含三螺吡喃单元大环分子的合成和酸致变色效应

合成了含有3个螺吡喃单元的大环分子,采用点击化学方法实现高效的闭环反应,大环分子产率为64%。 使用红外、核磁和质谱等方法检测和表征了反应中间产物和目标产物,质谱分析结果证实环化结构。 使用紫外-可见光谱仪观察到大环产物和线性螺吡喃前体分子在pH值接近4时的酸致变色效应。 与线性螺吡喃前体分子的最大紫外吸收峰位置（476 nm）相比,螺吡喃大环分子在最大紫外吸收峰位置（464 nm）发生蓝移。 螺吡喃大环分子比线性前体分子具有更大的摩尔消光系数,其pH响应性能更加优异。     

含四硫富瓦烯大环化合物的合成与研究进展

简要介绍了含有四硫富瓦烯(TTF)单元的大环化合物的分类, 概括了各类含四硫富瓦烯大环化合物的合成方法, 主要包括含有1,3-二硫杂环戊烯-2-硫酮单元的大环化合物在亚磷酸三烷基酯参与下的偶合反应, 以及带有氰乙基硫等取代基的预先合成的官能化TTF与二卤代低聚醚的反应. 综述了含四硫富瓦烯大环化合物的电化学性能及其在分子识别方面应用研究的最新进展, 提出了含四硫富瓦烯大环化合物的发展趋势.     

Macrocyclic polymerization - a new approach to molecular engineering

2,2-Dibutyl-2-stanna-1,3-dioxacycloalkanes were used as cyclic initiators for the ring-opening polymerization of various lactons. This method exclusively yielded series of macrocyclic polylactones without any competition with linear polymers. Under optimized reaction conditions these macrocyclic polymerizations obey the pattern of “living polymerizations”. The living chain ends allow the syntheses of macrocyclic blockcopolymers. The macrocyclic polylactones react with carboxylic acid chlorides by ring-opening yielding telechelic oligo or polylactones. Furthermore, the tin containing macrocyclic polylactones can be used as difunctional “monomers” for polycondensations with dicarboxylic acid dichlorides.     

S-Methylation of polythiolactam: chemical transformation of macrocyclic anion receptor into new macrocyclic ligand for metal ions

The S-methylation of a macrocyclic tetrathiolactam afforded a new macrocyclic thioimidate that exhibited good affinity toward metal ions. The molecular structures of the macrocyclic ligand and its metal complexes were determined by X-ray crystallography.     

Synthetic macrocyclic receptors in chiral analysis and separation

Chiral synthetic macrocyclic receptors that can achieve chiral discrimination by NMR spectroscopy and/or chiral separation by HPLC are overviewed. Synthetic macrocycles introduced here include crown ethers, calixarenes/calixresorcinarenes/calixpyrroles, macrocyclic amides/amines, and porphyrins. These macrocyclic frameworks are advantageous because intermolecular interactions can take place effectively, such as the ion–dipole interactions in crown ethers, the CH/π and π–π interactions in calixarenes, hydrogen bonding and salt formation in macrocyclic amides and amines, and π–π stacking and metal coordination in porphyrins. Additional functional groups on the periphery of the macrocyclic platforms not only make the whole molecule chiral but also act as the interaction sites. Chiral macrocyclic receptors can show a high degree of chiral recognition/discrimination by using the peripheral functional groups as well as the macrocyclic skeletons (preorganization). Both hosts and guests are shown in the figures to quickly overview the molecular recognition scope of synthetic macrocyclic receptors in chiral analysis and separation.     

Selective syntheses of novel polyether fullerene multiple adducts

We have applied a modified macrocyclic tether approach to control multiple additions to C60. The technique of 3He NMR was used to confirm the selective formation of specific C60 multiple adducts by the macrocyclic tether approach. An oligoglycol was used as a flexible linker to produce macrocyclic polyether-linked malonates 5, 6, 8, and 9 under solid-liquid PTC (phase-transfer-catalysis) conditions. The formation of a single C60 tris-adduct, 3, from macrocyclic malonate 1 and 3He@C60 was proven by 3He NMR. Similarly, multiple additions to C60 of macrocyclic polyether malonate 5 gave C60 bis-adduct 10 selectively, while the reaction of C60 with macrocyclic malonate 8 gave bis-adducts 11 and 12. A similar process with macrocyclic malonate 6 gave tris-adduct 13 with high selectivity as well. Saponification of these C60 multiple adducts gives the corresponding polyacids that are potentially useful in biological applications. Macrocyclic polyether fullerenes are a new class of ionophores, which could be interesting for molecular recognition and for the development of biosensors.     

The origin of global and macrocyclic aromaticity in porphyrinoids

The global and macrocyclic aromaticity of porphyrinoids was characterized using our graph theory of aromaticity. The sequential line plots of topological resonance energy (TRE) against the number of π-electrons (N(π)) for different porphyrinoids are similar with four major extrema to those for five-membered heterocycles. This supports the view that five-membered rings are the main origin of global aromaticity in porphyrinoids. Macrocyclic circuits contribute significantly to macrocyclic π-circulation but modestly to global aromaticity. Macrocyclic aromaticity/antiaromaticity in oligopyrrolic macrocycles can be predicted by formally applying Hückel's [4n + 2] rule to an annulene-like main macrocyclic conjugation pathway (MMCP). This bridged annulene model can be justified by examining the contribution of individual macrocyclic circuits to macrocyclic aromaticity. A Hückel-like rule of macrocyclic aromaticity was found for porphyrinoid species.     

新型含芳基 恶二唑带支臂大环多胺和磊环聚醚的 合成研究

利用稀释法合成了五个不同结构类型的芳基恶二唑类大环多胺和大环聚醚,并研究了它们对金属离子的络合作用。     

New approach to the synthesis of macrocyclic tetralactones via ring-closing metathesis using Grubbs' first-generation catalyst

A facile and efficient route to synthesize macrocyclic tetralactones with different ring sizes having a wide variety of spacers is described. The application of ring-closing metathesis for the synthesis of macrocyclic tetralactones is demonstrated with many examples in excellent yield. The representative structure of macrocyclic tetralactones is characterized by X-ray crystallography.     

Macrocyclic sulfide syntheses: A review

The syntheses of various macrocyclic sulfides are reviewed. Tables containing information on hundreds of compounds are included. The types of cyclic compounds reviewed include: macrocyclic aliphatic dithioethers, macrocyclic mercaptals and mercaptoles, macrocyclic polysulfides, dithiacyclophanes, tris-bridged polythiacyclophanes, dithia[2,6]pyridinophanes, thiophene macrocycles, and macrocyclic polyether sulfides.     

Synthesis and characterization of organic–inorganic macrocyclic molecular brushes with poly(ε-caprolactone) side chains

In this work, we reported the synthesis of a dodecahydroxyl-functionalized macrocyclic oligomeric silsesquioxane (MOSS). The novel 24-membered hydroxyl-functionalized MOSS was employed as a macroinitiator for the ring-opening polymerization of ε-caprolactone (CL) and the organic–inorganic macrocyclic molecular brushes with poly(ε-caprolactone) (PCL) side chains were successfully synthesized. The organic–inorganic macrocyclic molecular brushes were characterized by means of nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). The results of wide angle X-ray diffraction (XRD) indicate that the architecture of the organic–inorganic macrocyclic molecular brushes did not alter the structure of PCL crystals. Differential scanning calorimetry (DSC) shows that the architecture of organic–inorganic macrocyclic molecular brushes significantly affected the rearrangement of PCL crystals. Compared to linear PCL, the organic–inorganic macrocyclic molecular brushes possessed the improved thermal stability in terms of the temperatures at the maximum of degradation rate and the yields of degradation residues.     

Preparation and characterisation of copper,cobalt and nickel complexes of tetradentate N6 macrocyclic ligand

Macrocyclic complexes of copper, nickel and cobalt were synthesised via template reactions. These 14-membered N₆ tetradentate macrocyclic complexes were characterised by magnetic, conductance, electronic and IR spectral studies. The macrocyclic ligand coordinates through the four azomethine nitrogen atoms which are bridged by 2,3-butanedione, moieties, but far IR spectra suggest that the pyridine nitrogens are not coordinated. These macrocyclic complexes are considered to have distorted octahedral configurations.     

Synthesis Efforts of Acyclic Bis(monoalkylamino)maleonitriles and Macrocyclic Bis(dialkylamino)maleonitriles as Fluorescent Probes for Cations and a New Colorimetric Copper(II) Chemodosimeter

In this article, we report on the synthesis of acyclic bis(monoalkylamino)maleonitriles and on the intended synthesis of macrocyclic bis(dialkylamino)maleonitriles to get fluorescent probes for cations. During our efforts to synthesize macrocyclic bis(dialkylamino)maleonitriles, we were only able to isolate macrocyclic bis(dialkylamino)-fumaronitriles. The synthesis of macrocyclic bis(dialkylamino)maleonitriles is challenging, due to the fact that bis-(dialkylamino)fumaronitriles are thermodynamically more stable than the corresponding bis(dialkylamino)-maleonitriles. Further, it turned out that the acyclic bis(monoalkylamino)maleonitriles and macrocyclic bis-(dialkylamino)fumaronitriles are no suitable tools to detect cations by a strong fluorescence enhancement. Further, only the bis(monoalkylamino)maleonitriles, which are bearing a 2-pyridyl unit as an additional complexing unit, are able to selectively recognize copper(II) by a color change from yellow to red.     

Chiral separations using the macrocyclic antibiotics: a review

The macrocyclic antibiotics have recently gained popularity as chiral selectors in CE, HPLC and TLC. The macrocyclic antibiotics used for chiral separations include the ansamycins, the glycopeptides, and the polypeptide antibiotic thiostrepton. Although not strictly considered macrocyclic antibiotics, the aminoglycosides are antibiotics that have been used for chiral separations in CE. More chiral analytes have been resolved using the glycopeptides than with the other macrocyclic antibiotics combined. The glycopeptides vancomycin, ristocetin A and teicoplanin have been used extensively as chiral selectors in CE, with ristocetin A appearing to be the most useful chiral selector followed by vancomycin and teicoplanin, respectively. The macrocyclic antibiotics have also been used as chiral bonded phases in HPLC, and HPLC stationary phases based on vancomycin, ristocetin A and teicoplanin have been commercialized. Ristocetin A seems to be the most useful glycopeptide HPLC bonded phase, but its greater expense can be a drawback. The macrocyclic antibiotics have been used with micelles to improve efficiency, provide unique selectivity, and extend the range of separations to neutral solutes. Changing the macrocyclic antibiotic used in CE or HPLC can significantly alter the enantioselectivity of the separations. In fact, the glycopeptide antibiotics are complementary to one another, where if a partial enantioresolution is obtained with one glycopeptide, there is a high probability that a baseline or better separation can be obtained with another.     

镧系元素十八元六氮大环配合物的研究

本文采用“模板反应”合成了十四个三价镧系金属和一个二价铕的十八元六氮大环固体配合物和一个自由大环,推测了所合成的配合物的组成、结构和配位数,研究了某些配合物的热稳定性、价态稳定性和在水溶液中的行为。     

Part 1. modular approach to obtaining diverse tetrahydroquinoline-derived polycyclic skeletons for use in high-throughput generation of natural-product-like chemical probes

A practical synthesis of a tetrahydroaminoquinoline scaffold (12) was developed that used a stereocontrolled aza Michael as the key reaction. Three tetrahydroquinoline alkaloid-like, tricyclic derivatives 16, 18, and 19 with different medium to macrocyclic ring skeletons were obtained, using this scaffold as the starting material, in a modular manner. The macrocyclic compounds with an isolated olefin and an electron-deficient olefin were obtained by ring-closing metathesis approaches. Compounds 16 and 18 are unique and contain bridged 10- and 12-membered functionalized rings. The NMR studies of these compounds revealed interesting information on the conformation of the bicyclic scaffolds that was dependent on the nature and the size of the macrocyclic rings. Finally, this modular methodology, using compound 21 anchored onto the solid support, successfully led to the generation of different macrocyclic derivatives, 23, 25, and 27 in solid-phase synthesis. The solid-phase synthesis approach outlined in this article has the potential to generate tetrahydroquinoline-based tricyclic compounds containing different medium to macrocyclic architectures.     

大环Schiff碱化合物的合成、表征及其荧光活性研究

含乙酰丙酮类大环Schiff碱化合物一般都具有良好的荧光活性．采用模板合成法,用对苯二胺与乙酰丙酮反应合成得到的Schiff碱配体（H2L）与烷基二胺（即1,2-乙二胺,1,3-丙二胺,1,4-丁二胺）反应合成了3种新型大环Schiff碱化合物,通过元素分析,^1H NMR,IR,MS,UV,摩尔电导等手段对合成得到的化合物进行了组成和结构表征,同时在DMF溶液中对大环Schiff碱锌（Ⅱ）配合物的荧光活性进行了初步研究．     

Macrocyclic Ligands in Separations

The selectivity of macrocyclic ligands such as crown ethers and cryptands in binding metal and other cations in aqueous and nonaqueous solvents can be exploited to make ion separations. Cations are usually separated by direct interaction with the ligand. In addition, anions associated with the positively charged macrocyclic complexes can be separated in novel separations systems. We have incorporated macrocyclic ligands into high performance ion chromatography, liquid membranes, and solvent extraction separation systems involving coalescence extraction.     

Formation of molecular ladder elements with macrocyclic platforms via linear bifunctional ligands

Reaction between 4-aminopyridine and a dinuclear zinc(II) component of a Robson macrocyclic ligand has resulted in the formation of a molecular ladder element motif. X-ray single crystal structural analysis indicates that two pyridine rings are assembled at the same direction of the macrocycle, which are placed in a nearly parallel way via pi-pi interactions, forming a concavity structure with a macrocyclic base. It is significantly noted that one hydrogen-bond cycle generated from hydrogen atoms of two amino groups with two perchlorate anions has sustained such an assembly of two 4-aminopyridine species to stand in a face to face pattern through a weak molecular interaction on the macrocyclic platform by one-end coordination bonding. The self-assembly of 4-carboxylic pyridine acid and the same macrocyclic component in the presence of sodium hydroxide has yielded an interesting wheel-like complex. Two macrocyclic dinuclear zinc(II) components have been linked through coordination bonding with two pyridine derivatives situated on the same direction of a macrocycle. X-ray structural results suggest that the compound has a unique sandwich-like structure consisting of two macrocyclic covers with two inversely positioned bridging pyridine carboxylic groups in the middle.     

溶胶-凝胶法制备丙二酰胺型二氧大环多胺用作开管柱电色谱固定相的研究

开管柱毛细管电色谱（OTCEC）兼有HPLC和CE的优点^[1] 。柱内径相同时,柱效是OTLC的2倍^[2]。现在常用的直接键合法的制备步骤多,周期长,柱容量小。溶胶－凝胶（sol-gel)能在很温和的条件下使有机物附着在无机介质的表面上,经化学键合作用使涂层对基质有强烈的粘附性。与通常方法相比,sol-gel法制得的涂层有高的相比和抗水解能力。Guo等^[3]用sol-gel技术制备了高相比、高样品容量的OTCEC柱,叶明亮等6[4]用sol-gel法制备了C8开管柱电色谱柱并进行了评价。我们^[5]用sol-gel法将含羟基的冠醚涂渍固化在毛细管内,用于GC分析取得满意结果。丙二酰胺型二氧大环多胺具有大环多胺和寡肽的双重性质,用作OTCEC的固定相更有助于提高分离物的选择性。本文采用sol-gel技术制备含有丙二酰胺型二氧大环多胺的OTCEC柱,可将大环化合物键合在多孔的玻璃状基体上,使毛经表面粗糙化和固定相键合两步合二为一。用制得的OTCEC柱成功地分离了苯二酚、硝基酚、氨基酚和苯二胺的位置异构体及邻卤代苯胺和生物单胺神经递质。与键合法制得的二氧大环多胺柱子^[6,7]比较,用该法制得的柱子有较高的柱效,重现性好,迁移时间短,可进行快速分析。