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71.
Dr. Fredrik Schaufelberger Karolina Seigel Prof. Dr. Olof Ramström 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15581-15588
The reversibility of imine bonds has been exploited to great effect in the field of dynamic covalent chemistry, with applications such as preparation of functional systems, dynamic materials, molecular machines, and covalent organic frameworks. However, acid catalysis is commonly needed for efficient equilibration of imine mixtures. Herein, it is demonstrated that hydrogen bond donors such as thioureas and squaramides can catalyze the equilibration of dynamic imine systems under unprecedentedly mild conditions. Catalysis occurs in a range of solvents and in the presence of many sensitive additives, showing moderate to good rate accelerations for both imine metathesis and transimination with amines, hydrazines, and hydroxylamines. Furthermore, the catalyst proved simple to immobilize, introducing both reusability and extended control of the equilibration process. 相似文献
72.
Dr. Yong-Zhi Li Gang-Ding Wang Hong-Yun Yang Prof. Lei Hou Prof. Yao-Yu Wang Prof. Zhonghua Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16402-16407
To develop efficient adsorbent materials for storage and separation of C2H2, an unprecedented supercage MOF, [Me2NH2]⋅[Zn3(ALP)(TDC)2.5]⋅3.5DMF⋅2 H2O ( 1 ) was constructed through medicinal molecule allopurinol (ALP) and S-containing 2,5-thiophenedicarboxylic acid (H2TDC). 1 contains a novel linear trinuclear cluster that is composed by ALP and carboxylates and forms a final uncommon 5-connected yfy topological framework. The framework possesses three types of interlinked cages decorated by rich functional sites, and reveals not only high adsorption capacity for C2H2 but also excellent selective separation for C2H2/CO2 and C2H2/CH4 at 298 K. Dynamic breakthrough experiments on C2H2/CO2 (1:1) mixture and C2H2/CH4 (1:1) mixture also demonstrated the potential of the material to separate C2H2 from CO2 or CH4 mixtures. Molecular simulations were also studied to identify the different CO2- and C2H2- binding sites in 1 , such as carboxylate groups, S atoms and carbonyl groups. 相似文献
73.
Sara Bertuzzi Dr. Ana Gimeno Reyes Núñez-Franco Dr. Ganeko Bernardo-Seisdedos Sandra Delgado Dr. Gonzalo Jiménez-Osés Dr. Oscar Millet Prof. Dr. Jesús Jiménez-Barbero Dr. Ana Ardá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15643-15653
The interaction of human galectin-1 with a variety of oligosaccharides, from di-(N-acetyllactosamine) to tetra-saccharides (blood B type-II antigen) has been scrutinized by using a combined approach of different NMR experiments, molecular dynamics (MD) simulations, and isothermal titration calorimetry. Ligand- and receptor-based NMR experiments assisted by computational methods allowed proposing three-dimensional structures for the different complexes, which explained the lack of enthalpy gain when increasing the chemical complexity of the glycan. Interestingly, and independently of the glycan ligand, the entropy term does not oppose the binding event, a rather unusual feature for protein-sugar interactions. CLEANEX-PM and relaxation dispersion experiments revealed that sugar binding affected residues far from the binding site and described significant changes in the dynamics of the protein. In particular, motions in the microsecond-millisecond timescale in residues at the protein dimer interface were identified in the presence of high affinity ligands. The dynamic process was further explored by extensive MD simulations, which provided additional support for the existence of allostery in glycan recognition by human galectin-1. 相似文献
74.
Dr. Laura Ielo Prof. Dr. Vittorio Pace Prof. Dr. Wolfgang Holzer Md. Mahbubur Rahman Dr. Guangrong Meng Dr. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16246-16250
The structure and properties of amides are of tremendous interest in organic synthesis and biochemistry. Traditional amides are planar and the carbonyl group non-electrophilic due to nN→π*C=O conjugation. In this study, we report electrophilicity scale by exploiting 17O NMR and 15N NMR chemical shifts of acyclic twisted and destabilized acyclic amides that have recently received major attention as precursors in N-C(O) cross-coupling by selective oxidative addition as well as precursors in electrophilic activation of N-C(O) bonds. Most crucially, we demonstrate that acyclic twisted amides feature electrophilicity of the carbonyl group that ranges between that of acid anhydrides and acid chlorides. Furthermore, a wide range of electrophilic amides is possible with gradually varying carbonyl electrophilicity by steric and electronic tuning of amide bond properties. Overall, the study quantifies for the first time that steric and electronic destabilization of the amide bond in common acyclic amides renders the amide bond as electrophilic as acid anhydrides and chlorides. These findings should have major implications on the fundamental properties of amide bonds. 相似文献
75.
Alessio Melli Simone Potenti Dr. Mattia Melosso Dr. Sven Herbers Dr. Lorenzo Spada Dr. Andrea Gualandi Kevin G. Lengsfeld Prof. Luca Dore Philipp Buschmann Prof. Pier Giorgio Cozzi Prof. Jens-Uwe Grabow Prof. Vincenzo Barone Prof. Cristina Puzzarini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):15016-15022
Phenylmethanimine is an aromatic imine with a twofold relevance in chemistry: organic synthesis and astrochemistry. To tackle both aspects, a multidisciplinary strategy has been exploited and a new, easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, based on the thermal decomposition of hydrobenzamide, with a state-of-the-art computational characterization of phenylmethanimine laid the foundation for its first laboratory observation by means of rotational electric resonance spectroscopy. Both E and Z isomers have been accurately characterized, thus providing a reliable basis to guide future astronomical observations. A further characterization has been carried out by nuclear magnetic resonance spectroscopy, showing the feasibility of this synthetic approach in solution. The temperature dependence as well as possible mechanisms of the thermolysis process have been examined. 相似文献
76.
Tania Dr. Sevan D. Houston Lachlan Sharp-Bucknall Tiffany B. Poynder Dr. Mohammad Albayer Prof. Jason L. Dutton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15863-15866
PhI(OTf)2 has been used for the past 30 years as a strong I(III) oxidant for organic and inorganic transformations. It has been reported to be generated in situ from the reactions of either PhI(OAc)2 or PhI=O with two equivalents of trimethylsilyl trifluoromethanesulfonate (TMS-OTf). In this report it is shown that neither of these reactions generate a solution with spectroscopic data consistent with PhI(OTf)2, with supporting theoretical calculations, and thus this compound should not be invoked as the species acting as the oxidant for transformations that have been associated with its use. 相似文献
77.
Polyhydroxyalkanoates (PHAs) are considered promising “green” alternatives to synthetic polymers because they are bio-derived, biodegradable and biocompatible. The properties of bacterial PHA copolymers depend on their microstructures, which can be modified with the use of different fermentation processes and feed materials. Thus, it is desirable to have an improved testing method for the determination of PHA microstructures. In this work, a detailed NMR analysis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) microstructure was made. Previously only two of the hydroxyvalerate 13C NMR peaks have been assigned at the triad level. In this work, three of the 13C hydroxyvalerate peaks and two of the hydroxybutyrate peaks were found to be split into four peaks each due to comonomer sequence effects. Using eight copolymer samples with a wide compositional range, we were able to assign all these peaks to B-centered and V-centered triad sequences. Through curve deconvolution, the triad intensities were determined. These triad sequence intensities can then be analyzed via both the first-order Markovian and two-component Bernoullian models to obtain more in-depth information on copolymer composition and comonomer reactivities. 相似文献
78.
Gert-Jan Bekker Mitsugu Araki Kanji Oshima Yasushi Okuno Narutoshi Kamiya 《Journal of computational chemistry》2020,41(17):1606-1615
Multicanonical molecular dynamics based dynamic docking was used to exhaustively search the configurational space of an inhibitor binding to the N-terminal domain of heat-shock protein 90 (Hsp90). The obtained structures at 300 K cover a wide structural ensemble, with the top two clusters ranked by their free energy coinciding with the native binding site. The representative structure of the most stable cluster reproduced the experimental binding configuration, but an interesting conformational change in Hsp90 could be observed. The combined effects of solvation and ligand binding shift the equilibrium from a preferred loop-in conformation in the unbound state to an α-helical one in the bound state for the flexible lid region of Hsp90. Thus, our dynamic docking method is effective at predicting the native binding site while exhaustively sampling a wide configurational space, modulating the protein structure upon binding. 相似文献
79.
80.
Ana Salomé Pires João Batista Dina Murtinho Célia Nogueira Anna Karamysheva M. Luísa Ramos Bruce F. Milne Nuno Tiago Tavares José Gonçalves Ana Cristina Gonçalves Ana Margarida Abrantes Rui Soares Teresa Gonçalves Maria Filomena Botelho M. Elisa Silva Serra 《应用有机金属化学》2020,34(5):e5569
Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC50 of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment. 相似文献