Facile Synthesis via Electrospinning of a Tetraethoxysilane/Polyvinylpyrrolidone Sol and Characterization of Ultrafine Crystalline SiO2 Nanofibers

Silica nanofibers were developed by a combination of an electrospinning technique and the sol–gel method. In the process, tetraethoxysilane (TEOS), polyvinylpyrrolidone (PVP) and N, N-Dimethylformamide (DMF) were the components of the sol for the production of silica/PVP composite nanofibers by electrospinning. During a thermal treatment, PVP in the hybrid fibers was removed; in this way, we produced ultrafine crystalline silica nanofibers. Scanning electron microscopy, energy dispersive X-ray analyzer, X-ray diffraction, and Fourier transform infrared spectroscopy were used to characterize the nanofibers. These silica nanofibers should be potentially useful in catalyst support, adsorbent, energy storage, and gas storage applications.     

Synthesis and spectroscopic characterization of Kiton Red-620 dye doped silica gel rods

The work was carried out to achieve two different but interdependent objectives; one to synthesis a transparent silica matrix with enough strength and thermal stability, by sol–gel technique, to host an organic dye molecule without quenching its fluorescence and two to find the probability if the said material is suitable for the construction of solid state dye lasers. Crack-free transparent silica gel rods with good mechanical strength, thermal stability and dimensions were successfully synthesized by sol–gel techniques. The rods were doped with Kiton Red-620 dye in different concentration separately. Effect of various synthesis parameters like time, temperature and aging condition was extensively studied to obtain crack-free silica rods doped with dye. Optical properties of prepared rods were studied by FTIR, UV/VIS–NIR and fluorescence spectroscopy. It is observed that Kiton Red-620 dye doped silica gel rods show good fluorescence with sharp peaks in the visible range. Their UV–VIS spectrum indicates the absorption in visible range. Thermal stability of rods were studied by DSC/TGA methods. Eventually it is found that these dye doped silica gel materials explore the possibility for new solid-state dye laser materials.     

Photopatternable and refractive-index-tunable sol–gel-derived silica–titania nanohybrid materials

Silica–titania nanohybrid materials were synthesized using functionalized organosilanes and organically chelated titanium alkoxide in a simple sol–gel process. The synthesized silica–titania nanohybrid materials exhibited good solution processability and homogeneous dispersion without any phase separation regardless of the ratio of the mixture of the two components. The silica–titania nanohybrid materials exhibited good photoinitiator solubility and effective photocurability with a high degree of degree under ultraviolet (UV) exposure. Because of their high photocurability and solution processability, the silica–titania nanohybrid materials were readily converted into silica–titania nanohybrid films and were used for direct photopatterning without requiring the developing process used in the photomask method. In particular, the refractive indices of the silica–titania nanohybrid materials could be decreased by decreasing the content of chelated titanium alkoxide in the materials. Moreover, the silica–titania nanohybrid films exhibited high transmittance in the visible wavelength range, and their surface roughnesses were very smooth, exhibiting values <1 nm. On the basis of these observations, the fabricated silica–titania nanohybrid materials can be used in solution-processable materials for producing optical and electro-optical elements.     

Densification of sol–gel silica thin films induced by hard X‐rays generated by synchrotron radiation

In this article the effects induced by exposure of sol–gel thin films to hard X‐rays have been studied. Thin films of silica and hybrid organic–inorganic silica have been prepared via dip‐coating and the materials were exposed immediately after preparation to an intense source of light of several keV generated by a synchrotron source. The samples were exposed to increasing doses and the effects of the radiation have been evaluated by Fourier transform infrared spectroscopy, spectroscopic ellipsometry and atomic force microscopy. The X‐ray beam induces a significant densification on the silica films without producing any degradation such as cracks, flaws or delamination at the interface. The densification is accompanied by a decrease in thickness and an increase in refractive index both in the pure silica and in the hybrid films. The effect on the hybrid material is to induce densification through reaction of silanol groups but also removal of the organic groups, which are covalently bonded to silicon via Si—C bonds. At the highest exposure dose the removal of the organic groups is complete and the film becomes pure silica. Hard X‐rays can be used as an efficient and direct writing tool to pattern coating layers of different types of compositions.     

Sol–gel concave micro-lens arrays fabricated by combining the replicated PDMS soft mold with UV-cured imprint process

Photosensitive TiO₂/organically modified silane organic–inorganic hybrid thin films were synthesized by combining a low-temperature sol–gel process with a spin-coating method. Optical transmittance properties and the photochemical activities of the planar hybrid films were characterized by UV–Visible spectroscopy and Fourier transform infrared spectroscopy. Advantages for fabrication of the concave micro-lens arrays (MLAs) based on the photosensitive hybrid films were demonstrated by using the replicated polydimethylsiloxane (PDMS) soft mold as the imprint mold and a UV soft imprint technique. Morphological and surface profile properties of the master, the PDMS soft molds and the as-fabricated sol–gel concave MLAs were observed by scanning electron microscopy and laser confocal scanning microscopy. Contact angles of water on the PDMS soft molds baked at different temperatures were studied. Optical imaging properties of the as-fabricated concave MLAs were confirmed by a self-made optical test system. Results indicate that the as-prepared photo-patternable hybrid materials have great applicability for the fabrication of photonic components, thus providing an effective method to fabricate concave MLAs based on the as-synthesized hybrid films by combining the UV-cured imprint technique with the replicated PDMS soft mold, which has advantages of simplicity, cost-effective and mass production and potential application in industry production.     

Azobenzene-containing small molecules organic–inorganic hybrid sol–gel materials for photonic applications

Azobenzene-containing germania-ormosil hybrid materials are prepared by combining a low-temperature sol–gel technique with a spin-coating process, which can be used for the simple and low cost fabrication of waveguide devices for photonic applications. The planar waveguide and structural properties of the hybrid waveguide films are characterized by a prism coupling technique and Fourier transform infrared spectroscopy. The effects of azobenzene content and heat treatment temperature on the photo-responsive properties of the hybrid films are also studied by photoirradiation with UV light. The results indicate that the azobenzene in hybrid materials can undergo trans–cis–trans photoisomerization efficiently by photoirradiation with UV light, and surface pattern structure induced due to UV light photoirradiation can be easily observed on such azobenzene-doped hybrid materials. Thus, this as-prepared organic–inorganic hybrid sol–gel material shows promising candidates for optical switch applications and allows for directly integrating on a single chip waveguide device with optical data storage and optical switching devices.     

Nanoparticle-Reinforced Silica Gels with Enhanced Mechanical Properties and Excellent pH-Sensing Performance

Silica gels offer excellent wear resistance, high chemical stability, good insulation, and light transmittance, are therefore promising to engineer 2D sensing films. However, their practical applications are greatly hampered by their poor structural stability, low sensitivity, reliability, and repeatability. Incorporation of nanoelements into glasses and ceramics is a promising new pathway to tackle these challenges. Unfortunately, it is difficult to disperse nanoparticles uniformly in any glass and ceramics. Herein, a facile sol–gel approach is applied to synthesize novel silica gel nanocomposites with dispersed nanoparticles (NPs) as additives and thymol blue as an indicator. Titanium dioxide (TiO₂) NPs with a diameter of 5 nm can be dispersed uniformly in the silica gel, with enhanced modulus and hardness (up to 230% and 138%, respectively) and good alkaline resistance. The addition of nanoparticles improves the film's stability, sensitivity, and repeatability of spectral responses (in pH 1–12), and reduces the indicator leakage. The interaction of indicator with silica gel substrate, nanoparticles, and H⁺ is analyzed to elucidate the principle of reversible color change. This novel simplified method to produce glass-like functional materials under much lower temperatures is groundbreaking in materials science and engineering.     

铝对过渡金属离子掺杂的二氧化硅溶胶凝胶玻璃发光性质的影响

用溶胶凝胶法制备了过渡金属离子(Ni2+,Mn2+和Cu2+)单掺、铝共掺的二氧化硅玻璃,测量了荧光光谱、吸收光谱和红外光谱,研究了Al3+对过镀金属离子在二氧化硅玻璃中发光性质的影响。研究结果表明,Al3+对过渡金属离子的发光性质有着显著影响:Ni2+,Mn2+和Cu+的发光强度大幅度提高,Mn2+的发光峰峰位改变。     

Synthesis and characterization of covalent diphenylalanine nanotube-folic acid conjugates

Traditionally, organosilica nanoparticles have been prepared inside micelles with an external silica shell for mechanical support. Here, we compare these hybrid core–shell particles with organosilica particles that are robust enough to be produced both inside micelles and alone in a sol–gel process. These particles form from octadecyltrimethoxy silane as silica source either in microemulsions, resulting in water-dispersible particles with a hydrophobic core, or precipitate from an aqueous mixture to form particles with both hydrophobic core and surface. We examine size and morphology of the particles by dynamic light scattering and transmission electron microscopy and show that the particles consist of Si–O–Si networks pervaded by alkyl chains using nuclear magnetic resonance, infrared spectroscopy, and thermogravimetric analysis.     

Silica doped tin oxide composite anodes for lithium-ion batteries

Silica doped tin oxide composites prepared by a sol gel method have been studied as negative electrode materials for lithium-ion batteries. The composite powders fired at 500 °C were analysed by means of XRD and SEM and showed that the composite consists of a blend of crystalline and amorphous structure with different particle size distribution. The electrochemical properties of this anode material were examined by charge-discharge measurements and cyclic voltammetry. The silica doped tin oxide composite anode, which was cycled between 0.1 to 2.0 V, showed a reversible capacity of 270 mAh/g. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Reversible Gelation and Phase Transition of Aqueous Solution of Hydrophobically Modified Poly(N‐Isopropylacrylamide)

Abstract

We investigated physical gelation and phase transition of aqueous solutions of hydrophobically modified poly(N‐isopropylacrylamide) (HM‐PNIPAAm) with stearyl acrylate (SA). Aqueous solutions of HM‐PNIPAAm form a reversible gel cross‐linked with hydrophobic aggregations of stearyl groups. The physically cross‐linked HM‐PNIPAAm gel with relatively low SA content shows a two‐step volume transition with increasing temperature. Moreover, overlapping of the reversible gel–sol transition and phase separation results in the phase diagrams of the aqueous solutions of HM‐PNIPAAm, having five distinct regions: dilute sol, gel, gel–sol, sol–sol, and condensed sol regions. The overlapping of the two different phase transitions causes the two‐step volume transition.     

Visible,near-infrared and infrared optical properties of silica aerogels

Silica aerogel is an excellent thermal insulation material with a low thermal conductivity and a high porosity and has attracted great concern in applications. This paper was to experimentally investigate the optical properties of optically thick silica aerogel in the visible, near-infrared and infrared spectrum region. The fiber-loaded silica aerogel sample was prepared through sol–gel technique and supercritical drying process. Silica fibers were added into the aerogel during the preparation procedure to strength the skeleton of aerogel. As a comparison with the fiber-load silica aerogel, a silica fiber composite sample with the same chemical component and different physical structure was also prepared. A simplified two-flux model neglecting the boundary effect was used to describe the radiation propagation characteristics inside the samples. The spectral normal-hemispherical reflectances, transmittances, and normal emittances of silica aerogel and silica fiber samples were measured and compared in the wavelengths of 0.38–15 μm. Then the spectral optical constants of samples were determined using the experimental data. The spectral absorption and scattering coefficients of silica aerogel were within (0.01 cm⁻¹, 31.0 cm⁻¹) and (1.4 cm⁻¹, 25.8 cm⁻¹). The results showed that the spectrum region where the scattering coefficient is low usually corresponds to a high absorption coefficient. In addition, the total radiation properties of samples were predicted at high temperatures. The analysis of optical properties of silica aerogel is necessary to provide valuable data in applications.     

Surface‐enhanced Raman scattering characteristics of CuO : Mn/Ag heterojunction probed by methyl orange: effect of Mn2+ doping

Interest in the synthesis of hybrid substrates for surface‐enhanced Raman scattering (SERS) has surged recently. Hereof, in the present work, a hybrid SERS substrate CuO : Mn/Ag heterojunction has been synthesised. To accomplish this, the nanostructred Ag island film and CuO : Mn nanoparticles are synthesised by vacuum thermal evaporation method and sol–gel method respectively, and thereafter, a heterojunction between the CuO : Mn and Ag is fabricated by adsorption of CuO : Mn (10^‐3 m in ethanol) on Ag island film. Further, the SERS sensitivity of CuO : Mn/Ag heterojunctions has been studied by probing methyl orange. We observed that with Mn‐doping in the lattice of CuO, the SERS signal is enhanced considerably because of ferromagnetic ordering in CuO : Mn. DFT/B3LYP/6‐311 G(d, p) method is used to calculate the energy of HOMO and LUMO level of methyl orange. Copyright © 2016 John Wiley & Sons, Ltd.     

Time-Resolved Flavin Adenine Dinucleotide Fluorescence Study of the Interaction Between Immobilized Glucose Oxidase and Glucose

Time-resolved fluorescence experiments have shown that flavin adenine dinucleotide (FAD) fluorescence emission of sol–gel immobilized glucose oxidase (GOD) exhibits a three-exponential decaying behaviour characterized by long- (about 2.0–3.0 ns), intermediate- (about 300 ps) and short- (less than 10 ps) lifetime, each one being characteristic of a peculiar conformational state of the FAD structure. In the present work time-resolved fluorescence is used to monitor FAD signals in the time interval immediately following the addition of glucose at various concentrations in order to detect the conformational changes occurring during the interaction between sol–gel immobilized GOD and glucose. The analysis of time-dependent fluorescence emission signal has shown that the FAD conformational state changes during the process from a configuration with a prevalence of the state characterized by the long lifetime to a configuration with increased contribution from the process with the intermediate lifetime. The time needed to complete this configuration change decreases with the concentration of added glucose. The results here reported indicate that time-resoled fluorescence can be extremely useful for a better understanding of solid phase biocatalysis that is particularly important in light of their clinical and biotechnological applications.     

Ultra-fast synthesis of magnetic and luminescent silica beads for versatile bioanalytical applications

A method for the synthesis of both spherically shaped micro/nano silica particles and silica hybrid particles using a novel inverse sol–gel suspension technique was developed. The technique enables the synthesis of beads within seconds and provides a simple basis for quantum dot and biosubstances encapsulation. The carriers can be used as DNA adsorbents, individually addressable optical codes for bioassays and biomolecule library screening as well as photonic crystals.     

Irradiation effect of low-energy ion on polyurethane nanocoating containing metal oxide nanoparticles

Irradiation effect of low-energy ion beam has been investigated on nanocoating developed with silica, titania and silica–titania core–shell nanoparticles embedded in an organic binder for nanopaint application. In this work, we have taken polyurethane as a model organic binder. Silica nanoparticles have been prepared through sol–gel synthesis with a particle size of 85?nm. Titania and core–shell nanoparticles have been prepared through both sol–gel and peptization process. Particle sizes obtained were 107?nm for titania and 240?nm for core–shell nanoparticles prepared through sol–gel process and 75?nm for TiO₂ and 144?nm for core–shell nanoparticles prepared through peptization process. The coating formulations were developed with the above nanoparticles individually and nanoparticle concentration was varied from 1 to 6?wt% and the best performance in terms of hydrophobicity was obtained with 4?wt % of the nanoparticles in polyurethane coating formulation. All the coating formulations prepared were applied on a glass substrate and dried at 100°C. The dry film thickness obtained was around 100?µm in each case. These films dried on glass substrate were irradiated by nitrogen and argon ion beam with energy of 26?keV at fluences of 10¹⁴ to 10¹⁶?ions/cm². The anti-algal property of the irradiated samples was improved and hydrophobicity was reduced.     

Fluorescence and Textural Characterization of Ortho-Amine Tetraphenylporphyrin Covalently Bonded to Organo–Modified Silica Xerogels

Most of the studies performed with porphyrins involve these species functionalized with peripheral substituents lying on the same macrocyclic molecular plane. The main objective of this work deals with the successful preservation and optimization of the fluorescence of a uncommonly used porphyrin species, i.e. tetrakis-(ortho-amino-phenyl)-porphyrin; a molecule with substituents localized not only at one but at both sides of its molecular plane. In cases like this, it must be stressed that fluorescence can only be partially preserved; nevertheless, intense fluorescence can still be reached by following a twofold functionalization strategy involving: (i) the bonding of substituted macrocycles to the pore walls of (ii) organo-modified silica monoliths synthesized by the sol–gel method. The analysis of both absorption and emission UV spectra evidenced a radiation energy transfer taking place between the porphyrin and the host silica matrix. Our results showed that the adequate displaying of the optical properties of macrocyclic species trapped in SiO₂ xerogels depend on the polarity existing inside the pores, a property which can be tuned up through the adequate selection of organic groups used to modify the surface of the pore cavities. Additionally, the pore widths attained in the final xerogels can vary depending on the identity of the organic groups attached to the network. All these facts finally demonstrated that, even if using inefficient surface functionalization species, such as ortho-substituted tetraphenylporphyrins, it is still possible to modulate the pore shape, pore size, and physicochemical environment created around the trapped macrocycles. The most important aspect related to this research deals with the fact that the developed methodology offers a real possibility of controlling both the textural and morphological characteristics of a new kind of hybrid porous materials and to optimize the physicochemical properties of diverse active molecules trapped inside the pores of these materials.     

Ionic conductivity of covalently interconnected polyphosphazene–silicate hybrid networks

Silicate sol–gel precursors of poly[bis(methoxyethoxyethoxy)phosphazene] and their corresponding hybrid networks were synthesized by hydrolysis and condensation reactions. Conversion of the precursor polymers to covalently interconnected hybrid networks with controlled morphologies and physical properties was achieved. Thermal analyses showed no melting transitions for the networks and low glass transition temperatures that ranged from approximately − 38 to − 67 °C. Solid solutions with lithium bis(trifluoromethanesulfonyl)amide in the network showed a maximum ionic conductivity value of 7.69 × 10^− 5 S/cm, making these materials interesting candidates for dimensionally stable solid polymer electrolytes.     

Properties and Preparation of Chitosan/Silanol Quaternary Ammonium Modified Silica Hybrids Using Sol–Gel Process

Chitosan/modified silica nanocomposites, with a sol–gel process being used to prepare a silanol quaternary ammonium modified silica possessing antimicrobial activity, were investigated, as well as the thermal properties, morphology, optical, mechanical, antimicrobial, and adsorption properties of this type of nanocomposite. Grafting of the modifier onto nanosilica was confirmed through the Fourier transform infrared (FTIR) spectra. X-ray diffraction patterns indicated that the chitosan structure was not disrupted from the incorporation of the modified silica. Fracture surfaces with no clear micro-phase separation were observed by scanning electron microscopy (SEM), which indicated the good interaction of chitosan and the modified silica. The organic modifier tended to cause the aggregation of the modified silica at higher content on a submicron scale based on transmission electron microscopy (TEM) analysis, which might be due to a decrease of the stability factor originating from the negative charges on silica. With the introduction of modified silica, the optical transmittance decreased at higher organic modifier content in agreement with TEM analysis. The elongation at break remained largely unchanged, but tensile strength and Young's moduli deteriorated in modified silica filled systems in comparison with pure silica filled systems. The introduction of the organic modified silica gave a higher antibacterial activity. All nanocomposites were capable of chelating Cu (II) as well as Fe (III) at a different degree. Thus, the prepared chitosan/modified silica nanocomposites exhibited both antimicrobial and chelating properties.     

Versatile Preparation of Silica Nanocapsules for Biomedical Applications

Core–shell nanocapsules are receiving increasing interest for drug delivery applications. Silica nanocapsules have been the focus of intensive studies due to their biocompatibility, versatile silica chemistry, and tunable porosity. However, a versatile one-step preparation of silica nanocapsules with well-defined core–shell structure, tunable size, flexible interior loading, and tailored shell composition, permeability, and surface functionalization for site-specific drug release and therapeutic tracking remains a challenge. Herein, an interfacially confined sol–gel process in miniemulsion for the one-step versatile preparation of functional silica nanocapsules is developed. Uniform nanocapsules with diameters from 60 to 400 nm are obtained and a large variety of hydrophobic liquids are encapsulated in the core. When solvents with low boiling point are loaded, subsequent solvent evaporation converts the initially hydrophobic cavity into an aqueous environment. Stimuli-responsive permeability of nanocapsules is programmed by introducing disulfide or tetrasulfide bonds in the shell. Selective and sustained release of dexamethasone in response to glutathione tripeptide for over 10 d is achieved. Fluorescence labeling of the silica shell and magnetic loading in the internal cavity enable therapeutic tracking of nanocapsules by fluorescence and electron microscopies. Thus, silica nanocapsules represent a promising theranostic nanoplatform for targeted drug delivery applications.