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1.
磷酸酯类前药与原药相比,不仅能够提高药物靶向性、稳定性和生物利用度,减少药物毒副作用,还能掩蔽药物不适气味、提高水溶性从而改善给药途径。含羟基药物的磷酸酯化是该类药物前药设计的重要方法之一。本文根据中心磷原子的价态和化合物结构进行分类,综述了各种P(Ⅴ)四配位分子、P(Ⅲ)三配位分子和H-亚磷酸酯类化合物作为磷酸酯化试剂在磷酸酯类前药合成方法中的研究进展,并阐述了这些磷酸酯类药物的应用,最后总结了各类磷酸酯化试剂的优势与局限,并结合连续流反应技术应用案例展望了其发展趋势。 相似文献
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Georges Belfort 《Angewandte Chemie (International ed. in English)》2019,58(7):1892-1902
After 70 years, modern pressure‐driven polymer membrane processes with liquids are mature and accepted in many industries due to their good performance, ease of scale‐up, low energy consumption, modular compact construction, and low operating costs compared with thermal systems. Successful isothermal operation of synthetic membranes with liquids requires consideration of three critical aspects or “legs” in order of relevance: selectivity, capacity (i.e. permeation flow rate per unit area) and transport of mass and momentum comprising concentration polarization (CP) and fouling (F). Major challenges remain with respect to increasing selectivity and controlling mass transport in, to and away from membranes. Thus, prediction and control of membrane morphology and a deep understanding of the mechanism of dissolved and suspended solute transport near and in the membrane (i.e. diffusional and convective mass transport) is essential. Here, we focus on materials development to address the relatively poor selectivity of liquid membrane filtration with polymers and discuss the critical aspects of transport limitations. Machine learning could help optimize membrane structure design and transport conditions for improved membrane filtration performance. 相似文献
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Polyether Natural Product Inspired Cascade Cyclizations: Autocatalysis on π‐Acidic Aromatic Surfaces
Miguel Paraja Xiaoyu Hao Stefan Matile 《Angewandte Chemie (International ed. in English)》2020,59(35):15093-15097
Anion‐π catalysis functions by stabilizing anionic transition states on aromatic π surfaces, thus providing a new approach to molecular transformation. The delocalized nature of anion–π interactions suggests that they serve best in stabilizing long‐distance charge displacements. Aiming therefore for an anionic cascade reaction that is as charismatic as the steroid cyclization is for conventional cation‐π biocatalysis, reported here is the anion‐π‐catalyzed epoxide‐opening ether cyclizations of oligomers. Only on π‐acidic aromatic surfaces having a positive quadrupole moment, such as hexafluorobenzene to naphthalenediimides, do these polyether cascade cyclizations proceed with exceptionally high autocatalysis (rate enhancements kauto/kcat >104 m ?1). This distinctive characteristic adds complexity to reaction mechanisms (Goldilocks‐type substrate concentration dependence, entropy‐centered substrate destabilization) and opens intriguing perspectives for future developments. 相似文献
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Yu Hoshino Shohei Taniguchi Hinata Takimoto Sotaro Akashi Sho Katakami Yusuke Yonamine Yoshiko Miura 《Angewandte Chemie (International ed. in English)》2020,59(2):679-683
Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences. 相似文献
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Marie‐Claire Giel Christopher J. Smedley Emily R. R. Mackie Taijie Guo Jiajia Dong Tatiana P. Soares da Costa John E. Moses 《Angewandte Chemie (International ed. in English)》2020,59(3):1181-1186
The boom in growth of 1,4‐disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the CuI‐catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1‐substituted‐1,2,3‐triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click‐inspired protocol for the synthesis of 1‐substituted‐1,2,3‐triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal‐free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1‐substituted‐1,2,3‐triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1‐substituted triazolium sulfonyl fluoride salts. 相似文献
9.
Dr. Chao Ma Bo Li Dr. Baiqi Shao Dr. Baiheng Wu Prof. Dong Chen Dr. Juanjuan Su Prof. Hongjie Zhang Prof. Kai Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(48):21665-21671
Hydrogels enable a variety of applications due to their dynamic networks, structural flexibility, and tailorable functionality. However, their mechanical performances are limited, specifically in the context of cellular mechanobiology. It is also difficult to fabricate robust gel networks with a long-term durability. Thus, a new generation of soft materials showing outstanding mechanical behavior for mechanobiology applications is highly desirable. We combined synthetic biology and supramolecular assembly to prepare elastin-like protein (ELP) organogel fibers with extraordinary mechanical properties. The mechanical performance and stability of the assembled anisotropic proteins are superior to other organo-/hydrogel systems. Bone-derived mesenchymal cells were introduced into the organofiber system for stem-cell lineage differentiation. This approach demonstrates the feasibility of mechanically strong and anisotropic organonetworks for mechanobiology applications and holds great potential for tissue-regeneration translations. 相似文献
10.
Yu‐Hui Wang Jun‐Song Tian Peng‐Wei Tan Qiang Cao Xue‐Xin Zhang Zhong‐Yan Cao Feng Zhou Xin Wang Jian Zhou 《Angewandte Chemie (International ed. in English)》2020,59(4):1634-1643
Azacycles such as indoles and tetrahydroquinolines are privileged structures in drug development. Reported here is an unprecedented regiodivergent intramolecular nucleophilic addition reaction of imines as a flexible approach to access N‐functionalized indoles and tetrahydroquinolines, by the control of reaction at the N‐terminus and C‐terminus, respectively. Using ketimines derived from 2‐(2‐nitroethyl)anilines with isatins or α‐ketoesters, the regioselective N‐attack reaction gives N‐functionalized indoles, while the catalytic enantioselective C‐attack reaction affords chiral tetrahydroquinolines featuring an α‐tetrasubstituted stereocenter. Mechanistic studies reveal that hydrogen‐bonding interactions may greatly facilitate such unusual N‐attack reactions of imines. The utility of this protocol is highlighted by the catalytic enantioselective formal synthesis of (?)‐psychotrimine, and the construction of various fused aza‐heterocycles. 相似文献