压力和温度对4-甲基二苯并噻吩和二苯并噻吩加氢脱硫反应的影响

研究了4-甲基二苯并噻吩(4-MDBT)和二苯并噻吩(DBT)在CoMo/γ-Al2O3上的加氢脱硫反应产物分布及其可能的反应网络,通过反应压力和温度对产物分布影响的研究,揭示了加氢脱硫反应的可能机理。研究发现4-MDBT在CoMo/γ-Al2O3上的加氢脱硫反应主要通过直接氢解路径和加氢路径进行,且两者反应速率相当；DBT在 CoMo/γ-Al2O3上的加氢脱硫反应主要通过直接氢解路径进行。4-MDBT分子位于4位的甲基阻碍其在催化剂表面通过硫原子的端连吸附,从而降低了其直接氢解脱硫路径的反应速率,因而也降低了其总的加氢脱硫转化率。反应压力降低,DBT和4-MDBT加氢脱硫反应中加氢路径反应速率明显下降,而其对氢解路径影响较小,但效果却与加氢路径相反,反应压力对4-MDBT转化率的影响大于DBT。反应温度对DBT和4-MDBT加氢脱硫反应中加氢路径和氢解路径都有明显影响,但是对DBT加氢脱硫反应中氢解路径的影响小于加氢路径,而对4-MDBT加氢脱硫反应中氢解路径的影响稍高于加氢路径,4-MDBT分子中甲基的供电子作用有利于相连苯环的加氢反应。     

Theoretical Study on the Isomerization Mechanism of Enol Ester from 2-Acyl-1, 3-cyclohexanediones

The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.     

Selection of Anodic Material Used in Electrolytic Process for Producing Hypophosphorous Acid

Black lead, Ti-Ru and Ti-PbO2 were used as anode and stainless steel was used as cathode The electrolytic process of producing hypophosphorous acid with four-compartment electrodialytic cell was studied. The comparison of some factors, such as anodic voltage, product concentration and current efficiency, of black lead, Ti-Ru, and Ti-PbO2 electrodes was conducted. As a result, theTi-PbO2 electrode is the optimal anode material used, it can be in electrolytic process for producing hypophosphorous acid.     

Clean Aerobic Liquid Oxidation of Aldehydes with Solid Catalyst

Clean liquid oxidation of aldehydes can be accomplished using solid catalyst in the presence of molecular oxygen at room temperature, which is a valuable alternative to traditional counterparts.     

Effect of Ultrasonication on Optical Properties and Electronic States of Conjugated Polymer MEH-PPV

Poly[2-methoxy-5-（2＇-ethyl-hexyloxy）-1,4-phenylene vinylene]（MEH-PPV）solutions with different concen-trations were prepared in chloroform for different ultrasonication times.The ultraviolet absorption and photoluminescence（PL）spectra of the MEH-PPV solutions were measured,and the electronic states of the polymer chains under different experimental conditions were studied.The results showed that the effects of ultrasonication on the dilute and concentrated solutions were different.After ultrasonication,the intensity of the absorption peak at 280 nm significantly decreased,relative to the absorption peak at 500 nm for both dilute and concentrated solutions,indicating that the proportion of the two excited states in the polymer chains had changed.For dilute MEH-PPV solutions,the blue-shifted absorption（at about 500 nm）and PL spectra show that ultrasonication also led to polymer chain degradation and thus shortened the effective conjugation length.For concentrated solutions,however,the peak positions of the absorption spectra remained unchanged.In addition,the effects of the solution temperatures on the optical spectra for the MEH-PPV solutions were also discussed.     

Adjuvant Effects of Dual Co-stimulatory Molecules on Cellular Responses to HIV Multiple-epitope DNA Vaccination

Designing adjuvants that can induce strong cytotoxic T cell responses is largely required for preparing DNA vaccines. In this study we explored dual costimulatory molecules 4-1BBL and OX40L as adjuvants to improve the efficiency of the HIV multiple-epitope DNA vaccine. When explored in the human dendritic cell-T cell based coculture system,dual costimulatory molecules significantly enhanced the anti-HIV T cell response of the HIV mul-tiple-epitope DNA vaccine,as detected by intracellular cytokine staining t...     

Fluorescence-quenching of Tryptophan Ion-18-crown-6 Complex——A Different Observation from Its Neutral Counterpart

It is well-known that primary amines form inclusive complexes with crown ethers. This kind of noncova-lently inclusive complexes,exemplified tryptophan complex with 18-crown-6,was studied by combination of two experimental methods,fluorimetry and mass spectrometry,with theoretical calculation. Fluorescence intensity of tryptophan in the absence and the presence of 18-crown-6 in aqueous HAc-NaAc buffer solution at pH=3.73 has been studied by fluorometry. The fluorescence intensity decreases significantly wit...     

诺氟沙星与DNA的拉曼光谱研究

报道了诺氟沙星(NFX)及诺氟沙星胶囊内容物的FT-Raman光谱和在银胶基底上的表面增强拉曼光谱(SERS),归属了各个振动;研究了诺氟沙星与DNA的相互作用的SERS,结果表明:胶囊内容物的拉曼光谱图与对照品的拉曼光谱图的特征振动峰:C-F键的伸缩振动,C=C伸缩振动,O-C-O的对称伸缩振动峰值未发生变化,发生变化主要是分子骨架振动峰,诺氟沙星胶囊的辅料对拉曼光谱无实质影响,可建立拉曼光谱法检测诺氟沙星药物的分析方法;诺氟沙星可以在没有金属离子的存在下与DNA直接作用,与DNA相互作用的主要键合模式是插入作用,NFX分子中的平面结构插入DNA的双螺旋碱基平面,为深入了解喹诺酮类抗生素的抗菌机理提供可靠依据.     

矿化剂对铝酸钙粉的结构与光谱性能的影响

研究了矿化剂对制备铝酸钙粉的结构与性能的影响.研究中以铝矾土和石灰石为原料,加入一定量的矿化剂,混合均匀,经高温煅烧制得铝酸钙粉.借助于红外光谱、X射线粉末衍射、差热-热重分析等手段对不同原料的铝酸钙粉的结构、组成及性能进行了表征和研究,并对矿化剂在合成铝酸钙中的矿化机理进行探讨.研究表明:加入矿化剂后,可在更低温度条件下煅烧制备出铝酸钙粉,有利于节能减排.红外光谱分析、XRD分析、DTA-TG分析显示:未加矿化剂煅烧时,生成的产物主要是Ca3Al10O18,CaAl2Si2O8.加入矿化剂后煅烧生成的产物主要是易浸出Al2O3的CaAl3BO7和Ca3Al10O18,而不易浸出Al2O3的CaAl2Si2O8的含量大大降低.同时显示,加入矿化剂后,原料中的方解石(CaCO3)分解更容易;CaCO3与铝矾土反应更充分;更有利于促使铝矾土中的Al-Si键断裂,将铝矾土中的Al释放出来;并可降低铝酸钙的煅烧温度.研究还显示:加入矿化剂后,可以改变原产物的晶体结构与成分,有利于降低煅烧反应温度.     

ATP-Co2+-脱氧胆酸-凝胶体系的分形/周期沉淀

在体外模拟胆结石形成的实验中,选取腺苷-5'-三磷酸(ATP)-金属离子-脱氧胆酸(DC)凝胶体系进行了分形/周期有序结构的生长实验,研究ATP对Co2+-脱氧胆酸凝胶体系形成的分形/周期沉淀的影响,用FTIR表征有序沉淀物的结构.结果表明:在ATP存在下的Co2+-DC凝胶体系中,可形成周期沉淀及分形结构共存的复杂时空图案,ATP对Co2+-脱氧胆酸凝胶体系形成的图案模式较AMP的影响显著,体系的图案从分形模式转化为周期沉淀,ATP、脱氧胆酸钠、Co2+-存在复杂的相互作用,生成透明晶体新物质;红外光谱结果显示该晶体为脱氧胆酸,周期沉淀物为ATP、DC共同与金属离子配位的结果.此结果说明核苷酸作为重要的生命物质在结石形成过程中起到重要作用,结石的形成具有复杂的、非线性化学特性.