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71.
Pierre Thureau Simone Sturniolo Miri Zilka Fabio Ziarelli Stéphane Viel Jonathan R. Yates Giulia Mollica 《Magnetic resonance in chemistry : MRC》2019,57(5):256-264
Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed 1H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using 13C-13C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although 13C-13C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions. 相似文献
72.
A new Schiff base hydrazone (Z)‐2‐(2‐aminothiazol‐4‐yl)‐N′‐(2‐hydroxy‐3‐methoxybenzylidene) acetohydrazide (H2L) and its chelates [VO (HL)2]·5H2O, [Cu (HL)Cl(H2O)]·2H2O and [Fe(L)Cl(H2O)2]·3H2O have been isolated and characterized using different physico‐chemical methods, for example infrared (IR), electron paramagnetic resonance (EPR), thermogravimetric analysis and DTG in the solid state, and 1H‐NMR, 13C‐NMR and UV in solution. Magnetic and UV–visible measurements proposed that the coordination environments are square pyramidal, tetrahedral and octahedral geometries for oxovanadium (IV), Cu (II) and Fe (III), respectively. The ligand acts as mono‐negative NO towards oxovanadium (IV) and Cu (II) ions, and bi‐negative ONO for Fe (III) ion. The geometries of the ligand and its complexes were performed using Gaussian 9 program with density functional theory. The EPR spectral data of oxovanadium (IV) and Cu (II) chelates confirmed the mentioned geometries. The molecular modeling was done, and illustrated bond lengths, bond angles, molecular electrostatic potential, Mulliken atomic charges and chemical reactivity for the inspected compounds. Theoretical IR and 1H‐NMR of the free ligand were calculated. Furthermore, thermodynamic and kinetic parameters for thermal decomposition steps were studied. Docking study of H2L was applied against the proteins of both bacterial strains Staphylococcus aureus and Escherichia coli, as well as the protein of xanthine oxidase as antioxidant agent by Schrödinger suite program utilizing XP glide protocol. Furthermore, antimicrobial, antioxidant and DNA‐binding activities of the compounds have been carried out. 相似文献
73.
We consider the problem of optimizing heat transport through an incompressible fluid layer. Modeling passive scalar transport by advection-diffusion, we maximize the mean rate of total transport by a divergence-free velocity field. Subject to various boundary conditions and intensity constraints, we prove that the maximal rate of transport scales linearly in the r.m.s. kinetic energy and, up to possible logarithmic corrections, as the one-third power of the mean enstrophy in the advective regime. This makes rigorous a previous prediction on the near optimality of convection rolls for energy-constrained transport. On the other hand, optimal designs for enstrophy-constrained transport are significantly more difficult to describe: we introduce a “branching” flow design with an unbounded number of degrees of freedom and prove it achieves nearly optimal transport. The main technical tool behind these results is a variational principle for evaluating the transport of candidate designs. The principle admits dual formulations for bounding transport from above and below. While the upper bound is closely related to the “background method,” the lower bound reveals a connection between the optimal design problems considered herein and other apparently related model problems from mathematical materials science. These connections serve to motivate designs. © 2019 Wiley Periodicals, Inc. 相似文献
74.
The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs () routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes. 相似文献
75.
Monika Kořenková Dr. Ing. Martin Hejda Prof. Milan Erben Dr. Ing. Robert Jirásko Prof. Dr. Roman Jambor Prof. Aleš Růžička Dr. Elena Rychagova Prof. Sergey Ketkov Prof. Libor Dostál 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12884-12888
The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C6H3-2,6-(CH=NtBu)2) with selected N-alkyl/aryl-maleimides RN(C(O)CH)2 (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound. 相似文献
76.
The current paper presents a thorough study on the pull-in instability of nanoelectromechanical rectangular plates under intermolecular, hydrostatic, and thermal actuations. Based on the Kirchhoff theory along with Eringen's nonlocal elasticity theory, a nonclassical model is developed. Using the Galerkin method(GM), the governing equation which is a nonlinear partial differential equation(NLPDE) of the fourth order is converted to a nonlinear ordinary differential equation(NLODE) in the time domain. Then, the reduced NLODE is solved analytically by means of the homotopy analysis method. At the end, the effects of model parameters as well as the nonlocal parameter on the deflection, nonlinear frequency, and dynamic pull-in voltage are explored. 相似文献
77.
78.
Lea Kremer Elisabeth Hennes Alexandra Brause Andrei Ursu Lucas Robke Hideaki T. Matsubayashi Yuta Nihongaki Jana Flegel Ivana Mejdrov Jan Eickhoff Matthias Baumann Radim Nencka Petra Janning Susanne Kordes Hans R. Schler Jared Sterneckert Takanari Inoue Slava Ziegler Herbert Waldmann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16770-16781
79.
80.
Ben Jadi S. El Guerraf A. Bazzaoui E.A. Wang R. Martins J.I. Bazzaoui M. 《Journal of Solid State Electrochemistry》2019,23(8):2423-2433
Journal of Solid State Electrochemistry - Due to their distinctive chemical, electronic, and environmental properties, polypyrrole is used as a blocking barrier for methanol leakage in direct... 相似文献