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81.
Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account. 相似文献
82.
Ikuo Kawashima Hiroaki Imoto Masatoshi Ishida Hiroyuki Furuta Shunsuke Yamamoto Masaya Mitsuishi Susumu Tanaka Toshiki Fujii Kensuke Naka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):11812-11816
Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green‐to‐red region (500–700 nm) and the near‐ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S1) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S1 states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S1 states. 相似文献
83.
Synthesis and Magnetic Properties of (Pyrrolidin‐1‐oxyl)–(Nitronyl Nitroxide)/(Iminonitroxide)‐Dyads
Haruki Tsujimoto Shuichi Suzuki Masatoshi Kozaki Daisuke Shiomi Kazunobu Sato Takeji Takui Keiji Okada 《化学:亚洲杂志》2019,14(10):1801-1806
Unlike extensively studied diradicals linked by π‐conjugated systems, only a few studies have investigated weakly coupled diradicals linked by an sp3 carbon atom. Herein, we prepared pyrrolidin‐1‐oxyl–(nitronyl nitroxide)‐dyad 5 and pyrrolidin‐1‐oxyl–iminonitroxide‐dyad 6 . From the observed temperature dependence of the magnetic susceptibility, 5 and 6 were determined to be in singlet ground states with 2Jintra/kB=?35.2 K and ?13.6 K, respectively. From these results and theoretical calculations of related diradicals, the spin‐polarization model counting the small spin density of the sp3 carbon atom could be used as a spin‐prediction model. 相似文献
84.
Prof. Yukishige Ito Prof. Yasuhiro Kajihara Prof. Yoichi Takeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15461-15470
The introduction of Asn-linked glycans to nascent polypeptides occurs in the lumen of the endoplasmic reticulum of eukaryotic cells. After the removal of specific sugar residues, glycoproteins acquire signals in the glycoprotein quality control (GPQC) system and enter the folding cycle composed of lectin-chaperones calnexin (CNX) and calreticulin (CRT), glucosidase II (G-II), and UDP-Glc:glycoprotein glucosyltransferase (UGGT). G-II initiates glycoproteins’ entry and exit from the cycle, and UGGT serves as the “folding sensor”. This account summarizes our effort to analyze the properties of enzymes and lectins that play important roles in GPQC, especially those involved in the CNX/CRT cycle. To commence our study, general methods for the synthesis of high-mannose-type glycans and glycoproteins were established. Based on these, various substrates to analyze components of the GPQC were created, and properties of CRT, G-II, and UGGT have been clarified. 相似文献
85.
K. Yanagisawa H. Takeda K. Miyamoto S. Fuma N. Ishii 《Journal of Radioanalytical and Nuclear Chemistry》2002,251(2):277-280
Tracer experiments on the transfer of carbon from culture solution to Daphnia magna through phytoplankton have been carried out using 13C and infrared absorption method. The purpose of this experiment is to investigate the experimental systems for the use of 13C in aquatic system. Daphnia magna was cultured in a 100 ml of solution containing phytoplankton and 20 mg of NaH13CO3 for 24 hours in the light and dark conditions (2000 lux, 14 hour light and 10 hours dark at 25 C). The concentration of 13C in Daphnia magna under light condition was about 2.0% (atom% excess), while in the dark condition 13C tracer was not detected. The concentration of 13C in phytoplankton under light condition was around 20%. It was suggested that 13C added as carbonate in the culture solution was photosynthetically assimilated by phytoplankton and then transferred to Daphnia magna. Using this system, the effect of UV-B exposure on the 13C uptake of Daphnia magna has been examined. The UV-B intensity was 95 mW/cm2 and exposure time was 15, 30, and 60 minutes. The concentration of 13C in Daphnia magna decreased with increasing exposure time. The Daphnia magna exposed to UV-B for 15 minutes intakes phytoplankton as much as control, while 30 minutes and 60 minutes exposures were lower than control. The lower concentrations of 13C observed in Daphnia magna were due to less intake of phytoplankton caused by the UV-B exposure. 相似文献
86.
Prof. Dr. Yoshihiko Yamamoto Shota Mori Dr. Masatoshi Shibuya 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12034-12041
The transfer‐hydrogenative cyclization of 1,6‐diynes with Hantzsch 1,4‐dihydropyridine as a H2 surrogate was performed in the presence of a cationic ruthenium catalyst of the type [Cp′Ru(MeCN)3PF6]. Exocyclic 1,3‐dienes or their 1,4‐hydrogenation products, cycloalkenes, were selectively obtained, depending on the substrate structure and the reaction conditions. 相似文献
87.
The self-motion of a benzoquinone (BQ) disk on NADPH was investigated as the coupling of an autonomous motor and an enzyme reaction. In the absence of the enzyme reaction, features of motion changed depending on the concentration of NADPH, that is, continuous motion→ intermittent oscillatory motion→ no motion. When the reverse reaction from NADP(+) to NADPH was introduced into the system with the addition of an enzyme reaction, continuous motion changed to intermittent oscillatory motion with small amplitude. The mechanism of this mode change is discussed in relation to the surface tension as a driving force and the time course of UV spectra as a window to the progress of the reaction. Characteristic features of the mode change were qualitatively reproduced by a numerical calculation. 相似文献
88.
The reaction of allyltitanocenes with five- to seven-membered cyclic enones proceeded with good to high diastereoselectivity depending on the ring size of enones. The stereochemistry of the major isomers produced by the reaction of cinnamyltitanocene was opposite to that of crotyltitanocene. 相似文献
89.
In many polymers under corrosive liquids, degradation followed after permeation of environmental solution for a long period. The permeation rate of environmental solution, in many cases, is very low in corrosion-resistant polymeric materials. Therefore, the observation of the permeation of environmental solution and degradation of polymeric materials are very difficult in practical application. A simulation of permeation of solution is required in order to understand the permeation behavior of environmental solution and polymer degradation. A detailed analysis of the permeation behavior of solution accompanied by chemical reaction is important to study for improving the lifetime of polymers. Polyamide 66 (PA66) and sulfuric acid solution were used to investigate the quantitative study of permeation of environmental solution and its relation to degradation of polymeric materials. Correlation between diffusion process and degradation of PA66 related to the decrease of weight average molecular weight was defined. The diffusion rate of sulfuric acid solution was found to increase by decreasing weight average molecular weight of PA66 due to the established chain scission by hydrolysis reaction. The permeation of sulfuric acid solution that affected the decomposition reaction was modeled and quantitative evaluation of permeation of sulfuric acid was established. 相似文献
90.
Dr. Vivien Rauch Dr. Yoshihiro Kikkawa Dr. Matthieu Koepf Dr. Ismail Hijazi Dr. Jennifer A. Wytko Dr. Stéphane Campidelli Antoine Goujon Dr. Masatoshi Kanesato Dr. Jean Weiss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13437-13444
The assembly of imidazole‐functionalized phenanthroline‐strapped zinc porphyrins (ZnPorphen) with alkyl or polyethylene glycol (PEG) side chains was studied in solution and by AFM after casting on highly oriented pyrolytic graphite (HOPG) or mica. The nature of the solvent and its evaporation time influenced the morphology of the objects observed. On HOPG, short rods of about 100 nm were observed after fast evaporation of solutions of the alkyl derivatives in CHCl3, THF, or pyridine, whereas islands of aligned rows of longer wires were obtained from methylcyclohexane (MCH). Slow evaporation of MCH led to a three‐dimensional assembly. The PEG porphyrin assembled into short wires on HOPG or fibers on mica after slow evaporation of solutions in THF. This study shows the role of surface–molecule interactions in the interfacial assembly of ZnPorphen derivatives and contributes to understanding the parameters that control their noncovalent assembly into molecular wires on a surface. 相似文献