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61.
Tetsuro Shimo 《Tetrahedron》2005,61(33):8059-8064
Solid-state photosensitized reactions of 4-acyloxy-2-pyrones (1b,c) with maleimide (2) afforded endo-endo double-[4+2] cycloadducts (3b,c) with high stereoselectivity. Sensitized photoreactions of 1a-d with 2 in solution gave exo-endo double-[4+2] cycloadducts (4a-d). 2-Pyrones 1a-d were photolyzed to give carboxylic acids (5a-d) via their valence isomerization in the solid state and in solution. Such kinds of photoreaction of the 4-acyloxy-2-pyrones were dramatically different from regio- and stereoselective [2+2] cycloadditions of 4-alkyloxy-2-pyrones. The photoreaction mechanisms of 1 with 2 and 1 itself were analyzed by powder X-ray diffraction analysis and MO calculations. 相似文献
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Dr. Kenta Arai Takahiko Matsunaga Haruhito Ueno Nozomi Akahoshi Yuumi Sato Dr. Gaurango Chakrabarty Prof. Dr. Govindasamy Mugesh Prof. Dr. Michio Iwaoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(55):12751-12760
At the redox-active center of thioredoxin reductase (TrxR), a selenenyl sulfide (Se−S) bond is formed between Cys497 and Sec498, which is activated into the thiolselenolate state ([SH,Se−]) by reacting with a nearby dithiol motif ([SHCys59,SHCys64]) present in the other subunit. This process is achieved through two reversible steps: an attack of a cysteinyl thiol of Cys59 at the Se atom of the Se−S bond and a subsequent attack of a remaining thiol at the S atom of the generated mixed Se−S intermediate. However, it is not clear how the kinetically unfavorable second step progresses smoothly in the catalytic cycle. A model study that used synthetic selenenyl sulfides, which mimic the active site structure of human TrxR comprising Cys497, Sec498, and His472, suggested that His472 can play a key role by forming a hydrogen bond with the Se atom of the mixed Se−S intermediate to facilitate the second step. In addition, the selenenyl sulfides exhibited a defensive ability against H2O2-induced oxidative stress in cultured cells, which suggests the possibility for medicinal applications to control the redox balance in cells. 相似文献
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Kazuhisa Sato Shunya Tashiro Shuhei Matsunaga Yohei Yamaguchi Takanori Kiguchi Toyohiko J. Konno 《哲学杂志》2018,98(21):1945-1960
We have studied three-dimensional (3D) structures and growth processes of 14H-type long-period stacking order (LPSO) formed in Mg97Zn1Gd2 cast alloys by single tilt-axis electron tomography (ET) using high-angle annular dark-field scanning transmission electron microscopy. Evolution of the solute-enriched stacking faults (SFs) and the 14H LPSO by ageing were visualised in 3D with a high spatial resolution in multi-scale fields of views from a few nanometres to ~10 μm. Lateral growth of the solute-enriched SFs and the LPSO in the (0?0?0?1)Mg plane is notable compared to the out-of-plane growth in the [0?0?0?1]Mg direction. The 14H LPSO grows at the cost of decomposition of the (Mg, Zn)3Gd-type precipitates, and accompany a change of in-plane edge angles from 30 to 60°. We have updated the Time–Temperature–Transformation diagram for precipitation in Mg97Zn1Gd2 alloys: starting temperatures of both solute-enriched SFs and LPSO formation shifted to a shorter time side than those in the previous diagram. 相似文献
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Hiroki Matsunaga Hiroto Habu Atsumi Miyake 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1387-1394
Ammonium dinitramide (ADN) is one of the several promising new solid propellant oxidizers. ADN is of interest because its oxygen balance and energy content are high, and it also halogen-free. One of the most important characteristics of a propellant oxidizer, however, is stability and ADN is known to degrade to ammonium nitrate (AN) during storage, which will affect its performance. This study focused on the effects of aging on the thermal decomposition mechanism of ADN. The thermal behaviors of ADN and ADN/AN mixtures were studied, as were the gases evolved during their decomposition, using differential scanning calorimetry (DSC), thermogravimetry–differential thermal analysis-infrared spectrometry (TG–DTA-IR), and thermogravimetry–differential thermal analysis-mass spectrometry (TG–DTA-MS). The results of these analyses demonstrated that the decomposition of ADN occurs via a series of distinct stages in the condensed phase. The gases evolved from ADN decomposition were N2O, NO2, N2, and H2O. In contrast, ADN mixed with AN (to simulate aging) did not exhibit the same initial reaction. We conclude that aging inhibits early stage, low temperature decomposition reactions of ADN. Two possible reasons were proposed, these being either a decrease in the acidity of the material due to the presence of AN, or inhibition of the acidic dissociation of dinitramic acid by NO 3 ? . 相似文献
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