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41.
In heat exchange calorimetry, sample and reference vessels are fixed differentially in a water bath. The heat evolved in the sample vessel is exchanged freely with the ambient water. The accuracy and precision of the calorimetry depend on the temperature range of the drift and fluctuation in the bath water. In the present report, a simple temperature-control system with no empirical factors is proposed for the precision water bath. The heat exchange between the inside of the vessels and the ambient water is expressed by a differential equation or a Newtonian cooling equation. Similarly, the thermal behaviour of a water bath placed in a non-air-conditioned laboratory was also considered to be expressed by the same equation. The heat exchanged with the surroundings, the non-stationary heat flow from warm stirrer motors, and other thermal factors were considered to be part of the heat sources. Cooling water about 2°C lower than the set temperature was circulated in the water bath. The difference between the set temperature and the observed temperature was fed into a microcomputer every second. The latest four data points were used to fit a modified Newtonian equation by the common method of least-squares. The control input to the bath was calculated and given to the heater circuit after power amplification. The program written in basic was about 3.3 kbyte. The controlled range of drift and fluctuation was almost the same, or better, as that previously reported. 相似文献
42.
Matsumoto K Davis BG Jones JB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4129-4137
A significant enhancement of the applicability of the serine protease subtilisin Bacillus lentus (SBL) in peptide synthesis was achieved by using the strategy of combined site-directed mutagenesis and chemical modification to create chemically modified mutant (CMM) enzymes. The introduction of polar and/or homochiral auxiliary substituents, such as X=oxazolidinones, alkylammonium groups, and carbohydrates at position 166 at the base of the primary specificity S(1) pocket created SBL CMMs S166C-S-X with strikingly broad structural substrate specificities. These CMMs are capable of catalyzing the coupling reactions of not only L-amino acid esters but also D-amino acid esters as acyl donors with glycinamide to give the corresponding dipeptides in good yields. These powerful enzymes are also applicable to the coupling of L-amino acid acyl donors with alpha-branched acyl acceptor, L-alaninamide. Typical increases in isolated yields of dipeptides of 60-80 % over SBL-WT (e.g. 0 % yield of Z-D-Glu-GlyNH(2) using SBL-WT-->74 % using S166C-S-(CH(2))(2) NMe(3) (+)) demonstrate the remarkable synthetic utility of this "polar patch" strategy. Such wide-ranging systems displaying broadened and therefore similarly high, balanced yields of products (e.g. 91 % Z-L-Ala-GlyNH(2) and 86 % yield of Z-D-Ala-GlyNH(2) using S166C-S-(3R,4S)-indenooxazolidinone) may now allow the use of biocatalysts in parallel library synthesis. 相似文献
43.
Osamu Matsumoto Eiji Hayami Mamoru Samejima Yasushi Kanzaki 《Plasma Chemistry and Plasma Processing》1984,4(1):33-42
The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10–10–10–8 g2 cm–4 s–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed. 相似文献
44.
Akira Matsumoto Tsunehiko Terada Masayoshi Oiwa 《Journal of polymer science. Part A, Polymer chemistry》1987,25(3):775-781
The cyclization constant Kc in the radical cyclopolymerization of acrylic and methacrylic anhydrides was evaluated in detail under various conditions. No linear relationship between in Kc and 1/T was observed; cyclization was acceleratively enhanced at elevated temperatures. The Kc values also increased with decreased monomer concentration and increased solvent polarity. These increasing dependencies of Kc are ascribed to the increased significance of depropagation, demonstrating a new interpretation of the temperature dependence of the cyclization constant in the radical cyclopolymerization of nonconjugated dienes. 相似文献
45.
Yoshihisa Kurasawa Tomoyoshi Hosaka Yuko Matsumoto Aiko Ishikura Kazue Ikeda Atsushi Takada Ho Sik Kim Yoshihisa Okamoto 《Journal of heterocyclic chemistry》1994,31(6):1697-1700
The reaction of 7-chlorotetrazolo[1,5-α]quinoxaline 5-oxide 6a with acetic anhydride gave 7-chloro-5-(7-chlorotetrazolo[1,5-α]quinoxalin-4-yl)-4,5-dihydro-4-oxotetrazolo[1,5-α]quinoxaline 7a , while the reaction of 7-chloro-1,2,4-triazolo[4,3-α]quinoxaline 5-oxide 6b with acetic anhydride afforded 7-chloro-5-(7-chloro-1,2,4-triazolo[4,3-α]quinoxalin-4-yl)-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 7b and 7-chloro-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 8b . The reaction of compound 6a or 6b with acetic anhydride/acetic acid provided 7-chloro-4,5-dihydro-4-oxo-tetrazolo[1,5-α]quinoxaline 8a or compound 8b , respectively. 相似文献
46.
Ishikawa A Takata T Kondo JN Hara M Kobayashi H Domen K 《Journal of the American Chemical Society》2002,124(45):13547-13553
A Ti-based oxysulfide, Sm(2)Ti(2)S(2)O(5), was studied as a visible light-driven photocatalyst. Under visible light (440 nm < or = lambda < or = 650 nm) irradiation, Sm(2)Ti(2)S(2)O(5) with a band gap of approximately 2 eV evolved H(2) or O(2) from aqueous solutions containing a sacrificial electron donor (Na(2)S-Na(2)SO(3) or methanol) or acceptor (Ag(+)) without any noticeable degradation. This oxysulfide is, therefore, a stable photocatalyst with strong reduction and oxidation abilities under visible-light irradiation. The electronic band structure of Sm(2)Ti(2)S(2)O(5) was calculated using the plane-wave-based density functional theory (DFT) program. It was elucidated that the S3p orbitals constitute the upper part of the valence band and these orbitals make an essential contribution to the small band gap energy. The conduction and valence bands' positions of Sm(2)Ti(2)S(2)O(5) were also determined by electrochemical measurements. It indicated that conduction and valence bands were found to have satisfactory potentials for the reduction of H(+) to H(2) and the oxidation of H(2)O to O(2) at pH = 8. This is consistent with the results of the photocatalytic reactions. 相似文献
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50.
Kondo F Saito H Hayashi R Onda H Kobayashi S Matsumoto M Suzuki M Ito Y Oka H Nakanishi T Shimizu A 《The Analyst》2003,128(11):1360-1364
We developed a rapid and reliable identification method for Shiga toxins in Shiga toxin-producing Escherichia coli (STEC) using immunoprecipitation and high-performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS). Polyclonal antisera specific for Shiga toxin 1 (Stx1) and Shiga toxin 2 (Stx2) were raised in rabbits so as to be used for the immunoprecipitation. The immunoprecipitaion was carried out by mixing sample solutions with 50 microl each of the antisera to Stx1 and Stx2 followed by allowing the mixed solutions to stand for 30 min. The quantity required to obtain the immunoprecipitate was more than 0.5 microg of Shiga toxins. HPLC-ESI-MS analysis of the resulting immunoprecipitates provided accurate molecular weight information on Shiga toxins, leading to direct evidence for the presence of these toxins. It requires at most two days to perform our procedure from toxin extraction to measurement of HPLC-ESI-MS whereas the previous method using isolation procedures required about two weeks to complete. The usefulness of the present method has been demonstrated by identifying Stx1, Stx2 and a variant of Stx2 (Stx2e) in the immunoprecipitates prepared from STEC strains. 相似文献