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131.
Helen R. Thomas Alexander J. Marsden Dr. Marc Walker Dr. Neil R. Wilson Dr. Jonathan P. Rourke 《Angewandte Chemie (International ed. in English)》2014,53(29):7613-7618
The treatment of graphene oxide (GO) with potassium thioacetate followed by an aqueous work‐up yields a new material via the ring‐opening of the epoxide groups. The new material is a thiol‐functionalized GO (GO‐SH) which is able to undergo further functionalization. Reaction with butyl bromide gives another new material, GO‐SBu, which shows significantly enhanced thermal stability compared to both GO and GO‐SH. The thiol‐functionalized GO material showed a high affinity for gold, as demonstrated by the selective deposition of a high density of gold nanoparticles. 相似文献
132.
Chongqing Wang Christopher Lambert Maurice Hauser Adrian Deuschmann Dr. Carsten Zeilinger Prof. Dr. Klemens Rottner Prof. Dr. Theresia E. B. Stradal Prof. Dr. Marc Stadler Dr. Elizabeth J. Skellam Prof. Dr. Russell J. Cox 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13578-13583
Mutasynthesis of pyrichalasin H from Magnaporthe grisea NI980 yielded a series of unprecedented 4′-substituted cytochalasin analogues in titres as high as the wild-type system (≈60 mg L−1). Halogenated, O-alkyl, O-allyl and O-propargyl examples were formed, as well as a 4′-azido analogue. 4′-O-Propargyl and 4′-azido analogues reacted smoothly in Huisgen cycloaddition reactions, whereas p-Br and p-I compounds reacted in Pd-catalysed cross-coupling reactions. A series of examples of biotin-linked, dye-linked and dimeric cytochalasins was rapidly created. In vitro and in vivo bioassays of these compounds showed that the 4′-halogenated and azido derivatives retained their cytotoxicity and antifungal activities; but a unique 4′-amino analogue was inactive. Attachment of larger substituents attenuated the bioactivities. In vivo actin-binding studies with adherent mammalian cells showed that actin remains the likely intracellular target. Dye-linked compounds revealed visualisation of intracellular actin structures even in the absence of phalloidin, thus constituting a potential new class of actin-visualisation tools with filament-barbed end-binding specificity. 相似文献
133.
Dr. Paula Morales Dr. Gemma Navarro Marc Gómez-Autet Laura Redondo Prof. Dr. Javier Fernández-Ruiz Dr. Laura Pérez-Benito Dr. Arnau Cordomí Prof. Dr. Leonardo Pardo Prof. Dr. Rafael Franco Dr. Nadine Jagerovic 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15839-15842
Single chemical entities with potential to simultaneously interact with two binding sites are emerging strategies in medicinal chemistry. We have designed, synthesized and functionally characterized the first bitopic ligands for the CB2 receptor. These compounds selectively target CB2 versus CB1 receptors. Their binding mode was studied by molecular dynamic simulations and site-directed mutagenesis. 相似文献
134.
Serhii Krykun Maksym Dekhtiarenko David Canevet Vincent Carr Frdric Aubriet Eric Levillain Magali Allain Zoia Voitenko Marc Sall Sbastien Goeb 《Angewandte Chemie (International ed. in English)》2020,59(2):716-720
Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway. 相似文献
135.
Niels Van Herck Diederick Maes Kamil Unal Marc Guerre Johan M. Winne Filip E. Du Prez 《Angewandte Chemie (International ed. in English)》2020,59(9):3609-3617
The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross‐linkers for thiols. The click‐like thiol–yne cross‐linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross‐linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne‐based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross‐linker. 相似文献
136.
137.
Susanne Bhr Sabine Brinkmann‐Chen Marc Garcia‐Borrs John M. Roberts Dimitris E. Katsoulis K. N. Houk Frances H. Arnold 《Angewandte Chemie (International ed. in English)》2020,59(36):15507-15511
Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450BM3 from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C?H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C?H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire. 相似文献
138.
Eder Toms‐Mendivil Marc Devillard Vianney Regnier Jacques Pecaut David Martin 《Angewandte Chemie (International ed. in English)》2020,59(28):11516-11520
Oxyallyl derivatives are typically elusive compounds. Even recently reported “stabilized” 1,3‐diaminooxyallyl species are still highly reactive and have short lifetimes at room temperature. Herein, we report the synthesis and preliminary study of mesoionic pyrimidine derivatives that feature 1,3‐bis(dimethylamino)oxyallyl patterns with an unprecedented level of stabilization. The latter are not only insensitive towards air and moisture, but they are also compatible with the formation of an ancillary stable N‐heterocyclic carbene moiety. As the oxyallyl pattern is proton‐responsive, it allows the reversible switching of the electronic properties of the carbene, as a ligand. 相似文献
139.
Nicolas Armanino Julie Charpentier Felix Flachsmann Andreas Goeke Marc Liniger Philip Kraft 《Angewandte Chemie (International ed. in English)》2020,59(38):16310-16344
This review is the sequel to the 2000 report on the recent advances in the chemistry of odorants and it summarizes the developments in fragrance chemistry over the past 20 years. Following the olfactory spectrum set out in that report, trendsetting so‐called captive odorants (patent‐protected ingredients unavailable to the market) are presented according to the main odor families: “fruity”, “marine”, “green”, “floral”, “spicy”, “woody”, “amber”, and “musky”. The design of odorants, their chemical synthesis, and their use in modern perfumery are illustrated with prominent examples. Featured are new fruity odorants that provide signature in the top note, as well as precursor technology. In the green domain, focus is on leafy notes and green pear. New benzodioxepines and benzodioxoles have modernized the marine family and required a revision of the existing olfactophore models. The replacement of Lilial and Lyral kept the industry busy in the floral domain with a plethora of new “muguets”. There was continued activity in the domain of rose odorants, especially in the area of rose ketones. Biotechnology became significant, for example, with Clearwood and Ambrofix, and the principal odorants of vetiver oil in the woody family have been found. Fourth and fifth families of musk odorants were also discovered and populated. Thus, new avenues for further explorations into fragrance chemistry have been opened. 相似文献
140.
Starch nanoparticle (SNP)‐based pressure sensitive adhesives (PSAs) with core‐shell particle morphology (starch nanoparticle core/acrylic polymer shell) are produced via seeded, semi‐batch emulsion polymerization at 15 wt% SNP loading (relative to total polymer weight) and 40 wt% latex solids. Crosslinker and chain transfer agent (CTA) are introduced to the acrylic shell polymer formulation at a range of concentrations according to a 32 factorial design to tailor the latex and adhesive properties of SNP‐based latexes. The crosslinker and CTA show no significant effect on polymerization kinetics, particle size, and viscosity. Latex gel content is predicted using an empirical model, which is a function of crosslinker and CTA concentration. Both the gel content and glass transition temperature strongly affect the adhesive properties (tack, peel strength, and shear strength) of the SNP‐based latex films. 3D response surfaces for the adhesive properties are constructed to facilitate the design of SNP‐based PSAs with desired properties. 相似文献