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71.
Characterization of clarithromycin polymorph was performed by solid-state cross polarization and magic angle spinning (CP/MAS) 13C-NMR spectroscopy. Two polymorphs, form II and form I, of clarithromycins indicated characteristic resonances of C1 carbonyl carbon at 176.2 and 175.2 ppm, respectively. Since each peak of C1 carbon was well separated in the spectrum of the two polymorphs, we performed quantitative analysis of the polymorphic fraction from the peak area of these peaks. The peak area of form I was found to linearly increase with an increase of its content, with a correlation coefficient of above 0.99. Solid-state NMR was found to be a useful technique to determine the characteristics of the polymorphic forms. 相似文献
72.
Fumiyuki Ozawa Takashi Ito Yoshiyuki Nakamura Akio Yamamoto 《Journal of organometallic chemistry》1979,168(3):375-391
New palladium(0) complexes with a variety of coordinated olefins [Pd(olefin)(PMePh2)2] (II) (olefin = styrene, ethyl methacrylate, methyl methacrylate, methyl acrylate, methacrylonitrile, and dimethyl maleate), were prepared by the reactions of [PdEt2(PMePh2)2] (I) with corresponding olefins in toluene. These complexes were characterized by means of elemental analysis, IR and 1H NMR spectroscopy and the chemical reactions. The dissociation of the coordinated olefin from complex II in solution was confirmed by spectroscopic studies of [Pd(mma)(PMePh2)2] (mma = methyl methacrylate). From the variable temperature NMR study, kinetic parameters for the dissociation process were determined as Ea = 7 kcal/mol, and ΔS3 (293 K) = -30 cal/deg · mol. Some new hydrido complexes, [Pd(H)ClL2] (IV) (L = PMePh2, PEtPh2 and PEt2Ph), were prepared by the reactions of [Pd(olefin)L2] with dry HCl. 相似文献
73.
74.
Masahiko Okada Keigo Aoi Wataru Mizuno Shinji Ito 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1135-1140
New polyesters 6a–6c consisting of 2,4-linked tetrahydrofuran rings were synthesized by bulk polycondensation of methyl trans- and cis-4-hydroxytetrahydrofuran-2-carboxylates ( 5a and 5b ) and a stereoisomeric mixture of methyl 4-hydroxy-5-methyltetrahydrofuran-2-carboxylate ( 5c ) at high temperature. These monomers were prepared from methyl glycolate or methyl lactate and diethyl maleate through a four-step reaction sequence. The polycondensation was carried out without solvent at different temperatures ranging from 150 to 220°C. Titanium isopropoxide was most effective among the catalysts examined, giving polyesters with number-average molecular weights up to 2 × 104. Polyester 6a consisting of trans-2,4-linked tetrahydrofuran rings was soluble in trifluoroacetic acid and a mixed solvent of chloroform and methanol (10/1, v/v). Polyester 6b composed of cis-2,4-linked tetrahydrofuran rings was soluble in dimethyl sulfoxide and dimethylformamide in addition to the two solvents for 6a . Polyester 6c with 5-methyl-substituted tetrahydrofuran rings was composed of a mixture of stereoisomeric units and thus was soluble in a variety of solvents including chloroform, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide. The glass transition temperatures of 6a, 6b , and 6c determined by DSC were 109, 88, and 66°C. These polyesters were found to be very slowly hydrolyzed in a neutral phosphate buffer solution at ambient temperature. © 1993 John Wiley & Sons, Inc. 相似文献
75.
Takeshi Takeda Tomohiro ShonoKenji Ito Hironori SasakiAkira Tsubouchi 《Tetrahedron letters》2003,44(43):7897-7900
Aldehydes, ketones, esters and lactones are transformed into enol ethers or 1,2-dialkoxy-1-alkenes by treatment with organotitanium species prepared from alkoxymethyl chlorides and a titanocene(II) complex. 相似文献
76.
The diffusion of six azo and five anthraquinone derivatives through nylon 6, poly(ethylene terephthalate) and secondary cellulose acetate films were studied under high hydrostatic pressures of up to 3000 bar and at temperatures 80–130 °C, by analyzing the diffusion profiles yielded in a stacked multiple film, placed in the solution of the diffusant. It was found that the diffusion coefficient,D, of the diffusant decreased with increasing pressure, giving a linear relationship between InD and the pressure, the slope of which gave the activation volume for the diffusion,V
. It was revealedV
increased linearly with increasing intrinsic molecular volume of the diffusant,V
w
, the slopes being different between the azo and the anthraquinone derivatives. The ratio ofV
toV
w
(V
/V
w
) ranged from 0.13 to 0.93, depending in a sensitive manner on the degree of swelling of the polymer matrix which in turn was varied by the solvent. The overall results could be explained in accordance with the formulation,V
f, local +V
=V
w
, whereV
f, local represents the free volume contribution. It was proposed thatV
w
is increased by solvation when the solvent is good for the diffusant. 相似文献
77.
Probing the donor-acceptor proximity on the physicochemical properties of porphyrin-fullerene dyads: "tail-on" and "tail-off" binding approach. 总被引:1,自引:0,他引:1
F D'Souza G R Deviprasad M E El-Khouly M Fujitsuka O Ito 《Journal of the American Chemical Society》2001,123(22):5277-5284
A new approach of probing proximity effects in porphyrin-fullerene dyads by using an axial ligand coordination controlled "tail-on" and "tail-off" binding mechanism is reported. In the newly synthesized porphyrin-fullerene dyads for this purpose, the donor-acceptor proximity is controlled either by temperature variation or by an axial ligand replacement method. In o-dichlorobenzene, 0.1 M (TBA)ClO(4), the synthesized zincporphyrin-fullerene dyads exhibit seven one-electron reversible redox reactions within the accessible potential window of the solvent and the measured electrochemical redox potentials and UV-visible absorption spectra reveal little or no ground-state interactions between the C(60) spheroid and porphyrin pi-system. The proximity effects on the photoinduced charge separation and charge recombination are probed by both steady-state and time-resolved fluorescence techniques. It is observed that in the "tail-off" form the charge-separation efficiency changes to some extent in comparison with the results obtained for the "tail-on" form, suggesting the presence of some through-space interactions between the singlet excited zinc porphyrin and the C(60) moiety in the "tail-off" form. The charge separation rates and efficiencies are evaluated from the fluorescence lifetime studies. The charge separation via the singlet excited states of zinc porphyrin in the studied dyads is also confirmed by the quick rise-decay of the anion radical of the C(60) moiety within 20 ns. Furthermore, a long-lived ion pair with lifetime of about 1000 ns is also observed in the investigated zinc porphyrin-C(60) dyads. 相似文献
78.
The authors have examined the tumor affinity of various 99mTc-labelled radiopharmaceuticals to Ehrlich's tumor for the purpose of delineating positively human malignant neoplasm. This paper includes biologic distributions of 99mTc-Sn-diphosphonate (99mTc-EHDP), 99mTc-Sn-dimercaptosuccinic acid (99mTc-DMSA) and 99mTc-Sn-diethyl stilbestrol diphosphate (99mTc-DSDP, 99mTc-Honvan) as the second report on the tumor affinity to the Ehrlich-bearing mice. (a) Tumor concentration of 99mTc-EHDP was lowest and the positive delineation of implanted tumor with 99mTc-EHDP was poorest in sequential images, though the active accumulation to some soft tissue maglinant neoplasms, the breast cancer and the thyroid cancer, has been reported. (b) Tumor concentration and tumor to blood ratio of 99mTc-DMSA were not so high on the contrary of our expectation that 197Hg-DMSA may show the high tumor concentration and the high tumor to blood ratio like 197Hg chlormerodrin as same renal scanning radiopharmaceuticals. (c) Tumor concentration of 99mTc-DSDP was highest. Tumor to blood concentration ratio, however, was lower than that of the above mentioned radiopharmaceuticals but tumor to liver ratio and/or tumor to lung ratio was over 1.0 at the earlier time. Biologic distribution of 99mTc-DSDP was similar to that of 32P labeled DSDP and then it is presumed that 99mTc is labeled at phosphate ester of DSDP which is dephospholytated immediately by phospholylase in vivo following the intravenous injection. Therefore, it may be assumed that the accumulation mechanism of 99mTc-DSDP to Ehrlich's tumor is related to the phospholylase activity in neoplasms but is not known precisely. 相似文献
79.
Katsukiyo Ito 《Journal of polymer science. Part A, Polymer chemistry》1976,14(7):1761-1771
In the copolymerization of monomers M1 and M2 which form polymer radicals of chain length n of N1n with electron on a M1 type and N2n with one on a M2 type, it is assumed that the specific rates of termination between N1n and N1n and N1s, N1n and N2s, and N2n and N2s are kα(ns)?a, kβ(ns)?a, and kγ(ns)?a, respectively, where kα, kβ, and kγ are the rate constants of reaction between segment radicals in the respective termination, and a is constant. The relation between kinetic chain length n? and polymerization rate Rp is derived as: 1/n? = 1/n?0 + const. (Rp)A(a), where n?0 is the kinetic chain length of the polymer formed by transfer and A (a) is unity (predominance of transfer) and 1/(1–2a) (no transfer). In the copolymerization between methyl methacrylate (M1) and styrene (M2) at 60°C, when Rp → 0, kr12/k12 + kr21/k21 = 5.9× 10?5 is obtained, where kr12 and kr21 are the rate constants of transfer of N1 to M2 and N2 to M1, and k12 and k21 are the rate constants of propagation of N1 to M2 and N2 to M1. In the absence of transfer, the a value is found to be 0.065 ± 0.008, from the relation between n? and Rp, regardless of the monomer composition. Such a value is also estimated by setting b = 0.72 in a = 0.153 (2b–1), where b is the constant in the Mark-Houwink equation. Further, the value of kβ is found to be 1.18 × 109l./mole-sec, which is comparable with the diffusion-controlled rate of reaction between small molecules. The rate of reaction between segment radicals is fivefold larger than the polymer-polymer termination when transfer predominates. 相似文献
80.