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71.
Ogawa Y Ogawa K Kokufuta E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2546-2552
Polyampholyte gels were prepared by free radical polymerization of aqueous monomer solutions with the following composition: 69% N-isopropylacrylamide (thermosensitive neutral monomer), 1% N,N'-methylenebisacrylamide (cross-linker), 15% 1-vinylimidazole (cationic monomer), and either 15% acrylic acid (AAc, anionic monomer) or poly(acrylic acid) (PAAc, polyanion). We thus obtained two sorts of polyampholyte gels; that is, G1 with immobilized PAAc and G2 with randomly copolymerized AAc. The equilibrium swelling ratio (Qe) was studied as a function of the pH, NaCl concentration, and temperature. Also studied was the kinetics of swelling and shrinking in response to a sudden pH change. The significant results obtained were as follows: (i) A fully collapsed state was observed at pH 4.5-9.0 for G1 and at pH 4.5-7.0 for G2. (ii) Below and above these pH ranges, both gels were in a swollen state; therefore, an isoelectric point (pI) appeared in a wide pH range. (iii) At alkaline pH regions where a hysteresis was observed in the Qe versus pH curves of G1 and G2 as the pH was first increased then decreased, G1 exhibited very slow swelling-shrinking kinetics. (iv) An increase in the NaCl concentration allowed the gel to swell at pH approximately pI (antipolyelectrolyte behavior) but to shrink at pHs below and above the pI range (polyelectrolyte behavior). (v) The magnitude of the salt-induced shrinking of G1 is smaller than that of G2 at pH 10 and at NaCl concentrations > 0.01 M. (vi) At pH 10, an increase in the temperature from 35 to 50 degrees C led to a shrinking change of G1 but not of G2. These results were found to be explicable in terms of a different distribution of negative charges within the polyampholyte gel network. 相似文献
72.
Akimoto Tachibana Masahiko Koizumi Iwao Okazaki Hiroyuki Teramae Tokio Yamabe 《Theoretical chemistry accounts》1987,71(1):7-19
The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function. 相似文献
73.
Some molecules with a molecular skeleton similar to that of stilbenes and azobenzenes show orientational disorder in the crystals. If the disorder is dynamic, a conformational interconversion takes place through a pedal motion. In this study X-ray diffraction analyses of (E)-stilbene (1) and azobenzene (2) were carried out at various temperatures. We succeeded in observing thermodynamic nonequilibrium states that were generated by fast freezing of the conformational interconversion at low temperatures. The populations of the two conformers in crystals of 1 at 90 K varied with the cooling rate. Flash cooling of a crystal of 2 from room temperature to 90 K made it possible to observe the minor unstable conformer that does not exist in the equilibrium state at the same temperature. 相似文献
74.
Takahiro Makino Kimihiko Kato Hiroyuki Lyozumi Hiroe Honzawa Yoshiaki Tachiiri Mitsuo Hiramatsu † 《Photochemistry and photobiology》1996,64(6):953-956
Abstract— Ultraweak luminescence generated by sweet potato and nonpathogenic Fusarium oxysporum interactions associated with a defense response was detected by a photoncounting method using ultrahigh-sensitive photodetectors. The time-dependent intensity variation, the spectrum and the two-dimensional imaging of the ultraweak luminescence are indicative of the defense response of the sweet potato to F. oxysporum. The production of ipomeamarone as a phytoalexin means that F. oxysporum induced the defense response in the sweet potato. 相似文献
75.
Distribution of pirarubicin in human blood. 总被引:1,自引:0,他引:1
K Nagasawa N Kitada C Tsuji M Ogawa T Yokoyama N Ohnishi S Iwakawa K Okumura 《Chemical & pharmaceutical bulletin》1992,40(10):2866-2869
We investigated the distribution and stability of pirarubicin in human blood obtained from 12 healthy volunteers. The distribution of pirarubicin into blood cells showed marked temperature- and concentration-dependencies and the Arrhenius plot for pirarubicin uptake in blood was biphasic. Therefore, pirarubicin appears to be taken up into blood cells by a carrier-mediated system. Pirarubicin was mainly enzymatically metabolized to pirarubicinol in blood cells, but pirarubicin was not metabolized into doxorubicin in either blood or plasma. On the other hand, in plasma, pirarubicin was degraded to unknown inactive compounds instead of pirarubicinol. It is therefore suggested that blood cells serve to protect against the degradation of pirarubicin into inactive compounds in blood. Accordingly, when the monitoring of pirarubicin and its active metabolites is carried out in patients, both blood and plasma must be frozen immediately after blood collection. 相似文献
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79.
Nakamura Y Asami A Ogawa T Inokuma S Nishimura J 《Journal of the American Chemical Society》2002,124(16):4329-4335
The reactions of [60]fullerene with bis-o-quinodimethane precursors 3, 4, and 5 containing a dibenzo-18-crown-6, 24-crown-8 and 30-crown-10 moiety, respectively, were investigated. Both 3 and 4 provided trans-4 bisadducts 6a and 7a, respectively, as major product, though the selectivity in the latter was lower than that in the former. As minor product, 6b (cis-2) was produced from 3, while 7c (e) as well as 7b (cis-2) were produced from 4. Precursor 5 exclusively afforded e bisadduct 8 without any other regioisomers. These bisadducts showed different ionophoric properties from one another; for instance, 6a and 7b exhibited a high complexing ability toward the K+ ion, while 6b hardly showed complexation with any alkali metal ions. The selectivity coefficients (K(Na,K)(pot)) of 6a and 7b toward K+ over Na+ ion, determined with an ion-selective electrode, were much higher than that of dibenzo-18-crown-6. 相似文献
80.
Komatsu T Hayakawa S Tsuchida E Nishide H 《Chemical communications (Cambridge, England)》2003,(1):50-51
alpha-Cyclodextrin (alpha CD)-penetrating 2-methyl-1-phenethylimidazole coordinates to the zinc(II) and iron(II) complexes of meso-tetrakis[o-(N-methyl)pyridinium] porphyrinate, giving non-covalently linked alpha CD-porphyrin ensembles; the iron(II) complex can reversibly bind and release dioxygen in aqueous DMF solution. 相似文献