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Andrei V. Afonin Igor A. Ushakov Dmitry V. Pavlov Andrei V. Ivanov Al'bina I. Mikhaleva 《Magnetic resonance in chemistry : MRC》2010,48(9):685-692
The 1H, 13C and 15N NMR studies have shown that the E and Z isomers of pyrrole‐2‐carbaldehyde oxime adopt preferable conformation with the syn orientation of the oxime group with respect to the pyrrole ring. The syn conformation of E and Z isomers of pyrrole‐2‐carbaldehyde oxime is stabilized by the N? H···N and N? H···O intramolecular hydrogen bonds, respectively. The N? H···N hydrogen bond in the E isomer causes the high‐frequency shift of the bridge proton signal by about 1 ppm and increase the 1J(N, H) coupling by ~3 Hz. The bridge proton shows further deshielding and higher increase of the 1J(N, H) coupling constant due to the strengthening of the N? H···O hydrogen bond in the Z isomer. The MP2 calculations indicate that the syn conformation of E and Z isomers is by ~3.5 kcal/mol energetically less favorable than the anti conformation. The calculations of 1H shielding and 1J(N, H) coupling in the syn and anti conformations allow the contribution to these constants from the N? H···N and N? H···O hydrogen bondings to be estimated. The NBO analysis suggests that the N? H···N hydrogen bond in the E isomer is a pure electrostatic interaction while the charge transfer from the oxygen lone pair to the antibonding orbital of the N? H bond through the N? H···O hydrogen bond occurs in the Z isomer. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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Tetsuo Asaji Janez Seliger Veselko Žagar Hiroyuki Ishida 《Magnetic resonance in chemistry : MRC》2010,48(7):531-536
Proton transfer in hydrogen‐bonded organic co‐crystals of chloranilic acid with some organic bases was investigated by nuclear quadrupole resonance (NQR) spectroscopy. The 35Cl NQR frequencies of chloranilic acid molecule as well as 14N NQR frequencies of the organic base molecule were measured with the conventional pulse methods as well as double‐resonance methods, respectively. The extent of proton transfer in the O···H···N hydrogen bond was estimated from Townes–Dailey analysis of the 14N NQR parameters. The 35Cl NQR frequency and molecular geometry of chloranilic acid are correlated to the extent of proton transfer in the protonation process of the organic base molecule. It is shown that the hydrogen bond affects the π‐electron system of chloranilic acid. Geometry dependence of the O···H···N hydrogen bond, i.e. the H? N valence bond order versus the hydrogen‐bond geometry correlation is also discussed. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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The use of the far‐infrared spectral range presents a novel approach for analysis of the hydrogen bonding in proteins. Here it is presented for the analysis of Fe? S vibrations (500–200 cm?1) and of the intra‐ and intermolecular hydrogen bonding signature (300–50 cm?1) in the Rieske protein from Thermus thermophilus as a function of temperature and pH. Three pH values were adequately chosen in order to study all the possible protonation states of the coordinating histidines. The Fe? S vibrations showed pH‐dependent shifts in the FIR spectra in line with the change of protonation state of the histidines coordinating the [2Fe? 2S] cluster. Measurements of the low‐frequency signals between 300 and 30 K demonstrated the presence of a distinct overall hydrogen bonding network and a more rigid structure for a pH higher than 10. To further support the analysis, the redox‐dependent shifts of the secondary structure were investigated by means of an electrochemically induced FTIR difference spectroscopic approach in the mid infrared. The results confirmed a clear pH dependency and an influence of the immediate environment of the cluster on the secondary structure. The results support the hypothesis that structure‐mediated changes in the environment of iron? sulfur centers play a critical role in regulating enzymatic catalysis. The data point towards the role of the overall internal hydrogen bonding organization for the geometry and the electronic properties of the cluster. 相似文献
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Fei Li Jianzhong Yang Yang Qin 《Journal of polymer science. Part A, Polymer chemistry》2013,51(16):3339-3350
We report the synthesis and characterization of a polythiophene block copolymer (P4) selectively functionalized with diaminopyrimidine moieties and a thymine tethered fullerene derivative (F1). Self‐assembly between P4 and F1 through “three‐point” complementary hydrogen bonding is studied by 1H NMR spectroscopy and differential scanning calorimetry. A large Stern‐Volmer constant (KSV) of 1.2 × 105 M?1 is observed from fluorescence quenching experiments, revealing strong complexation between these two components. Solar cells employing P4 and F1 at different weight ratios as active layers are fabricated and tested; corresponding thin film morphologies are studied in detail by optical imaging and atomic force microscopy. Correlations between polymer complex structures, film morphologies, and device performance are discussed. Thermal stability of benchmark poly(3‐hexylthiophene) bulk heterojunction solar cells is found to be improved by the addition of a few weight percent of P4/F1 complexes as compatibilizers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3339–3350 相似文献
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