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11.
Despite the fact that many transition-metal-catalyzed reactions of organosulfur compounds with internal alkynes are ineffective, cobalt carbonyl (Co2(CO)8) is an excellent catalyst for carbonylative cyclization of internal alkynes with carbon monoxide. When Co2(CO)8-catalyzed reactions of internal alkynes with organic thiols are conducted in acetonitrile under 4 MPa pressure of carbon monoxide, thiolative lactonization of internal alkynes successfully takes place with incorporation of two molecules of CO. This carbonylation provides a useful tool to prepare the corresponding α,β-unsaturated γ-thio-γ-lactones (butenolide derivatives) in good yields. In the cases of unsymmetrical alkynes, such as 2-octyne and 6-methyl-2-heptyne, the thiolative lactonization proceeds with moderate regioselectivity to give the butenolide derivatives on which the carbonyl group preferentially bonds to the less hindered acetylenic carbon. Mechanistic pathways about the present thiolative lactonization are also discussed. 相似文献
12.
The interrogation of fiber-Bragg-grating (FBG) sensors using a vertical-cavity surface-emitting laser (VCSEL) is discussed. A long-wavelength (1.54 μm) VCSEL was used as a wavelength-tunable source by variation in the current. Temperature stabilization was performed with a thermoelectric device. Characteristics of temperature and strain sensing were investigated. FBGs with different reflectivities were compared. For temperature sensing, the root-mean-square error in the measurement was reduced to 1/3 that without temperature stabilization. The dependence of the measurement error on the reflectivities of the FBGs was investigated. The measurement error was larger for FBGs with lower reflectivities in both temperature and strain sensing. Improvement on the sensing with low-reflectivity FBGs is discussed. 相似文献
13.
Nobuyasu Hanari Taichi Yamazaki Nobuyasu Itoh Takashi Yarita Naomi Fujiki Ryoko Iwasawa Yoshie Aoyagi Masahiko Numata 《Accreditation and quality assurance》2014,19(5):391-396
A certified reference material (CRM) for the determination of perfluorooctanoic acid (PFOA) has been issued as NMIJ CRM 4056-a by the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Purity (kg kg?1) based on a titration method was determined by subtracting the mass fractions of impurities measured using liquid chromatography/mass spectrometry (LC/MS) from those of acids expressed as PFOA measured by a neutralization potentiometric titration. To validate an obtained result, purity based on a mass balance method was determined by subtracting the mass fractions of impurities, measured using LC/MS, Karl-Fischer titration (KFT), and vacuum evaporation, from 1 kg kg?1. Results from both titration and mass balance methods were in agreement within the accepted limits of uncertainty. The certified purity of NMIJ CRM 4056-a was determined to be 0.959 kg kg?1, calculated as the mean of the results obtained with the two methods. The standard uncertainty of the certified purity was evaluated from purity evaluations as well as from sample homogeneity and stability obtained from LC/MS and KFT analyses. Consequently, the expanded uncertainty was estimated to be 0.005 kg kg?1 with a coverage factor of k = 2. 相似文献
14.
We described a simple and quick miniaturized sequencing gel system for DNA analysis. Two major modifications were made to the previously reported miniaturized DNA sequencing gel system to achieve high-resolution hydroxyl radical cleavage analysis: including formamide in the miniaturized gel and providing uniform heating during electrophoresis. Our method enables one to reduce the cost for chemicals and to significantly reduce electrophoresis time. Furthermore, minimal gel handling simplifies the entire process. We show that the resolution of DNA fragments obtained by hydroxyl radical cleavage for the miniaturized gel is similar to that of a large conventional sequencing gel. 相似文献
15.
[reaction: see text] The synthetic utility of chiral N-heterocyclic carbenes, which have been used mainly in transition metal-catalyzed reactions as a ligand, was demonstrated by the enantioselective acylation of secondary alcohols. 相似文献
16.
Sadamoto R Niikura K Ueda T Monde K Fukuhara N Nishimura S 《Journal of the American Chemical Society》2004,126(12):3755-3761
UDP-MurNAc-pentapeptide derivative bacterial cell-wall precursors were synthesized as effective tools for surface display on living bacteria. Lactobacilli were incubated in the ketone-modified precursor-containing medium, and the ketone moiety was displayed on the bacterial surface through cell-wall biosynthesis. Oligomannose was coupled with the ketone moiety on the bacterial surface via a aminooxyl linker, thereby displaying this oligosaccharide on the surface of the bacteria. The increase in the adhesion of the sugar-displaying bacteria onto a concanavalin A-attached film compared to that of native bacteria was confirmed by microscopic observation and surface plasmon resonance measurement. The incorporation of the artificial cell-wall precursors was enhanced when incubated with fosfomycin, an inhibitor of cell-wall precursor biosynthesis. 相似文献
17.
Satoshi Motodate Takuya Kobayashi Mikio Fujii Prof. Tomoyuki Mochida Dr. Taichi Kusakabe Shigeki Katoh Prof. Hiroyuki Akita Prof. Keisuke Kato 《化学:亚洲杂志》2010,5(10):2221-2230
Bis(oxazoline)‐palladium(II) catalyzed carbonylation of homopropargyl alcohols afforded acyclic methoxyacrylate 2 and 6‐membered lactone 3a , 3b , 3d , 3e , 3f , 3g , 3h , 3i , 3j , 3k in good combined yield. In the case of propargyl alcohols, 5‐membered lactones 3p , 3q , 16 were obtained in moderate yields. The one‐pot synthesis of kawa lactones 3a , 3r , 3s and formal synthesis of dihydroxycystothiazole A and dihydroxycystothiazole C are presented. To elucidate the stereochemistry of (+)‐annularin G and (?)‐annularin H, the first asymmetric syntheses of these natural products were achieved. 相似文献
18.
We study the permutation complexity of finite-state stationary stochastic processes based on a duality between values and orderings between values. First, we establish a duality between the set of all words of a fixed length and the set of all permutations of the same length. Second, on this basis, we give an elementary alternative proof of the equality between the permutation entropy rate and the entropy rate for a finite-state stationary stochastic processes first proved in [J.M. Amigó, M.B. Kennel, L. Kocarev, The permutation entropy rate equals the metric entropy rate for ergodic information sources and ergodic dynamical systems, Physica D 210 (2005) 77-95]. Third, we show that further information on the relationship between the structure of values and the structure of orderings for finite-state stationary stochastic processes beyond the entropy rate can be obtained from the established duality. In particular, we prove that the permutation excess entropy is equal to the excess entropy, which is a measure of global correlation present in a stationary stochastic process, for finite-state stationary ergodic Markov processes. 相似文献
19.
Nishizuka T Fujita Y Sato Y Nakano A Kakino A Ohshima S Kanda T Yoshimoto R Sawamura T 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2011,87(3):104-113
Lectin-like oxidized LDL receptor-1 (LOX-1) is an endothelial receptor for oxidized LDL (oxLDL) and plays multiple roles in the development of cardiovascular diseases. We screened more than 400 foodstuff extracts for identifying materials that inhibit oxLDL binding to LOX-1. Results showed that 52 extracts inhibited LOX-1 by more than 70% in cell-free assays. Subsequent cell-based assays revealed that a variety of foodstuffs known to be rich in procyanidins such as grape seed extracts and apple polyphenols, potently inhibited oxLDL uptake in Chinese hamster ovary (CHO) cells expressing LOX-1. Indeed, purified procyanidins significantly inhibited oxLDL binding to LOX-1 while other ingredients of apple polyphenols did not. Moreover, chronic administration of oligomeric procyanidins suppressed lipid accumulation in vascular wall in hypertensive rats fed with high fat diet. These results suggest that procyanidins are LOX-1 inhibitors and LOX-1 inhibition might be a possible underlying mechanism of the well-known vascular protective effects of red wine, the French Paradox. 相似文献