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11.
Tsubaki H Tohyama S Koike K Saitoh H Ishitani O 《Dalton transactions (Cambridge, England : 2003)》2005,(2):385-395
Intramolecular pi-pi and CH-pi interactions between the bpy and PR3 ligands of fac-[Re(bpy)(CO)3(PR3)]+ affect their structure, and electrochemical and spectroscopic properties. Intramolecular CH-pi interaction was observed between the alkyl groups on the phosphine ligand (R =nBu, Et) and the bpy ligand, and intramolecular pi-pi and CH-pi interactions were both observed between the aryl group(s) on the phosphorus ligand (R =p-MeOPh, p-MePh, Ph, p-FPh, OPh) and the bpy ligand, while no such interactions were found in the trialkylphosphite complexes (R = OiPr, OEt, OMe). The intramolecular interactions distort the pyridine rings of the bpy ligand as long as 3.7 x 10(-2)A in crystals. Molecular orbital calculations of the bpy ligand suggest that this distortion decreases the energy gap between its pi and pi* orbitals. An absorption band attributed to the pi-pi*(bpy) transition of the distorted rhenium complexes, measured in a KBr pellet, was red-shifted by 1-5 nm compared to the complexes without the distorted bpy ligand. Even in solution, similar red shifts of the pi-pi*(bpy) absorption were observed. The redox potential E1/2(bpy/bpy*-) of the complexes with the trialkylphosphine and triarylphosphine ligand are shifted positively by 110-120 mV and 60-80 mV respectively, compared with those derived from the electron-attracting property of the phosphorus ligand. In contrast with these properties, three nu(CO) IR bands, which are sensitive to the electron density on the central rhenium because of pi-back bonding, were shifted to higher energy, and a Re(I/II)-based oxidation wave was observed at a more positive potential according to the electron-attracting property of the phosphorus ligand. 相似文献
12.
Using modern NMR techniques, including DQF-COSY, NOESY, HETCOR and HMBC, the full assignments of all 1H and 13C chemical shifts were made for stigmastane-3,6-dione and stigmast-4-ene-3,6-dione, isolated from the roots of Piper nigrum (Piperaceae). Their stereochemistry was resolved by a combination of 2D NOESY data and analysis of coupling constants. The two compounds were isolated from the genus Piper for the first time. 相似文献
13.
The thermal properties and gas Chromatographie behaviour of manganese(II) and manganese(III) trifluoroacetylacetonates (TFA) were investigated by using the ligand vapour technique. The two chelates, Mn(TFA); and Mn(TFA)3, can be quantitatively eluted on a mixed-liquid phase (1.9% OV-17 ÷ 0.1% PEG-20M) at column temperatures above 210°C and 130–150°C, respectively; Mn(TFA)3 is completely converted to Mn(TFA)2 by thermal dissociation at column temperatures above 180°C and completely eluted as Mn(TFA)2 above 210°C. The chelates can be determined separately within errors of about 1% after a preliminary extraction. 相似文献
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An on-line purification method for catecholamines was studied using a flow system equipped with an alumina microcolumn. The procedure involves catecholamine adsorption, column washing and catecholamine elution steps. The system is designed not to decompose catecholamines under alkaline conditions in the adsorption step. Flow-rates and times for different solutions delivered in each step (alkaline buffer for adsorption, water for washing and an acidic solution for elution), column length and sample volume to be loaded were systematically investigated by liquid chromatography. Under optimum conditions, norepinephrine, epinephrine, dopamine and 3,4- dihydroxybenzylamine (internal standard) can be purified with recoveries of ? 90% within 11 min with manual operation. This method was efficiently applied to urine samples and the results indicate the possibility that catecholamines in biological samples are automatically purified. 相似文献
16.
Amanda C.R. Koike Amanda G. Santillo Flávio T. Rodrigues Renato C. Duarte Anna Lucia C.H. Villavicencio 《Radiation Physics and Chemistry》2012,81(8):1068-1070
The minimally processed food provided the consumer with a product quality, safety and practicality. However, minimal processing of food does not reduce pathogenic population of microorganisms to safe levels. Ionizing radiation used in low doses is effective to maintain the quality of food, reducing the microbiological load but rather compromising the nutritional values and sensory property. The association of minimal processing with irradiation could improve the quality and safety of product. The purpose of this study was to evaluate the effectiveness of low-doses of ionizing radiation on the reduction of microorganisms in minimally processed foods. The results show that the ionizing radiation of minimally processed vegetables could decontaminate them without several changes in its properties. 相似文献
17.
Frantisek Mikes Hongxiang Teng Yasuhiro Koike Yoshiyuki Okamoto 《Journal of polymer science. Part A, Polymer chemistry》2012,50(22):4717-4720
Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r1 (HFIB) = 0, r2 (VPFB) = 0.373, and r1r2 = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average Tgs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the Tg of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of Tgs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
18.
Copolymers of pentafluorophenylhexafluoroisopropyl methacrylate (FPPMA) with trifluoroethyl methacrylate (TFEMA) were prepared in THF solution and in bulk using azobisisobutyronitrile as a free radical initiator. The monomer reactivity ratios of TFEMA (M1) and FPPMA (M2) were calculated as r1 = 0.55 and r2 = 0.07. The refractive indices of poly(TFEMA) and poly(FPPMA) are very similar as 1.435 and 1.430, respectively, at 532 nm, and the copolymer films were transparent. The glass transition temperatures (Tg) of the copolymers were in the range of 80–90°C and showed a negative deviation from the Gordon–Taylor equation. The thermal decomposition temperature (Td) was increased with the content of FPPMA in copolymers. Low water absorption for 1:1 FPPMA/TFEMA copolymer was detected. Copolymers of FPPMA with hexafluoroisopropyl methacrylate (HFPMA) were also prepared. The monomer reactivity ratios of HFPMA (M1) and FPPMA (M2) were calculated as r1 = 0.43 and r2 = 0.10. The Tgs of the copolymers were in the range of 88–95°C and showed also a negative deviation from the Gordon–Taylor equation. Tg and Td of the copolymers were increased with the content of FPPMA. The refractive index of poly(HFPMA) (1.384 at 532 nm) is much lower than that of FPPMA homopolymer, but copolymer films obtained were clear and transparent. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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20.
Tooru Ooya Hideharu Mori Minoru Terano Nobuhiko Yui 《Macromolecular rapid communications》1995,16(4):259-263
A novel design of a biodegradable carrier for drug delivery was established by constructing a supramolecular assembly of drugs and polymer backbones without any covalent bonds. A biodegradable polyrotaxane was synthesized in which α-cyclodextrins (α-CDs) as drug carriers were threaded onto poly(ethylene glycol) chains which then were capped at each chain end by L -phenylalanine via peptide linkages. The release of α-CDs was observed only when the terminal peptide linkages were degraded. 相似文献