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631.
Rhile IJ Markle TF Nagao H DiPasquale AG Lam OP Lockwood MA Rotter K Mayer JM 《Journal of the American Chemical Society》2006,128(18):6075-6088
Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants. The bases are a primary amine (-CPh(2)NH(2)), an imidazole, and a pyridine. The product of chemical and quasi-reversible electrochemical oxidations in each case is the phenoxyl radical in which the phenolic proton has transferred to the base, (*)OAr-BH(+), a proton-coupled electron transfer (PCET) process. The redox potentials for these oxidations are lower than for other phenols, predominately from the driving force for proton movement. One-electron oxidation of the phenols occurs by a concerted proton-electron transfer (CPET) mechanism, based on thermochemical arguments, isotope effects, and DeltaDeltaG(++)/DeltaDeltaG degrees . The data rule out stepwise paths involving initial electron transfer to form the phenol radical cations [(*)(+)HOAr-B] or initial proton transfer to give the zwitterions [(-)OAr-BH(+)]. The rate constant for heterogeneous electron transfer from HOAr-NH(2) to a platinum electrode has been derived from electrochemical measurements. For oxidations of HOAr-NH(2), the dependence of the solution rate constants on driving force, on temperature, and on the nature of the oxidant, and the correspondence between the homogeneous and heterogeneous rate constants, are all consistent with the application of adiabatic Marcus theory. The CPET reorganization energies, lambda = 23-56 kcal mol(-)(1), are large in comparison with those for electron transfer reactions of aromatic compounds. The reactions are not highly non-adiabatic, based on minimum values of H(rp) derived from the temperature dependence of the rate constants. These are among the first detailed analyses of CPET reactions where the proton and electron move to different sites. 相似文献
632.
A synthetic methodology for the synthesis of alpha-amino acid precursors directly from the corresponding aldehydes using N,O-dialkylated hydroxylamines and masked acyl cyanide (MAC) reagents was developed. The one-pot reaction can be carried out under mild conditions and without a separate purification step of the imino species. The method was applied to the synthesis of optically pure (+)-4-methylphenylglycine and the derivatives by using an Abiko-Masamune's tricyclic 1,2-oxazolidine as the chiral auxiliary. 相似文献
633.
Shunji Kishimoto Fumihiko Nishikido Rie Haruki Kengo Shibuya Masanori Koshimizu 《Hyperfine Interactions》2012,204(1-3):101-110
We have developed fast scintillation detectors for nuclear resonant scattering experiments using synchrotron radiation and a nuclear excited level existing in >30?keV. A fast x-ray detector using an organic-inorganic perovskite scintillator of phenethylamine lead bromide (PhE-PbBr4) had a dominant light emission with a fast decay time of 9.9?ns. An x-ray detector equipped with a 0.9-mm-thick PhE-PbBr4 crystal (size: ~8 × 7?mm2) was used to detect nuclear resonant scattering in 61Ni (the first excited level: 67.41?keV; half-life: 5.3?ns). We could successfully record the decaying gamma rays emitted from 61Ni with a relatively high detection efficiency of 24%. A lead-doped plastic scintillator (NE142, Pb ~5?wt% doped) had been known to have a faster decay time of 1.7?ns. Following a test of a single NE142 detector, a four-channel NE142 detector was fabricated and successfully applied to the synchrotron-radiation based M?ssbauer spectroscopy experiment on 61Ni. 相似文献
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635.
636.
Juzo Nakayama Ayako Kaneko Yoshiaki Sugihara Akihiko Ishii Akihiro Oishi Isao Shibuya 《Heteroatom Chemistry》2000,11(6):434-440
It was shown that dimethyl 2‐thiono‐1,3‐dithiole‐4,5‐dicarboxylate ( 2 ) and dimethyl acetylenedicarboxylate (DMAD) undergo a 1,3‐dipolar cycloaddition to produce a short‐lived ylide intermediate ( 3 ). The 1,3‐dipolar cycloaddition took place even at room temperature, although sluggishly, but took place much more rapidly under application of a high pressure of 500 MPa. The 1,3‐dipolar cycloaddition is reversible and the ylide 3 immediately splits into 2 and DMAD. When the reaction of 2 with DMAD was carried out at room temperature without solvent, a spiro‐1,3‐dithiole ( 11 ) was formed in 11% yield, whereas the reaction at 150°C provided a thiophene derivative ( 13 ) in 41% yield. It was found that 11 undergoes a thermal rearrangement to 13 . Results of attempted chemical trapping of the ylide 3 are also reported. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:434–440, 2000 相似文献
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638.
Prof. Ming-Shui Yao Prof. Ken-ichi Otake Jiajia Zheng Masahiko Tsujimoto Dr. Yi-Fan Gu Lu Zheng Dr. Ping Wang Dr. Shivanna Mohana Dr. Mickaele Bonneau Tomoyuki Koganezawa Tetsuo Honma Hirotaka Ashitani Shogo Kawaguchi Prof. Yoshiki Kubota Prof. Susumu Kitagawa 《Angewandte Chemie (International ed. in English)》2023,62(35):e202308990
A one-stone, two-bird method to integrate the soft porosity and electrical properties of distinct metal–organic frameworks (MOFs) into a single material involves the design of conductive-on-insulating MOF (cMOF-on-iMOF) heterostructures that allow for direct electrical control. Herein, we report the synthesis of cMOF-on-iMOF heterostructures using a seeded layer-by-layer method, in which the sorptive iMOF core is combined with chemiresistive cMOF shells. The resulting cMOF-on-iMOF heterostructures exhibit enhanced selective sorption of CO2 compared to the pristine iMOF (298 K, 1 bar, S from 15.4 of ZIF-7 to 43.2–152.8). This enhancement is attributed to the porous interface formed by the hybridization of both frameworks at the molecular level. Furthermore, owing to the flexible structure of the iMOF core, the cMOF-on-iMOF heterostructures with semiconductive soft porous interfaces demonstrated high flexibility in sensing and electrical “shape memory” toward acetone and CO2. This behavior was observed through the guest-induced structural changes of the iMOF core, as revealed by the operando synchrotron grazing incidence wide-angle X-ray scattering measurements. 相似文献
639.
Hirotaka Nakajima Kaiji Uchida Dr. Takefumi Yoshida Dr. Yoji Horii Dr. Tetsu Sato Zhang Luming Dr. Satoshi Yamashita Dr. Yasuhiro Nakazawa Dr. Verdad C. Agulto Dr. Makoto Nakajima Dr. Brian K. Breedlove Dr. Masahiro Yamashita Dr. Hiroaki Iguchi Dr. Shinya Takaishi 《Chemphyschem》2023,24(4):e202200618
We report the water adsorption/desorption behavior and dynamic magnetic properties of the Pt−Cl chain complex [{[Pt(en)2][PtCl2(en)2]}3][{(MnCl5)Cl3}2] ⋅ 12H2O ( 1 ). Upon heating 1 in a vacuum, we obtained the dehydrated form [{[Pt(en)2][PtCl2(en)2]}3][{(MnCl5)Cl3}2] ( 1DH ). The framework structures of 1 and 1DH are identical, and both complexes underwent slow magnetic relaxation. However, the magnetic relaxation times for 1DH were shorter than those for 1 , meaning that the dynamic magnetic properties were controlled upon water vapor adsorption/desorption. From detailed analyses of the dynamic magnetic behavior, a phonon-bottleneck effect contributes to the magnetic relaxation processes. We discuss the mechanism for the changes in the magnetic relaxation processes upon dehydration in terms of the heat capacity and thermal conductivity. 相似文献
640.
Prof. Dr. Hongyao Zhou Hirotaka Inoue Mizuha Ujita Prof. Dr. Teppei Yamada 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(2):e202213449
Thermocells are a thermoelectric conversion technology that utilizes the shift in an electrochemical equilibrium arising from a temperature difference. This technology has a long history; however, its low conversion efficiency impedes its practical usage. Recently, an increasing number of reports have shown drastic improvements in thermoelectric conversion efficiency, and thermocells could arguably represent an alternative to solid thermoelectric devices. In this Minireview, we regard thermocells as molecular systems consisting of successive molecular processes responding to a temperature change to achieve energy generation. Various molecular technologies have been applied to thermocells in recent years, and could stimulate diverse research fields, including supramolecular chemistry, physical chemistry, electrochemistry, and solid-state ionics. These research approaches will also provide novel methods for achieving a sustainable society in the future. 相似文献