杯芳烃的合成及性能研究的新进展

简要介绍了杯芳烃的结构、性能及应用,重点综述了：（1）新型杂原子杯芳烃的合成及超分子自组装;（2）杯芳烃衍生物的合成及对金属离子的识别;（3）杯[4]吡咯席夫碱衍生物的合成。     

杯[4]芳烃偶氮衍生物的合成及其金属离子萃取性能

杯芳烃作为超分子化学的重要组成部分,近年来得到了快速发展并成为化学家的研究热点。以脱叔丁基-杯[4]芳烃为原料合成了杯[4]芳烃偶氮衍生物,其结构经IR和1H NMR所表征。研究了该主体分子对金属离子的萃取性能,实验结果表明,该主体分子对Mg2＋具有较高的萃取作用。讨论了主客体间配位作用的机制。     

杯芳烃合成研究进展

杯芳烃是一类超分子主体化合物,主要有杯[4]、杯[6]和杯[8]芳烃的杯芳烃衍生物、杯芳烃聚合物及杯芳烃配合物等。介绍了不同杯芳烃及其衍生物的合成工艺的研究进展。     

杯芳烃及其衍生物在生命科学中的研究进展

通过查阅近五年来的文献,对被称为第三代主体超分子化合物的杯芳烃及其衍生物在生命科学领域中的研究进展进行了综述。主要阐述了杯芳烃对生物分子的识别作用、生物分子在杯芳烃化合物功能修饰中的应用及杯芳烃与生物分子相互作用的应用研究,同时还对杯芳烃及其衍生物在生命科学领域中的应用前景进行了展望。     

氮杂杯[6]芳烃及其叠氮衍生物与RDX、HMX的配合研究

研究了氮原子桥连杯[3]芳烃[3]三嗪化合物(简称氮杂杯[6]芳烃)与黑索今、奥克托今的配合能力。通过紫外光谱和X射线衍射(XRD)对氮杂杯[6]芳烃及其叠氮衍生物与黑索今、奥克托今的配合性能进行了表征分析。结果表明主客体之间发生了相互作用,为超分子炸药的制备提供了理论支持。     

硫杂杯芳烃的应用研究进展

硫杂杯芳烃是一类以硫原子取代桥联亚甲基的新型杯芳烃,作为新一代超分子砌块,在分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用,己成为当今超分子化学研究的新热点.     

杯芳烃及其衍生物的合成与工业应用

杯芳烃是继环糊精，冠醚之后又一类新兴的大环化合物，以其出色的超分子化学性能日益引起化学，化工界的关注。本文综合近年来的文献报道，介绍了杯芳烃及其衍生物的合成以及目前杯芳烃在诸多工业领域中的应用与发展前景。     

杯芳冠醚衍生物的发展与应用

杯芳冠醚作为超分子化学中的研究热点之一,以其独特的结构和性质引起学界广泛的关注。本文主要介绍了近几年杯芳冠醚衍生物的合成进展及其在吸附、分子传感器、离子识别等领域的应用。     

杯[4]芳烃咪唑盐的微波合成及在氟化反应中的应用

以杯[4]芳烃为起始原料,首先制得中间体杯[4]芳烃双溴代烷基衍生物,然后经微波辐射和阴离子交换,共得9种杯[4]芳烃咪唑盐衍生物,化合物的结构与构象经元素分析、IR、1HNMR、19FNMR、31PNMR表征.研究了它们在对氯硝基苯氟化反应中的催化性能以及对K+的萃取性能.结果表明,这9种化合物在氟化反应中的催化效果良好,对氟硝基苯的收率为80.89％～92.67％;同时化合物对K+具有较好的萃取效果,其中以化合物25,27-二[4-(3-甲基咪唑)乙氧基]-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃六氟磷酸盐的萃取效果最好,萃取率可达75.45％.     

柱芳烃合成及应用研究进展

柱芳烃是一类结构对称、由对苯二酚或对苯二酚醚通过亚甲基对位桥联的新型“柱”状大环低聚超分子主体化合物。本文主要回顾了烷氧基柱芳烃、水溶性柱芳烃、两亲性柱芳烃的合成发展过程,介绍了柱芳烃的结构与构象,柱芳烃及其衍生物的主客体化学,阐述了它们在构筑超分子自组装体系、医药、生物、相转移催化方面的应用研究进展。目前,柱[5,6]芳烃的合成方法已经比较成熟,而高阶柱芳烃的合成仍有待进一步改善,同时,随着研究的不断深入,柱芳烃及其衍生物将有望用于催化、生物模拟、石油化工等更广泛的领域。     

Nitrogen and oxygen bridged calixaromatics: synthesis, structure, functionalization, and molecular recognition

Pedersen, Lehn, and Cram established supramolecular chemistry through their pioneering work with crown ethers, cryptands, and spherands. Since then, the hallmark of supramolecular science has been an increasing sophistication in the design and construction of macrocyclic molecules, as manifested in cyclodextrin derivatives, calixarenes, resorcinarenes, cyclotriveratrylenes, cucurbiturils, calixpyrroles, cyclophanes, and many other examples. Indeed, macrocyclic compounds provide unique models for the study of noncovalent molecular interactions. They also constitute building blocks for constructing high-level molecular and supramolecular architectures and fabricating molecular devices and advanced materials. As a postgraduate in the Huang laboratory in the late 1980s, I became interested in the calix[n]arenes because of their unique conformational structures and versatile complexation properties. The notion of introducing heteroatoms, and particularly nitrogen, into the bridging position of conventional calixarenes was particularly intriguing. Nitrogen, unlike methylene, can adopt either an sp(2) or sp(3) electronic configuration, providing different conjugation systems with adjacent aromatic rings. Consequently, depending on the configuration and conjugation, a range of C-N bond lengths and C-N-C bond angles is possible. The conformation and cavity size in heteroatom-bridged calixarenes might thus be tuned through the bridging heteroatoms and the number of aromatic rings. Furthermore, because heteroatom linkages significantly affect the electron density and distribution on aromatic rings, the electronic features of macrocyclic cavities might be regulated by heteroatoms. Given the essentially limitless combinations possible, only synthetic hurdles would prevent access to numerous diverse heteracalixaromatics. We began a systematic study on nitrogen- and oxygen-bridged calixarenes in 2000, years later than originally envisioned. Before this study, very few heteracalixaromatics had been reported, owing to the formidable synthetic challenges involved. Apart from thiacalixarene, the synthesis of nitrogen- and oxygen-bridged calixarenes appeared very difficult. But since our first publications in 2004, we have been delighted to see the rapid and tremendous development of the supramolecular chemistry of this new generation of macrocycles. In this Account, I summarize the synthesis of N- and O-bridged calixaromatics and their regiospecific functionalization on the rims and bridging positions, focusing on the fragment coupling approach and contributions from our laboratory. I describe the construction of molecular cages based on heteracalixaromatics and discuss the effect of both bridging heteroatoms and substituents on macrocyclic conformations and cavity sizes. Molecular recognition of neutral organic molecules and charged guest species is also demonstrated. The easy accessibility, rich molecular diversity, unique conformation, and cavity tunability of heteracalixaromatics make them invaluable macrocycles for research in supramolecular chemistry. New heteracalixaromatics, with well-defined conformations and cavity properties, will provide powerful tools for probing noncovalent interactions, leading to the development of new molecular sensing and imaging systems. Multicomponent molecular self-assembly of heteracalixaromatics as functional modules with metals, metal clusters, or charge-neutral species should result in multidimensional solid and soft materials with diverse applications. The profitable incorporation of heteracalixaromatics into molecular devices can also be anticipated in the future. Moreover, the construction of enantiopure, inherently chiral heteracalixaromatics should provide important applications in chiral recognition and asymmetric catalysis.     

新型超分子化合物的合成分子识别自组装及应用新进展

简要介绍了超分子化学的产生发展及应用。详细介绍了:超分子配体的合成及其应用;新型超分子配体的合成分子识别及应用;超分子金属配合物的合成及催化作用。并对超分子化学的发展进行了展望。     

Inherently chiral calixarenes: synthesis, optical resolution, chiral recognition and asymmetric catalysis

Inherently chiral calixarenes, whose chirality is based on the absence of a planar symmetry or an inversion center in the molecules as a whole through the asymmetric array of several achiral groups upon the three-dimensional calix-skeletons, are challenging and attractive chiral molecules, because of their potential in supramolecular chemistry. The synthesis and optical resolution of all varieties of inherently chiral calixarenes are systematically discussed and classified, and their applications in chiral recognition and asymmetric catalysis are thoroughly illustrated in this review.     

杯芳烃应用研究进展

杯芳烃具有离子载体和分子识别及包合两大功能,可应用于分子识别、络合化合物、电极材料、生物模拟酶、催化反应、化学传感器等领域。简要介绍了杯芳烃的性质及其应用的研究进展,并对其开发前景进行了展望。     

Fluorine in medicinal chemistry

Fluorinated compounds are synthesized in pharmaceutical research on a routine basis and many marketed compounds contain fluorine. The present review summarizes some of the most frequently employed strategies for using fluorine substituents in medicinal chemistry. Quite often, fluorine is introduced to improve the metabolic stability by blocking metabolically labile sites. However, fluorine can also be used to modulate the physicochemical properties, such as lipophilicity or basicity. It may exert a substantial effect on the conformation of a molecule. Increasingly, fluorine is used to enhance the binding affinity to the target protein. Recent 3D-structure determinations of protein complexes with bound fluorinated ligands have led to an improved understanding of the nonbonding protein-ligand interactions that involve fluorine.     

识别中性分子客体荧光传感和开关的研究进展

分子识别是超分子化学的核心概念，而荧光开关PET(photo-induced electron transfer)体系又是分子识别中的重要组成部分，是超分子化学和光物理学科相结合的成就。本文总结了近年来对中性客体分子的荧光传感和开关的研究进展。     

水溶性含氟丙烯酸酯乳液的合成研究进展

含氟丙烯酸酯类聚合物因具有突出的成膜性能及耐老化性能而成为优良的成膜材料。其中，水溶性含氟丙烯酸酯乳液的合成研究，具有广泛的单体种类，聚合方式简单多样，在涂料领域受到了广泛的应用和关注。选择合适的乳液共聚单体及聚合工艺，不仅能够根据实际需要调节含氟聚合物的分子结构，而且可以获得最佳含氟量，以满足特殊性能需要的含氟丙烯酸酯乳液。综述了水溶性含氟丙烯酸酯乳液的聚合方法、常用含氟单体和非氟单体以及改性研究进展。     

硫桥杯芳烃的研究进展

在过去的几十年里,因其构象及结构上的灵活多变性,使得杯芳烃及其衍生物被作为分子离子识别的载体而引起广泛关注。硫桥杯芳烃是杯芳烃家族的新成员,硫桥的引入使其拥有了许多不同于经典杯芳烃的特点。文章介绍了硫桥杯芳烃的研究进展,其中包括硫桥杯芳烃的特点、母体及其衍生物的合成、分子识别功能及应用。