Effect of acidity on the formation of silica–chitosan hybrid materials and thermal conductive property

In this study, the formation of silica–chitosan hybrid materials via sol–gel process under pH values of 2–6 were investigated using N₂ sorption analysis, scanning electron microscopy, transmission electron microscopy, thermal analysis and zeta potential analyzer. The hierarchical structure consisting of meso- and macropore was formed when pH value was higher than 2. Mesopores were formed as the interparticle channels of silica nanoparticles aggregates, whereas macropores were the void between the aggregates (clusters). The clusters size was decreased with increasing the pH value, resulting in the increase of the macroporosity. The thermal conductivity of the products was controlled in the range of 0.06 and 0.13 W m⁻¹ K⁻¹ by varying the product porosity between 88 and 69% (pH 6 and pH 2, respectively).     

Temperature induced phase separation of luminescent silica nanoparticles in Triton X-100 solutions

The aggregation and cloud point behavior of Tb(III)-doped silica nanoparticles has been studied in Triton X-100 (TX-100) solutions at various concentration conditions by fluorimetry, dynamic light scattering, electrophoresis and transmission electron microscopy methods. The temperature responsive behavior of nanoparticles is observed at definite concentration of TX-100, where the aggregation of TX-100 at the silica/water interface is evident from the increased size of the silica nanoparticles. The reversible dehydration of TX-100 aggregates at the silica/water interface should be assumed as the main reason of the temperature induced phase separation of silica nanoparticles. The distribution of nanoparticles between aqueous and surfactant rich phases at the phase separation conditions can be modified by the effect of additives.     

Fabrication of silica nanoparticles and hollow spheres using ionic liquid microemulsion droplets as templates

Silica products with two different morphologies were synthesized using nonaqueous ionic liquid microemulsion droplets as templates. The morphologies of the obtained products were characterized by both transmission electron microscopy (TEM) and scanning electron microscopy (SEM). By adjusting the reaction conditions, ellipsoidal nanoparticles were formed under acidic conditions, while hollow silica spheres were obtained under alkaline conditions. It is demonstrated that the size distribution of hollow silica spheres was narrower than that of the ellipsoidal nanoparticles. The various vibration modes of different functional groups in the silica materials were revealed by Fourier transform infrared (FTIR) spectroscopy. The two samples were both shown to be amorphous, not crystalline by X-ray diffraction (XRD). A simple diagram of the formation process including the hydrolysis and condensation reactions is given. Furthermore, a probable mechanism for the formation of silica materials under acidic or alkaline conditions is presented, which may be helpful for better understanding the different silica materials obtained under different conditions.     

Using of silica particles as porogen for preparation of macroporous chitosan macrospheres suitable for enzyme immobilization

Porous chitosan macrospheres were prepared at the first time by using silica particles as porogen, and the optimal weight ratio of silica to chitosan during preparation was determined. Scanning electron microscopy micrographs showed that the support with silica as porogen (support I) had a much more porous surface structure than the support without porogen (support II). Both supports were applied to immobilize β-galactosidase from Aspergillus oryzae. Much higher specific activity and yield of galactose hydrolysis products were observed for the support I. Properties of both immobilized enzyme were determined and compared with the free enzyme, satisfactory results were obtained in thermostability, pH arid operational stability, Michaelis constants K _m and in maximum velocity of hydrolysis (V _m). Suggested method allow to prepare chitosan macrospheres as immobilized enzyme carrier with moreporous surface structure and more active reaction groups.     

Influence of surfactant surface coverage and aging time on physical properties of silica nanoparticles

The experimental results on the influence of surfactant surface coverage and aging time on physical properties of silica nanoparticles were reported. The spherical silica nanoparticles have been synthesized using polyethylene glycol (PEG) as the surfactant and oil shale ash (OSA) as a new silica source. In order to identify the optimal condition for producing the best quality silica nanoparticles with the good dispersion and uniformity, the effects of surfactant surface coverage and aging time were investigated. It was found that the particle size and distribution of silica nanoparticles depend on the concentration of PEG in dispersion. At relatively low concentration, 0–2 wt.%, the existing PEG is not sufficient to prevent further growth of the initially formed silica nanoparticles, leading to large aggregates of silica particles. When the PEG concentration increases to 3 wt.%, self-assembled PEG layer on the surface stabilizes the initially formed silica nanoparticles and the silica particles with average diameter of 10 nm are uniformly distributed. With further increasing the concentration of PEG, the number of PEG aggregates increases and silica nanoparticles are mainly formed inside the entangled PEG chains, resulting in an observation of clusters of silica nanoparticles. Moreover, it was found that as the aging time increased, the shape of silica nanoparticles becomes regular and the particle size distribution becomes narrow.     

Size-controllable synthesis of monodispersed colloidal silica nanoparticles via hydrolysis of elemental silicon

A new method is presented for preparing monodisperse and uniform-size silica nanoparticles using a two-stage hydrolysis of silicon powder in aqueous medium. The influence of synthesis conditions including solution composition and temperature on the formation of silica nanoparticles were systematically investigated. The structure and morphology of the silica particles were characterized via transmission electron microscopy (TEM) and dynamic light scattering (DLS). Various-sized particles in the range 10–100 nm were synthesized. The size of the nanoparticles can be precisely controlled by using a facile regrowth procedure in the same reaction media.     

Preparation and properties of silica–gold core–shell particles

Silica-metal core–shell particles, as for instance those having siliceous core and nanostructured gold shell, attracted a lot of attention because of their unique properties resulting from combination of mechanical and thermal stability of silica and magnetic, electric, optical and catalytic properties of metal nanocrystals such as gold, silver, platinum and palladium. Often, the shell of the core–shell particles consists of a large number of metal nanoparticles deposited on the surface of relatively large silica particles, which is the case considered in this work. Namely, silica particles having size of about 600 nm were subjected to surface modification with 3-aminopropyltrimethoxysilane. This modification altered the surface properties of silica particles, which was demonstrated by low pressure nitrogen adsorption at ?196 °C. Next, gold nanoparticles were deposited on the surface of aminopropyl-modified silica particles using two strategies: (i) direct deposition of gold nanoparticles having size of about 10 nm, and (ii) formation of gold nanoparticles by adsorption of tetrachloroauric acid on aminopropyl groups followed by its reduction with formaldehyde.The overall morphology of silica–gold particles and the distribution of gold nanoparticles on the surface of modified silica colloids were characterized by scanning electron microscopy. It was shown that direct deposition of colloidal gold on the surface of large silica particles gives more regular distribution of gold nanopartciles than that obtained by reduction of tetrachloroauric acid. In the latter case the gold layer consists of larger nanoparticles (size of about 50 nm) and is less regular. Note that both deposition strategies afforded silica–gold particles having siliceous cores covered with shells consisting of gold nanoparticles of tunable concentration.     

Direct formation of thermally stabilized amorphous mesoporous Fe2O3/SiO2 nanocomposites by hydrolysis of aqueous iron III nitrate in sols of spherical silica particles

Nanocomposite materials containing 10% and 20% iron oxide/silica, Fe2O3/SiO2 (w/w), were prepared by direct hydrolysis of aqueous iron III nitrate solution in sols of freshly prepared spherical silica particles (St?ber particles) present in their mother liquors. This was followed by aging, drying, calcination up to 600 degrees C through two different ramp rates, and then isothermal calcinations at 600 degrees C for 3 h. The calcined and the uncalcined (dried at 120 degrees C) composites were characterized by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), N2 adsorption/desorption techniques, and scanning electron microscopy as required. XRD patterns of the calcined composites showed no line broadening at any d-spacing positions of iron oxide phases, thereby reflecting the amorphous nature of Fe2O3 in the composite. The calcined composites showed nitrogen adsorption isotherms characterizing type IV isotherms with high surface area. Moreover, surface area increased with the increasing of the iron oxide ratio and lowering of the calcination ramp rate. Results indicated that iron oxide particles were dispersed on the exterior of silica particles as isolated and/or aggregated nanoparticles. The formation of the title composite was discussed in terms of the hydrolysis and condensation mechanisms of the inorganic FeIII precursor in the silica sols. Thereby, fast nucleation and limited growth of hydrous iron oxide led to the formation of nanoparticles that spread interactively on the hydroxylated surface of spherical silica particles. Therefore, a nanostructured composite of amorphous nanoparticles of iron oxide (as a shell) spreading on the surface of silica particles (as a core) was formed. This morphology limited the aggregation of Fe2O3 nanoparticles, prevented silica particle coalescence at high temperatures, and enhanced thermal stability.     

Synthesis,characterization and properties of magnetic colloids supported on chitosan

This work proposes the synthesis, characterization and investigation of the stabilization capabilities of chitosan doped with magnetic nanoparticles. Nanoparticles of Fe, Co, Co(II,III) oxide, Ni and Ni/Ag mixture in 2-propanol were synthesized by chemical liquid deposition and the incorporation on the polymeric matrix was performed by solvated metal atom dispersion. Colloids and nanoparticles supported on chitosan were characterized by ultraviolet, Fourier-transform infrared, thermogravimetric analysis, electron diffraction X-ray and magnetic behaviour; transmission and field electronic scanning electron microscopy. The particle size distribution of colloids ranges from 6 to 50 nm with low particle stability due to flocculation after 120 days. The nanoparticles supported on chitosan had a particle size distribution of approximately between 10 and 80 nm, with low particle distribution; however, these particles do not flocculate because the matrix increases the stabilization of nanoparticles. All compounds present superparamagnetic behaviour at low temperature.     

Uniform and size-tunable mesoporous silica with fibrous morphology for drug delivery

A family of mesoporous silica microspheres with fibrous morphology and different particle sizes ranging from about 400 to 900 nm has been successfully synthesized through a facile self-assembly process. The structural, morphological, and textural properties of the samples were well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), N(2) adsorption/desorption, and thermal gravimetry (TG). The results reveal that this silica-based mesoporous material exhibits excellent physical properties, including a fibrous spherical morphology, good thermal stability, large pore volume, high specific surface area and narrow size distribution. Additionally, the size and textural properties can be tuned by altering the silica precursor/template molar ratio. The formation and the self-assembly evolution process have also been proposed. The obtained materials were further used as a drug delivery carrier to investigate the in vitro drug release properties using doxorubicin (DOX) as a representative model drug. It was found that this kind of silica exhibits good biocompatibility and obvious sustained drug release properties, suggesting its potential application in biological fields.     

Synthesis of narrowly distributed polystyrene-encapsulated silica nanoparticles via emulsion polymerization

Polystyrene (PS)-encapsulated silica nanoparticles were successfully synthesized by conventional emulsion polymerization for solving the aggregation matter of nanoscaled silica. The grafting coupling agents and PS on the silica surface were detected by Fourier Transform Infrared (FTIR) spectroscopy. The influence of silica and monomer to water ratios and initiator concentration on particle size distribution of the nanocomposite latex was investigated. The particle size distribution firstly narrowed and then broadened with the increase of silica and monomer to water ratios and initiator concentration. The narrow distribution could be controlled in an appropriate silica and monomer to water ratio and an initiator concentration of 1/15 and 2 wt%, respectively. From the evaluation of transmission electron microscopy (TEM) micrographs and dynamic light scattering (DLS) measurement, it was proved that the nanocomposite latex did not have all sphere-like shape, but contained tiny amounts of irregular bodies. The formation mechanism of PS-encapsulated silica nanoparticles was also discussed.     

Biomimetic growth of silica tubes in confined media

Polymer membranes were used as biomimetic environments to study the effect of confinement on silica formation. Within membrane pores, silica tubes were formed, consisting of a dense silica shell incorporating nanoparticle aggregates. The shell structure does not depend on the membrane pore size, suggesting that its formation proceeds via interfacial interactions with the pore surface. In contrast, the size of primary nanoparticles within core aggregates is influenced by pore dimensions, indicating an effect of confinement on the diffusion-limited growth of silica. A parallel can be drawn with reported roles of confinement in biomineralization processes, providing a basis for future developments in biosilicification mimetic approaches and biofunctional nanomaterials design.     

Silica nanoparticle crystals and ordered coatings using lys-sil and a novel coating device

Silica nanoparticles with a narrow particle size distribution and controlled diameters of 10-20 nm are synthesized via hydrolysis and hydrothermal aging of tetraethylorthosilicate in an aqueous L-lysine solution. Cryo-transmission electron microscopy (cryo-TEM) reveals that the silica nanoparticles assemble to form close-packed nanoparticle crystals over short length scales on carbon-coated grids. Evaporative drying of the same sols results in nanoparticle stability and remarkable long-range facile ordering of the silica nanoparticles over scales greater than 10 microm. Whereas small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) discount the possibility of a core (silica)-shell (lysine) structure, the possibility remains for lysine occlusion within the silica nanoparticles and concomitant hydrogen bonding effects driving self-assembly. Facile ordering of the silica nanoparticles into multilayer and monolayer coatings over square-centimeter areas by evaporation-induced self-assembly is demonstrated using a novel dip-coating device.     

Characterization and biocompatibility of chitosan nanocomposites

Chitosan nanocomposites were prepared from chitosan and gold nanoparticles (AuNPs) or silver nanoparticles (AgNPs) of ～5 nm size. Transmission electron microscopy (TEM) showed the NPs in chitosan did not aggregate until higher concentrations (120-240 ppm). Atomic force microscopy (AFM) demonstrated that the nanocrystalline domains on chitosan surface were more evident upon addition of AuNPs (60 ppm) or AgNPs (120 ppm). Both nanocomposites showed greater elastic modulus, higher glass transition temperature (T(g)) and better cell proliferation than the pristine chitosan. Additionally, chitosan-Ag nanocomposites had antibacterial ability against Staphylococcus aureus. The potential of chitosan-Au nanocomposites as hemostatic wound dressings was evaluated in animal (rat) studies. Chitosan-Au was found to promote the repair of skin wound and hemostasis of severed hepatic portal vein. This study indicated that a small amount of NPs could induce significant changes in the physicochemical properties of chitosan, which may increase its biocompatibility and potential in wound management.     

不同形貌纳米二氧化硅的制备及形成机理研究

在水醇体系中,以正硅酸四乙酯(TEOS)作为硅源、氨水作为催化剂,快速合成了哑铃状、纤维状及链状3种形貌的纳米SiO2;利用透射电子显微镜分析了产物的微观结构,着重探讨了氨水浓度、TEOS浓度及TEOS滴加速度对纳米SiO2形貌的影响,并提出了不同形貌纳米SiO2的形成机理.     

Facile strategy for synthesis of silica/polymer hybrid hollow nanoparticles with channels

The silica/polymer hybrid hollow nanoparticles with channels and gatekeepers were successfully fabricated with a facile strategy by using thermoresponsive complex micelles of poly(ethylene glycol)-b-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) and poly(N-isopropylacrylamide)-b-poly(4-vinylpyridine) (PNIPAM-b-P4VP) as the template. In aqueous solution, the complex micelles (PEG-b-PNIPAM/PNIPAM-b-P4VP) formed with the PNIPAM block as the core and the PEG/P4VP blocks as the mixed shell at 45 °C and pH 4.0. After shell cross-linking by 1,2-bis(2-iodoethoxyl)ethane (BIEE), tetraethylorthosilicate (TEOS) selectively well-deposited on the P4VP block and processed the sol-gel reaction. When the temperature was decreased to 4 °C, the PNIPAM block became swollen and further soluble, and the PEG-b-PNIPAM block copolymer escaped from the hybrid nanoparticles as a result of swelled PNIPAM and weak interaction between PEG and silica at pH 4.0. Therefore, the hybrid hollow silica nanoparticles with inner thermoresponsive PNIPAM as gatekeepers and channels in the silica shell were successfully obtained, which could be used for switchable controlled drug release. In the system, the complex micelles, as a template, could avoid the formation of larger aggregates during the preparation of the hybrid hollow silica nanoparticles. The thermoresponsive core (PNIPAM) could conveniently control the hollow space through the stimuli-responsive phase transition instead of calcination or chemical etching. In the meantime, the channel in the hybrid silica shell could be achieved because of the escape of PEG chains from the hybrid nanoparticles.     

Pattern formation of zinc nanoparticles in silica film by electrodeposition

Zinc nanoparticles were grown within gel-derived silica films by applying a direct current voltage. Pattern formation of metallic Zn was studied as a function of applied voltage and metal-silica ratio. Average particle size varied from 5.2 to 20.2 nm by changing the applied voltage and silica concentration. It was found that the transition from fractal to dendritic morphology was possible due to crystalline anisotropy. From high-resolution transmission electron microscopy images and X-ray diffraction pattern a possible model is proposed to explain this observation.     

Preparation of chitosan nanoparticles using methacrylic acid

In this work the preparation of chitosan nanoparticle was investigated using methacrylic acid in different conditions and studied by particle size analyzer, zeta-potential, Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM). The particle size was dependent on the chitosan concentration used during the preparation method. Nanoparticles with sizes as small as 60 nm were achieved, that can be extremely important for several applications. The nanoparticles solution was also pH-sensitive, due to swelling and aggregation of the nanoparticles. The nanoparticles obtained presented a very homogeneous morphology showing a quite uniform particles size distribution and a rather spherical shape.     

Aggregation of silica nanoparticles directed by adsorption of lysozyme

The interaction of the globular protein lysozyme with silica nanoparticles of diameter 20 nm was studied in a pH range between the isoelectric points (IEPs) of silica and the protein (pH 3-11). The adsorption affinity and capacity of lysozyme on the silica particles is increasing progressively with pH, and the adsorbed protein induces bridging aggregation of the silica particles. Structural properties of the aggregates were studied as a function of pH at a fixed protein-to-silica concentration ratio which corresponds to a surface concentration of protein well below a complete monolayer in the complete-binding regime at pH > 6. Sedimentation studies indicate the presence of compact aggregates at pH 4-6 and a loose flocculated network at pH 7-9, followed by a sharp decrease of aggregate size near the IEP of lysozyme. The structure of the bridged silica aggregates was studied by cryo-transmission electron microscopy (cryo-TEM) and small-angle X-ray scattering. The structure factor S(q) derived from the scattering profiles displays characteristic features of particles interacting by a short-range attractive potential and can be represented by the square-well Percus-Yevick potential model, with a potential depth not exceeding 3k(B)T.     

Preparation and properties of ionically cross‐linked chitosan nanoparticles

Chitosan nanoparticles were fabricated by a method of tripolyphosphate (TPP) cross‐linking. The influence of fabrication conditions on the physical properties and drug loading and release properties was investigated by transmission electron microscopy (TEM), dynamic light scattering (DLS), and UV–vis spectroscopy. The nanoparticles could be prepared only within a zone of appropriate chitosan and TPP concentrations. The particle size and surface zeta potential can be manipulated by variation of the fabrication conditions such as chitosan/TPP ratio and concentration, solution pH and salt addition. TEM observation revealed a core–shell structure for the as‐prepared nanoparticles, but a filled structure for the ciprofloxacin (CH) loaded particles. Results show that the chitosan nanoparticles were rather stable and no cytotoxicity of the chitosan nanoparticles was found in an in vitro cell culture experiment. Loading and release of CH can be modulated by the environmental factors such as solution pH and medium quality. Copyright © 2008 John Wiley & Sons, Ltd.