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51.
Ryosuke Matsui Erina Niijima Tomomi Imai Hiroyuki Kobayashi Akiko Hori Azusa Sato Yuko Nakamura Osamu Kitagawa 《Molecules (Basel, Switzerland)》2022,27(7)
The halogen bond has been widely used as an important supramolecular tool in various research areas. However, there are relatively few studies on halogen bonding related to molecular chirality. 3-(2-Halophenyl)quinazoline-4-thione derivatives have stable atropisomeric structures due to the rotational restriction around an N-C single bond. In X-ray single crystal structures of the racemic and optically pure N-C axially chiral quinazoline-4-thiones, we found that different types of intermolecular halogen bonds (C=S⋯X) are formed. That is, in the racemic crystals, the intermolecular halogen bond between the ortho-halogen atom and sulfur atom was found to be oriented in a periplanar conformation toward the thiocarbonyl plane, leading to a syndiotactic zig-zag array. On the other hand, the halogen bond in the enantiomerically pure crystals was oriented orthogonally toward the thiocarbonyl plane, resulting in the formation of a homochiral dimer. These results indicate that the corresponding racemic and optically pure forms in chiral molecules are expected to display different halogen bonding properties, respectively, and should be separately studied as different chemical entities. 相似文献
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Shahi Imam Reja Yuichiro Hori Takuya Kamikawa Kohei Yamasaki Miyako Nishiura Steven D. Bull Kazuya Kikuchi 《Chemical science》2022,13(5):1419
The ability to monitor proteolytic pathways that remove unwanted and damaged proteins from cells is essential for understanding the multiple processes used to maintain cellular homeostasis. In this study, we have developed a new protein-labeling probe that employs an ‘OFF–ON–OFF’ fluorescence switch to enable real-time imaging of the expression (fluorescence ON) and degradation (fluorescence OFF) of PYP-tagged protein constructs in living cells. Fluorescence switching is modulated by intramolecular contact quenching interactions in the unbound probe (fluorescence OFF) being disrupted upon binding to the PYP-tag protein, which turns fluorescence ON. Quenching is then restored when the PYP-tag–probe complex undergoes proteolytic degradation, which results in fluorescence being turned OFF. Optimization of probe structures and PYP-tag mutants has enabled this fast reacting ‘OFF–ON–OFF’ probe to be used to fluorescently image the expression and degradation of short-lived proteins.An “OFF–ON–OFF” fluorescence probe for real-time imaging of the expression (fluorescence ‘OFF’) and degradation (fluorescence ‘ON’) of short lived PYP-tag proteins in cellular systems. 相似文献
54.
Wide distribution of relaxation times is taken into consideration in determination of the activation energy of the molecular motion associated with the motional narrowings of line widths of magnetic resonance spectra. The molecular motion of rotational vibration around the chain axis of polyethylene in urea-polyethylene inclusion complex is examined. Relaxation spectra can be obtained from the data of the motional narrowings of EPR and NMR by assuming the activation energy as a parameter. Also, the representative relaxation times corresponding to EPR and NMR observations can be estimated. These relaxation times give us an activation energy since EPR and NMR observations correspond to different time constants of observations. The activation energy estimated from the data of the representative correlation times is identical with the activation energy obtained as a parameter in determination of the identical relaxation spectrum from the data of motional narrowings of EPR and NMR observations. 相似文献
55.
Stable conformations of 12-crown-O3N and its Li complexes in aqueous solution were investigated. To calculate the free energy differences of conformers of 12-crown-O3N and its Li+ complex, our procedure was to make use of two programs, CONFLEX and BOSS. The former generates conformers, and the latter calculates the differences in free energy of solvation between two conformers in aqueous solution. It was confirmed that the present procedure is applicable in solving the question of what is the most stable conformation of 12-crown-O3N in aqueous solution. Results of the calculations suggest that the order of stability for conformers in a vacuum is different from that in aqueous solution. It was also confirmed that the coordination geometry of solvent waters to Li+ changes depending on the distance between the cation and the crown ring. 相似文献
56.
Uto Y Hirata A Fujita T Takubo S Nagasawa H Hori H 《The Journal of organic chemistry》2002,67(7):2355-2357
We have demonstrated that prenylation of p-halophenols was dependent on the solvent effect and succeeded in o,o'-diprenylation of p-halophenols in water. Following the Mizoroki-Heck coupling of the diprenyl-p-iodophenol 3c with methyl acrylate and then hydrolysis, we first synthesized artepillin C [3-(4-hydroxy-3,5-di(3-methyl-2-butenyl)phenyl)-2(E)-propenoic acid] (1), which is a biologically active constituent of propolis. These reactions may be applicable to the synthesis of various useful natural products such as 2,4,6-trisubstituted phenol derivatives. 相似文献
57.
Widmann E Eades J Ishikawa T Sakaguchi J Tasaki T Yamaguchi H Hayano RS Hori M Torii HA Juhász B Horváth D Yamazaki T 《Physical review letters》2002,89(24):243402
Using a newly developed laser-microwave-laser resonance method, we observed a pair of microwave transitions between hyperfine levels of the (n,L)=(37,35) state of antiprotonic helium. This experiment confirms the quadruplet hyperfine structure arising from the interaction of the antiproton orbital angular momentum, the electron spin and the antiproton spin as predicted by Bakalov and Korobov. The measured frequencies of nu(+)(HF)=12.895 96+/-0.000 34 GHz and nu(-)(HF)=12.924 67+/-0.000 29 GHz agree with recent theoretical calculations on a level of 6x10(-5). 相似文献
58.
Hori M Eades J Hayano RS Ishikawa T Sakaguchi J Tasaki T Widmann E Yamaguchi H Torii HA Juhász B Horváth D Yamazaki T 《Physical review letters》2002,89(9):093401
Initial distributions of metastable antiprotonic (4)He and (3)He atoms over principal (n) and angular momentum (l) quantum numbers have been deduced using laser spectroscopy experiments. The regions n = 37-40 and n = 35-38 in the two atoms account for almost all of the observed fractions [(3.0 +/- 0.1)% and (2.4 +/- 0.1)%] of antiprotons captured into metastable states. 相似文献
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