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81.
Mathematical meaning of the Clar's “aromatic sextet” is clarified by analysing the topological dependency of the sextet polynomial. Generalised recursive method for obtaining the sextet polynomial of a polyhex graph is presented. It is shown that the concept of the “super sextet” is necessarily introduced, if one-to-one correspondence between the Kekulé and sextet patterns is assumed. Topological dependency of the maximum number of resonant sextets is clarified and discussed in relation to the aromaticity and stability of polycyclic benzenoid hydrocarbons. 相似文献
82.
[Ac-D-Tyr1, D-Ala2, Leu5-OMe]Enkephalin and [Ac-Tyr1, D-Ala2, Leu5-OMe]Enkephalin were successfully synthesized by the coupling of dipeptide units and tripeptide units which were readily obtained by the asymmetric hydrogenation of the corresponding dehydropeptide building blocks. 相似文献
83.
Column-switching techniques for high-performance liquid chromatography of two acidic drugs, ibuprofen and mefenamic acid, in human serum with short-wavelength ultraviolet detection are described. The method involved extraction of the analyte from acidified serum followed by the chromatographic analysis using column switching. Three ODS columns were used each with different mobile phase, utilizing the difference of ion-pair formation or of ionization caused by pH change. The method offered high sensitivity and selectivity, with short-wavelength ultraviolet detection at 221 nm for ibuprofen and at 219 nm for mefenamic acid. The detection limits were 0.5 ng/ml (2.4 pmol/ml) for ibuprofen and 0.1 ng/ml (0.4 pmol/ml) for mefenamic acid using 1 ml of serum, both at a signal-to-noise ratio of 3. With some modifications, the principle of the method would be applicable to other acidic compounds in biological fluids. 相似文献
84.
Issei Kasahara Masami Kanai Masako Taniguchi Ayako Kakeba Noriko Hata Shigeru Taguchi Katsumi Goto 《Analytica chimica acta》1989
The singly charged complex anion bis[2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulphopropylamino)phenolato]cobaltate(III) is intensely purple-violet and is stable over the pH range 1–13. Its absorption spectrum remains the same over this pH range. At pH2, it forms extractable ion pairs with long-chain quaternary ammonium ions and protonated alkylamines. Only the quaternary ammonium ions are extracted into chloroform at pH 11, hence separate extractions allow both types to be determined. The absorbance of the organic phase is measured at 594 nm. The apparent molar absorptivity is 7.0 × 104 l mol?1 cm?1. Calibration graphs for zephiramine, benzethonium and hexadecylpyridinium ions are linear over the range 0.1–2 × 10?6 M. The only interference found was from anionic surfactants. The method is applied to hair and fabric conditioners. 相似文献
85.
A new synthetic method for the preparation of vinyl chlorides and vinyl bromides from acyclic and cyclic ketones is described. Vinyl halides are practically obtained from the corresponding vinyl phosphate intermediates with triphenylphosphine dihalide. 相似文献
86.
Diverted total synthesis and biological evaluation of gambierol analogues: elucidation of crucial structural elements for potent toxicity 总被引:2,自引:0,他引:2
Fuwa H Kainuma N Tachibana K Tsukano C Satake M Sasaki M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4894-4909
Gambierol is a polycyclic ether toxin, which has been isolated from the marine dinoflagellate Gambierdiscus toxicus. A series of gambierol analogues have been prepared from an advanced intermediate of our total synthesis of gambierol and investigated for their toxicity against mice, thus providing the first systematic structure-activity relationships (SAR) of this polycyclic ether class of marine toxin. The SAR studies described herein clearly indicate that 1) the C28=C29 double bond within the H ring and the unsaturated side chain are the crucial structural elements required for exerting potent biological activity and 2) the C1 and C6 hydroxy groups, the C30 methyl group, and the C37=C38 double bond have little influence on the degree of neurotoxicity against mice. 相似文献
87.
88.
Takehiro Yamagishi Atsushi Kinbara Noriko Okubo Shunpei Sato Haruhiko Fukaya 《Tetrahedron: Asymmetry》2012,23(24):1633-1639
The diastereoselective synthesis of Pro-Phe phosphinyl dipeptide isosteres in protected form was achieved by starting from optically active 1,1-diethoxyethyl(aminomethyl)phosphinate. Our methodology involves diastereoselective α-alkylation and β′-alkylation of phosphinate derivatives with an asymmetric center at the phosphorus atom. 相似文献
89.
Density functional theory (DFT) calculations were made on the hydrolysis of hydantoin (2,4-imidazolidinedione). In the neutral hydrolysis, reacting systems composed of hydantoin and (H2O)n with n = 1+3, 2+3, 3+3, and 4+3 were adopted. Three water molecules (“+3”) participate in the in-plane hydrogen-bond circuit, and the n–3 = 1, 2, 3 or 4 water cluster works for the out-of-plane nucleophilic attack onto the carbonyl carbon of hydantoin. Transition states (TSs) involving bond interchanges prompted by proton transfers were determined. The reaction path with n = 3+3 containing N-carbamoyl glycine, N-carboxy glycine and three tetrahedral intermediates was found to be most likely. In the acid-catalyzed hydrolysis, a reacting system composed of hydantoin and H3O+(H2O)7 was employed. Ten TSs and nine intermediates were obtained. N-carbamoyl glycine and N-carboxy glycine were confirmed to be detectable stable species. The product consists of glycine, carbonic acid (not CO2), NH4+, and (H2O)5. It has the exothermic energy, whereas the product in the neutral hydrolysis is of the endothermic one for all n values. For both neutral (n = 3+3) and acid-catalyzed hydrolyses, the rate-determining steps were calculated to be for formation of the tetrahedral intermediate, HOOC-CH2-NH-C(OH)2NH2. The pattern of proton transfers along hydrogen bonds was carefully investigated. 相似文献
90.