共查询到20条相似文献,搜索用时 15 毫秒
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Dr. Weiwei Fang Yang Zhang Jiajie Wu Cong Liu Dr. Haibo Zhu Prof. Dr. Tao Tu 《化学:亚洲杂志》2018,13(7):712-729
Over the past two decades, supramolecular gels have attracted significant attention from scientists in diverse research fields and have been extensively developed. This review mainly focuses on the significant achievements in supramolecular gels and catalysis. First, by incorporating diverse catalytic sites and active organic functional groups into gelator molecules, supramolecular gels have been considered as a novel matrix for catalysis. In addition, these rationally designed supramolecular gels also provide a variety of templates to access metal nanocomposites, which may function as catalysts and exhibit high activity in diverse catalytic transformations. Finally, as a new kind of biomaterial, supramolecular gels formed in situ by self‐assembly triggered by catalytic transformations are also covered herein. 相似文献
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Dr. Rafael Gramage‐Doria Joeri Hessels Stefan H. A. M. Leenders Dr. Oliver Tröppner Maximilian Dürr Prof. Dr. Ivana Ivanović‐Burmazović Prof. Dr. Joost N. H. Reek 《Angewandte Chemie (International ed. in English)》2014,53(49):13380-13384
Homogeneous transition‐metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mM or μM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self‐assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M , inside well‐defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mM levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular C? O and C? C bond‐forming cyclization reactions. 相似文献
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Dr. Cui-Lian Liu Dr. Mhamad Aly Moussawi Givi Kalandia Dr. David E. Salazar Marcano Dr. William E. Shepard Prof. Dr. Tatjana N. Parac-Vogt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(19):e202401940
The artificial microenvironments inside coordination cages have gained significant attention for performing enzyme-like catalytic reactions by facilitating the formation of labile and complex molecules through a “ship-in-a-bottle” approach. Despite many fascinating examples, this approach remains scarcely explored in the context of synthesizing metallic clusters such as polyoxometalates (POMs). The development of innovative approaches to control and influence the speciation of POMs in aqueous solutions would greatly advance their applicability and could ultimately lead to the formation of elusive clusters that cannot be synthesized by using traditional methods. In this study, we employ host–guest stabilization within a coordination cage to enable a novel cavity-directed synthesis of labile POMs in aqueous solutions under mild conditions. The elusive Lindqvist [M6O19]2− (M=Mo or W) POMs were successfully synthesized at room temperature via the condensation of molybdate or tungstate building blocks within the confined cavity of a robust and water-soluble Pt6L4(NO3)12 coordination cage. Importantly, the encapsulation of these POMs enhances their stability in water, rendering them efficient catalysts for environmentally friendly and selective sulfoxidation reactions using H2O2 as a green oxidant in a pure aqueous medium. The approach developed in this paper offers a means to synthesize and stabilize the otherwise unstable metal-oxo clusters in water, which can broaden the scope of their applications. 相似文献
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Dr. Chunxia Tan Dr. Dandan Chu Dr. Xianhui Tang Prof. Dr. Yan Liu Weimin Xuan Prof. Dr. Yong Cui 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):662-672
Inspired by the high efficiency and specificity of enzymes in living systems, the development of artificial catalysts intrinsic to the key features of enzyme has emerged as an active field. Recent advances in supramolecular chemistry have shown that supramolecular coordination cages, built from non-covalent coordination bonds, offer a diverse platform for enzyme mimics. Their inherent confined cavity, analogous to the binding pocket of an enzyme, and the facile tunability of building blocks are essential for substrate recognition, transition-state stabilization, and product release. In particular, the combination of chirality with supramolecular coordination cages will undoubtedly create an asymmetric microenvironment for promoting enantioselective transformation, thus providing not only a way to make synthetically useful asymmetric catalysts, but also a model to gain a better understanding for the fundamental principles of enzymatic catalysis in a chiral environment. The focus here is on recent progress of supramolecular coordination cages for asymmetric catalysis, and based on how supramolecular coordination cages function as reaction vessels, three approaches have been demonstrated. The aim of this review is to offer researchers general guidance and insight into the rational design of sophisticated cage containers for asymmetric catalysis. 相似文献
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Sayuri L. Higashi Dr. Aya Shibata Dr. Yoshiaki Kitamura Koichiro M. Hirosawa Prof. Kenichi G. N. Suzuki Prof. Kazunori Matsuura Prof. Masato Ikeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11955-11962
Aqueous hybrid soft nanomaterials consisting of plural supramolecular architectures with a high degree of segregation (orthogonal coexistence) and precise hierarchy at the nano- and microscales, which are reminiscent of complex biomolecular systems, have attracted increasing attention. Remarkable progress has been witnessed in the construction of DNA nanostructures obtained by rational sequence design and supramolecular nanostructures of peptide derivatives through self-assembly under aqueous conditions. However, orthogonal self-assembly of DNA nanostructures and supramolecular nanostructures of peptide derivatives in a single medium has not yet been explored in detail. In this study, DNA microspheres, which can be obtained from three single-stranded DNAs, and three different supramolecular nanostructures (helical nanofibers, straight nanoribbons, and flowerlike microaggregates) of semi-artificial glycopeptides were simultaneously constructed in a single medium by a simple thermal annealing process, which gives rise to hybrid soft nanomaterials. Fluorescence imaging with selective staining of each supramolecular nanostructure uncovered the orthogonal coexistence of these structures with only marginal impact on their morphology. Additionally, the biostimuli-responsive degradation propensity of each supramolecular architecture is retained, and this may allow the construction of active soft nanomaterials exhibiting intelligent biofunctions. 相似文献
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Lorenzo Catti Qi Zhang Prof. Dr. Konrad Tiefenbacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9060-9066
Control over the local chemical environment of a molecule can be achieved by encapsulation in supramolecular host systems. In supramolecular catalysis, this control is used to gain advantages over classical homogeneous catalysis in bulk solution. Two of the main advantages concern influencing reactions in terms of substrate and product selectivity. Due to size and/or shape recognition, substrate selective conversion can be realized. Additionally, noncovalent interactions with the host environment facilitate alternative reaction pathways and can yield unusual products. This Concept article discusses and highlights literature examples utilizing self‐assembled molecular capsules to achieve catalytic transformations displaying a high degree of substrate and/or product selectivity. Furthermore, the advantage of supramolecular hosts in multicatalyst tandem reactions is covered. 相似文献
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Bohan Tang Jiantao Zhao Prof. Dr. Jiang-Fei Xu Prof. Dr. Xi Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15446-15460
The control over chemical reactivity and selectivity are always pursued. Using non-covalent interactions to achieve efficient and selective catalysis is an essential goal of supramolecular catalysis. Supramolecular catalysis based on cucurbit[n]urils (CB[n]s) possesses distinct characteristics for the unique structure of CB[n]s. CB[n]s are a family of pumpkin-shaped host molecules with various molecular sizes, rigid structures, electronegative portals and wealthy host-guest chemistry. Herein, we summarize the three major mechanisms of CB[n]s based supramolecular catalysis. Owing to the structural properties of CB[n]s, CB[n]s can serve as nanoreactors and steric hindrance to modulate the reactivity of substrates. They can also catalyze the reactions by modulating the reactivity of ionized intermediates. Recent progresses on the CB[n]s based supramolecular catalysis are introduced in this Minireview and the future development in this field is discussed. It is anticipated that this review provides insights into the mechanism of CB[n]s based supramolecular catalysis and may help scientists find new opportunities in this field. 相似文献
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Dr. Paolo Zardi Dr. Thierry Roisnel Dr. Rafael Gramage-Doria 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):627-634
Inspired by enzymes such as cytochrome P-450, the study of the reactivity of metalloporphyrins continues to attract major interest in the field of homogeneous catalysis. However, little is known about benefitting from the substrate-recognition properties of porphyrins containing additional, catalytically relevant active sites. Herein, such an approach is introduced by using supramolecular ligands derived from metalloporphyrins customized with rigid, palladium-coordinating nitrile groups. According to different studies (NMR and UV/Vis spectroscopy, XRD, control experiments), the supramolecular ligands are able to accommodate pyridine derivatives as substrates inside the porphyrin pocket while the reactivity occurs at the peripheral side. By simply tuning a remote metal center, different binding events result in different catalyst reactivity, and this enzyme-like feature leads to high degrees of substrate selectivity in representative palladium-catalyzed Suzuki–Miyaura reactions. 相似文献
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Mild Friedel–Crafts Reactions inside a Hexameric Resorcinarene Capsule: C−Cl Bond Activation through Hydrogen Bonding to Bridging Water Molecules 下载免费PDF全文
Pellegrino La Manna Dr. Carmen Talotta Giuseppe Floresta Dr. Margherita De Rosa Prof. Dr. Annunziata Soriente Prof. Dr. Antonio Rescifina Prof. Dr. Carmine Gaeta Prof. Dr. Placido Neri 《Angewandte Chemie (International ed. in English)》2018,57(19):5423-5428
A novel catalytic feature of a hexameric resorcinarene capsule is highlighted. The self‐assembled cage was exploited to promote the Friedel–Crafts benzylation of several arenes and heteroarenes with benzyl chloride under mild conditions. Calculations showed that there are catalytically relevant hydrogen‐bonding interactions between the bridging water molecules of the capsule and benzyl chloride, which is fundamental for the activation of the C?Cl bond. The capsule controls the reaction outcome. Inside the inner cavity of the capsule, N‐methylpyrrole is preferentially benzylated in the unusual β‐position while mesitylene reacts faster than 1,3‐dimethoxybenzene despite the greater π‐nucleophilicity of the latter compound. 相似文献
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Barry C. Pemberton Ramya Raghunathan Sabine Volla Jayaraman Sivaguru 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12178-12190
Cucurbiturils are a family of molecular container compounds with superior molecular recognition properties. The use of cucurbiturils for supramolecular catalysis is highlighted in this concept. Both photochemical reactions as well as thermal transformations are reviewed with an eye towards tailoring substrates for supramolecular catalysis mediated by cucurbiturils. 相似文献
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Highly Efficient Supramolecular Catalysis by Endowing the Reaction Intermediate with Adaptive Reactivity 下载免费PDF全文
Yang Jiao Bohan Tang Yucheng Zhang Dr. Jiang‐Fei Xu Prof. Zhiqiang Wang Prof. Xi Zhang 《Angewandte Chemie (International ed. in English)》2018,57(21):6077-6081
A new strategy of highly efficient supramolecular catalysis is developed by endowing the reaction intermediate with adaptive reactivity. The supramolecular catalyst, prepared by host–guest complexation between 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) and cucurbit[7]uril (CB[7]), was used for biphasic oxidation of alcohols. Cationic TEMPO+, the key intermediate, was stabilized by the electrostatic effect of CB[7] in aqueous phase, thus promoting the formation of TEMPO+ and inhibiting side reactions. Moreover, through the migration into the organic phase, TEMPO+ was separated from CB[7] and recovered the high reactivity to drive a fast oxidation of substrates. The adaptive reactivity of TEMPO+ induced an integral optimization of the catalytic cycle and greatly improved the conversion of the reaction. This work highlights the unique advantages of dynamic noncovalent interactions on modulating the activity of reaction intermediates, which may open new horizons for supramolecular catalysis. 相似文献
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Yeray Dorca Elisa E. Greciano Jorge S. Valera Prof. Rafael Gómez Prof. Luis Sánchez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):5848-5864
The formation of helical structures through the supramolecular polymerization of a variety of self-assembling units is reviewed. These scaffolds are usually obtained by efficient transfer or amplification of chirality phenomena, in which the starting self-assembling molecules possess different elements of asymmetry, such as point or axial chirality. Relevant examples of helical supramolecular structures investigated under thermodynamic control are reviewed, and the helical outcome of remarkable examples of chiral entities obtained through kinetic control are also highlighted. Finally, selected examples of flexible macroscopic chirality and catalysis are described to illustrate the applicability of helical aggregates. 相似文献
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Rationally Designed Multifunctional Supramolecular Iminium Catalysis: Direct Vinylogous Michael Addition of Unmodified Linear Dienol Substrates 下载免费PDF全文
Yun Gu Dr. Yao Wang Tian‐Yang Yu Prof. Dr. Yong‐Min Liang Prof. Dr. Peng‐Fei Xu 《Angewandte Chemie (International ed. in English)》2014,53(51):14128-14131
The development of a direct vinylogous Michael addition of linear nucleophilic substrates is a long‐standing challenge because of the poor reactivity and the considerable difficulty in controlling regioselectivity. By employing a rationally designed multifunctional supramolecular iminium catalysis strategy, the first direct vinylogous Michael addition of unmodified linear substrates to α,β‐unsaturated aldehydes, to afford chiral 1,7‐dioxo compounds with good yields and excellent regio‐ as well as enantioselectivity, has been developed. 相似文献
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Shuanggen Wu Changyong Cai Fenfang Li Zhijian Tan Shengyi Dong 《Angewandte Chemie (International ed. in English)》2020,59(29):11871-11875
Application of new strategies for supramolecular self‐assembly can significantly impact the properties and/or functions of supramolecular polymers. To realize a facial strategy for the development of solvent‐free supramolecular polymers in bulk, “deep eutectic solvents” were employed. Cyclodextrins and natural acids were used to prepare deep eutectic supramolecular polymers ( DESP s). Deep eutectic solvents have special characteristics that endow DESP s with unique macroscopic properties and excellent processability. DESP s exhibit supramolecular adhesion and temperature‐dependent behavior originating from the combined effects of deep eutectic solvents and supramolecular polymerization. Because DESP s are solvent‐free and display interesting macroscopic properties, they have potential as new adaptive materials. 相似文献
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Dr. Ryou Kubota Keisuke Nakamura Shogo Torigoe Prof. Dr. Itaru Hamachi 《ChemistryOpen》2020,9(1):67-79
Multicomponent supramolecular hydrogels are promising scaffolds for applications in biosensors and controlled drug release due to their designer stimulus responsiveness. To achieve rational construction of multicomponent supramolecular hydrogel systems, their in-depth structural analysis is essential but still challenging. Confocal laser scanning microscopy (CLSM) has emerged as a powerful tool for structural analysis of multicomponent supramolecular hydrogels. CLSM imaging enables real-time observation of the hydrogels without the need of drying and/or freezing to elucidate their static and dynamic properties. Through multiple, selective fluorescent staining of materials of interest, multiple domains formed in supramolecular hydrogels (e. g. inorganic materials and self-sorting nanofibers) can also be visualized. CLSM and the related microscopic techniques will be indispensable to investigate complex life-inspired supramolecular chemical systems. 相似文献