磷脂核苷缀合物甘油结构修饰新方法及应用

通过环甘油磷脂核苷缀合物的亲核开环,为甘油结构修饰提供了一条简便有效的新路线.三乙胺对环甘油磷脂核苷缀合物的亲核开环,在室温下就能进行,合成了一类结构新型的以卵磷脂类似物作载体的核苷前药.     

Modified GC-phases for the enantiomeric separation of optically active compounds: Crosslinking experiments with polymeric chiral compounds

Crosslinking experiments for immobilization of the well-known chiral stationary phases XE 60-L -valine-(S)- and XE 60-L -valine-(R)-α-phenylethylamide within capillary columns have been successfully carried out. Crosslinking was also obtained with mixtures of the chiral compound acrylyl-L -valine-(S)-α-phenylethylamide and the polyethylene glycol Carbowax 20M. Immobilization of 75% to 90% was achieved by crosslinking the polymeric chiral phases, but sometimes up to 100% of these phases remained within the columns after the usual subsequent solvent treatment. The crosslinking of Carbowax 20M with acrylyl-L -valine-(S)-α-phenylethylamide led to a chiral polymer of a polarity different from that of the common siloxane type chiral phases.     

骨架金属原子对Keggin阴离子电子结构和物化性质的研究

使用第一原理密度泛函理论中的离散变分方法(DFT-DVM)对(PM~1~2O~4~0)^n^-(M=Mo,W,V),(PMo~9W~3O~4~0)^3^-,(PMo~9V~3O~4~0)^6^-五种Keggin结构杂多阴离子进行了电子结构计算,讨论了骨架金属原子对Keggin结构杂多阴离子的电荷分布、成键作用、热稳定性、氧化还原性等的影响。结果表明,骨架金属原子对Keggin阴离子的电荷分布和成键作用均有一定的影响,以Mo,W,V作骨架金属原子的Keggin阴离子(PM~1~2O~4~0)^n^-的热稳定性顺序为:(PW~1~2O~4~0)~3^->(PMo~1~2O~4~0)^3^->(PV~1~2O~4~0)^1^5^-。提出了判断杂多阴离子氧化性强弱的两因素法---脱出晶格氧的难易程度和LUMO轨道电负性,并根据两因素法得到氧化性强弱顺序为:(PV~1~2O~4~0)^1^5^->(PMo~1~2O~4~0)^3^->(PW~1~2O~4~0)~3^-。同时,讨论了当(PMo~1~2O~4~0)~3^-中的Mo部分被W和V取代后,即(PMo~9W~3O~4~0)^3^-,(PMo~9V~3O~4~0)^6^-,其中取代原子对电子结构的影响,结果表明,W取代使整个阴离子的稳定性增强,但氧化性减弱,V取代,使稳定性减弱,但氧化性增强。     

On Presentations of Bruck–Reilly Extensions

We first consider the class of monoids in which every left invertible element is also right invertible, and prove that if a monoid belonging to this class admits a finitely presented Bruck–Reilly extension then it is finitely generated. This allow us to obtain necessary and sufficient conditions for the Bruck–Reilly extensions of this class of monoids to be finitely presented. We then prove that thes 𝒟-classes of a Bruck–Reilly extension of a Clifford monoid are Bruck–Reilly extensions of groups. This yields another necessary and sufficient condition for these Bruck–Reilly extensions to be finitely generated and presented. Finally, we show that a Bruck–Reilly extension of a Clifford monoid is finitely presented as an inverse monoid if and only if it is finitely presented as a monoid, and that this property cannot be generalized to Bruck–Reilly extensions of arbitrary inverse monoids.     

一类马尔可夫骨架过程的强大数定律和中心极限定理

基于马尔可夫骨架过程极限分布的已有研究结果,本文运用波莱尔-康特立引理、更新理论、科尔莫哥洛夫的强大数定律以及独立同分布情形的中心极限定理等重要理论,分别给出了一类马尔可夫骨架过程对应的累积过程满足强大数定律和中心极限定理的充分条件.     

Entropy in good manufacturing system: Tool for quality assurance

It has been customary to implement Good Manufacturing Practices (GMP) in pharmaceutical organizations as a systematic and comprehensive quality approach and sometimes by regulatory enforcement. In this scenario, determination of the obvious entropy/disorder arising during the implementation has not been taken care of yet. Therefore, this paper gives the basis for applying query and visual perception of GMP system driven visualization approach, particularly the Laplace equation, to the determination of disorder and deviation pattern inside the GMP system applied in the organization. In this study, a three-dimensional mesh approached with raw and intermediate input handled under GMP parameter is considered to produce high quality products with minimum entropy (variation distribution) by adding the analogy wise different GMP parameters and process variables with Gauss Seidel iteration and thus producing visual picture of the entire system. The approximation involved in applying the equations to the GMP compliant aseptic region was analyzed. Using numerical technique and computer program, the Gauss Seidel iteration equations have been solved with appropriate GMP parameter and process variable. The result indicates that deviations vary over the GMP compliant system and that the process entropy affects the totality of disorderness. Experiments with model of GMP compliant reproductive medicine laboratory confirm that the new method provides optimal manufacturing maintaining GMP and high product quality through the visual representation of the entire system and activity to bring into notice the deviations.     

手性螺环配体及催化剂在不对称催化反应中的应用研究进展

金属参与的不对称催化反应是制备光学活性化合物的重要途径之一, 其中新型手性配体的设计合成一直是不对称催化领域中十分关键且富有挑战性的课题. 从20世纪90年代末开始, 化学家们尝试在手性配体中引入螺环结构, 创造性地发展了螺[4.4]壬烷骨架、 螺双二氢茚骨架、 螺[4.4]壬二烯骨架和螺二色满骨架等手性螺环单齿配体, 多齿配体及其催化剂, 并成功应用于不对称催化氢化、 不对称碳碳键形成或碳杂键形成等不对称转化反应中, 合成了众多富有价值的手性产品, 有力地推动了不对称催化反应的工业应用化进程. 本文综合评述了手性螺环配体的早期发现、 发展历程以及近期的研究成果, 介绍了螺环配体在药物及天然产物中的应用研究进展, 并对手性螺环结构的小分子催化剂的研究进展进行叙述和说明.     

基于RGO-Au-ZIF-8复合材料的电化学传感器制备及其在铅离子和铜离子同时检测中的应用

金属有机骨架（MOFs）材料因其结构和组成特点在重金属离子的吸附和预富集方面表现出独特优势,在重金属离子的光学传感方面显示出极大的应用潜力,但其导电性较差,这大大限制了其在电化学传感领域的应用.制备了一种功能化的金属有机骨架复合材料——热还原氧化石墨烯-金-沸石咪唑酯骨架材料（RGO-Au-ZIF-8）.该复合材料具有较本体MOF显著改善的电化学性质,利用其构建电化学传感平台实现了对水相溶液中铅离子（Pb²⁺）和铜离子（Cu²⁺）的同时灵敏检测.借助扫描电子显微镜、透射电子显微镜、紫外可见吸收光谱法和各种电化学技术对所制备材料及其修饰电极的形貌、结构和电化学特性进行了表征.采用阳极溶出伏安法（DPASV）对水相溶液中的Pb²⁺和Cu²⁺进行检测,并对检测溶液pH、沉积时间和沉积电位等实验参数进行了优化.在最优化条件下,该传感平台对Pb²⁺和Cu²⁺的检测线性浓度范围分别为0.005～10（Pb²⁺）和0.01～10（Cu²⁺）μmol·L^-1,检测限为2.6×10^-9（Pb²⁺）和7.8×10^-9（Cu²⁺） mol·L^-1.此外,还对该传感平台的选择性、重现性和稳定性进行了考察,并进行了实际水样中Pb²⁺和Cu²⁺的回收实验.该工作为重金属离子的同时、快速且灵敏的检测提供了一种新的平台,并大大拓展了MOFs材料的电化学应用.     

手性4-取代色满骨架的立体选择性构建研究进展

手性4-取代色满骨架在很多具有生物活性的天然产物及其类似物中广泛存在,该骨架的不对称构建策略在新药开发中扮演着重要角色。本文从加成反应、氢化反应、烷基化反应、烯/炔丙基化反应、去对称化反应、羰基α位芳基化反应和重排反应七个方面综述了手性4-取代色满骨架的立体选择性构建策略,以期为含有该类骨架的活性天然产物的不对称合成提供参考。     

Anwendung von 85Kr–Bremsstrahlung zur Erweiterung des Dickenmeβbereichs

In der vorliegenden Arbeit wird zunächst der Aufbau der ⁸⁵Kr-Bremsstrahlungsquellen behandelt. Die Anwendung für die Dickenmessung von Schwermetall- und Aluminiumbändern und die aus diesen Untersuchungen erhaltenen Meβbereiche für das Flächengewichtsmeβgerät mit Automatik VA-T-75 werden dargestellt.