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131.
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
132.
Takeshi Suwa Terutaka Watanabe Jiro Okamoto Sueo Machi 《Journal of polymer science. Part A, Polymer chemistry》1978,16(11):2931-2944
The radiation-induced emulsifier-free emulsion polymerization of tetrafluoroethylene was carried out at an initial pressure of 2–25 kg/cm2, temperature of 30–110°C, and under a dose rate of 0.57 × 104?3.0 × 104 rad/hr. The rate of polymerization was shown to be proportional to 1.0 and 1.3 powers of the dose rate and initial pressure, respectively, and is maximal at about 70°C. The molecular weight of polytetrafluoroethylene (PTFE) lies in the range of 105?106, increases with reaction time in the early stage of polymerization, and is maximal at 70°C but is almost independent of the dose rate. An interesting discovery is that PTFE, a hydrophobic polymer, forms as a stable latex in the absence of emulsifier. When PTFE latex coagulates during polymerization under certain conditions, the polymerization rate decreases, probably because polymerization proceeds mainly on the polymer particle surface. The observed rate acceleration and successive increase in polymer molecular weight may be due to slow termination of propagating radicals in the rigid PTFE particles. 相似文献
133.
Nobukatsu Nemoto Keiichiro Kakimoto Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1698-1705
This work deals with the cationic ring‐opening polymerization of cyclic thiocarbonates with a norbornene or norbornane moiety, that is, 5,5‐(bicyclo[2.2.1]hept‐2‐ene‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC1 ) or 5,5‐(bicyclo[2.2.1]heptane‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC2 ), respectively. The reaction of TC1 initiated by trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), boron trifluoride etherate (BF3OEt2), or triethyloxonium tetrafluoroborate (Et3OBF4) afforded unidentified products; however, TC1 underwent cationic ring‐opening polymerization with methyl iodide as an initiator to afford polythiocarbonate because the propagating end was stabilized by the covalent‐bonding property. The polymerization of TC2 initiated by TfOH, TfOMe, BF3OEt2, or Et3OBF4 afforded polythiocarbonate with good solubility in common organic solvents and a narrow molecular weight distribution because of the absence of a double‐bond moiety. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1698–1705, 2002 相似文献
134.
Kuroyanagi M Sugiyama K Kanazawa M Kawahara N 《Chemical & pharmaceutical bulletin》2000,48(12):1917-1920
From the needles of Abies sachalinensis, novel rearranged lanostane type triterpenes, 1-4, were isolated along with a known triterpene (5). The structures of the new compounds, 1-4, were elucidated to be 3,4-seco-8-(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14(30),22Z,24-pentaen-26,23-olide-3-oic acid, methyl 3,4-seco-8-(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14(30),22Z,24-penten-26,23-olide-3-oate, 3,4-seco-8(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14,22Z,24-pentaene-26,23-olide-3-oic acid and methyl 3,4-seco-8(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14,22Z,24-pentaene-26,23-olide-3-oate, respectively, by means of spectral experiments, especially two dimensional NMR spectroscopy, such as 1H-detected multiple quantum coherence (HMQC), 1H-detected heteronuclear multiple bond connectivity (HMBC) and 1H-1H-correlation spectroscopy (COSY) experiments. These new compounds have novel structures containing A-seco, rearranged spiro structure and a gamma-lactone conjugated with a diene. Some of these compounds showed potent antibacterial activity against gram positive bacteria. 相似文献
135.
The present efficient synthesis of [5'-13C]ribonucleosides and 2'-deoxy[5'-13C]ribonucleosides is characterized by the synthesis of the D-[5-13C]ribose derivative as an intermediate via the Wittig reaction of 4-aldehydo-D-erythrose dialkyl acetals with Ph3P13CH3I-BuLi to introduce the 13C label at the 5-position of a pentose. This was followed by the highly diastereoselective osmium dihydroxylation for the preparation of 2,3-di-O-benzyl-D-[5-13C]ribose dialkyl acetal and the cyclization from D-[5-13C]ribose dialkyl acetal derivatives to the alkyl D-[5-13C]ribofuranoside derivative by the use of LiBF(4). The obtained D-[5-13C]ribose derivative was converted into [5'-13C]ribonucleosides and subsequently into the corresponding 2'-deoxynucleosides. 相似文献
136.
Masaoki Oku Toetsu Shishido Takeshi Shinohara Qiang Sun Yoshiyuki Kawazoe Kazuo Nakajima Kazuaki Wagatsuma 《Journal of solid state chemistry》2004,177(2):457-460
The solid solutions of ScBRh3-ScRh3 and CeBRh3-CeRh3 are synthesized by the arc melting method, where RBRh3 and RRh3 (R=rare earth element) have perovskite and AuCu3 type structures, respectively. The binding energy of Sc 2p3/2 for ScBxRh3 increases with the boron concentration. The Knight shift of 45Sc observed by nuclear magnetic resonance spectroscopy decreases with increase of boron concentration. The decrement of the Knight shift corresponds the Sc 4s electron density at the Fermi level. The intensity ratio of f2: f1: f0 of Ce 3d XPS spectrum changes with boron concentration of CeBxRh3. It is concluded that in both cases of ScBxRh3 and CeBxRh3 the charge on the atoms on A-site changes with the concentration of the atoms on B-site, where the atoms are not directly bound. 相似文献
137.
GaInAsP-InP double-heterostructure lasers which are the most promising optical sources for the long wavelength region have been investigated. In the crystal growth, it was found that the liquidus and solidus isotherms are affected by the orientation of InP source and substrate crystals in the liquid phase epitaxial growth of GaInAsP alloys. The unit cell of the GaInAsP epitaxial layer is tetragonally deformed due to the interface lattice misfit such that the lattice constant parallel to the wafer surface is invariant across the interfaces in the GaInAsP-InP wafers. Two kinds of stripe lasers, planar stripe and buried lasers, have been fabricated by use of GaInAsP cap layer for good p-type contact. The planar stripe lasers of 10,15 and 20 m wide stripe operated in fundamental-transverse mode with 20–30% differential external efficiencies per facet. The 15 m wide stripe laser showed good mode characteristics to operate in a fundamental-transverse mode up to the cw output power of 22 mW per facet and in a single longitudinal mode over a wide range of currents. The buried stripe laser operated in a fundamental-transverse mode with the threshold current as low as 30 mA by making the stripe width narrower than 2 (m. The laser succeeded in cw operation at 100 °C because of its low threshold current and low thermal resistance.The authors would like to thank K. Noda, N. Kuroyanagi and Y. Furukawa for their encouragement. Thanks are also due to H. Kano for permission to use his results of buried stripe lasers prior to publication, and S. Ando for his technical assistance. 相似文献
138.
An analytical method was established for the simultaneous determination of 39 polycyclic aromatic hydrocarbons (PAHs) in air. The method was applied to a survey of gaseous and particulate PAHs in household indoor air. The survey was performed in 21 houses in the summer of 1999 and in 20 houses in the winter of 1999-2000 in Fuji, Japan. Thirty-eight PAHs were determined in indoor and outdoor air in the summer, and 39 PAHs were determined in indoor and outdoor air in the winter. The concentrations of gaseous PAHs in indoor air tended to be higher than those in outdoor air in the summer and winter. The concentrations of particulate PAHs in indoor air were the same as or lower than those in outdoor air in the summer and winter. PAH profiles, correlations between PAH concentrations, and multiple regression analysis were used to determine the factors affecting the indoor PAH concentrations. These results showed that gaseous PAHs in indoor air were primarily from indoor emission sources, especially during the summer, and that indoor particulate PAH concentrations were significantly influenced by outdoor air pollution. 相似文献
139.
Tatsuya Takahashi Tsutomu Yokozawa Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1992,30(4):583-587
The cationic polymerizations of γ-methylphenylallene ( 1 ) and α-methylphenylallene ( 2 ) were carried out with some Lewis acids at 25 and 0°C in dichloromethane to obtain the corresponding polymers through allyl cations, respectively. Tin (IV) chloride was found to be an effective catalyst for the cationic polymerization of both allenes 1 and 2 compared with other Lewis acids. Thus, in the polymerization of 1 , methanol-insoluble polymer was only obtained using Tin (IV) chloride, and M?n of methanol-insoluble polymer obtained by Tin (IV) chloride was the highest in the polymerization of 2 . From the analysis of 1H- and 13C-NMR spectra of the obtained polymers, the polymer from 1 consisted of two kinds of units polymerized by each double bonds of allene 1 , whereas the polymer from 2 consisted of only one unit polymerized by terminal double bond of allene 2 . Moreover, effect of solvent on the cationic polymerizations of 1 and 2 were discussed. 相似文献
140.
Takayuki Otsu Bunichiro Yamada Shigeru Sugiyama Shigeki Mori 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2197-2207
Radical polymerization and copolymerization of some o-alkylphenyl methacrylates were carried out and the effect of the ortho-substituents on the ability to homopolymerize, on the monomer reactivities, and on the ceiling temperatures of the monomers was studied. The effect of the substituent on tacticities and thermal stabilities of the polymers formed was also discussed. The ability to honiopolymerize and the monomer reactivity were considerably decreased by the introduction of the o-substituent. 2,6-Di-tert-butylphenyl methacrylate formed no methanol-insoluble polymer at 60°C. On the basis of the tacticity determined it was noted that the o-substituted phenyl methacrylates preferred syndiotactic addition in the propagation reaction less than did phenyl methacrylate or methyl methacrylate. The polymers formed from the o-substituted monomers were thermally less stable than poly(phenyl methacrylate), and, consistent with this finding, ceiling temperatures of the o-substituted phenyl methacrylates seemed to be lower than that of phenyl methacrylate. The effects observed were characteristic of the o-substituents conformationally close to the carbon-carbon double bond of the monomer or the carbon carrying the unpaired electron of the polymer radical. 相似文献