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201.
Osuna RM Ortiz RP Ruiz Delgado MC Sakamoto Y Suzuki T Hernandez V López Navarrete JT 《The journal of physical chemistry. B》2005,109(44):20737-20745
In this Article, we report on the synthesis and full characterization of three perfluorinated oligothiophenes, ranging in length from the trimer to the pentamer (PF-nT, with n = 3, 4, or 5). The differential pulse voltammetry (DPV) analysis of the compounds showed that they can be both oxidized and reduced (i.e., they display a dual or amphoteric electrochemical behavior), with the reduction peaks positively shifted relative to those of the corresponding unsubstituted oligothiophenes. The electrochemically determined energy gaps are in agreement with those measured from the UV-vis-NIR absorption spectra in solution. The conjugational properties have been investigated by means of FT-Raman spectroscopy, both as pure solids and as dilute solutes in CH(2)Cl(2), revealing that: (i) pi-conjugation does not still reach saturation with chain length for the longest oligomer, and (ii) conformational distortions from a nearly coplanar arrangement of the successive thiophene units upon solution are not too large. DFT and TDDFT quantum chemical calculations have been performed, at the B3LYP/6-31G level, to assess information about the optimized molecular structure, equilibrium atomic charges distribution, energies and topologies of the frontier molecular orbitals (MO) around the gap, vibrational normal modes associated with the most outstanding Raman scatterings, and vertical one-electron excitations that give rise to the main optical absorptions. 相似文献
202.
Yeast biomass was methylated in a 0.1 M HCl methyl alcohol solution at room temperature and the methylated yeast (MeYE) was applied to the adsorptive separation of Cr(VI) and As(V) anions from aqueous solutions. At near-neutral pH, while Cr(VI) and As(V) anions were scarcely adsorbed onto unmethylated yeast biomass, the amounts adsorbed increased with increasing methylation degree. The amount of Cr(VI) adsorbed onto MeYE was almost constant at pH 4-6 and decreased with increasing pH above pH 6. The amount of As(V) adsorbed onto MeYE was rather lower than that of Cr(VI) and it had a peak at about pH 7. A metal-binding model was used to describe the adsorption characteristics of Cr(VI) and As(V) on MeYE. The results showed that MeYE has two different types of adsorption sites. The saturated amount of Cr(VI) and As(V) adsorbed onto MeYE having methylation degree 0.94 was 0.55 mmol g(-1). 相似文献
203.
Two new bisabolane-type sesquiterpenoids, (3R,4R,6S)-3,4-epoxybisabola-7(14),10-dien-2-one and (1R,3R,4R,5S,6S)-1-acetoxy-8-angeloyloxy-3,4-epoxy-5-hydroxybisabola-7(14),10-dien-2-one, and a new oplopane-type sesquiterpenoid, 14(R)-hydroxy-7beta-isovaleroyloxyoplop-8(10)-en-2-one, were isolated from Farfarae Flos along with three known compounds. The structures of these compounds were elucidated on the basis of spectroscopic evidence. 相似文献
204.
Killing and mutation of dry X174 phages (amber mutant) were investigated with vacuum-UV (130, 150 and 190 nm) and far-UV (254 nm) radiations. The sensitivity to killing was greatest at 130 nm; the sensitivity (in terms of energy fluence) at 130 nm was about 17 times higher than that at 150 nm. The reversion frequency of amber mutants to pseudo-wild type at 190 nm was lower than at 254 nm. Comparison of the induction rate of revertants per survivor showed that mutagenicity after 130 nm radiation, which may raise the ionization process, and after X-rays was similar. 相似文献
205.
Kenshu Fujiwara Akiyoshi Goto Daisuke Sato Hidetoshi Kawai Takanori Suzuki 《Tetrahedron letters》2005,46(20):3465-3468
A simple stereoselective synthesis of cis- and trans-2,3-disubstituted medium-sized cyclic ethers has been developed based on geometry-selective synthesis of 3-alkoxy-2-propenyl glycolate esters, Ireland-Claisen rearrangement of the glycolate esters, and ring-closing olefin metathesis. 相似文献
206.
Toshikazu SaitohToshio Suzuki Norihiro OnoderaHideya Sekiguchi Hisahiro HagiwaraTakashi Hoshi 《Tetrahedron letters》2003,44(13):2709-2712
An efficient and versatile method for the stereospecific construction of α,ω-cis- and α,ω-trans-disubstituted eight- and nine-membered cyclic ethers was developed. Cyclization of the hydroxy epoxides promoted by Eu(fod)3 proceeded via an SN2 process and exo mode to provide the corresponding cyclic ethers in excellent yields. 相似文献
207.
Hideki Moriishi Osamu Kikuchi Keizo Suzuki Gilles Klopman 《Theoretical chemistry accounts》1984,64(5):319-338
Reaction potential maps (RPM) have been introduced as a new tool for the study of molecular reactivity. The equipotential energy maps, which are created on given planes around a molecule, define reaction contours towards specific counter-reagent models and are evaluated by perturbation theory. Since the calculated interaction energy involves electrostatic, polarization, exchange, and charge transfer energies, the RPM's can be used to predict site selectivity in a variety of chemical reactions. We found that the calculated RPM's of the SCN– anion explained well the experimental observations that it reacts at the S atom with soft electrophiles and at the N atom with hard electrophiles. The difference in reactivity between SCN– and OCN– was clearly shown by the RPM's of these anions. The ambident nucleophilic nature of the NO
2
–
and the CH2CHO– anions was also well represented by their RPM's. 相似文献
208.
Kaori Suzuki Takayoshi Kobayashi Hiroyuki Ohtani Hiroshi Yesaka Saburo Nagakura Yoshinori Shichida Tôru Yoshizawa 《Photochemistry and photobiology》1980,32(6):809-811
Difference spectra between squid rhodopsin and its bathorhodopsin at room temperature were measured ca. 150 ps and ca. 500 ps after the excitation at 347.2 nm by a double-beam picosecond time-resolved spectrometer. The spectra measured showed a red shift of the isosbestic point between squid rhodopsin and its bathorhodopsin and a lower ΔAmax/ΔAmin value compared with those measured at low temperatures by conventional spectrophotometry. 相似文献
209.
Miyuki Narita Fumio Hamada Mayumi Sato Iwao Suzuki Tetsuo Osa 《Journal of inclusion phenomena and macrocyclic chemistry》1999,34(4):421-430
Flexible hosts, 6A,6B-; 6A,6C-; 6A,6D-; and 6A,6E-bis dansylglycine-modified -cyclodextrins (-1, -2, -3, and -4, respectively) have been synthesized as a sensing molecule for organic guests including terpenoids and bile acids. These host compounds show a pure monomer fluorescence whose intensity is decreased or enhanced upon addition of guest species. The value I/I0, where I and I0 are fluorescence intensities in the presence and absence of a guest and I is I0- I, was used as a parameter of sensitivity. These hosts exhibit highly sensitive and selective molecular recognition ability, particularly, for lithochoic acid, chenodeoxycholic acid, and ursodeoxycholic acid. The behaviors of the appended moieties of these hosts when host–guest complexation occurs are studied by induced circular dichroism (ICD) spectra and fluorescence spectral change on accommodation of a guest. The ICD pattern of these hosts alone or on accommodation of a guest is very similar, indicating that the behavior of the appended moieties are very similar. The guest-induced variations in the fluorescence or ICD intensity suggest that the appended moieties act as a hydrophobic cap that enables the cyclodextrin to form 1 : 1 host–guest complexes. 相似文献
210.
Sigenari Suzuki Masabumi Yamaguchi Masao Onda Takesffi Sakaizumi Osamu Ohashi Ichiro Yamaguchi 《Journal of Molecular Structure》1981,73(1):41-47
Microwave spectra of thionyl chloride, SO35Cl2 and SO35Cl37Cl, in the frequency range 8–25 GHz have been analyzed. The rotational constants have been obtained from the low J transition frequencies. The rS coordinates of Cl atoms and the ro structure have been evaluated with some assumptions: r(S-O) = 1.435 ± 0.011± Å, r(S—Cl) = 2.072 0.005 Å, ∠ OSCl = 108.00 ± 0.06°, ∠ ClSCl = 97.15 ± 0.30°. Nuclear quadrupole coupling constants have been obtained for the SO35Cl2, species: xaa = ?25.02 ± 0.04 MHz, x(bb = ?0.25 ± 0.04 MHz, Xcc = 25.27 ± 0.08 MHz, and Xzz = ?96.75 MHz. The values obtained are compared with those of other workers. 相似文献