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21.
Hiroshi Ikeda Takumi Sugiyama Akihiko Ueno 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):83-87
A new chemosensor for larger guests was prepared. The new chemosensor bears hydrophobic units at the primary hydroxy side
and a dansyl unit at the secondary hydroxy side of β-cyclodextrin. Due to the hydrophobic units, the new chemosensor is sensitive
to large or slender guests such as SDS and insensitive to 1-adamantanol, which is a good guest for the natural β-CD. 相似文献
22.
C-H to N substitution dramatically alters the sequence-specific DNA alkylation, cytotoxicity, and expression of human cancer cell lines 总被引:2,自引:0,他引:2
Bando T Narita A Iwai A Kihara K Sugiyama H 《Journal of the American Chemical Society》2004,126(11):3406-3407
We designed and synthesized sequence-specific alkylating conjugates 1 and 2, which selectively alkylate matched sequences at nanomolar concentrations. Conjugates 1 and 2 differ only in that the C-H is substituted by an N in the second ring, which precisely recognizes and effectively alkylates DNA according to the recognition rule of Py-Im polyamides. We investigated sequence-specific DNA alkylation, cytotoxicity in 39 human cancer cell lines, and the effect on expression levels in cancer cell lines by Py-Im conjugates 1 and 2. The COMPARE analysis of the mean graphs showed that conjugates 1 and 2 did not correlate well with each other (r = 0.65) despite having a common DNA alkylating mechanism (purine N3 alkylation). Array-based gene expression analysis demonstrated that there are several oppositely regulated genes. The results suggest the intriguing possibility that DNA alkylating agents recognizing longer base-pair sequences may provide a promising approach for developing new types of antigene agents. 相似文献
23.
Bando T Narita A Sasaki S Sugiyama H 《Journal of the American Chemical Society》2005,127(40):13890-13895
We examined DNA alkylation by pyrrole (Py)-imidazole (Im) hairpin polyamides, which possess 1,2,9,9a-tetrahydrocyclopropa[1,2-c]benz[1,2-e]indol-4-one (CBI) or cyclopropapyrroloindole (CPI) as DNA alkylating moieties. High-resolution denaturing gel electrophoresis revealed that alkylation by CBI conjugates 2 and 4 occurred specifically at adenines (A) in matched sequences, whereas CPI conjugates 1 and 3 alkylated both A and guanines (G) in matched sequences. The origin of the different reactivity of CBI and CPI conjugates is discussed in relation to the electrophilicity of the cyclopropane moiety. The high selectivity of the CBI conjugate gives additional sequence specificity relative to CPI conjugates that would be useful for the biological applications. 相似文献
24.
Atsuya Muranaka Yoshiaki Asano Akihiko Tsuda Atsuhiro Osuka Nagao Kobayashi 《Chemphyschem》2006,7(6):1235-1240
The electronic excited states of a meso-meso beta-beta doubly linked bis-porphyrin are comprehensively investigated by measuring its circular dichroism (CD) and magnetic circular dichroism (MCD) spectra. The observed spectroscopic properties are rationalized by DFT calculations. The frontier molecular orbitals (MOs) are constructed by the linear combinations of the constituent monomers' four MOs. Comparison of a theoretical CD spectrum based on time-dependent DFT (TDDFT) with the experimental spectra resulted in the assignment of the helical conformation of the dimer. This assignment is contrary to the previous assignment based on the point-dipole approximation (exciton coupling theory). 相似文献
25.
Sanyo Hamai Hiroshi Ikeda Akihiko Ueno 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(3):265-273
As -cyclodextrin (-CD) was added to D2Osolutions of 2-methylnaphthalene, its proton signals shifted to lower fieldsat low concentrations of -CD. At 2.0 × 10-2 moldm-3 of -CD, however, a reverse, higher-field shift wasobserved for the H-8 signal, indicating the formation of 1 : 1 and 2 : 1-CD–2-methylnaphthalene inclusion complexes. Intrinsic chemicalshift differences of all the protons in 2-methylnaphthalene have beenevaluated for both the 1 : 1 and the 2 : 1-CD–2-methylnaphthalene inclusion complexes. These intrinsicchemical shift differences suggest that the first -CD molecule has noselectivity in accommodating one end of uncomplexed 2-methylnaphthalene;-CD binds to a methyl group, as well as a naphthalene ring-end havingno methyl group, to form the 1 : 1 inclusion complex, resulting in theformation of two kinds of 1 : 1 complexes. 相似文献
26.
Photophysical properties of porphyrin tapes 总被引:1,自引:0,他引:1
Cho HS Jeong DH Cho S Kim D Matsuzaki Y Tanaka K Tsuda A Osuka A 《Journal of the American Chemical Society》2002,124(49):14642-14654
The novel fused Zn(II)porphyrin arrays (Tn, porphyrin tapes) in which the porphyrin macrocycles are triply linked at meso-meso, beta-beta, beta-beta positions have been investigated by steady-state and time-resolved spectroscopic measurements along with theoretical MO calculations. The absorption spectra of the porphyrin tapes show a systematic downshift to the IR region as the number of porphyrin pigments increases in the arrays. The fused porphyrin arrays exhibit a rapid formation of the lowest excited states (for T2, approximately 500 fs) via fast internal conversion processes upon photoexcitation at 400 nm (Soret bands), which is much faster than the internal conversion process of approximately 1.2 ps observed for a monomeric Zn(II)porphyrin. The relaxation dynamics of the lowest excited states of the porphyrin tapes were accelerated from approximately 4.5 ps for the T2 dimer to approximately 0.3 ps for the T6 hexamer as the number of porphyrin units increases, being explained well by the energy gap law. The overall photophysical properties of the porphyrin tapes were observed to be in a sharp contrast to those of the orthogonal porphyrin arrays. The PPP-SCI calculated charge-transfer probability indicates that the lowest excited state of the porphyrin tapes (Tn) resembles a Wannier-type exciton closely, whereas the lowest excited state of the directly linked porphyrin arrays can be considered as a Frenkel-type exciton. Conclusively, these unique photophysical properties of the porphyrin tapes have aroused much interest in the fundamental photophysics of large flat organic molecules as well as in the possible applications as electric wires, IR sensors, and nonlinear optical materials. 相似文献
27.
Akihiko Kanazawa Tomiki Ikeda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):3003-3011
Polyesters were prepared which retained phosphonium biocides as counter ions of sodium sulfonate moieties incorporated into the polymers, and surface antibacterial activity of the polyester films against Staphylococcus aureus and Escherichia coli was explored. These films exhibited a high surface antibacterial activity against S. aureus and E. coli, particularly against S. aureus, and the activity was affected by the structure and the compositional ratio of the phosphonium salts. Amount of the released phosphonium salts was very small, so that liberation of the phosphonium biocides can be expected to occur over a long period. Morphological changes of the cells of S. aureus and E. coli in contact with the polyester films were evaluated by scanning electron microscopy. It was found that the surface antibacterial activity of the polyester films was rather bacteriostatic than bactericidal as evidenced by no morphological changes of the bacterial cells in contact with the phosphonium biocides © 1993 John Wiley & Sons, Inc. 相似文献
28.
The liquid-liquid extraction of copper(I) with 12-, 13-, 15- and 16-membered cyclic tetrathio ethers ([n]aneS4, where n represents the total number of carbon and sulphur atoms in the cyclic ligand ring) was examined stoichiometrically using picrate ion (Pic?) for the formation of the ion pair. Copper(I) was extracted with four ligands (L) into 1,2-dichloroethane as the ion-pair compound, [Cu(I)L]+Pic?. The extraction constant, Kex, with each ligand was determined. As the ring size of cyclic tetrathio ethers increases, the log Kex values, including that previously reported for [14]aneS4, increase from 7.7 to 9.4. The value of Δ log Kex, which represents the increase in log Kex due to the addition of one carbon atom to the macrocyclic ring, was large between [13]aneS4 and [14]aneS4 (Δ log Kex=1.0) and small between [14]aneS4 and [15]aneS4 (Δ log Kex=0.1). 相似文献
29.
30.
Yuzo Yamazawa Tadashi Iwai Akihiko Ito Koichiro Hayashi 《Journal of polymer science. Part A, Polymer chemistry》1971,9(2):257-263
The in-source polymerization of trioxane in the solid state was investigated over a wide range of temperature and pressure, i.e., from 30 to 140°C and up to 7000 kg/cm2, respectively. In the polymerization that was carried out slightly below the melting point under pressure, the higher the pressure, the higher the rate of polymerization. It was confirmed that the maximum rate of solid-state polymerization of trioxane occurs near the melting points, even under elevated pressure. The rate of polymerization decreased with increasing pressure at constant temperature. The shape of the time–conversion curves may be classified into two types, i.e., one which is typical of high pressure and low temperature, and the other which is typical of low pressure and high temperature. Changes in the shape of the conversion—intrinsic viscosity curves occurred coincidentally. Thus, three regions for the different “polymerization characteristic” were determined as functions of polymerization temperature and pressure. Explanations are given for the above-mentioned polymerization characteristic. 相似文献