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11.
The purpose of this study is to examine whether molecular dynamics (MD) simulations using a commercially available software for personal computers can estimate the glass transition temperature (Tg) of amorphous systems containing pharmaceutically-relevant excipients. MD simulations were carried out with an amorphous matrix model constructed from isomaltoheptaose, and the Tg estimated from the calculated density versus temperature profile was compared with the Tg measured by differential scanning calorimetry (DSC) for freeze-dried isomalto-oligomer having an average molecular weight close to that of isomaltoheptaose. The Tg values determined by DSC were lower by 10 to 20 K than those extrapolated from the Tg values estimated by MD simulation. Fragility parameter was estimated to be 56 and 51 from MD simulation and from DSC measurement, respectively. Thus, the results suggest that MD simulation can provide approximate estimates for the Tg and fragility parameter of amorphous formulations. However, a reduction of the cooling rate, achievable by sufficiently elongating the simulation duration, is necessary for more accurate estimation. 相似文献
12.
Kazuyuki MiyashitaHidenobu Murafuji Hiroshi IwakiEito Yoshioka Takeshi Imanishi 《Tetrahedron》2003,59(26):4873-4879
As a second-generation pyridoxal model compound for cystathionine β-synthase, we designed a novel model compound having an ionophore function and an imidazole function, application of which to the β-replacement reaction with various thiols smoothly took place to give S-substituted cysteines. Peptides having a serine-O-carbonate residue at the N-terminal position were also converted to the corresponding peptides having an S-substituted cysteine residue under the catalytic conditions of the novel pyridoxal model compound. 相似文献
13.
Itoh F Yoshioka Y Yukishige K Yoshida S Ootsu K Akimoto H 《Chemical & pharmaceutical bulletin》2000,48(9):1270-1280
The glutamic acid moiety of N-[4-[3-(2,4-diamino-7H-pyrrolo[2,3-d]pyrimidin-5-yl)propyl]benzoyl]-L-g lutamic acid (1b, TNP-351) and the related compound (1a), was replaced with various N(omega)-acyl-, sulfonyl-, carbamoyl- and aryl-2,omega-diaminoalkanoic acids, and the inhibitory effects of the resulting products (9, 11, 14, 18, 21, 23, 25, 30, 36) on dihydrofolate reductase (DHFR), the growth of murine fibrosarcoma Meth A cells, and methotrexate-resistant human CCRF-CEM cells, were examined. Compounds (9a-f) acylated with a hemiphthaloyl group were efficiently synthesized by coupling pyrrolo[2,3-d]pyrimidine carboxylic acids (7a,b) and N(omega)-phthaloyl 2,omega-diaminoalkanoic acid methyl esters (6a-c) and subsequent hydrolysis. The other N(omega)-acyl- and sulfonyl-ornithine analogs (21, 23, 25) were synthesized by acylation of free amino intermediates (19a,b) derived from tert-butoxycarbonyl-ornithine analogs (17a,b). A free ornithine analog (18) did not strongly inhibit Meth A cell growth, whereas all N(omega)-acyl-, sulfonyl-, carbamoyl- and aryl-ornithine analogs (9, 11, 21, 23, 25, 30, 36) exhibited much more potent inhibitory activities against both DHFR and Meth A cell growth. In particular, compounds 9c, 21k and 36a also showed remarkable growth-inhibitory activities against methotrexate-resistant CCRF-CEM cells. These results demonstrate that the potent inhibitory activities of N(omega)-masked ornithine analogs against the growth of Meth A cells and methotrexate-resistant CCRF-CEM cells, results from effective uptake via reduced folate carrier and their potent DHFR inhibition. 相似文献
14.
Application of dibutyltin oxide method to regioselective acylation and alkylation of tylosin at C-4' 总被引:1,自引:0,他引:1
K Kiyoshima M Sakamoto T Ishikura Y Fukagawa T Yoshioka H Naganawa T Sawa T Takeuchi 《Chemical & pharmaceutical bulletin》1989,37(4):861-865
4'-O-Acyl-, 4'-O-alkyl- and 4'-deoxy-tylosin derivatives were synthesized using 2'-O-acetyl-3',4'-O-(dibutyl-stannio)tylosin as a synthetic intermediate. The in vitro biological evaluation showed that the new derivatives were active against macrolide-resistant clinical isolates of bacteria and mycoplasmas, and that they were resistant to hepatic esterase. 相似文献
15.
T. Kambara K. Hasegawa H. Yoshioka Y. Kamiya T. Kotani K. Tabei 《Journal of Radioanalytical and Nuclear Chemistry》1977,36(1):87-94
Variations of125Sb valency states in HCl solutions were investigated by the use of the N-benzoyl-N-phenyl-hydroxylamine (BPHA) extraction
method.125Sb(V) is completely reduced to Sb(III) by one hour refluxing in conc. HCl.125Sb(III) is gradually oxidized to Sb(V) in solutions of low HCl concentrations by the effects of their own radiations. Natural
light promotes such oxidation reactions. By utilizing such oxidation-reduction effects125Sb(V) can be easily prepared from125Sb(III) and also125Sb(III) can be prepared by the reduction of Cl
aq
−
. Their valency states were stable on keeping them in brown-colored bottles at 6M HCl concentrations. 相似文献
16.
The Photochemistry of Open-Chained 2,6- or 2,7-Dien-Carbonyl Compounds On 1n, π*-excitation (λ > 347 nm) citral (5) and the methyl ketone 10 isomerize to compounds A (7, 19) and B (6, 20) , whereas the phenyl ketone 11 changes into the isomer 24 of type E. Evidence is given that the conversions to A and B may arise from the 3n, π*-state of the 2,6-diene-carbonyl compounds. On 1n, π*-excitation (λ = 254 nm) 5 and 10 yield the isomers A (7, 19) and D (18, 22) , but no products of type B. Furthermore, conversion of 10 to the isomer 21 of type C is observed. Selective 1n, π*-excitation (λ = 254 nm) as well as selective 1n, π*-excitation (λ > 347 nm) of the 2,7-diene-carbonyl compounds 12 and 13 give rise to isomerization to the compounds F (25, 28) , exclusively. The intramolecular [2 + 2]-photocycloadditions are shown to be triplet processes. UV.-irradiation (λ > 280 nm) of compounds F (25, 28) furnishes the isomeric products G (26, 29) which photoisomerize to oxetanes of type H (27, 30). 相似文献
17.
18.
Michiko Iwamura Yuka Gotoh Tomoyuki Hashimoto Reiko Sakurai 《Tetrahedron letters》2005,46(37):6275-6277
Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions. 相似文献
19.
When preparing an affinity column and a biosensor, it is desirable to immobilize a unimolecular layer of pure protein on a matrix. In this work, we tried to immobilize a monoclonal antibody on a surface of a glass test-tube as a model, to confirm the stability of this ultra-thin layer by an enzyme immunoassay, and to estimate the thickness of the layer on a slide glass by Fourier transform infrared reflection spectrometry. A new test-tube was washed and dried. The tube was filled with 5% 3-aminopropyltriethoxysilane. The 3-aminopropylsilylated surface was treated with glutaraldehyde and 5.6.10(-2) mg/ml solution of a normal mouse monoclonal antibody. The Schiff base between glutaraldehyde and the antibody was further reduced with 7.9.10(-3)% NaBH4. The tube was washed with 0.05% Tween 20 to block non-specific binding. The antibody immobilized on the surface was measured by an enzyme immunoassay based on a reaction of anti-mouse immunoglobulin G labelled with alkaline phosphatase, with which p-nitrophenol was produced from p-nitrophenylphosphate as a substrate. Meanwhile, various amounts of the antibody were immobilized on slide glasses in the same manner. The antibody on each surface was measured by Fourier transform infrared reflection spectrometry. The antibody immobilized under the final conditions was detectable by the enzyme immunoassay, and stable at 4 degrees C for ten days. The antibody on the slide glass was a unimolecular layer, as judged from the Fourier transform infrared spectra referred to -CONH- band semiquantitatively. Thus, we found the optimal conditions for immobilizing an ultra-thin layer of the monoclonal antibody on the glass surface.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
20.