用双氧水绿色氧化环己酮合成己二酸的研究

以30%的双氧水为氧化剂, 钨酸钠与含N或O的双齿有机配体(草酸)形成的络合物为催化剂, 在无有机溶剂、无相转移剂的条件下, 研究了环己酮氧化制己二酸的反应. 研究结果表明, 用廉价的草酸为配体, 最佳反应条件为钨酸钠∶草酸∶环己酮∶30%的双氧水的物质的量比为2.0∶3.3∶100∶350, 在92 ℃下反应12 h, 可制得80.6%的己二酸; 用GC-MS跟踪了氧化过程中三种主要物质环己酮、己内酯及己二酸含量随反应时间的变化关系, 提出了其主要氧化机理为环己酮首先经Beayer-Villiger氧化反应生成己内酯, 己内酯进一步氧化成己二酸.     

2D层状焦磷酸锰(Ⅱ)[NH4]2[Mn3(P2O7)2(H2O)2]的结构和磁性研究

A two-dimensional layered manganese(Ⅱ) pyrophosphate, [NH₄]₂[Mn₃(P₂O₇)₂(H₂O)₂] (1), has been synthesized hydrothermally. Its structure is determined by single-crystal X-ray diffraction analysis. Its structure is built up by MnO₆ octahedra and P₂O₇ units, with ammonium NH₄⁺ cations residing in the interlayer regions. The manganese pyrophosphate layer consists of infinite chains of cis and trans edge sharing MnO₆ octahedra linked by P₂O₇ units. Magnetic susceptibility measurements show that this compound exhibits ferrimagnetic-like ordering below 3.2 K. Further study shows that there are two possible superexchange pathways via the oxygen anions in Mn²⁺ ions. Owing to the different bridging modes of O^2-, the competition between ferromagnetic interactions and antiferromagnetic interactions in Mn²⁺ ions results in the ferrimagnetic behavior of 1.     

基于非生物折叠体的分子识别

利用分子自组装的方法控制大分子量的线性有机分子的构象是物理有机化学一个富于挑战性的研究课题. 近年来, 化学家已经成功利用不同的分子内非共价键作用力如氢键和疏溶剂作用等诱导线性分子的折叠乃至螺旋构象的产生. 综述了近年来这种新的非生物二级结构形式在分子识别研究中的应用.     

Semirigorous bounds for the overlap of approximate wavefunctions

Alexander's probable upper and lower bounds to the overlap S between an approximate and the true wavefunctions are based on second-order perturbation theory and a special ordering of configurations. These weak points are removed in the present treatment and replaced by an exact expression for the energy lowering, plus a very reasonable postulate. The resulting lower bound to the overlap S is illustrated with examples taken from the literature.     

一维链状锰配位聚合物[Mn(4-CPOA)(2,2-bipy)(H_2O)]_n的合成与晶体结构(英文)

0IntroductionThe solid-state chemistry of manganese!car-boxylate coordination polymers has received growingattention over the past few years,owing to their fasci-nating network topologies and potential application inthe field of molecular magnetism and bi…     

CCl2(A1B1)被O2及取代甲烷类分子猝灭的动力学研究

对CCl4／Ar混合气体放电产生CCl2自由基，再用541.52nm激光将电子基态CCl2激发到激发态A^1B1（0，4，0）振动态k=0能级上，通过检测 激发态CCl2时间分辨荧光信号，测得室温下CCl2(A^1B1)被O2，CF4，CF2Cl，CH3NO2，CH2Br2等分子猝灭的实验结果，用改进的三能级模型分析处理实验数据，获得态分辨速常数KA和Ka值，并对实验结果进行了讨论。     

Microporous activated carbons prepared from palm shell by thermal activation and their application to sulfur dioxide adsorption

Textural characterization of activated carbons prepared from palm shell by thermal activation with carbon dioxide (CO(2)) gas is reported in this paper. Palm shell (endocarp) is an abundant agricultural solid waste from palm-oil processing mills in many tropical countries such as Malaysia, Indonesia, and Thailand. The effects of activation temperature on the textural properties of the palm-shell activated carbons, namely specific surface area (BET method), porosity, and microporosity, were investigated. The activated carbons prepared from palm shell possessed well-developed porosity, predominantly microporosity, leading to potential applications in gas-phase adsorption for air pollution control. Static and dynamic adsorption tests for sulfur dioxide (SO(2)), a common gaseous pollutant, were carried out in a thermogravimetric analyzer and a packed column configuration respectively. The effects of adsorption temperature, adsorbate inlet concentration, and adsorbate superficial velocity on the adsorptive performance of the prepared activated carbons were studied. The palm-shell activated carbon was found to have substantial capability for the adsorption of SO(2), comparable to those of some commercial products and an adsorbent derived from another biomass.     

胶束催化作用下实现聚苯乙烯的氯甲基化

用紫外分光光度法测定了离子型表面活性剂胶束溶液对聚苯乙烯四氯化碳溶液的增溶性能; 用胶束催化法实现了聚苯乙烯的氯甲基化, 用红外光谱法和佛尔哈德法表征了氯甲基化聚苯乙烯的化学结构与组成; 通过比较阴、 阳离子表面活性剂及结构不同的阳离子表面活性剂的催化效果, 探索了胶束催化的作用机理, 考察了表面活性剂结构对催化作用的影响规律. 结果表明, 表面活性剂胶束溶液可增溶聚苯乙烯的四氯化碳溶液, 随着四氯化碳在胶束中的增溶, 聚苯乙烯可转移至表面活性剂的胶束中; 胶束催化是实现聚苯乙烯的氯甲基化的有效途经, 仅用3.35 g/L的十六甲基三甲基溴化铵(CTAB),  于65 ℃， 5 h内即可使聚苯乙烯大分子链中的苯环氯甲基化程度达到37%; 聚苯乙烯与甲醛、 氯化氢的反应过程由亲电取代和亲核取代串联而成, 阳离子表面活性剂比阴离子表面活性剂的催化作用更加有效, 说明亲核取代是慢步骤; 阳离子表面活性剂疏水链越长, 对聚苯乙烯的增溶效果越好, 催化作用越强.     

氧化酶及烷烃氧化

记述了氧化酶在生物催化中的应用. 较之传统的化学反应, 氧化还原生物催化反应有较好的选择性、可控性和经济性, 人们正在积极地寻找这类催化剂. 自然界中被高度还原的烃类品种丰富, 因此催化烷烃末端或近末端氧合反应的酶也相对容易找到. 很多这一类的酶生化特性已作了详细的描述, 烷烃加氧酶催化高附加值反应的潜力已得到了广泛地认可.     

血镁水平与糖尿病肾病

为探讨糖尿病肾病 (DN)患者血镁水平 ,以 1 5 9例 2型糖尿病 (T2DM)患者为研究对象 ,用xylidylblue比色法测定了其正常白蛋白尿期、微量白蛋白尿期 (早期DN)、临床DN及晚期DN血镁水平 ,与 2 0例正常对照组相比较 ;同时将 1 1 0例DN患者分为肾功能不全代偿组、失代偿组和肾功能衰竭组 ,将其血镁水平与 1 0 2例慢性肾小球肾炎 (CGN)患者相比较 ,组间比较采用t检验 ;对 79例T2DM正常白蛋白尿期及微量白蛋白尿期患者尿白蛋白排泄率 (UAER)与血镁水平进行了等级相关分析。结果表明 ,T2DM正常白蛋白尿期、早期DN及临床DN血镁水平降低 ,晚期DN血镁水平升高 ,各组与正常对照组相比存在显著性差异 (P <0 0 5或P <0 0 1 ) ;T2DMDN及CGN肾功能不全代偿期、失代偿期及肾功能衰竭期血镁水平渐升高 ,且肾功能处于同一期的DN和CGN相比 ,前者血镁水平均较后者显著降低 (P <0 0 1或P <0 0 5 ) ;T2DM正常白蛋白尿期和微量白蛋白尿期血镁水平与UAER呈负相关 (r=0 5 47,P <0 0 1 )。提示T2DM患者肾功能正常时存在低镁倾向 ,但晚期DN血镁水平升高 ;随着肾功能不全进展 ,DN和CGN患者血镁水平升高 ,但前者血镁水平仍较后者低 ,镁代谢紊乱与DM及其并发症的相互关系有待进一步研究 ;血镁水平测定可否作为DN的早期诊断指标亦