新型聚合物载体茂金属催化剂

均相茂金属催化剂虽然有许多优点和特点,但也存在着某些不足之处,例如,不适于现在通用的气相和淤浆聚合工艺;要想达到足够的聚合活性需大量价格昂贵的MAO;相当多的均相茂金属催化剂不适于高温聚合（活性降低,分子极低）,不能很好地控制聚合物的形态,为了在工业上得到实际应用,必须将它们载体（非均相）化。通常采用的载体都是无机物,如SiO2、MgCl2、Al2O3等。由于无机载体表面具有酸性,负载茂金属催化剂活性有所降低,用聚合和作茂金属催化剂的载体很少有报道,我们研制了一种新型的聚合物载体茂金属催化剂,即可保持均相茂金属催化特点和优点,又能克服其缺点。其合成路线如下。     

1-甲基-1-乙氧基-1-烷硫基甲烷类化合物的合成研究

本文以乙缩醛和烷基硫醇为原料,在30－35℃于四氯化碳中反应20min左右,分别合成1－甲基－1－乙氧基－1－烷硫基甲烷,经红外光谱,质谱以及核磁共振谱检测,确证了产物结构。     

基于卤键的选择性吸附层层组装多层膜

以超支化聚乙烯亚胺为构筑基元、以卤键为推动力制备了可以选择性吸附带有负电荷小分子的层层组装多层膜. 为了将超支化聚乙烯亚胺引入多层膜体系中, 我们首先制备了接枝有卤键给体分子-碘全氟苯的超支化聚乙烯亚胺(BPEI-I). 然后将BPEI-I和含有卤键受体的聚(4-乙烯吡啶)(PVPy)在四氢呋喃和三氯甲烷的混合溶剂中组装成膜, 并用紫外可见光谱、AFM和XPS对膜的组装过程、形貌、厚度和推动力进行了表征. 制备得到的BPEI-I和PVPy多层膜可以吸附含有负电荷的2-蒽甲酸钠小分子, 而对有类似结构但带有正电荷的溴化-N-(2-蒽甲基)吡啶盐却没有吸附作用. 这种选择性吸附能力主要得益于包覆在多层膜中的超支化聚乙烯亚胺基元的正电荷空腔和由卤键构筑的弱极性微环境. 本文的研究为制备选择性吸附薄膜提供了一种新的思路, 在传感、富集分离和微接触印刷等领域都有潜在应用价值.     

A silicone-based stretchable micropost array membrane for monitoring live-cell subcellular cytoskeletal response

External forces are increasingly recognized as major regulators of cellular structure and function, yet the underlying mechanism by which cells sense forces and transduce them into intracellular biochemical signals and behavioral responses ('mechanotransduction') is largely undetermined. To aid in the mechanistic study of mechanotransduction, herein we devised a cell stretching device that allowed for quantitative control and real-time measurement of mechanical stimuli and cellular biomechanical responses. Our strategy involved a microfabricated array of silicone elastomeric microposts integrated onto a stretchable elastomeric membrane. Using a computer-controlled vacuum, this micropost array membrane (mPAM) was activated to apply equibiaxial cell stretching forces to adherent cells attached to the microposts. Using the mPAM, we studied the live-cell subcellular dynamic responses of contractile forces in vascular smooth muscle cells (VSMCs) to a sustained static equibiaxial cell stretch. Our data showed that in response to a sustained cell stretch, VSMCs regulated their cytoskeletal (CSK) contractility in a biphasic manner: they first acutely enhanced their contraction to resist rapid cell deformation ('stiffening') before they allowed slow adaptive inelastic CSK reorganization to release their contractility ('softening'). The contractile response across entire single VSMCs was spatially inhomogeneous and force-dependent. Our mPAM device and live-cell subcellular contractile measurements will help elucidate the mechanotransductive system in VSMCs and thus contribute to our understanding of pressure-induced vascular disease processes.     

Charge-charge and cation-<Emphasis Type="Italic">π</Emphasis> interactions in ligand binding to G protein-coupled receptors

To study the importance of charge–charge and cation-π interactions for the binding of positively charged amine ligands to their receptors, the energies of interaction between [(CH₃)₄–N]⁺, [(CH₃)₃–NH]⁺, and [(CH₃)₄–NH₃]⁺ and acetate, as a model of Asp and Glu, and with benzene, as a model of aromatic side chains, were obtained at the MP2/aug-cc-pVDZ level of theory. The free energies of solvation in water were also calculated for the different amines. It was found that, although primary amines form stronger charge–charge interactions with acetate than tertiary or quaternary amines, the difference is not large enough to compensate their higher solvation energy. Quaternary amines show the weakest interaction with acetate. However, their alkyl groups can interact with various aromatic groups, enhancing ligand binding to the receptor. The analysis was completed with MD calculations on amine binding to the G protein-coupled receptors β₂AR and CCR5. The calculations on the model systems were found to be in good agreement with the simulations of the ligand-receptor complexes. Contribution to the Serafin Fraga Memorial Issue.     

Dynamical (e,2e) studies of tetrahydrofurfuryl alcohol

Cross section data for electron scattering from DNA are important for modelling radiation damage in biological systems. Triply differential cross sections for the electron impact ionization of the highest occupied outer valence orbital of tetrahydrofurfuryl alcohol, which can be considered as an analogue to the deoxyribose backbone molecule in DNA, have been measured using the (e,2e) technique. The measurements have been performed with coplanar asymmetric kinematics at an incident electron energy of 250 eV, an ejected electron energy of 20 eV, and at scattered electron angles of -5°, -10°, and -15°. Experimental results are compared with corresponding theoretical calculations performed using the molecular 3-body distorted wave model. Some important differences are observed between the experiment and calculations.     

M2 Proton Channel Structural Validation from Full-Length Protein Samples in Synthetic Bilayers and E. coli Membranes

Validation: Membrane protein structures are sensitive to the environment used for structural characterization. NMR spectra of the full-length M2 proton channel from influenza?A were measured directly in E.?coli membranes and compared to spectra of the protein in synthetic lipid bilayers. The results demonstrate that these bilayers provide a native-like membrane environment.     

PEG辅助氧化锌纳米棒的水热法制备

采用PEG辅助水热法合成了ZnO纳米棒,XRD显示产物为结晶良好的六角结构晶体ZnO,PL谱表明适当退火处理后产物有较好的光致发光性能.利用TEM和SAED研究了纳米棒的形貌和生长机制,并研究了氢氧化钠浓度和反应时间对产物形态和尺寸的影响.     

Composite Electrode SnO2／TiO2 for Dye-Sensitized Solar Cells

Composite nanoporous electrode SnO2/TiO2 was fabricated for the dye sensitized solar cell (DSSC) with N3 (Cis-Ru). After introducing of TiO2, the open-circuit photovoltage (Voc) was higher than that of the pure SnO2 electrode, while short-circuit photocurrent (Isc) was varied with the ratio of the TiO2. Appropriate content of the TiO2 can be beneficial to the efficiency of the solar cell, and it gives negative impact on the composite electrode when the content of TiO2 is higher.