OCS,CO2,N2O与烯、炔烃之间π…π作用的电子密度拓扑研究

采用MP2/aug-cc-pVDZ方法对氧硫化碳(OCS)、二氧化碳(CO2)、一氧化二氮(N2O)与乙烯(C2H4)、乙炔(C2H2)、2-丁炔(C4H6)之间形成的平行构型复合物中的分子间相互作用进行了理论研究.复合物的相互作用能按照B…C2H4B…C2H2>B…C4H6(B=OCS,CO2,N2O)的顺序依次减小.采用电子密度拓扑分析理论方法,讨论了复合物中π…π作用的成键特性.电子密度拓扑分析表明复合物中形成了弱的分子间相互作用,且以静电作用为主;π电子密度分子图与全电子密度分子图中键径方向是一致的,说明π…π作用在本文所讨论的体系中起着很重要的作用.NBO分析表明净电荷迁移从电子给体C2H4,C2H2,C4H6到电子受体OCS,CO2,N2O,迁移数按照B…C2H4相似文献   

碱(土)金属离子与2-(3′-羟基-2′-吡啶基)苯并噁唑阳离子-π复合物及其分子内质子转移过程的理论研究

采用密度泛函B3LYP方法,在6-311++G(d,p)基组水平上对碱(土)金属离子(Li+,Na+,K+,Be2+,Mg2+和Ca2+)与2-(3’-羟基-2’-吡啶基)苯并噁唑(HPyBO)的36种阳离子-π复合物的初始构型进行了几何全优化,并计算了其相互作用能.结果表明,碱(土)金属离子与HPyBO复合物有较强的阳离子-π相互作用,部分复合物甚至达到了化学键的强度.相对能量的变化表明碱(土)金属离子的作用能改变HPyBO分子内质子转移过程的能垒,甚至可以导致优势构型反转.当考虑水的溶剂效应后,各质子转移异构体的相对能量及质子转移的能垒均有一定程度的改变.另外,应用分子中的原子(AIM)方法对复合物分子内氢键的键临界点性质进行了分析.     

天然丝光沸石多步脱铝-钛化制备钛硅分子筛

以优选的天然丝光沸石为原料, 采用多步脱铝-钛化法合成钛硅分子筛, 利用 X 射线粉末衍射、紫外-可见光谱、电感耦合等离子体原子发射光谱、N2 吸附-脱附法以及氨程序升温脱附等手段对其进行了表征, 并考察了它在苯乙烯氧化反应中的催化性能. 结果表明, 该方法可成功地将 Ti 同晶取代到天然丝光沸石的骨架中, 其 Si/Ti 达到 79, 且能稳定地保持天然丝光沸石的结构. 该钛硅分子筛在以 H2O2 水溶液为氧化剂的苯乙烯氧化反应中表现有良好的催化活性, 是商业 TS-1 催化剂的 75%, 具有一定的应用前景.     

一种多功能的角动量定理演示仪

介绍了一种用于课堂的多功能角动量定理演示仪,结构简单,操作方便,能演示出多种角动量定理相关实验,揭示刚体定点转动中深刻的物理规律,并采用在"自然坐标系"下的角动量定理对实验现象加以理论分析.     

混合制冷剂循环膨胀机内复叠天然气液化流程设计

提出一种混合制冷剂循环膨胀机内复叠天然气液化流程(Hybrid JT-exp)。采用自主开发的流程模拟程序,分别对C3/MRC流程、AP-XTM流程和Hybrid JT-exp流程进行了模拟,并以单位能耗为指标对三种流程进行了优化。优化结果发现,Hybrid JT-exp流程综合特性曲线匹配效果最好,其流程总功耗和单位能耗与AP-XTM流程相当;与C3/MRC流程相比,其流程总功耗降低约9.5%,单位能耗降低约9.6%。Hybrid JT-exp流程可作为AP-XTM流程的一种替代技术方案。     

Evaluation the pozzolanic reactivity of sonochemically fabricated nano natural pozzolan

Natural pozzolans are appropriate supplementary cementitious materials in cement and concrete industry. A simple sonochemical method was developed to synthesize nanostructures of natural pozzolan. Chemical composition, crystallinity, morphology and reactivity of the natural pozzolan samples were compared before and after the sonochemical process, by using powder X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Thermal Gravimetry and Differential Thermal Analysis (TG/DTA). Compressive strength tests were performed to evaluate the properties of blended cements incorporating nano natural pozzolan. Under optimized conditions, the nano natural pozzolans showed a superior reactivity as compared with the bulk natural pozzolan. Also higher compressive strength was obtained for the cement specimen incorporating nano natural pozzolan.     

Assignment of Relative Configuration of Desoxypropionates by 1H NMR Spectroscopy: Method Development,Proof of Principle by Asymmetric Total Synthesis of Xylarinic Acid A and Applications

The determination of the relative configuration of 1,3‐dimethyl‐substituted alkyl chains is possible by interpretation of ¹H NMR shift differences. Additionally, assignments are feasible in a variety of deuterated solvents, because the corresponding shift differences are not significantly influenced by the solvent. The trends for Δδ values depending on functional groups adjacent to the stereogenic centers are shown. Based on a thorough comparison with literature data, the relative configuration of natural products can be predicted. For this purpose, we derived an empirical rule for the ranges in which Δδ values usually occur. Furthermore, we were able to proof the validity of our method by the successful prediction of the relative configuration for the polyketide natural product xylarinic acid A, which was confirmed by the asymmetric total synthesis of its enantiomer. Based on the proposed simple analysis of published ¹H NMR data and the determination of the relevant chemical‐shift differences, we predicted the relative configurations of several previously unassigned natural products.     

Cost/risk balanced management of scarce resources using stochastic programming

We consider the situation when a scarce renewable resource should be periodically distributed between different users by a Resource Management Authority (RMA). The replenishment of this resource as well as users demand is subject to considerable uncertainty. We develop cost optimization and risk management models that can assist the RMA in its decision about striking the balance between the level of target delivery to the users and the level of risk that this delivery will not be met. These models are based on utilization and further development of the general methodology of stochastic programming for scenario optimization, taking into account appropriate risk management approaches. By a scenario optimization model we obtain a target barycentric value with respect to selected decision variables. A successive reoptimization of deterministic model for the worst case scenarios allows the reduction of the risk of negative consequences derived from unmet resources demand. Our reference case study is the distribution of scarce water resources. We show results of some numerical experiments in real physical systems.     

Direct Determination of Labile Monomeric Aluminum in Natural Waters By A.C. Oscillopolarography in the Presence of Rubeanic Acid

ABSTRACT

A simple and sensitive electrochemical method for the direct determination of labile (monomeric inorganic Al speciation) Al concentration in natural waters is developed in this paper. It is based on the use of a.c. oscillopolarography in the presence of rubeanic acid (RA). The optimal experimental conditions are: 1 mol/L NaAc-HAc buffer (pH 5.4) and a RA concentration of 6x10^?4 mol/L. The response is linear over the 2x10^?7 to 2x10^?6 mol/L concentration range. The detection limit is 1x10^?7 mol/L and the relative standard deviation (at the 1.2 x 10^?6 mol/L level) is 5.5%. The method has been applied to the direct determination of labile monomeric Al concentrations in various natural samples. The results were verified by the classic ion exchange method.