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841.
A highly sensitive and convenient gas chromatographic-mass spectrometric (GC-MS) method is described for the determination of 5-fluorouracil in the presence of 2'-deoxy-5-fluorouridine (which breaks down into 5-fluorouracil during ordinary GC derivatization) in biological samples such as plasma and urine. After extraction with ethyl acetate, 5-fluorouracil and 5-chlorouracil, the latter being used as an internal standard, were converted into their tert.-butyldimethylsilyl derivatives by allowing the mixture to stand for 30 min at room temperature and were assayed by electron-impact ionization GC-MS. Under these conditions, 2'-deoxy-5-fluorouridine did not decompose or interfere with the determination of 5-fluorouracil. The assay method, including the extraction and tert.-butyldimethylsilyl derivatization of 5-fluorouracil, showed good linearity in the range 0-100 ng/ml for 5-fluorouracil in plasma (detection limit 0.5 ng/ml) and urine (detection limit 1 ng/ml). The usefulness of this method was demonstrated by determining plasma concentrations of 5-fluorouracil in rats treated intravenously with 5-fluorouracil and 2'-deoxy-5-fluorouridine. 相似文献
842.
A cyclobarbital-imprinted polymer was prepared using a fluorescent functional monomer, 2,6-bis(acrylamido)pyridine, and the polymer showed not only selective binding of cyclobarbital but also enhancement of fluorescence intensity, suggesting that the polymer could be utilized as a selective fluorescence probe. 相似文献
843.
Lindner HJ Yuan DQ Fujita K Kubo K Lichtenthaler FW 《Chemical communications (Cambridge, England)》2003,(14):1730-1731
The title compound is elliptically distorted due to the unusual 1C4 geometry of the altrose portion. In packing, a unique fourfold helical structure is elaborated with head-to-head dimers as the repeating motif. The imidazolyl moieties mutually reside on each other's cavities thereby resembling the Yin-Yang type balancing of antagonisms. 相似文献
844.
[reaction: see text] DNA-peptide conjugates were synthesized by condensing partially protected peptide fragments and oligonucleotides on a CPG support using diisocyanatoalkane as a linker. After cleavage and deprotection with aqueous ammonia, pure products were obtained by single RPHPLC purification in satisfactory yields and identified by a MALDI-TOF MS spectrometer. This method allows one to prepare DNA-peptide conjugates with any components and sequences of DNA and peptides. 相似文献
845.
Katsumi Tanigaki Mayumi Kosaka Takahashi Manako Yoshimi Kubo Ichiro Hirosawa Kenshiro Uchida Kosmas Prassides 《Chemical physics letters》1995,240(5-6):627-632
The electronic states in metallic alkali fullerides K3C60 and Rb3C60, are studied in detail by cw- and pulsed-ESR. The ESR linewidth associated with conduction electrons varies substantially, depending sensitively on the alkali metals used. It is clearly revealed that the linewidth is homogeneous and is strongly controlled by the spin-lattice relaxation times (T1) determined via the spin-orbit interactions of the small fraction of s electrons remaining on the alkali atoms. The results indicate that the electron transfer from the alkali atoms to C60 is not perfectly complete, with the remaining fraction being much greater in the tetrahedral sites than in the octahedral sites of the face-centered cubic lattice. 相似文献
846.
847.
Ishi-i T Hirayama T Murakami K Tashiro H Thiemann T Kubo K Mori A Yamasaki S Akao T Tsuboyama A Mukaide T Ueno K Mataka S 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1261-1268
This paper reports unique and unusual formations of columnar liquid crystals and organogels by self-assembling discotic molecules, which are composed of an aromatic hexaazatriphenylene (HAT) core and six flexible aromatic side chains. In HAT derivatives 3a, with 4'-(N,N-diphenylamino)biphenyl-4-yl chains, 3b, with 4'-[N-(2-naphthyl)-N-phenylamino]biphenyl-4-yl chains, and 3c, with 4'-phenoxybiphenyl-4-yl chains, the two-dimensional hexagonal packings can be created by their self-assembling in the liquid crystalline phase, which were characterized by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction analysis. In certain solvents, HAT molecules 3a-c can form the viscoelastic fluid organogels, in which one-dimensional aggregates composed of the HAT molecules are self-assembled and entangled into three-dimensional network structures. The organogel structures were analyzed by scanning electron microscopy observation, (1)H NMR, UV-vis, and circular dichroism spectroscopy. In contrast to 3a-c, none of the liquid crystalline and organogel phases could be formed from 3d and 3e with short aromatic side chains including a phenylene spacer, and 3f (except a few specific solutions) and 3g without terminal diarylamino and phenoxy groups. In 3a-c, the aromatic side chains with terminal flexible groups make up soft regions that cooperatively stabilize the liquid crystalline and organogel supramolecular structures together with the hard regions of the hexaazatriphenylene core. 相似文献
848.
Y Nomoto H Takai T Hirata M Teranishi T Ohno K Kubo 《Chemical & pharmaceutical bulletin》1990,38(11):3014-3019
A series of novel 1-(6,7-dimethoxy-4-quinazolinyl)piperidines carrying substituted hydantoin and 2-thiohydantoin rings was synthesized and examined for cardiotonic activity in anesthetized dogs. Introduction of isopropyl and sec-butyl group at the 5-position of the hydantoin and thiohydantoin rings led to potent inotropic activity. Effects of insertion of an alkyl chain between the piperidine and the hydantoin rings were also examined. The structural requirements necessary for optimal cardiotonic activity within the series were investigated. 相似文献
849.
The 2H‐1‐benzo/naphthopyran‐2‐one‐4‐yl (un)substituted phenyl‐1,3,4‐oxadiazoles has been synthesized by the oxidative cyclization of benzoic acid hydrazides formed in situ by the condensation of the respective 2H‐1‐benzo/naphthopyran‐2‐one‐4‐carboxaldehyde and (un)substituted monobenzoyl hydrazide in moderate yields. Also, spiro[indoline‐thiozolidine]‐2,4′‐diones has been syhthesized in a similar way from 3‐phenyl‐spiro[3H‐indoline‐3,2′‐thiozolidine]‐2,4′‐(1 H)dione monohydrazide and (un)substituted benzaldehydes. 相似文献
850.
Takano Y Taniguchi T Isobe H Kubo T Morita Y Yamamoto K Nakasuji K Takui T Yamaguchi K 《Journal of the American Chemical Society》2002,124(37):11122-11130
The phenalenyl radical (1) is a prototype of the hydrocarbon radical. Recently, the single crystal of 2,5,8-tri-tert-butylphenalenyl (2) was isolated and showed that the two phenalenyl radicals form a staggered dimeric pair, giving rise to strong antiferromagnetic interactions. The origin of the antiferromagnetic interactions and the nature of the chemical bond for the dimeric pair are challenging issues for chemists. First, spin-polarized hybrid DFT (Becke's half and half LYP (UB2LYP)) and CASSCF calculations were performed for 2 and its simplified model, the staggered-stacking phenalenyl radical dimeric pair (3a), to elucidate the origin of the strong antiferromagnetic coupling and the characteristics of the chemical bond. The calculated results showed that a SOMO-SOMO overlap effect was responsible for the strong antiferromagnetic interactions and weak or intermediate covalent bonding between phenalenyl radicals. The tert-butyl groups introduced at three beta-positions hardly affected the magnetic coupling, mainly causing steric hindrances in the crystalline state. Next, to obtain insight into ferromagnetic stacking, we investigated the stacking effect of staggered (3a)- and eclipsed (3b)-stacking phenalenyl radical dimeric pairs with a change of the SOMO-SOMO overlap on the basis of the extended McConnell model. We found that the stacking mode of the dimeric pair with both a small SOMO-SOMO overlap and a ferromagnetic spin polarization effect provided a ferromagnetic coupling. 相似文献