Photo‐induced surface transformations of silica nanocomposites

The photo‐induced, physicochemical surface transformations to silica nanoparticle (SiNP) ‐ epoxy composites have been investigated. The silica nanocomposites (SiNCs) were prepared using a two‐part epoxy system with a 10% mass fraction of SiNPs and exposed to varying doses of high intensity, ultraviolet (UV) radiation at wavelengths representative of the solar spectrum at sea level (290 nm to 400 nm) under constant temperature and humidity. Visibly apparent physical modifications to the SiNC surface were imaged with scanning electron microscopy. Surface pitting and cracking became more apparent with increased UV exposure. Elemental and surface chemical characterization of the SiNCs was accomplished through X‐ray energy dispersive spectroscopy and X‐ray photoelectron spectroscopy, while attenuated total reflectance Fourier transform infrared spectroscopy revealed changes to the epoxy's structure. During short UV exposures, there was an increase in the epoxy's overall oxidation, which was accompanied by a slight rise in the silicon and oxygen components and a decrease in overall carbon content. The initial carbon components (e.g. aliphatic, aromatic and alcohol/ether functionalities) decreased and more highly oxidized functional groups increased until sufficiently long exposures at which point the surface composition became nearly constant. At long exposure times, the SiNC's silicon concentration increased to form a surface layer composed of approximately 75% silica (by mass). Published 2012. This article is a U.S. Government work and is in the public domain in the USA.     

Diazonium Salts as Grafting Agents and Efficient Radical‐Hydrosilylation Initiators for Freestanding Photoluminescent Silicon Nanocrystals

The reactivity of diazonium salts towards freestanding, photoluminescent silicon nanocrystals (SiNCs) is reported. It was found that SiNCs can be functionalized with aryl groups by direct reductive grafting of the diazonium salts. Furthermore, diazonium salts are efficient radical initiators for SiNC hydrosilylation. For this purpose, novel electron‐deficient diazonium salts, highly soluble in nonpolar solvents were synthesized. The SiNCs were functionalized with a variety of alkenes and alkynes at room temperature with short reaction times.     

Recognition of melting of nanoparticle catalysts with cubically shaped Co3O4 nanoparticles

Cubically shaped cobalt oxide nanoparticle catalysts were used for the first time to investigate the melting of the nanoparticle catalysts responsible for the synthesis of silica nanocoils at 1050 degrees C and straight nanowires at 1100 degrees C. Cobalt nanoparticles remained morphologically highly anisotropic after the growth of nanocoils at 1050 degrees C, whereas they became predominately spherical after straight nanowires were made at 1100 degrees C. These results strongly indicated that cobalt nanoparticles responsible for the synthesis of straight nanowires were completely molten and that melting occurred to these nanoparticles between 1050 and 1100 degrees C.     

Preparation of well-defined polystyrene/silica hybrid nanoparticles by ATRP

Immobilization of the atom transfer radical polymerization (ATRP) macroinitiators at the silica nanoparticle surfaces was achieved through surface modification with excess toluene-2,4-diisocynate (TDI), after which the residual isocyanate groups were converted into ATRP macroinitiators. Structurally well-defined polystyrene chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined, densely grafted outer polystyrene by ATRP, which was initiated by the as-synthesized silica-based macroinitiator. FTIR, NMR and gel permeation chro-matography (GPC) were used to characterize the polystyrene/silica hybrid particles.     

Diamond-hexagonal semiconductor nanocones with controllable apex angle

We report on the synthesis of nanostructured and crystalline tapered Si and Ge polyhedra via metal-catalyzed chemical vapor deposition. These Si and Ge nanocones (SiNCs, GeNCs) possess tips with near-atomic sharpness, micron-scaled bases, hexagonal cross-sections, and controllable apex angles. High-resolution transmission electron microscopy, selected-area electron diffraction and Raman scattering spectroscopy and analysis indicate that the SiNCs are of the diamond-hexagonal Si(IV) phase.     

Direct Arylation of Silicon Nanocrystals with Hexadehydro-Diels–Alder-Derived Benzynes

Colloidal silicon nanocrystals (SiNCs) have garnered significant interest in optoelectronics and biomedical applications. Direct arylation provides pathways to enhance the solution processability of particles and manipulate the photophysical and electronic properties of SiNCs. Unfortunately, existing methods employed to prepare aryl-functionalized SiNCs are based on organometallic coupling or transition-metal-catalyzed strategies, which require metal-based reagents for preactivation or the precursors and complicated post-treatment processes for product purification. Herein, we demonstrate a metal-free method that directly functionalizes SiNCs with aryl-based ligands. We design a series of benzyne derivatives formed from the thermal cyclization of predesigned alkynes, allowing efficient arylation on hydride-terminated silicon surfaces under mild conditions. These aryl-functionalized SiNCs exhibit strong blue emissions with nanosecond-scaled decay, suggesting the formation of a new radiative recombination channel on SiNC surfaces.     

Functionalization of Hydride‐Terminated Photoluminescent Silicon Nanocrystals with Organolithium Reagents

Hydride‐terminated photoluminescent silicon nanocrystals (SiNCs) were functionalized with organolithium compounds. The reaction is proposed to proceed through cleavage of Si?Si bonds and formation of a Si?Li surface species. The method yields colloidally stabilized SiNCs at room temperature with short reaction times. SiNCs with mixed surface functionalities can be prepared in an easy two‐step reaction by this method by quenching of the Si?Li group with electrophiles or by addressing free Si?H groups on the surface with a hydrosilylation reaction.     

Monodisperse cobalt ferrite nanomagnets with uniform silica coatings

Ferro- and ferrimagnetic nanoparticles are difficult to manipulate in solution as a consequence of the formation of magnetically induced nanoparticle aggregates, which hamper the utility of these particles for applications ranging from data storage to bionanotechnology. Nonmagnetic shells that encapsulate these magnetic particles can reduce the interparticle magnetic interactions and improve the dispersibility of the nanoparticles in solution. A route to create uniform silica shells around individual cobalt ferrite nanoparticles--which uses poly(acrylic acid) to bind to the nanoparticle surface and inhibit nanoparticle aggregation prior to the addition of a silica precursor--was developed. In the absence of the poly(acrylic acid) the cobalt ferrite nanoparticles irreversibly aggregated during the silica shell formation. The thickness of the silica shell around the core-shell nanoparticles could be controlled in order to tune the interparticle magnetic coupling as well as inhibit magnetically induced nanoparticle aggregation. These ferrimagnetic core-silica shell structures form stable dispersion in polar solvents such as EtOH and water, which is critical for enabling technologies that require the assembly or derivatization of ferrimagnetic particles in solution.     

Size-dependent interaction of silica nanoparticles with different surfactants in aqueous solution

The size-dependent interaction of anionic silica nanoparticles with ionic (anionic and cationic) and nonionic surfactants has been studied using small-angle neutron scattering (SANS). The surfactants used are anionic sodium dodecyl sulfate (SDS), cationic dodecyltrimethyl ammonium bromide (DTAB), and nonionic decaoxyethylene n-dodecylether (C(12)E(10)). The measurements have been carried out for three different sizes of silica nanoparticles (8, 16, and 26 nm) at fixed concentrations (1 wt % each) of nanoparticles and surfactants. It is found that irrespective of the size of the nanoparticles there is no significant interaction evolved between like-charged nanoparticles and the SDS micelles leading to any structural changes. However, the strong attraction of oppositely charged DTAB micelles with silica nanoparticles results in the aggregation of nanoparticles. The number of micelles mediating the nanoparticle aggregation increases with the size of the nanoparticle. The aggregates are characterized by fractal structure where the fractal dimension is found to be constant (D ≈ 2.3) independent of the size of the nanoparticles and consistent with diffusion-limited-aggregation-type fractal morphology in these systems. In the case of nonionic surfactant C(12)E(10), micelles interact with the individual silica nanoparticles. The number of adsorbed micelles per nanoparticle increases drastically whereas the percentage of adsorbed micelles on nanoparticles decreases with the increase in the size of the nanoparticles.     

Fluorescent core-shell silica nanoparticles: towards "Lab on a Particle" architectures for nanobiotechnology

Novel nanoscale fluorescent materials are integral to the progress of emergent fields such as nanobiotechnology and facilitate new research in a variety of contexts. Sol-gel derived silica is an excellent host material for creating fluorescent nanoparticles by the inclusion of covalently-bound organic dyes. Significant enhancements in the brightness and stability of organic dye emission can be achieved for silica-based core-shell nanoparticle architectures at length scales down to tens of nanometers with narrow size distributions. This tutorial review will highlight these findings and describe the evolution of the fluorescent core-shell silica nanoparticle concept towards integration of multiple functionalities including mesoporosity, metal nanoshells and quantitative chemical sensing. These developments point towards the development of "lab on a particle" architectures with promising prospects for nanobiotechnology, drug development and beyond.     

A photoelectrochemical device with a nanostructured SnO2 electrode modified with composite clusters of porphyrin-modified silica nanoparticle and fullerene

A silica nanoparticle has been successfully employed as a nanoscaffold to self-organize porphyrin and C60 molecules on a nanostructured SnO2 electrode. The quenching of the porphyrin excited singlet state on the silica nanoparticle is suppressed significantly, showing that silica nanoparticles are promising scaffolds for organizing photoactive molecules three-dimensionally in nanometer scale. Marked enhancement of the photocurrent generation was achieved in the present system compared with the reference system, where a gold core was employed as a scaffold of porphyrins instead of a silica nanoparticle. The rather small incident photon-to-current efficiency relative to a similar photoelectrochemical device using a silica microparticle may result from poor electron and hole mobility in the composite film due to poor connection between the composite clusters of a porphyrin-modified silica nanoparticle and C60 in micrometer scale.     

Synthesis and Characterization of pH‐Sensitive Positive‐charge Silica Nanoparticles for Oral Anionic Drug Delivery

The objective of this study is to utilize the pH sensitivity of modified mesoporous silica nanoparticles (MSN) for oral drug delivery. In the first time, a pH‐sensitive ionic liquid was synthesized through the quaternization of 3‐aminopropyltrimethoxysilane (3‐ATMS) with sodium monochloroacetate (SMCA). Then, silica nanoparticle was modified by this pH‐sensitive ionic liquid and converted to a pH‐sensitive positive‐charge silica nanoparticle (PCSN). The nanoparticle was characterized by FTIR and SEM. Naproxen as anionic drug molecules was entrapped in this pH‐sensitive positive‐charge silica nanoparticles (PCSN) and the in vitro release profiles were established separately in both (SGF, pH 1) and (SIF, pH 7.4).     

IDM-1: A Zeolite with Intersecting Medium and Extra-Large Pores Built as an Expansion of Zeolite MFI

IDM-1 is a new silica zeolite with an ordered and well-defined framework constructed by alternating pentasil layers and interrupted layers, giving rise to an intersecting system of straight medium pores and undulating extra-large lobed pores. This unique structure was solved by rotation electron diffraction and refined against synchrotron powder X-ray diffraction data. Despite the presence of both Si(OSi)₃(OH) and Si(OSi)₂(OH)₂ sites, this new zeolite presents high thermal stability, withstanding calcination even to 1000 °C. The location of defects at specific sites of the structure results in alternating hydrophobic SiO₂ and hydrophilic SiO_(2−x)(OH)_2x intracrystalline regions. This peculiar combination of intersecting medium and extra-large pores and alternating regions of different chemical character may provide this zeolite with unique catalytic properties.     

Direct visual detection of DNA based on the light scattering of silica nanoparticles on a human papillomavirus DNA chip

A detection system for a human papillomavirus (HPV) DNA chip based on the light scattering of aggregated silica nanoparticle probes is presented. In the assay, a target HPV DNA is sandwiched between the capture DNA immobilized on the chip and the probe DNA immobilized on the plain silica nanoparticle. The spot where the sandwich reaction occurs appears bright white and is readily distinguishable to the naked eye. Scanning electron microscopy images clearly show the aggregation of the silica nanoparticle probes. When three different sized (55 nm, 137 nm, 286 nm) plain silica nanoparticles were compared, probes of the larger silica nanoparticles showed a higher scattering intensity. Using 286-nm silica nanoparticles, the spots obtained with 200 pM of target DNA were visually detectable. The demonstrated capability to detect a disease related target DNA with direct visualization without using a complex detection instrument provides the prerequisite for the development of portable testing kits for genotyping.     

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.     

Robust synthesis of mono-dispersed spherical silica nanoparticle from rice husk for high definition latent fingermark development

Silica is one of the most functional metalloid oxides with a widespread application as semiconductor, fillers, silicone and ceramic primarily due to its structural versatility. In this work, a robust step-wise thermochemical treatment was successfully formulated for the controlled fabrication of high-purity mono-dispersed spherical silica nanoparticle from rice husk. The silica nanoparticle with the desired morphology was formed in two stages; thermal-assisted seed particle formation followed by particle growth through acidification of the solvent modified sodium silicate solution. The obtained powder was characterised, and the effectiveness of the powder for latent fingermark development across varied donors and surfaces was tested at the introductory level. The formed spherical particles were in the range of 200 to 400 nm, as confirmed by FESEM and HRTEM analysis. Minimising the degree of silica nanoparticle agglomeration notably affected their selectivity to fingermark residue. There was a striking improvement in the selectivity of the silica nanoparticle to fingermark residue. The improvement was attributed to the strong interaction between the silica nanoparticle and the lipid components in the fingermark residue, as compared to the commercial white powder that works solely based on mechanical adherence. Additionally, the size and morphology of the fabricated silica nanoparticle were optimised to enhance the clarity of the developed fingermark. Findings of this study could improve quality of fingermarks obtained in a crime scene due to considerably lower background interference without compromising the effectiveness of fingermark development.     

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.     

Anisotropic magnetic porous assemblies of oxide nanoparticles interconnected via silica bridges for catalytic application

We report the microfluidic chip-based assembly of colloidal silanol-functionalized silica nanoparticles using monodisperse water-in-oil droplets as templates. The nanoparticles are linked via silica bridges, thereby forming superstructures that range from doublets to porous spherical or rod-like micro-objects. Adding magnetite nanoparticles to the colloid generates micro-objects that can be magnetically manipulated. We functionalized such magnetic porous assemblies with horseradish peroxidase and demonstrate the catalytic binding of fluorescent dye-labeled tyramide over the complete effective surface of the superstructure. Such nanoparticle assemblies permit easy manipulation and recovery after a heterogeneous catalytic process while providing a large surface similar to that of the individual nanoparticles.     

IDM‐1: A Zeolite with Intersecting Medium and Extra‐Large Pores Built as an Expansion of Zeolite MFI

IDM‐1 is a new silica zeolite with an ordered and well‐defined framework constructed by alternating pentasil layers and interrupted layers, giving rise to an intersecting system of straight medium pores and undulating extra‐large lobed pores. This unique structure was solved by rotation electron diffraction and refined against synchrotron powder X‐ray diffraction data. Despite the presence of both Si(OSi)₃(OH) and Si(OSi)₂(OH)₂ sites, this new zeolite presents high thermal stability, withstanding calcination even to 1000 °C. The location of defects at specific sites of the structure results in alternating hydrophobic SiO₂ and hydrophilic SiO_(2?x)(OH)_2x intracrystalline regions. This peculiar combination of intersecting medium and extra‐large pores and alternating regions of different chemical character may provide this zeolite with unique catalytic properties.     

Photoreactive azido-containing silica nanoparticle/polycation multilayers: durable superhydrophobic coating on cotton fabrics

In this study, we report the functionalization of silica nanoparticles with highly photoreactive phenyl azido groups and their utility as a negatively charged building block for layer-by-layer (LbL) electrostatic assembly to produce a stable silica nanoparticle coating. Azido-terminated silica nanoparticles were prepared by the functionalization of bare silica nanoparticles with 3-aminopropyltrimethoxysilane followed by the reaction with 4-azidobenzoic acid. The azido functionalization was confirmed by FTIR and XPS. Poly(allylamine hydrochloride) was also grafted with phenyl azido groups and used as photoreactive polycations for LbL assembly. For the photoreactive silica nanoparticle/polycation multilayers, UV irradiation can induce the covalent cross-linking within the multilayers as well as the anchoring of the multilayer film onto the organic substrate, through azido photochemical reactions including C-H insertion/abstraction reactions with surrounding molecules and dimerization of azido groups. Our results show that the stability of the silica nanoparticle/polycation multilayer film was greatly improved after UV irradiation. Combined with a fluoroalkylsilane post-treatment, the photoreactive LbL multilayers were used as a coating for superhydrophobic modification of cotton fabrics. Herein the LbL assembly method enables us to tailor the number of the coated silica nanoparticles through the assembly cycles. The superhydrophobicity of cotton fabrics was durable against acids, bases, and organic solvents, as well as repeated machine wash. Because of the unique azido photochemistry, the approach used here to anchor silica nanoparticles is applicable to almost any organic substrate.