Vesicle--biopolymer gels: networks of surfactant vesicles connected by associating biopolymers

The effect of adding an associating biopolymer to surfactant vesicles and micelles is studied using rheology and small-angle neutron scattering (SANS). The associating polymer is obtained by randomly tethering hydrophobic alkyl chains to the backbone of the polysaccharide, chitosan. Adding this polymer to surfactant vesicles results in a gel; that is, the sample transforms from a Newtonian liquid to an elastic solid having frequency-independent dynamic shear moduli. SANS shows that the vesicles remain intact within the gel. The results suggest a gel structure in which the vesicles are connected by polymer chains into a three-dimensional network. Vesicle-polymer binding is expected to occur via the insertion of polymer hydrophobes into the vesicle bilayer. Each vesicle thus acts as a multifunctional junction in the network structure. Significantly, gel formation does not occur with the native chitosan that has no hydrophobes. Moreover, adding the hydrophobically modified chitosan to a viscous sample containing wormlike micelles increases the viscosity further but does not give rise to a gel-like response. Thus, the formation of a robust gel network requires both the presence of hydrophobes on the polymer and vesicles in solution.     

Synthesis of polymer–inorganic patchy microcapsules with tunable patches

We introduce a facile and versatile approach for the formation of ball-like polymer–inorganic patchy microcapsules with a tunable shell by combining sol–gel chemistry of silica precursor and phase separation between the polymer and the precursor. Firstly, chloroform-in-water emulsion droplets containing poly(methyl methacrylate) (PMMA), silica precursor [tetraethyl orthosilicate (TEOS)] and co-surfactant sodium dioctyl sulfosuccinate (Aerosol OT or AOT) were prepared by shaking the mixture by hand. Due to the added AOT, water molecules diffuse into the chloroform droplets, and the tiny water droplets would coalesce gradually, triggering the formation of double emulsion droplets. Upon further solvent evaporation, the concentration of the polymer and the silica precursor in the oil shell of the double emulsions increases, leading to the phase separation between the polymer and the precursors (and partially formed silica through the hydrolysis and condensation of TEOS). Because of the confined geometry of the oil shell in the double emulsions, polymeric disc-like structures, stabilized by AOT, were dispersed in the silica precursors. Meanwhile, the silica precursor hydrolyzed and condensed when brought in contact with the aqueous solution, ultimately leading to the formation of a mineralized shell around the polymer domains and the hybrid patchy microcapsules. Effect of synthesis conditions, such as the amount of TEOS, AOT, and PMMA used, the pH value, and solvent evaporation rate on interfacial behavior of the solvent/water; and the morphology of the patchy microcapsules were investigated. Patchy microcapsules with tunable patch size and shape can be generated through tailoring the experimental parameters. Our study indicates that the hybrid patchy microcapsules can be formed by taking advantage of the sol–gel chemistry and the phase separation process, and the underlying generality of the synthesis procedure allows for a variety of applications, including drug storage, coatings, delivery, catalysis, and smart building blocks in self-assembling systems.     

Influence of boric acid on aging of freshly prepared tetraethoxysilane-based gels

The technique for kinetic examination of polycondensation of silicon alkoxides, which allows determining the rate of reaction between ammonium molybdate and various associates of silica for systems in which hydrolysis proceeds, was modified to examine similar systems after the gel point. Aging of freshly prepared tetraethoxysilane-based gels was for the first time studied spectrophotometrically as influenced by boric acid additions. The proportions of various molecular species of silica in the examined systems at different times after the gel point were determined in terms of the kinetic model of the molybdate reaction.     

海藻酸改性的中空SiO2微球的简易制备及应用

以CaCO3为模板,正硅酸四乙酯（TEOS）为硅源,用比较简单的方法制备了中空SiO2;然后将海藻酸钠嫁接在氨基化的中空SiO2表面;再利用海藻酸盐与钙离子的作用,在中空SiO2表面形成一个凝胶化层,制得海藻酸盐凝胶化的中空SiO2微球,粒径为1~2 μm。 采用FTIR、XRD、SEM、TEM和TGA等测试技术对微球进行表征。 此微球成功地用于柔红霉素的载负和缓释,最大载负率和载药量分别为55.6%和27.8%;缓释结果表明,海藻酸盐凝胶化层的存在,能更有效控制柔红霉素缓慢的释放,这种凝胶化载体对药效强、毒性较大的药物有潜在的临床应用前景。     

PFG NMR studies of lysine-silica solutions

The formation process of silica nanoparticles in lysine-silica mixtures was studied using dynamic light scattering (DLS) and pulsed-field gradient (PFG) NMR measurements. (1)H NMR shows line broadening of the lysine resonances during TEOS hydrolysis/nanoparticle formation. Analysis of the TEOS hydrolysis kinetics show that TEOS hydrolysis is the rate-limiting step in particle formation, and has an activation energy of 20.5 kJ/mol. Transverse relaxation measurements show a corresponding decrease in T(2) with TEOS hydrolysis, indicating a reduction in the lysine mobility due to lysine-silica interactions. PFG NMR results indicate a systemic decrease in the self-diffusion coefficient of lysine as particle formation proceeds. The results obtained can be described using a two-state model wherein lysine is either free in solution or bound to the nanoparticles. Analysis of the PFG data of samples made at various temperatures show that lysine coverage upon complete hydrolysis is between 2.5 and 2.8 mmol lysine/kg solution, and insensitive to the heating temperature. PFG NMR shows a linear increase in the amount of bound lysine with increasing lysine content, indicating an increase in the surface area present, i.e. more and smaller particles, with increased lysine content. The PFG NMR results presented give quantitative insights that indicate that while pH is likely the primary driver for the rate of particle formation and particle size, lysine is critical for stabilization of the nanoparticles.     

Mechanically controlled, morphologically determined sol–gel derived UV curable hybrid nanocomposites: SAXS and DMTA studies

This work reports preparation of organic–inorganic hybrid materials by sol–gel method. To this end, UV cured urethane acrylate and different functional monomers were used as organic network together with tetraethyl orthosilicate (TEOS) as inorganic network former and 3-methacryloxy propyltrimethoxy silane (MEMO) as network modifier. The effect of sol–gel precursor’s ratio on morphological properties of hybrid network was studied by small angle X-ray scattering (SAXS). Dynamic mechanical thermal analysis (DMTA) was performed to investigate the mechanical behavior of hybrid films. Whilst hybrids with low content of TEOS and high amounts of MEMO represented a “structural defect”, it was found that by increasing TEOS/MEMO ratio, the silica domain size decreased, showing a mass fractal behavior. This was attributed to a more compact structure of silica and a stronger hybrid network. The changes observed in compactness of hybrid films directly affected the glass transition temperature. By increasing the inorganic phase, more restriction in segmental motion of the polymeric phase occurred. Upon increasing TEOS/MEMO ratio a broader tan δ peak deduced from DMTA graphs was observed, indicating greater phase separation and higher heterogeneity.     

Three-Dimensional Nanoparticle Arrays Templated by Self-Assembled Block-Copolymer Gels

Water-soluble triblock copolymers (PEO-PPO-PEO) are utilized to provide thermoreversible micellar templates for three-dimensional nanoparticle arrays. The triblock forms a cubic micellar structure with typical dimensions of tens of nanometers. The temperature-dependent amphiphilic nature of the block copolymers provides increased structure control and allows the use of pre-made silica and gold nanoparticles as well as globular proteins. Using rheology and small-angle neutron scattering (SANS), we characterize the influence of the nanoparticles on the local particle structure and on the macroscopic mechanical properties. We are able to incorporate significant quantities of nanoparticles into the block copolymer gel without destroying the ordered structure. Contrast matching SANS demonstrates that some level of the template structure is transferred to the nanoparticles. This study demonstrates the feasibility and potential of using this simple approach to generate novel nanoparticles-polymer composites.     

Ammonia Catalyzed Hydrolysis-Condensation Kinetics of Tetraethoxysilane/Dimethyldiethoxysilane Mixtures Studied by <Superscript><Emphasis Type="Bold">29</Emphasis></Superscript>Si NMR and SAXS

In-situ ²⁹Si liquid-state nuclear magnetic resonance (NMR) was used to investigate the ammonia catalyzed hydrolysis and condensation of the mixed systems of tetraethoxysilane (TEOS) and dimethyldiethoxysilane (DDS) dissolved in methanol. With ammonia catalysis, the hydrolysis reaction orders for TEOS and DDS in the mixed systems remained first order, which is similar to that observed for their corresponding single silane component precursor systems. The hydrolysis rate constant for TEOS in the mixed systems was larger than that of TEOS in the single silane component precursor systems. Meanwhile, the hydrolysis rate constants of DDS in the mixed precursor systems were smaller than those of DDS in the single silane component precursor systems. The hydrolysis and condensation kinetics showed more compatible hydrolysis-condensation relative rates between TEOS and DDS, which remarkably affected the final microstructure of the resulting silica particles. Small angle X-ray scattering (SAXS) experiments showed a typical double fractal structure in the particulate networks.     

Template-free sol–gel synthesis of high surface area mesoporous silica based catalysts for esterification of di-carboxylic acids

High surface area mesoporous silica based catalysts have been prepared by a simple hydrolysis/sol–gel process without using any organic template and hydrothermal treatment. A controlled hydrolysis of ethyl silicate-40, an industrial bulk chemical, as a silica precursor, resulted in the formation of very high surface area (719 m²/g) mesoporous (pore size 67 Å and pore volume 1.19 cc/g) silica. The formation of mesoporous silica has been correlated with the polymeric nature of the ethyl silicate-40 silica precursor which on hydrolysis and further condensation forms long chain silica species which hinders the formation of a close condensed structure thus creating larger pores resulting in the formation of high surface mesoporous silica. Ethyl silicate-40 was used further for preparing a solid acid catalyst by supporting molybdenum oxide nanoparticles on mesoporous silica by a simple hydrolysis sol–gel synthesis procedure. The catalysts showed very high acidity as determined by NH₃-TPD with the presence of Lewis as well as Brønsted acidity. These catalysts showed very high catalytic activity for esterification; a typical acid catalyzed organic transformation of various mono- and di-carboxylic acids with a range of alcohols. The in situ formed silicomolybdic acid heteropoly-anion species during the catalytic reactions were found to be catalytically active species for these reactions. Ethyl silicate-40, an industrial bulk silica precursor, has shown a good potential for its use as a silica precursor for the preparation of mesoporous silica based heterogeneous catalysts on a larger scale at a lower cost.     

聚合物模板微球表面电性对中空二氧化硅微球形貌的影响

分别以过硫酸钾和偶氮二异丁基脒盐酸盐为引发剂,以聚乙烯吡咯烷酮(PVP)为分散剂,在水中引发苯乙烯聚合制备了2种表面分别带负电性和正电性基团的聚苯乙烯(PS)模板微球.在氨水催化下,利用正硅酸乙酯的水解缩合,形成PS/SiO_2复合微球,去除模板后得到中空SiO_2微球,并对其进行FTIR、电子显微镜、TGA以及氮气吸附等分析表征.结果表明,PS模板微球表面的电性决定了OH-的分布,从而导致PS模板微球表面SiO_2壳层不同的形成机制.当以表面带负电的PS微球为模板时,可得到树莓状的中空SiO_2微球;而以表面带正电的PS微球为模板时,得到是表面光滑的,具有介孔结构的中空SiO_2微球.     

甲基丙烯酸(3-三甲氧基硅)丙酯-马来酸二丁基锡共聚物/二氧化硅杂化材料的制备

甲基丙烯酸（３ 三甲氧基硅）丙酯 马来酸二丁基锡共聚物／二氧化硅杂化材料的制备周文董建华丘坤元（北京大学化学与分子工程学院高分子科学与工程系，１００８７１北京）ＷｅｉＹｅｎ（危岩）（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，Ｄｒｅｘｅｌ...     

Polymerization of w/o microemulsions for the preparation of transparent SiO2/PMMA nanocomposites

Reverse w/o microemulsions composed of methyl methacrylate (MMA) forming the oil phase, nonionic surfactants, and water are used for the synthesis of transparent SiO2/PMMA nanocomposites. An inorganic precursor, tetraethoxysilane (Si(OEt)(4), TEOS), is hydrolyzed in the reverse micelles containing aqueous ammonia. During the hydrolysis of TEOS, polymerization of the continuous MMA phase is initiated using AIBN (azobisisobutyronitrile), and after thermal polymerization at 333 K for 12 h, solid blocks of PMMA are obtained in which nanometer-sized silica particles are trapped in the solid polymer matrix. According to small-angle X-ray and dynamic light scattering experiments, the water droplets in MMA microemulsions are 12 nm (R(W) = 13) in diameter, whereas after polymerization of the microemulsion, the SiO2 particles in the transparent SiO2/PMMA composites are 26 nm in diameter. Transmission electron micrographs demonstrate a low degree of agglomeration in the composites. In comparison with materials generated from micelle-free solutions, the particle size distribution is narrow. The reverse micelle-mediated approach produces composites of high transparency comparable with that of pure PMMA.     

Synthesis of polymeric organic-inorganic hybrid materials. Partially deacetylated chitin-silica hybrid

This work reports the synthesis of a novel polymeric organic-inorganic hybrid. The inorganic component is a silica network obtained by controlled hydrolysis of tetraethyl orthosilicate via sol-gel process and the organic counterpart is partially deacetylated chitin (CHI). The resulting polymer hybrids were homogeneous transparent film forming glassy materials being compatible through a wide composition range. Simultaneous thermal analysis of a CHI/silica 1:1 mixture confirms the intermolecular complex formation between organic and inorganic polymers.     

PVC-silica hybrids: effect of sol–gel conditions on the morphology of silica particles and thermal mechanical properties of the hybrids

Hybrid materials from poly(vinyl chloride) (PVC) and silica have been prepared using different conditions by the sol–gel technique. In situ generation of silica network in the PVC matrix was carried out by hydrolysis/condensation of tetraethoxysilane (TEOS) in the matrix. Morphology of the silica particles produced in hybrid films was studied by scattering electron microscopy. The shape of silica particle produced in the matrix was modified by carrying out the sol–gel process under steam on the hybrid films using TEOS. The films were subjected to strain conditions during this process, which produced lamellar shaped particles in the matrix. It was possible to produce platelet type of structure with different aspect ratio by changing the composition and the stress conditions on the films during the steaming process. Addition of a very small amount of γ-glycidoxypropyltrimethoxysilane as compatibilizer drastically reduced the silica particles size in the matrix to nano-level. Thermal–mechanical properties of some of these hybrids were studied and related to the composition, structure and inter-phase interaction between the silica and the matrix.     

Water-soluble interpolyelectrolyte complexes of polyisobutylene-block-poly(methacrylic acid) micelles: formation and properties

We report on interpolyelectrolyte complexes (IPECs) formed by micelles of ionic amphiphilic diblock copolymers with polyisobutylene (PIB) and poly(sodium methacrylate) (PMANa) blocks interacting with quaternized poly(4-vinylpyridine) (P4VPQ). The interpolyelectrolyte complexation was followed by turbidimetry and small angle neutron scattering (SANS). The data obtained by means of a combination of SANS, dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryo-TEM) provide evidence on the core-shell-corona structure of the complex species with the shell assembled from fragments of electrostatically bound PMANa and quaternized P4VPQ fragments, original PIBx-b-PMAAy micelles apparently playing a lyophilizing part. The complex formation is followed by potentiometric titration as well. This process is initially kinetically controlled. In the second step larger aggregates rearrange in favor of smaller complexes with core-shell-corona structure, which are thermodynamically more stable. An increase in ionic strength of the solution results in dissociation of the complex species as proven by SANS and analytical ultracentrifugation (AUC). This process begins at the certain threshold ionic strength and proceeds via a salt-induced gradual release of chains of the cationic polyectrolyte from the complex species.     

Synthesis of silica hollow spheres assisted by ultrasound

A simple and effective method for synthesizing silica hollow spheres is presented. The synthesis utilizes vesicles from oppositely charged surfactants sodium dodecyl sulfate (SDS) and tetrapropylammonium bromide (TPAB) aqueous solution as template for the silica growth. Tetraethyl orthosilicate (TEOS) is added to the vesicular template as a precursor for the silica formation. Ultrasound was employed to accelerate the formation of vesicles template. The morphology of the silica spheres is uniform and well-defined (diameter: 200 nm-5 microm, wall thickness: 50 nm). The product was also characterized by FTIR, TG-DTA, N2 adsorption. TEM images reveal that the spheres have structure stability after calcinations at 550 degrees C.     

The Study of Formation of Amphiphilic Network Block Copolymer of <Emphasis Type="Italic">N</Emphasis>-Isopropylacrylamide

The regularities of formation of the structure of amphiphilic network copolymers on radical copolymerization of N-isopropylacrylamide and polyester dimethacrylate are investigated. The kinetic laws of the consumption of functional groups and the increase in the gel content during formation of a crosslinked product are studied. It is shown that the synthesis of crosslinked amphiphilic copolymers proceeds via competing reactions of N-isopropylacrylamide homopolymerization and its copolymerization with polyester dimethacrylate. With the excess of the monofunctional monomer, a homogeneous rubber-like network copolymer is formed, whereas the excess of the bifunctional reagent results in the morphological inhomogeneity of the reaction product.     

Coating and Gas Permeation Properties of Urushiol-Based Organic/Inorganic Hybrid Films

The silica and urushiol based organic/inorganic hybrid was prepared with TEOS and urushiol by sol-gel process. GLYMO, as a silane-coupling agent, was used to obtain crack-free homogeneous films in various molar ratios, and to improve the adhesion between corona-treated BOPP substrate and the coatings. Two kinds of coating solutions were prepared; one was composed of TEOS and urushiol, the other was a mixture of TEOS, GLYMO and urushiol. Urushiol created less cracks on the film in a narrow range of molar ratios. As the amounts of urushiol were increased, the coating solutions quickly became heterogeneous. GLYMO was sufficient to prevent microcracks on the coated film and provided homogeneous coating solution. TEOS/urushiol and TEOS/GLYMO/urushiol coating solution gave insignificant effect on the permeability coefficients of oxygen, nitrogen and carbon dioxide, because the unsaturated alkyl side chain of urushiol might retard the formation of a dense structure between the inorganic silicate and the organic urushiol phase. From the antibacterial test of uncoating PP substrate and the coated film with hybrid solution, the reduction of bacteria of coating film was calculated to be 99.8%.     

Surface silylation and pore structure development of silica aerogel composites from colloid and TEOS-based precursor

Flexible aerogel-fiber composites were prepared by silylation and ambient drying of colloidal silica and tetraethylorthosilicate (TEOS)-based sol. After immersing glass fiber matrices into silica sol with colloid-based, colloid/TEOS-based, and TEOS-based silica sol, it was surface-modified in a trimethylchlorosilane/n-hexane solution and heat-treated at 230 °C in ambient atmosphere. Surface silylation of silica aerogel synthesized from colloid and TEOS-based silica sols showed different behaviors. For colloid silica gel, it was comprised of small sized mesopores because colloid-based silica gel has dense networks through great degrees of hydrolysis and condensation. On the contrary, TEOS-based aerogel was consisted of relatively large-sized pores because of comparatively lesser degree of hydrolysis and condensation. Through this study, we can know that the pore structures of silica aerogel could be controlled by choosing colloid or TEOS-based precursor and surface silylation reaction.     

Effect of non-ionic surface active agents on TEOS-derived sols,gels and materials

The sol-gel process, starting from tetraethylorthosilicate precursor, is a suitable technique for the preparation of silica thin films. The use of specific organic additives, like non ionic surface-active agents, drastically modifies the gelation process and allows the preparation of microporous materials with a high microporous volume. The effects of additives on the sol, gel and material characteristics have been investigated by several methods such as ²⁹Si NMR, QELS, SAXS (for sols and gels), and N₂ adsorption, FESEM (for fired materials). It appears that the interactions of surface active agents with TEOS derived species limit condensation reactions and particle growing. A brittle gel structure is generated which leads to highly porous microporous silica after the elimination of organic chains by thermal treatment at 450°C. The material porous texture (specific surface area, pore size distribution and porous volume) can be varied especially by varying the surface active agent chain length and quantity. This kind of sol-gel system is suitable to prepare microporous silica membranes candidate for gas separation or catalytic reactor applications.