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Paul M. Bogie Lauren R. Holloway Courtney Ngai Tabitha F. Miller Divine K. Grewal Prof. Richard J. Hooley 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10232-10238
A self-assembled Fe4L6 cage complex internally decorated with acid functions is capable of accelerating the thioetherification of activated alcohols, ethers and amines by up to 1000-fold. No product inhibition is seen, and effective supramolecular catalysis can occur with as little as 5 % cage. The substrates are bound in the host with up to micromolar affinities, whereas the products show binding that is an order of magnitude weaker. Most importantly, the cage host alters the molecularity of the reaction: whereas the reaction catalyzed by simple acids is a unimolecular, SN1-type substitution process, the rate of the host-mediated process is dependent on the concentration of nucleophile. The molecularity of the cage-catalyzed reaction is substrate-dependent, and can be up to bimolecular. In addition, the catalysis can be prevented by a large excess of nucleophile, where substrate inhibition dominates, and the use of tritylated anilines as substrates causes a negative feedback loop, whereby the liberated product destroys the catalyst and stops the reaction. 相似文献
3.
Victoria A. Piunova Hans W. Horn Gavin O. Jones Julia E. Rice Robert D. Miller 《Journal of polymer science. Part A, Polymer chemistry》2016,54(4):563-569
This study reports an application of trichloroethanol (TCE) as a bifunctional initiator for the synthesis of block copolymers (BCPs) by organocatalyzed ring‐opening polymerization (OROP) and atom transfer radical polymerization (ATRP). TCE was employed to synthesize a low dispersity poly (valerolactone) macroinitiator, which was subsequently used for the ATRP of tert‐butyl methacrylate. While it is known that TCE can serve as an initiator in ATRP, the ability to induce polymerization under OROP is reported for the first time. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and 1H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 563–569 相似文献
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Dr. Jingjun Hao Prof. Arnold L. Rheingold Marzieh Kavand Dr. Kipp J. van Schooten Prof. Christoph Boehme Dr. Marçal Capdevila‐Cortada Prof. Juan J. Novoa Eva Wöss Prof. Günther Knör Prof. Joel S. Miller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12312-12315
The reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) and Cr(C6H6)2 forms diamagnetic σ‐[TCNPy]22? possessing a 1.572(3) Å intrafragment sp3–sp3 bond. This is in contrast to the structurally related 1,2,4,5‐tetracyanobenzene and 1,2,4,5‐tetracyanopyrazine that form π‐dimer dianions possessing long, multicenter bonds. 相似文献
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We propose a modification of the standard inverse scattering transform for the focusing nonlinear Schrödinger equation (also other equations by natural generalization) formulated with nonzero boundary conditions at infinity. The purpose is to deal with arbitrary-order poles and potentially severe spectral singularities in a simple and unified way. As an application, we use the modified transform to place the Peregrine solution and related higher-order “rogue wave” solutions in an inverse-scattering context for the first time. This allows one to directly study properties of these solutions such as their dynamical or structural stability, or their asymptotic behavior in the limit of high order. The modified transform method also allows rogue waves to be generated on top of other structures by elementary Darboux transformations rather than the generalized Darboux transformations in the literature or other related limit processes. © 2019 Wiley Periodicals, Inc. 相似文献
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Aileen M. Eagleton Emma K. Ambrogi Sophia A. Miller Dr. Nataliia Vereshchuk Prof. Katherine A. Mirica 《Angewandte Chemie (International ed. in English)》2023,62(49):e202309078
Owing to high modularity and synthetic tunability, metal–organic frameworks (MOFs) on textiles are poised to contribute to the development of state-of-the-art wearable systems with multifunctional performance. While these composite materials have demonstrated promising functions in sensing, filtration, detoxification, and biomedicine, their applicability in multifunctional systems is only beginning to materialize. This review highlights the multifunctionality and versatility of MOF-integrated textile systems. It summarizes the operational goals of MOF@textile composites, encompassing sensing, filtration, detoxification, drug delivery, UV protection, and photocatalysis. Building upon these recent advances, this review concludes with an outlook on emerging opportunities for the diverse applications of MOF@textile systems in the realm of smart wearables. 相似文献
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Zachary D. Miller Ruth Dorel Prof. John Montgomery 《Angewandte Chemie (International ed. in English)》2015,54(31):9088-9091
Methods for the highly stereoselective and regiodivergent hydrosilylation of 1,3‐disubstituted allenes have been developed. The synthesis of E allylsilanes is accomplished with palladium NHC catalysts, and trisubstituted Z alkenylsilanes are accessed with nickel NHC catalysts. Unsymmetrically substituted allenes are well tolerated with nickel catalysis and afford Z alkenylsilanes. Evidence for a plausible mechanism was obtained through an isotopic double‐labeling crossover study. 相似文献
9.
Corrigendum: Crowdsourcing Natural Products Discovery to Access Uncharted Dimensions of Fungal Metabolite Diversity 下载免费PDF全文
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Nannocystin A: an Elongation Factor 1 Inhibitor from Myxobacteria with Differential Anti‐Cancer Properties 下载免费PDF全文
Philipp Krastel Silvio Roggo Markus Schirle Nathan T. Ross Francesca Perruccio Peter Aspesi Jr. Thomas Aust Kathrin Buntin David Estoppey Brigitta Liechty Felipa Mapa Klaus Memmert Howard Miller Xuewen Pan Ralph Riedl Christian Thibaut Jason Thomas Trixie Wagner Eric Weber Xiaobing Xie Esther K. Schmitt Dr. Dominic Hoepfner 《Angewandte Chemie (International ed. in English)》2015,54(35):10149-10154
Cultivation of myxobacteria of the Nannocystis genus led to the isolation and structure elucidation of a class of novel cyclic lactone inhibitors of elongation factor 1. Whole genome sequence analysis and annotation enabled identification of the putative biosynthetic cluster and synthesis process. In biological assays the compounds displayed anti‐fungal and cytotoxic activity. Combined genetic and proteomic approaches identified the eukaryotic translation elongation factor 1α (EF‐1α) as the primary target for this compound class. Nannocystin A ( 1 ) displayed differential activity across various cancer cell lines and EEF1A1 expression levels appear to be the main differentiating factor. Biochemical and genetic evidence support an overlapping binding site of 1 with the anti‐cancer compound didemnin B on EF‐1α. This myxobacterial chemotype thus offers an interesting starting point for further investigations of the potential of therapeutics targeting elongation factor 1. 相似文献