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191.
New atom equivalents are introduced to convert BP/DN**//MMFF energies into formation enthalpies. As a result of using molecular mechanics structures, poor results are obtained for compounds outside the scope of the force field, such as those bearing NF2 groups or some nitrogenous systems. Notwithstanding these limitations, present procedures compare well with the results of previous atom equivalents schemes. Indeed, rms deviations from experiment are below 9 kJ/mol for hydrocarbons, and close to 16 kJ/mol for a variety of compounds reasonably well described by MMFF. The explicit inclusion of thermal and vibrational contributions, using calculated frequencies, does not improve the results. This study demonstrates that cost‐effective approaches to formation enthalpies may be developed on the basis of a combination of DFT with a suitable molecular mechanics force field. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 367–379, 2000 相似文献
192.
193.
Montassar Khalil Alexis Hocquigny Mathieu Berchel Tristan Montier Paul-Alain Jaffrs 《Molecules (Basel, Switzerland)》2021,26(24)
A convergent synthesis of cationic amphiphilic compounds is reported here with the use of the phosphonodithioester–amine coupling (PAC) reaction. This versatile reaction occurs at room temperature without any catalyst, allowing binding of the lipid moiety to a polar head group. This strategy is illustrated with the use of two lipid units featuring either two oleyl chains or two-branched saturated lipid chains. The final cationic amphiphiles were evaluated as carriers for plasmid DNA delivery in four cell lines (A549, Calu3, CFBE and 16HBE) and were compared to standards (BSV36 and KLN47). These new amphiphilic derivatives, which were formulated with DOPE or DOPE-cholesterol as helper lipids, feature high transfection efficacies when associated with DOPE. The highest transfection efficacies were observed in the four cell lines at low charge ratios (CR = 0.7, 1 or 2). At these CRs, no toxic effects were detected. Altogether, this new synthesis scheme using the PAC reaction opens up new possibilities for investigating the effects of lipid or polar head groups on transfection efficacies. 相似文献
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195.
Infrared spectra simulations require ab initio techniques to get reliable intensities. On the other hand, recent force fields can provide accurate molecular geometries and frequencies. Therefore, it is suggested that these new force fields could be used to simulate infrared spectra, dipole-moment surfaces being described at high levels of theory in order to get satisfactory intensities. As pointed out, for a system with N atoms, the cost of such a simulation would be reduced N-fold with respect to standard quantum approaches. Preliminary calculations based on this scheme are reported here. Encouraging results are obtained since no significant lost of accuracy is noted on going from the ab initio to the molecular mechanics potential energy surface. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 705–711, 1998 相似文献
196.
Stereoselective Synthesis of the Halaven C14–C26 Fragment from D‐Quinic Acid: Crystallization‐Induced Diastereoselective Transformation of an α‐Methyl Nitrile 下载免费PDF全文
Francis Belanger Dr. Charles E. Chase Dr. Atsushi Endo Dr. Francis G. Fang Dr. Jing Li Steven R. Mathieu Dr. Annie Z. Wilcoxen Huiming Zhang 《Angewandte Chemie (International ed. in English)》2015,54(17):5108-5111
Crystallization‐induced diastereoselective transformation (CIDT) of an α‐methyl nitrile completes an entirely non‐chromatographic synthesis of the halichondrin B C14–C26 stereochemical array. The requisite α‐methyl nitrile substrate is derived from D ‐quinic acid through a series of substrate‐controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14–C26 fragment were derived from the single chiral source D ‐quinic acid. 相似文献
197.
Jrmy Ternel Adrien Lopes Mathieu Sauthier Clothilde Buffe Vincent Wiatz Herv Bricout Sbastien Tilloy Eric Monflier 《Molecules (Basel, Switzerland)》2021,26(23)
Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%. 相似文献
198.
Pump−probe experiments at the TEMPO beamline using the low‐α operation mode of Synchrotron SOLEIL 下载免费PDF全文
Mathieu G. Silly Tom Ferté Marie Agnes Tordeux Debora Pierucci Nathan Beaulieu Christian Chauvet Federico Pressacco Fausto Sirotti Horia Popescu Victor Lopez-Flores Marina Tortarolo Maurizio Sacchi Nicolas Jaouen Philippe Hollander Jean Paul Ricaud Nicolas Bergeard Christine Boeglin Bharati Tudu Renaud Delaunay Jan Luning Gregory Malinowski Michel Hehn Cédric Baumier Franck Fortuna Damjan Krizmancic Luigi Stebel Rudi Sergo Giuseppe Cautero 《Journal of synchrotron radiation》2017,24(4):886-897
The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump–probe experiments. Among others, the low‐α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low‐α mode of the experimental set‐ups developed at the TEMPO beamline to perform pump–probe experiments with soft X‐rays based on photoelectron or photon detection are presented. A 282 kHz repetition‐rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two‐dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time‐resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high‐time‐resolution pump–probe experiments compared and discussed. 相似文献
199.
S. L. Chin H. L. Xu Q. Luo F. Théberge W. Liu J. F. Daigle Y. Kamali P. T. Simard J. Bernhardt S. A. Hosseini M. Sharifi G. Méjean A. Azarm C. Marceau O. Kosareva V. P. Kandidov N. Ak?zbek A. Becker G. Roy P. Mathieu J. R. Simard M. Chateauneuf J. Dubois 《Applied physics. B, Lasers and optics》2009,95(1):1-12
All matters in the path of filaments induced by an intense femtosecond laser pulse propagating in air could be fragmented
and result in the emission of characteristic fluorescence spectra from the excited fragments. The fluorescence spectra exhibit
specific signatures (fingerprints) that can be used for the identification of various substances including chemical and biological
species. In this paper, we present an overview of the recent progress in our laboratory concerning the “remote” sensing of
chemical and biological agents/pollutants in air using filamentation-induced nonlinear fluorescence techniques. 相似文献
200.
Romeo D. Tadjouate Nago Paul Nayim Armelle T. Mbaveng James D. Simo Mpetga Gabin T. Mbahbou Bitchagno Badawe Garandi Pierre Tane Bruno N. Lenta Norbert Sewald Mathieu Tene Victor Kuete Augustin Silvere Ngouela 《Molecules (Basel, Switzerland)》2021,26(16)
The local botanical Imperata cylindrica in Cameroon was investigated for its antibacterial potency. The methanol extract afforded a total of seven compounds, including five hitherto unreported compounds comprising three flavonoids (1–3) and two C-15 isoprenoid analogues (4 and 5) together with known derivatives (6 and 7). The novelty of the flavonoids was related to the presence of both methyl and prenyl groups. The potential origin of the methyl in the flavonoids is discussed, as well as the chemophenetic significance of our findings. Isolation was performed over repeated silica gel and Sephadex LH-20 column chromatography and the structures were elucidated by (NMR and MS). The crude methanol extract and isolated compounds showed considerable antibacterial potency against a panel of multi-drug resistant (MDR) bacterial strains. The best MIC values were obtained with compound (2) against S. aureus ATCC 25923 (32 µg/mL) and MRSA1 (16 µg/mL). 相似文献