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31.
Dominik Lungerich Jakob F. Hitzenberger Wolfgang Donaubauer Prof. Thomas Drewello Prof. Norbert Jux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16755-16759
A feasible two‐step synthesis and characterization of a full series of hexaarylbenzene (HAB) substituted porphyrins and tetrabenzoporphyrins is presented. Key steps represent the microwave‐assisted porphyrin condensation and the statistical Diels–Alder reaction to the desired HAB‐porphyrins. Regarding their applications, they proved to be easily accessible and effective high molecular mass calibrants for (MA)LDI mass spectrometry. The free‐base and zinc(II) porphyrin systems, as well as the respective tetrabenzoporphyrins, demonstrate in solid state experiments strong red‐ and near‐infrared‐light emission and are potentially interesting for the application in “truly organic” light‐emitting devices. Lastly, they represent facile precursors to large polycyclic aromatic hydrocarbon (PAH) substituted porphyrins. We prepared the first tetra‐hexa‐peri‐hexabenzocoronene substituted porphyrin, which represents the largest prepared PAH‐porphyrin conjugate to date. 相似文献
32.
Domino Staudinger/aza‐Wittig/Mannich Reaction: An Approach to Diversity of Di‐ and Tetrahydropyrrole Scaffolds 下载免费PDF全文
Dr. Anna S. Pavlova Dr. Olga A. Ivanova Dr. Alexey O. Chagarovskiy Nikolay S. Stebunov Dr. Nikolay V. Orlov Dr. Alexey N. Shumsky Dr. Ekaterina M. Budynina Dr. Victor B. Rybakov Prof. Dr. Igor V. Trushkov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(50):17967-17971
A highly efficient and selective domino reaction producing valuable di‐ and tetrahydropyrrole‐based skeletons from azidoethyl‐substituted CH‐acids and (thio)carbonyl compounds has been developed. By involving the additional functional groups in starting compounds into the domino reaction or postmodification of the primary reaction products, the simple construction of the pharmaceutically relevant three‐ and polycyclic azaheterocyclic scaffolds was demonstrated. 相似文献
33.
Inside Cover: Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory (Chem. Eur. J. 7/2015) 下载免费PDF全文
34.
Christian W. Pester Justin E. Poelma Benjaporn Narupai Shrayesh N. Patel Gregory M. Su Thomas E. Mates Yingdong Luo Christopher K. Ober Craig J. Hawker Edward J. Kramer 《Journal of polymer science. Part A, Polymer chemistry》2016,54(2):253-262
In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262 相似文献
35.
The importance of cell design to the development of convenient, laboratory organic electrosyntheses, popular with synthetic chemists, is highlighted. Although also influencing reaction selectivity, the cell design is the major factor determining the rate of conversion of reactant to product, the final conversion that can be achieved and the quantity of product formed. The recent literature contains a number of designs of flow electrolysis cells for electrosynthesis with examples of their application. 相似文献
36.
催化裂化是石油化工的核心单元之一.从催化裂化尾气中分离出来的碳四馏分富含许多的不饱和烯烃,如1-丁烯、顺、反式-2-丁烯以及少量的1,3-丁二烯,这些不饱和烯烃可以通过后续聚合反应,生成合成橡胶和工程塑料的重要原料,具有重要的应用价值.上述工艺过程对原料中1,3-丁二烯的含量(<100~200 ppm)有严苛的要求.采用选择性加氢技术对碳四馏分中的1,3-丁二烯进行选择性加氢,将其转化为更高附加值的单烯烃是一个理想的解决方案.然而,1,3-丁二烯加氢反应得到的单烯烃可能发生深度加氢得到副产物丁烷.因此,开发高效选择性加氢催化剂对碳四资源的利用具有重要的现实意义.另一方面,1,3-丁二烯加氢反应可以作为模型反应,用来考察选择性加氢催化剂的性能.基于此,该反应无论在工业界还是学术界均受到广泛关注.尽管如此,有关1,3-丁二烯加氢催化剂研究进展方面的综述极少.仅有关于1,3-丁二烯加氢作为模型反应的综述报道.本文对过去半个世纪以来1,3-丁二烯加氢反应中不同催化剂的发展历程进行系统综述,特别是包括Pd,Pt和Au等的单一贵金属催化剂.重点介绍以下内容:(1)固体催化剂构效关系,包括活性金属尺寸效应、晶面和形貌效应以及载体效应(晶相、孔道和酸碱性);(2)高性能催化剂的设计新策略,如单原子催化剂、核壳结构催化剂、金属-离子液复合催化体系以及载体的形貌调控;(3)催化剂的反应机理和失活机理.提出了1,3-丁二烯选择性加氢高性能催化剂开发面临的挑战,并对潜在的发展方向进行了展望.本文认为随着纳米技术和金属纳米材料合成方法的快速发展,对贵金属活性组分进行原子层面上的调控(包括形貌、尺寸以及单原子配位环境等)已成为可能.这将有助于研制出一类新型高性能选择性加氢催化材料,从而实现高转化率条件下高附加值单烯烃的定向转化.此外,载体的酸碱性和孔道结构的调控有助于进一步调节催化剂的抗积炭性能,也是未来发展的一个重要方向. 相似文献
37.
分子结构设计是开发新化合物和通过原子尺度操纵优化晶体结构的一种引人注目的策略. 在这个工作中, 利用分子工程的思想, 基于SBBO结构, 成功设计并合成两个新型氟碳酸盐KMgLi2(CO3)2F和RbMgLi2(CO3)2F. 在两个结构中, a-b平面是由CO3和LiO3F阴离子基团组成的无限[Li3C3O6F3]∞层, 进一步相邻的层通过F原子连接形成一个独特的[Li6C6O12F3]∞双层. 这种结构特征对改善晶体的层状生长习性和消除晶体的多晶性有很大的帮助. 光学测试表明, 该系列晶体具有大的双折射和短的紫外截止边, 是深紫外双折射晶体良好的候选材料. 相似文献
38.
Dr. Ulrich Lücking 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(56):e202201993
Extension of the medicinal chemistry toolbox is in the vital interest of drug designers. However, the diffusion of an innovation can be a lengthy process. Along these lines, it took almost 70 years before the use of the sulfoximine group reached a critical mass in medicinal chemistry. Even though interest in this versatile functional group has increased exponentially in recent years, there is ample room for further innovative applications. This Review highlights emerging trends and opportunities for drug designers for the utilization of the sulfoximine group in medicinal chemistry, such as in the construction of complex molecules, proteolysis targeting chimeras (PROTACs), antibody-drug conjugates (ADCs) and novel warheads for covalent inhibition. 相似文献
39.
Saurabh B. Ganorkar Suraj R. Chaudhari Preeti S. Bobade Sagar H. Pawar Atul A. Shirkhedkar 《Biomedical chromatography : BMC》2022,36(5):e5345
Rufinamide is used presently to treat Lenaux–Gastaut syndrome. A full factorial design and desirability approach was investigated for the optimization of hydrolytic stress via response surface curves (RSCs). The degradation impurities were identified and resolved using reversed-phase high-performance liquid chromatography (RP-HPLC) on the Qualisil® BDS C8 column. Acetonitrile–water (29:71, v/v) was optimized for the mobile phase and used at a flow rate of 1.0 ml/min with detection at a wavelength of 230 nm. Rufinamide showed appreciable susceptibility to hydrolysis under acidic and alkaline stress, and substantial degradation in the neutral condition. It degraded much less under oxidative stress. Exposure towards thermal and photolytic stress conditions indicated appreciable stability. The developed method was subjected to validation as per the recommendations of the International Conference on Harmonization. The proposed method showed no influence from the excipients and the degradation products. As well as good precision and accuracy in determination, the method showed a linear response between 2 and 12 μg ml−1. The method was extended for determination in a human plasma sample, which resulted in excellent recovery without interference from matrix effects. The combined use of desirability and design for the optimization of acidic and alkaline hydrolytic stress led to simple and rapid analysis. 相似文献
40.
空间填充设计在计算机试验中应用十分广泛,当拟合回归模型时,正交的空间填充设计保证了因子效应估计的独立性.基于广义正交设计,文章给出了构造二阶正交拉丁超立方体设计和列正交设计的方法,新构造的设计不仅满足任意两列之间相互正交,还能保证每一列与任一列元素平方组成的列以及任两列元素相乘组成的列都正交.当某些正交的空间填充设计不存在时,具有较小相关系数的近似正交设计可作为替代设计使用.设计构造的灵活性为计算机试验在实践中的广泛应用提供了必要的支持. 相似文献