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991.
Dr. Karin Mannerstedt Dr. Narendra Kumar Mishra Dr. Ebbe Engholm Dr. Morten Lundh Dr. Charlotte S. Madsen Dr. Philip J. Pedersen Dr. Priska Le-Huu Dr. Søren L. Pedersen Dr. Nina Buch-Månson Dr. Björn Borgström Dr. Thomas Brimert Dr. Lisbeth N. Fink Dr. Keld Fosgerau Prof. Niels Vrang Prof. Knud J. Jensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(9):3166-3176
A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals. 相似文献
992.
Fred U. Nnamdi Dr. Colin Diner Prof. Pier Alexandre Champagne Prof. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3855-3860
Two similar tridentate directing groups derived from glycine and 8-aminoquinoline were shown to enable the palladium-catalyzed anti-Markovnikov hydrofunctionalization of 4-pentenylamine with drastically different efficiencies. A computational investigation into the origin of the reactivity difference between these isomeric, carbonyl-transposed auxiliaries suggests that protonation state, thus charge of the substrate-metal complex prior to nucleopalladation is key. These investigations have culminated in a directing group design that can undergo Pd-catalyzed hydrofunctionalization under relatively mild conditions, as low as room temperature. 相似文献
993.
Subhrakant Jena Kiran Devi Tulsiyan Dr. Rajiv K. Kar Dr. Hemanta K. Kisan Dr. Himansu S. Biswal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4373-4383
Designing a potential protein–ligand pair is pivotal, not only to track the protein structure dynamics, but also to assist in an atomistic understanding of drug delivery. Herein, the potential of a small model thioamide probe being used to study albumin proteins is reported. By monitoring the Förster resonance energy transfer (FRET) dynamics with the help of fluorescence spectroscopic techniques, a twofold enhancement in the FRET efficiency of 2-thiopyridone (2TPY), relative to that of its amide analogue, is observed. Molecular dynamics simulations depict the relative position of the free energy minimum to be quite stable in the case of 2TPY through noncovalent interactions with sulfur, which help to enhance the FRET efficiency. Finally, its application is shown by pairing thiouracils with protein. It is found that the site-selective sulfur atom substitution approach and noncovalent interactions with sulfur can substantially enhance the FRET efficiency, which could be a potential avenue to explore in the design of FRET probes to study the structure and dynamics of biomolecules. 相似文献
994.
Oliver Andler Prof. Dr. Uli Kazmaier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):949-953
Application of ester dienolates as nucleophiles in Matteson homologations allows for the stereoselective synthesis of highly substituted α,β-unsaturated δ-hydroxy carboxyl acids, structural motifs widespread found in polyketide natural products. The protocol is rather flexible and permits the introduction of substituents and functionalities also at those positions which are not accessible by the commonly used aldol reaction. Therefore, this ester dienolate Matteson approach is an interesting alternative to the “classical” polyketide syntheses. 相似文献
995.
Yuya Nakatsuji Prof. Dr. Yusuke Kobayashi Sakyo Masuda Prof. Dr. Yoshiji Takemoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(8):2633-2637
Organo-radical catalysts have recently attracted great interest, and the development of this field can be expected to broaden the applications of organocatalysis. Herein, the first example of a radical-generating system is reported that does not require any photoirradiation, radical initiators, or preactivated substrates. The oxidative C−C-bond cleavage of 2-substituted cyclohexanones was achieved using an azolium salt and a hydroquinone as co-catalysts. A catalytic mechanism was proposed based on the results of diffusion-ordered spectroscopy and cyclic voltammetry measurements, as well as computational studies. 相似文献
996.
Subhasis Paul Dr. Joyram Guin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4412-4419
Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process. 相似文献
997.
Dr. Xiu-Du Zhang Dr. Kai Chen Prof. Dr. Wei-Yin Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(16):5107-5119
Cucurbit[n]urils (Q[n]s) are a relatively young family of macrocycles, consisting of glycoluril units bridged by methylene groups, and their unique structures have attracted extensive attention from chemists in recent decades. Due to the presence of a rigid hydrophobic inner cavity and two polar outer portals lined with carbonyl groups, Q[n]s not only encapsulate guest species into the cavity, but also coordinate with metal ions/clusters. Considerable achievements have been obtained in the fields of Q[n]s-based host–guest chemistry, coordination chemistry, as well as the combination of host–guest and coordination chemistry. Furthermore, the outer surface of Q[n]s has been demonstrated to be capable of interacting with definite species to generate supramolecular architectures in recent years. With more in-depth research into Q[n]s, their application studies have also emerged as a hot topic. This Minireview focuses on recent advances in the potential applications of solid-state materials based on Q[n]s and their derivatives for the capture and adsorption of hazardous chemicals from a solution or a gas mixture. 相似文献
998.
Saidbakhrom Saidjalolov Dr. Zainab Edoo Dr. Matthieu Fonvielle Louis Mayer Dr. Laura Iannazzo Dr. Michel Arthur Prof. Dr. Mélanie Etheve-Quelquejeu Dr. Emmanuelle Braud 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3542-3551
The carbapenem class of β-lactams has been optimized against Gram-negative bacteria producing extended-spectrum β-lactamases by introducing substituents at position C2. Carbapenems are currently investigated for the treatment of tuberculosis as these drugs are potent covalent inhibitors of l,d -transpeptidases involved in mycobacterial cell wall assembly. The optimization of carbapenems for inactivation of these unusual targets is sought herein by exploiting the nucleophilicity of the C8 hydroxyl group to introduce chemical diversity. As β-lactams are structure analogs of peptidoglycan precursors, the substituents were chosen to increase similarity between the drug and the substrate. Fourteen peptido-carbapenems were efficiently synthesized. They were more effective than the reference drug, meropenem, owing to the positive impact of a phenethylthio substituent introduced at position C2 but the peptidomimetics added at position C8 did not further improve the activity. Thus, position C8 can be modified to modulate the pharmacokinetic properties of highly efficient carbapenems. 相似文献
999.
Apurva Pandey Dr. Eszter Boros 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(26):7340-7350
Drug discovery aimed at the efficient eradication of life-threatening bacterial infections, especially in light of the emergence of multi-drug resistance of pathogenic bacteria, has remained a challenge for medicinal chemists over the past several decades. As nutrient acquisition and metabolism at the host-pathogen interface become better elucidated, new drug targets continue to emerge. Metal homeostasis is among these processes, and thus provides opportunities for medicinal inorganic chemists to alter or disrupt these processes selectively to impart bacteriostatic or bacteriotoxic effects. In this minireview, we showcase some of the recent work from the field of metal-based antibacterial agents and highlight divergent strategies and mechanisms of action. 相似文献
1000.
Dr. David Martínez-López Eduardo Santamaría-Aranda Dr. Marco Marazzi Dr. Cristina García-Iriepa Dr. Diego Sampedro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4420-4429
Donor–acceptor Stenhouse adducts (DASAs) are playing an outstanding role as innovative and versatile photoswitches. Until now, all the efforts have been spent on modifying the donor and acceptor moieties to modulate the absorption energy and improve the cyclization and reversion kinetics. However, there is a strong dependence on specific structural modifications and a lack of predictive behavior, mostly owing to the complex photoswitching mechanism. Here, by means of a combined experimental and theoretical study, the effect of chemical modification of the π-bridge linking the donor and acceptor moieties is systematically explored, revealing the significant impact on the absorption, photocyclization, and relative stability of the open form. In particular, a position along the π-bridge is found to be the most suited to redshift the absorption while preserving the cyclization. However, thermal back-reaction to the initial isomer is blocked. These effects are explained in terms of an increased acceptor capability offered by the π-bridge substituent that can be modulated. This strategy opens the path toward derivatives with infra-red absorption and a potential anchoring point for further functionalization. 相似文献