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81.
The one-carbon elongation of aldoses to ketoses using iodomethyllithium as the key reagent in the homologation step is exemplified by the preparation of two carbohydrates of chemical and biological interests: d-manno-hept-2-ulose from d-mannose and l-fructose from l-arabinose. 相似文献
82.
Delajon C Gutberlet T Steitz R Möhwald H Krastev R 《Langmuir : the ACS journal of surfaces and colloids》2005,21(18):8509-8514
The coupling of lipid molecules to polymer components in a planar biomimetic model membrane made of a lipid bilayer (dimyristoylphosphatidylcholine) supported by polyelectrolyte multilayers is studied. The polyelectrolyte support was prepared by layer-by-layer deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly(sodium 4-styrenesulfonate) (PSS). Two polymer sample terminations were considered: positively charged (PAH-terminated) and negatively charged (PSS-terminated). Neutron reflectometry studies showed that, whereas positively charged samples did not favor the deposition of lipid, negatively charged samples allowed the deposition of a lipid bilayer with a thickness of approximately 5 nm. In the latter case, formation of polyelectrolyte layers after the deposition of the lipid layer was also possible. 相似文献
83.
Quantum Machine Learning (QML) has not yet demonstrated extensively and clearly its advantages compared to the classical machine learning approach. So far, there are only specific cases where some quantum-inspired techniques have achieved small incremental advantages, and a few experimental cases in hybrid quantum computing are promising, considering a mid-term future (not taking into account the achievements purely associated with optimization using quantum-classical algorithms). The current quantum computers are noisy and have few qubits to test, making it difficult to demonstrate the current and potential quantum advantage of QML methods. This study shows that we can achieve better classical encoding and performance of quantum classifiers by using Linear Discriminant Analysis (LDA) during the data preprocessing step. As a result, the Variational Quantum Algorithm (VQA) shows a gain of performance in balanced accuracy with the LDA technique and outperforms baseline classical classifiers. 相似文献
84.
85.
Janis V. Musso Jordan De Jesus Silva Mathis J. Benedikter Jonas Groos Wolfgang Frey Christophe Copret Michael R. Buchmeiser 《Chemical science》2022,13(29):8649
Cationic d0 group 6 olefin metathesis catalysts have been recently shown to display in most instances superior activity in comparison to their neutral congeners. Furthermore, their catalytic performance is greatly improved upon immobilization on silica. In this context, we have developed the new family of molecular cationic molybdenum oxo alkylidene complexes stabilized by N-heterocyclic carbenes of the general formula [Mo(O)(CHCMe3)(IMes)(OR)[X−]] (IMes = 1,3-dimesitylimidazol-2-ylidene; R = 1,3-dimesityl-C6H3, C6F5; X− = B(3,5-(CF3)2C6H3)4−, B(ArF)4, tetrakis(perfluoro-t-butoxy)aluminate (PFTA)). Immobilization of [Mo(O)(CHCMe3)(IMes)(O-1,3-dimesityl-C6H3)+B(ArF)4−] on silica via surface organometallic chemistry yields an active alkene metathesis catalyst that shows the highest productivity towards terminal olefins amongst all existing molybdenum oxo alkylidene catalysts.The first cationic molybdenum oxo complexes were synthesized and immobilized on partially dehydroxylated silica. Vastly enhanced catalytic activity for terminal olefins was found compared to their neutral congeners. 相似文献
86.
Emanuele Antico Markus Leutzsch Niklas Wessel Thomas Weyhermüller Christophe Werl Walter Leitner 《Chemical science》2022,14(1):54
The development of earth-abundant catalysts for the selective conversion of silanes to silanols with water as an oxidant generating valuable hydrogen as the only by-product continues to be a challenge. Here, we demonstrate that [MnBr(CO)5] is a highly active precatalyst for this reaction, operating under neutral conditions and avoiding the undesired formation of siloxanes. As a result, a broad substrate scope, including primary and secondary silanes, could be converted to the desired products. The turnover performances of the catalyst were also examined, yielding a maximum TOF of 4088 h−1. New light was shed on the debated mechanism of the interaction between [MnBr(CO)5] and Si–H bonds based on the reaction kinetics (including KIEs of PhMe2SiD and D2O) and spectroscopic techniques (FT-IR, GC-TCD, 1H-, 29Si-, and 13C-NMR). The initial activation of [MnBr(CO)5] was found to result from the formation of a manganese(i) hydride species and R3SiBr, and the experimental data are most consistent with a catalytic cycle comprising a cationic tricarbonyl Mn(i) unit as the active framework.This study presents the use of MnBr(CO)5 for the selective conversion of silanes to silanols with water as an oxidant generating valuable hydrogen as the only by-product. 相似文献
87.
Michelyne Haroun Santosh S. Chobe Rajasekhar Reddy Alavala Savita M. Mathure Risy Namratha Jamullamudi Charushila K. Nerkar Vijay Kumar Gugulothu Christophe Tratrat Mohammed Monirul Islam Katharigatta N. Venugopala Mohammed Habeebuddin Mallikarjun Telsang Nagaraja Sreeharsha Md. Khalid Anwer 《Molecules (Basel, Switzerland)》2022,27(12)
Considering the importance of benzothiazepine pharmacophore, an attempt was carried out to synthesize novel 1,5-benzothiazepine derivatives using polyethylene glycol-400 (PEG-400)-mediated pathways. Initially, different chalcones were synthesized and then subjected to a cyclization step with benzothiazepine in the presence of bleaching clay and PEG-400. PEG-400-mediated synthesis resulted in a yield of more than 95% in less than an hour of reaction time. Synthesized compounds 2a–2j were investigated for their in vitro cytotoxic activity. Moreover, the same compounds were subjected to systematic in silico screening for the identification of target proteins such as human adenosine kinase, glycogen synthase kinase-3β, and human mitogen-activated protein kinase 1. The compounds showed promising results in cytotoxicity assays; among the tested compounds, 2c showed the most potent cytotoxic activity in the liver cancer cell line Hep G-2, with an IC50 of 3.29 ± 0.15 µM, whereas the standard drug IC50 was 4.68 ± 0.17 µM. In the prostate cancer cell line DU-145, the compounds displayed IC50 ranges of 15.42 ± 0.16 to 41.34 ± 0.12 µM, while the standard drug had an IC50 of 21.96 ± 0.15 µM. In terms of structural insights, the halogenated phenyl substitution on the second position of benzothiazepine was found to significantly improve the biological activity. This characteristic feature is supported by the binding patterns on the selected target proteins in docking simulations. In this study, 1,5-benzothiazepines have been identified as potential anticancer agents which can be further exploited for the development of more potent derivatives. 相似文献
88.
Laurent Aubry Thierry Sayd Claude Ferreira Christophe Chambon Annie Vnien Sylvie Blinet Marie Bourin Anglique Travel Maeva Halgrain Vronique Sant-Lhoutellier Laetitia Thron 《Molecules (Basel, Switzerland)》2021,26(12)
The marketing of poultry livers is only authorized as fresh, frozen, or deep-frozen. The higher consumer demand for these products for a short period of time may lead to the marketing of frozen–thawed poultry livers: this constitutes fraud. The aim of this study was to design a method for distinguishing frozen–thawed livers from fresh livers. For this, the spectral fingerprint of liver proteins was acquired using Matrix-Assisted Laser Dissociation Ionization-Time-Of-Flight mass spectrometry. The spectra were analyzed using the chemometrics approach. First, principal component analysis studied the expected variability of commercial conditions before and after freezing–thawing. Then, the discriminant power of spectral fingerprint of liver proteins was assessed using supervised model generation. The combined approach of mass spectrometry and chemometrics successfully described the evolution of protein profile during storage time, before and after freezing-thawing, and successfully discriminated the fresh and frozen–thawed livers. These results are promising in terms of fraud detection, providing an opportunity for implementation of a reference method for agencies to fight fraud. 相似文献
89.
Electrochemical blocking is a type of single-entity electrochemical measurement particularly well adapted to the detection of insulating particles. The digital detection of ultralow concentrations of artificial entities such as polymer particles or biotargets such as proteins and bacteria represents an exceptional opportunity for sensing applications. In this review, we explore the latest development in the field of electrochemical blocking and propose some perspectives. 相似文献
90.
Dr. Alexia Ville Dr. Julien Annibaletto Dr. Sébastien Coufourier Prof. Christophe Hoarau Dr. Rodolphe Tamion Dr. Guillaume Journot Dr. Cédric Schneider Dr. Jean-François Brière 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(56):13961-13965
An efficient primary-amine-directed, palladium-catalyzed C−H halogenation (X=I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suitable conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine as tertiary AA. 相似文献