyl, and carboxylate/octadecyl groups, were produced. Aggregation studies using SEM, dynamic light scattering, and zeta potential analysis indicate that severe aggregation among amine-modified silica nanoparticles can be reduced by adding inert functional groups, such as methyl phosphonate, to the surface. To determine the effect of various surface-modification schemes on nanoparticle nonspecific binding, the interaction between functionalized silica nanoparticles and a DNA chip was also studied using confocal imaging/fluorescence microscopy. Dye-doped silica nanoparticles functionalized with octadecyl and carboxylate groups showed minimal nonspecific binding. Using these surface-modification schemes, fluorescent dye-doped silica nanoparticles can be more readily conjugated with biomolecules and used as highly fluorescent, sensitive, and reproducible labels in bioanalytical applications.

Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate

In this study we modified the surface of silica nanoparticles with methyl methacrylate by UV-induced graft polymerization. It is a surface-initiated polymerization reaction induced by ultraviolet irradiation. The resulting organic–inorganic nanocomposites were near-monodisperse and fabricated without homopolymerization of the monomer. Substantial increase in mean particle size was observed by SEM image analysis after UV-induced grafting of methyl methacrylate onto pure silica particles. FT-Raman spectroscopy and X-ray photoelectron spectroscopy studies of these materials revealed the successful grafting of methyl methacrylate onto the silica surface. The formation of a covalent bond between the grafted PMMA chains and silica surface was indicated by FT-Raman spectra. Thermogravimetric analysis of the PMMA-grafted silica particles indicated the polymer contents in good agreement with SEM photographs.

Label-Free Detection of Peptide Nucleic Acid−DNA Hybridization Using Localized Surface Plasmon Resonance Based Optical Biosensor

The development of label-free optical biosensors for DNA and other biomolecules has the potential to impact life sciences as well as screening in medical and environmental applications. In this report, we developed a localized surface plasmon resonance (LSPR) based label-free optical biosensor based on a gold-capped nanoparticle layer substrate immobilized with peptide nucleic acids (PNAs). PNA probe was designed to recognize the target DNA related to tumor necrosis factor. The nanoparticle layer was formed on a gold-deposited glass substrate by the surface modified silica nanoparticles using silane-coupling reagent. The optical properties of gold-capped nanoparticle layer substrate were characterized through monitoring the changes in the absorbance strength, as the thickness of the biomolecular layer increased with hybridization. The detection of PNA-DNA hybridization with target oligonucleotides and PCR-amplified real samples were performed with a limit of detection value of 0.677 pM target DNA. Selective discrimination against a single-base mismatch was also achieved. Our LSPR-based biosensor with the gold-capped nanoparticle layer substrate is applicable to the design of biosensors for monitoring of the interaction of other biomolecules, such as proteins, whole cells, or receptors with a massively parallel detection capability in a highly miniaturized package.

Self-Regulated Structures in Nanocomposites by Directed Nanoparticle Assembly

Adding surface-modified silica nanoparticles (NPs) to polymer blend films, we demonstrate that directed interfacial segregation of NPs stabilize either three-dimensional (3D) interpenetrating or 2D discrete structures at high and low volume fractions of NPs, respectively. A simple interfacial energy argument provides a general guideline for predicting whether the NPs are directed to the interface between phases or into one phase. The final morphology and domain size can be predicted from the volume fraction of NPs, film thickness, and NP size.

Novel Retention System Based on (2,3-Epoxypropyl)trimethylammonium Chloride Modified Silica Nanoparticles and Anionic Polymer

This work investigated the synthesis, characterization, and evaluation of surface-modified cationic silica nanoparticles as part of retention or flocculation systems. Quaternary amine groups were introduced onto the fumed silica surface using the cationic reagent (2,3-epoxypropyl)trimethylammonium chloride under various reaction conditions. To characterize the surface properties of the modified silica particles, the ζ potential and charge density were determined. Dynamic flocculation experiments showed that, when used alone, the cationic silica nanoparticles contributed little to inducing clay flocculation. However, when the nanoparticles were used in conjunction with an anionic polymer of high Mw and low charge density, significant improvement in the flocculation of fine clay particles was achieved. The interaction between the cationic silica nanoparticles and anionic polymer, as well as the silica adsorption behavior on clay surfaces, was explored. The mechanism of flocculation induced by the dual-compo...

Surface modification of silica nanoparticles: a new strategy for the realization of self-organized fluorescence chemosensors

The self-organization of the proper subunits of a fluorescence chemosensor on the surface of silica nanoparticles allows the easy design and realization of new effective sensing systems. Commercially available silica particles (20 nm diameter) were functionalized with triethoxysilane derivatives of selective Cu(II) ligands and fluorescent dyes. Grafting of the sensor components to the particle surface ensures the spatial proximity between the sensor components and, as a consequence, binding of Cu(II) ions by the ligand subunits leads to quenching of the fluorescent units emission. In 9 : 1 DMSO–water solution, the coated silica nanoparticles (CSNs) selectively detect copper ions down to nanomolar concentrations. The operative range of the sensors can be tuned either by switching the ligand units or by modification of the components ratio. Sensors with the desired photophysical properties can be easily prepared by using different fluorescent dyes. Moreover, the organization of the network of sensor components gives rise to cooperative and collective effects: on one hand, the ligand subunits bound to the particle surfaces cooperate to form multivalent binding sites with an increased affinity for the Cu(II) ions; on the other hand, binding of a single metal ion leads to the quenching of several fluorescent groups producing a remarkable signal amplification.

Localized surface plasmon resonance based optical biosensor using surface modified nanoparticle layer for label-free monitoring of antigen–antibody reaction

In recent years, label-free biosensors not requiring external modifications have been receiving intense attention. A label-free optical biosensor, which retains many of the desirable features of conventional surface plasmon resonance (SPR) reflectometry, namely, the ability to monitor the kinetics of biomolecular interactions in real-time without a label has been developed with several important advantages: the biosensor device is easy to fabricate, and simple to implement, requiring only an UV–Vis spectrophotometer or flatbed scanner. Importantly, the label-free optical biosensor can be easily multiplexed to enable high-throughput monitoring of biomolecular interactions in an arraybased format. In this research,the development of a localized surface plasmon resonance (LSPR)-based label-free optical biosensor using a surface modified nanoparticle layer is aimed. This optical detection method promises to offer a massively parallel detection capability in a highly miniaturized package. The two-dimensional nanoparticle layer was formed by the surface modified silica nanoparticles. The optical properties and surface analysis of nanoparticle layer substrate were characterized through transmissionmeasurements and atomic force microscopy (AFM). Simultaneously, the nanoparticle layer substrate was applied to the optical LSPR-based biosensor for label-free monitoring of the antigen–antibody reaction. The anti-fibrinogen antibody wasimmobilized onto the nanoparticle layer substrate surface. Different concentrations of fibrinogen were introduced to the anti-fibrinogen antibody immobilized nanoparticle layer substrate surface, and the change in the absorption spectrum, caused by the antigen–antibody reaction, was observed. By using this anti-fibrinogen antibody immobilized nanoparticle layer substrate; the detection limit of this optical LSPR-based biosensor was 10 ng/ml.

Mechanical properties of silica nanoparticle reinforced poly(ethylene 2, 6-naphthalate)

We added surface-modified silica nanoparticles to poly(ethylene 2,6-naphthalate) (PEN) to investigate their effect on the mechanical properties on the PEN nanocomposite material. The torque and total torque values of the composites decreased in the silica nanoparticle composites. The tensile modulus of the composites reinforced with unmodified silica nanoparticles increased upon increasing the silica content, while the tensile strength and elongation decreased accordingly. In contrast, stearic acid-modified, silica nanoparticle reinforced PEN composites exhibited an increase in elongation and a decrease in tensile modulus upon addition of the silica nanoparticles because the stearic acid that had adsorbed onto the surface of the silica nanoparticle in multilayers could act as a plasticizer during melt compounding. Stearic acid modification had a small effect on the crystallization behavior of the composites. We calculated theoretical values of the tensile modulus using the Einstein, Kerner, and Nielsen equations and compared these values with the experimental data obtained from the composites. The parameters calculated using the Nielsen equation and the Nicolais- Narkis model revealed that the interfacial adhesion between silica nanoparticles and the PEN matrix could be improved.

Characterization of Surface Modified Silica Nanoparticles by 29 Si Solid State NMR Spectroscopy

Various aerosils surface modified with silane reagents were prepared and investigated by 29Si solid state NMR spectroscopy. The mode of bonding onto the silanol surface (mono- or divalent) can be specified by comparison with chemical shifts from solution. A detailed analysis also leads to the detection of products formed via hydrosilylation reactions. A rough quantification of the surface loading can be obtained by a signal deconvolution process of the silanol resonances on the Aerosil surface.