磁性高分子微球用于固定化酶的研究进展生物材料结构及性质的基础研究及其应用于药物的控制释放

磁性高分子微球是近20年来发展起来的一种新型功能高分子材料,并已在生物化工、细胞学、生物医学工程等领域得到了广泛应用。本文主要介绍磁性高分子微球的制备和性质以及在固定化酶中的应用。     

Effect of Chlorine Released during Hydrodechlorination of Chlorobenzene over Pd, Pt and Rh Supported Catalysts

Chlorobenzene hydrodechlorination in liquid phase has been studied. Chlorine released during the reaction inhibits conversion in large metallic particles. It was found comparing the behavior of Pd/SiO₂, Pd/Al₂O₃ and Pd/C catalysts that the support plays the role of a chlorine trap. The activity for Pt, Rh and Pd at similar dispersions corresponds to the chlorine adsorption affinity of the metals.     

碱性介质中甘氨酸在Pt电极上解离吸附和氧化反应的原位红外反射光谱研究

运用原位红外反射光谱研究了碱性介质中甘氨酸在Pt电极上的解离吸附和氧化反应行为,并利用纳米Pt膜电极的异常红外效应鉴定反应过程中生成的表面吸附物种.结果表明:甘氨酸在Pt电极上极易发生解离,生成强吸附于电极表面上的氰基负离子,该吸附物种在低于0V电位下能稳定存在,并抑制甘氨酸的进一步反应.当电位高于0.2V时,氰基负离子被氧化为氰酸根离子进入溶液,使甘氨酸发生氧化反应,生成氰酸盐和碳酸盐等产物.     

活性炭负载Pt/Fe3O4催化剂及其选择性转移加氢肉桂醛的催化性能

A variety of spherical and structured activated charcoal supported Pt/Fe₃O₄ composites with an average particle size of ～100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt (IV) and Fe (Ⅱ) precursors as driving force. The formed Fe₃O₄ nanoparticles (NPs) effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe₃O₄ nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe₃O₄ catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of cinnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.     

二甲醚在Pt(100)表面吸附的密度泛函理论研究

采用密度泛函理论(DFT)方法结合周期性平板模型,研究了二甲醚(DME)分子在Pt(100)表面上的吸附.通过对不同吸附位(顶位、空位和桥位)下的几何结构、吸附能和mulliken电荷布局计算发现,吸附后C-O键和C-H键都有不同程度的伸长,top位的吸附能最大,hcp位最小;top位吸附有利于C-O键的断裂,bri位吸附则更利于C-H键的断裂。     

离子凝聚法制备负载流感疫苗的壳聚糖微球

采用三聚磷酸钠(TPP)作为离子交联剂, 应用离子凝聚法制备负载流感疫苗的壳聚糖微球. 筛选出壳聚糖起始质量分数为1%. TPP的浓度对壳聚糖微球的制备影响较大, 采用低浓度的TPP(200 μg/mL)制备的微球放置过夜均出现沉淀现象, 高浓度的TPP(800 μg/mL)在制备过程中出现絮状沉淀. 固化比影响微球的释放行为, 固化比为1∶1的微球爆炸式释放率达到90％, 固化比为1∶3的微球6 h后逐步释放, 12 h后释放率达到95％. 固化比为1∶5的微球6 h后没有明显的释放行为. 壳聚糖溶液的pH对微球的制备和释放没有显著的影响. 通过对负载流感疫苗的壳聚糖微球的制备条件和释放行为的研究结果表明, pH=5.6的壳聚糖溶液, 固化比为1∶3, TPP的质量浓度为400 μg/mL是较理想的流感疫苗壳聚糖微球的制备条件.     

Preparation of Highly Active Pt-K/γ-AI203 Catalyst for 0-Phenylphenol Synthesis from 0-Cyclohexenyl-cyclohexanone Dehydrogenation

0.5%Pt-K/y-Al2O3 catalysts for the synthesis of 0-phenylphenol(OPP) from 0-cyclohexenyl-cyciohexanone (dimer) dehydrogenation were prepared by means of a two subsequent impregnation method.The effects of catalyst preparation parameters,such as K promoters,calcination,and reduction conditions,were investigated.The results showed that the addition of K2SO4 to Pt/y-Al2O3 catalyst notably promoted the selectivity of OPP,and its optimum content was found to be 6% in mass fraction.The higher activity was obtained when Pt/y-Al2O3 catalyst was calcined in nitrogen atmosphere at 400-500℃ and then reduced at the same temperature for 3 h in hydrogen atmosphere.The conversion of the dimer and the selectivity of OPP were always above 99% and 90%,respectively,over 0.5%Pt-6% K2SO4/γ-Al2O3 catalyst during the pilot scale test of 8000 h.     

球型Pt微粒电极的构建及其对甲醇电氧化的研究

以镍铬合金为基体,在其表面电化学沉积制备了Pt微粒电极,用扫描电子显微镜（SEM）对电极的表面形貌进行了表征,电化学方法考察了电极的电化学性能和甲醇在该电极上的电催化行为．结果表明镍铬合金表面沉积的球型Pt微粒电极对甲醇的电氧化具有良好的催化活性,相同实验条件下,该电极的催化活性比纯Pt电极高30倍．该电极对甲醇的电氧化显示出较高的催化性能．     

Protein adsorption: A quest for a universal mechanism

Recent theoretical and experimental results pertinent to protein adsorption kinetics obtained for well-defined systems using direct experimental techniques are discussed. Attention is focused on albumins and fibrinogen, whose structure and physicochemical characteristic are well-known. It is confirmed that the experimental data obtained by AFM imaging, QCM, OWLS, XPS and electrokinetic techniques (streaming potential) are prone to a quantitative interpretation in terms of the coarse-grained and molecular dynamics modeling. This allows to derive reliable data concerning the mass transfer rates, hydration functions, maximum coverages and adsorption/desorption kinetic constants. These results confirm that the protein adsorption mechanism is governed by electrostatic interactions among heterogeneously distributed charges. The protein substrate interactions promote the molecule transfer through the surface layer, control the free energy and in consequence the residence time of the molecule on substrate surfaces. On the other hand, the interactions among adsorbed molecules control the maximum coverage and the formation of bilayer structures. As a result of this complex electrostatics, one often observes in protein adsorption studies the formation of irreversibly bound fraction of molecules that contact the substrate and a reversibly adsorbed fraction otherwise. This leads to the appearance of anomalous isotherms, characterized by considerable adsorption for negligible bulk protein concentration, which deviate from the Langmuir model.     

Asymmetric Total Syntheses of Kopsane Alkaloids via a PtCl2-Catalyzed Intramolecular [3+2] Cycloaddition

A concise and asymmetric total synthesis of five kopsane alkaloids that share a unique heptacyclic caged ring system was accomplished. The key transformation in the sequence involved a remarkable PtCl₂-catalyzed intramolecular [3+2] cycloaddition, which allowed for the rapid assembly of pentacyclic carbon skeletons bearing 2,3-quaternary functionalized indoline. Expeditious construction of diverse indoline scaffolds with excellent control of diastereoselectivity demonstrated the broad scope and versatility of this key transformation.