Swelling and Drying Mechanisms of Freeze-Thawed Polyvinyl Alcohol/Egg White/Montmorillonite Bionanocomposite Hydrogels

Abstract

Polyvinyl alcohol and egg white bionanocomposite hydrogels loaded with montmorillonite clay were fabricated by a freezing-thawing technique. The bionanocomposite hydrogels showed an exfoliated morphology and they had a more interconnected and dense network as compared with the clay-free sample. The montmorillonite layers acted as multifunctional crosslinkers and the bionanocomposite hydrogels had nanoscale, slit-shaped pores. The swelling ratios of the bionanocomposite hydrogels were increased either by decreasing the content of incorporated montmorillonite or by increasing the pH of the swelling medium. It was found that the bionanocomposite hydrogels having a higher content of montmorillonite exhibited a slightly slower drying process with a longer drying duration. Using the Ritger-Peppas model, it was shown that the swelling and drying mechanisms for all bionanocomposite hydrogels were non-Fickian diffusion. According to the Peppas-Sahlin model, it was found that the absorption of the swelling agent molecules during the swelling process and also the removal of water molecules during the drying process in the early stages of the processes occurred mostly due to their diffusion. At higher swelling or drying times, the contribution of the relaxation (for swelling) and shrinkage (for drying) of the polyvinyl alcohol polymeric chains and egg white protein chains was increased.     

The first montmorillonite‐supported surface single‐structure titanium complex: synthesis,characterization and catalytic activity in alkene epoxidation

A well‐defined single‐site titanium‐modified montmorillonite (MMT) with only one geometric construction ((?SiO)₃–Ti–NMe₂) was obtained in moderate conditions. Reaction of tetrakis(dimethylamido)titanium with hydroxylated MMT was conducted by surface organometallic chemistry technique, and the surface structure was characterized by in situ Fourier transform infrared spectroscopy, ¹³C cross polarization magic angle spinning nuclear magnetic resonance, X‐ray photoelectron spectroscopy, extended X‐ray absorption fine structure, and elemental analysis. The catalytic activity in alkene epoxidation was evaluated, and the results revealed that the steric hindrance of the substances is responsible for the catalytic activity of the MMT‐supported titanium complex but to the characteristic restricted layer‐like structure of the MMT. Copyright © 2014 John Wiley & Sons, Ltd.     

反应温度对蒙脱石载银量及其缓释性能的影响

以钠基蒙脱石(Na-MMT)为载体,氧化银与氨水反应形成的银氨络合物[Ag(NH₃)₂OH]为前驱体,通过离子交换和三乙醇胺(TEA)还原两步法制备了载银蒙脱石(Ag-MMT)。 用佛尔哈德法测定了载银蒙脱石(Ag-MMT)的载银量,探讨了反应温度对MMT 载银量及其缓释性能的影响,并用FI-IR、XRD等技术手段对Na-MMT和Ag-MMT的结构进行了表征。 结果表明,在蒙脱石与Ag⁺的质量比为20:1、离子交换时间为1 h、反应温度50 ℃,然后再加入三乙醇胺和聚乙烯吡咯烷酮,50 ℃下反应2 h,MMT的载银量最大,银的利用率达到86.89%,释放时间最持久,并且MMT的层状结构没有被破坏。     

High pressure treatment of pharmaceutical drug delivery and related systems

Abstract

Solids like layer silicates (kaolinite and montmorillonite) as well as ZnO are in use in pharmacy. They are pressure treated and subsequently analyzed by means of ESR spectroscopy. The structural changes indicated by Fe³⁺ ions and paramagnetic defects are reponsible for the enhanced chemical activity of the pressurized systems.

Especially active Fe-O-species are formed which can react with intercacalated organic molecules. The most probable first step of such reactions will be a solid state single electron transfer. Spin probes and spin traps were used to prove this statements. The activation of the drug delivery systems by mechanical treatments is of importance for the stability of the drugs incorporated.     

Montmorillonite K10: Catalyst for Friedel–Crafts Alkylation of Indoles and Pyrrole with Nitroalkenes Under Solventless Conditions

Montmorillonite K10 was found to catalyze the Michael addition of indoles or pyrrole with nitroalkenes efficiently under solventless condition. The short reaction time, simple workup, and excellent yields were noteworthy. The green catalyst could be reused for three runs without considerable variation in yield.     

Regioselective Synthesis of Diltiazem Analogue Pyrazolo[4,3-c][1,5]benzothiazepines and Antifungal Activity

A dry media procedure has been developed for the synthesis of a series of new class of pyrazolo [4,3-c][1,5]benzothiazepines 6 under microwave irradiation using montmorillonite K10 as solid support. The catalyst can be recovered and reused. Thus, the procedure provides a simple and green synthetic methodology under environmentally friendly conditions. Antifungal screening of synthesized compounds has shown promising activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Study on ablative properties and mechanisms of hydrogenated nitrile butadiene rubber (HNBR) composites containing different fillers

The ablative properties of hydrogenated nitrile butadiene rubber (HNBR) composites filled with fumed silica, organically modified montmorillonite (OMMT), or expanded graphite (EG) were examined. The HNBR/OMMT composite has the lowest linear ablation rate and the highest mass ablation rate and does not tend to be carbonized. On the other hand, the HNBR/EG composite has the highest linear ablation rate and the lowest mass ablation rate, and is prone to carbonization. The ablative properties of the HNBR/silica composite are between those of HNBR/OMMT and HNBR/EG. From the viewpoint of thermal shielding capability, the HNBR/OMMT has the best ablation resistance. Thermogravimetric analysis (TGA) on different HNBR composites indicated that the filler type has no significant effect on the thermal stability of the composites. To understand the ablation mechanisms, the char layers of different HNBR composites after ablation experiments were characterized by scanning electron microscopy (SEM), energy disperse X-ray spectroscopy (EDS), and wide-angle X-ray diffraction (WAXD). The results showed that the porosity in the char layers of the HNBR/OMMT composite was the highest and the corresponding structure was the loosest of the three composites. The montmorillonite (MMT) dispersed in HNBR experienced phase transition, melting and vaporization when exposed to the flame with the temperature over 2000 °C. Fumed silica only melted at such situation. On the other hand, the EG kept their original crystalline structures after the ablation test. Based on these results, the effect of the filler type on the ablation mechanisms of the HNBR composites was discussed.     

Solvent-induced selectivity switching: intermolecular allylsilylation, arylsilylation, and silylation of alkynes over montmorillonite catalyst

Proton-exchanged montmorillonite showed catalytic activity for intermolecular allylsilylation, arylsilylation, and terminal silylation of alkynes with allylsilanes. The reaction selectivity greatly depended on the solvent used. Reactions proceeded with various terminal alkynes and allylsilanes in good to moderate yields. The reaction pathways involving cationic Si species on the montmorillonite surface were also investigated.     

聚吡咯/STAB-NaMMT/GC电极对苯二酚的电化学行为研究

利用十八烷基三甲基溴化氨（STAB）和聚吡咯（PPy）钠基蒙脱土制备了PPy/STAB钠基蒙脱土/GC电极（PPy/STAB-NaMMT/GC）.用循环伏安法和方波溶出伏安法（SWSV）研究了对苯二酚在该电极上的电化学行为.实验表明,在pH 6.0 PBS电解液中,对苯二酚在该电极的电极反应受扩散控制,转移的电子数与质...     

Quantitative evaluation on oil diffusion mechanisms in nano‐organic‐montmorillonite modified caster oil‐based polyurethane foam for oil/water separation

To improve the oil absorbency of caster oil‐based polyurethane foam, nano‐organic‐montmorillonite (OMMT) was used for the additives. The aim of this study is to evaluate the oil diffusion mechanism and dispersion uniformity of OMMT modified caster oil‐based polyurethane (MPU) using experiments and molecular dynamic simulation. Molecule movement and molecule trajectory of oil was investigated by molecular dynamic simulation and numerical simulation. According to the quantitative analyzing results, the diffusion model was put forward. The average diffusion coefficient of crude oil in 0, 1, 2 wt%, 4, and 6 wt% MPU is 2.4 × 10^?4 cm²/s, 2.6 × 10^?4 cm²/s, 3.0 × 10^?4 cm²/s, 3.2 × 10^?4 cm²/s, and 3.3 × 10^?4 cm²/s, respectively. It indicated that crude oil appeared gradient in the MPU. The optimal diffusion direction of crude oil is (0, 0, 1) crystal face, and the small particles of crude oil are easy to be adsorbed. The two‐dimensional diffusion trajectory of crude oil is nonlinear. The diffusion model includes the diffusion of crude oil at the interface of oil and polyurethane, surface diffusion and pore diffusion, and pore adsorption. Furthermore, the diffusion model showed that the van der Waals force was the main reason for crude oil diffusion or adsorption. OMMT could improve the ability of oil/water separation of polyurethane.