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21.
An enantioselective first total syntheis of amphidinolide T1 (1) is described. Amphidinolide T1 (1), a 19-membered macrolide isolated from Amphidinium sp., has shown potent antitumor properties against a variety of NCI tumor cell lines. The synthesis is convergent and involves the assembly of C1-C10 segment 2 and C11-C21 segment 3 by an oxocarbenium ion-mediated alkylation and Yamaguchi macrolactonization sequence. The synthesis of fragment 2 involves an efficient cross metathesis and hydrogenation sequence between the terminal olefins of 5 and 6 to form the C4-C5 carbon-carbon bond. Enol ether 4 is designed to be the surrogate of fragment 3 where the sensitive C16-exo-methylene and the C13-hydroxyl group were protected as the bromoether derivative during the Lewis acid-catalyzed alkylation process. Both stereocenters in fragment 5 as well as the C2 and C3 stereocenters in fragment 4 are accessed by a highly diastereoselective ester-derived titanium enolate-mediated syn-aldol reaction. The bromoether derivative 24 was unraveled at the final stage of the synthesis, providing (+)-amphidinolide T1. 相似文献
22.
Summary Xylenol orange reacts very sensitively with gallium(III), indium (III) and thallium(III) to form reddish violet colored chelates having max 560 nm in case of Ga and In and max 590 nm in case of Ti at PH 4.0. The molar ratio for all the chelates is 1 1 (metal reagent). Optimum conditions including the range for adherence to Beer's law, effect of PH on the color intensity, effect of excess reagent, and sensitivity are reported for the photometric determination of these metal ions using Xylenol orange.
Zusammenfassung Xylenolorange reagiert sehr empfindlich mit Gallium(III), Indium(III) und Thallium(III) unter Bildung rötlich-violetter Chelate mit einem Absorptionsmaximum bei 560 nm im Falle von Ga und In bzw. 590 nm für Tl bei pH 4,0. Das Molverhältnis ist in jedem Fall 11. Die besten Arbeitsbedingungen, der Gültigkeitsbereich des Beerschen Gesetzes, der Einfluß des PH auf die Farbintensität und des Reagensüberschusses sowie die Empfindlichkeit werden für die photometrische Bestimmung der genannten Ionen angegeben.相似文献
23.
Summary The formation of ternary complexes of the MAL3– type [where M = CuII, NiII and ZnII ; A = nitrilotriacetic acid (NTA); L = 1-hydroxy-2-naphthoic acid (1,2 HNA) and 2-hydroxy-1-naphthoic acid (2,1 HNA)] have been studied potentiometrically in 50% v/v aqueous — ethanol (25° and µ = 0.1). Under identical conditions the binary complexes of the 1,2- and 2,1-HNA ligands have also been examined. The values of mixed ligand formation constants KMAL have been found to be lower than KML (first step formation constant of binary complexes) and even less than
(second step formation constant of binary complexes). 相似文献
24.
Summary Chrome Azurol S permits a simple colorimetric determination of palladium with a sensitivity of 0.4g/cm2 (practical) or 0.04g/cm2
(Sandell), respectively. Conditions and interferences are described in detail.
Zusammenfassung Palladium läßt sich mit Hilfe von Chromazurol S auf einfache Weise kolorimetrisch bestimmen. Die praktische Empfindlichkeit der Methode beträgt 0,4g/cm2 bzw. 0,04g/cm2 nachSandell. Die Arbeitsbedingungen und die durch Fremdionen verursachten Störungen werden angegeben.
Résumé Le chromazurol S permet un dosage colorimétrique simple du palladium, avec une sensibilité de 0,4g/cm2 (en pratique) ou 0,04g/cm2 (Sandell) respectivement. On décrit en détail les conditions opératoires et les interférences.相似文献
25.
Summary A nitrate-selective electrode based on precipitated nitron nitrate in an epoxy resin matrix has been prepared. The lower detection limit is 10–5
M, the optimum pH range is 2.0–8.5, and the response time is 1 min. The electrode is selective in presence of CH3COO–, SO4
2–, C2O4
2–, PO4
3–, NO2
–, Cl– and Br–, but I– interferes. Results for nitrate in soil samples were in agreement with values obtained spectrophotometrically.
Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980. 相似文献
Eine neue nitrat-spezifische Elektrode auf der Basis gefällten Nitronnitrats
Zusammenfassung Eine nitrat-spezifische Elektrode auf der Basis gefällten Nitronnitrats in einer Epoxyharz-Matrix wurde hergestellt. Die untere Nachweisgrenze ist 10–5 M, das pH-Optimum liegt zwischen 2,0 und 8,5, die Reaktionszeit beträgt 1 Minute. Die Elektrode ist selektiv in Gegenwart von Acetat, Sulfat, Oxalat, Phosphat, Nitrit, Chlorid und Bromid; aber Jodid stört. Ergebnisse der Nitratbestimmung in Bodenproben stimmen mit spektrophotometrischen Resultaten überein.
Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980. 相似文献
26.
The polymer reference interaction site model theory is investigated for two-dimensional polymer melts composed of freely-jointed hard disk chains and tangent-disk rods. Exact results for the intramolecular pair correlation functions are input into the theory, and predictions of the theory for the intermolecular pair correlation functions are tested via comparison with simulation. The theory is not as accurate for this system as it is for three-dimensional polymer melts, and the quantitative predictions are not good except at the highest area fractions. Possible reasons for the deficiency in the theory are discussed. 相似文献
27.
A self-consistent integral equation theory is presented for the conformational properties and spinodal lines of random copolymer melts. The theory combines field-theoretic methods with the polymer reference interaction site model (PRISM) theory. The many-chain problem is replaced by a single chain where the sites interact via a bare plus a self-consistently determined medium-induced potential, and the conformational properties are obtained using a variational method. The theoretical prediction for the spinodal line is qualitatively similar to that of non-self-consistent PRISM theory. The theory predicts macroscopic phase separation for all values of the monomer correlation strength, lambda. The inverse spinodal temperature is a nonmonotonic function of lambda with a maximum at lambda(max). For large values of lambda( approximately 1), the values of spinodal temperatures are almost identical to those of non-self-consistent PRISM theory. For low values of lambda, however, the theory predicts higher values for spinodal temperatures than non-self-consistent PRISM theory. The theory predicts significant changes in the mean-square end-to-end distance as the temperature is decreased. 相似文献
28.
(E)-4-(2',4',5'-trimethoxyphenyl)but-1,3-diene (4) and (E)-4-(2',4',5'-trimethoxyphenyl)but-1-ene (6), bioactive phenylbutanoids of Zingiber cassumunar, were synthesized exclusively with trans geometry. Treatment of methylmagnesium iodide with (E)-2',4',5'-trimethoxycinnamaldehyde (2), an oxidized product of abundantly available toxic (Z)-phenylpropanoid (1) of Acorus calamus, gave (E)-4-(2',4',5'-trimethoxyphenyl)but-3-en-2-ol (3) which upon dehydration with copper sulphate/silica gel under microwave irradiation for 3 min afforded 4 in 58% yield. Further, catalytic hydrogenation of 4 with 10% Pd/C afforded 4-(2',4',5'-trimethoxyphenyl)butane (5) which upon dehydrogenation with DDQ/SiO2 afforded hypolipidemic 6 in 54% yield. 相似文献
29.
Subcellular distribution of Superoxide dismutase (SOD), catalase (CAT), selenium (SC) dependent glutathione peroxidase, and
Se-independent glutathione peroxidase (GSH-Px) activities were detected in different tissues (hepatopancreas, muscle, and
gill) of freshwater prawnsMacrobrachium malcolmsonii andMacrobrahium lamarrei lamarrei. CAT and SOD were found almost equally between the mitochondrial and cytosolic fraction. Both Se-dependent and Se-independent
GSH-Px activities were mainly found in cytosolic fraction. 相似文献
30.
Summary Copper(II) complexes with the Schiff bases derived from Salicylaldehyde and its 5-chloro-, 5-bromo-, 5-nitro-, 3-ethoxy- and 3,5-dichloro derivatives, or from 2-hydroxy-1-naphthaldehyde ando-hydroxybenzylamine, have been synthesized and characterized on the basis of elemental analysis, i.r. and electronic spectra and magnetic susceptibility measurements. The Schiff bases behave as tridentate dibasic O, N and O donor ligands and form complexes with 11 metal: ligand stoichiometry which exhibit subnormal magnetic moments (
eff=0.88–0.98 B.M.) and are involved in strong antifer-romagnetic exchange (–J=482–525 cm–1). The complexes exhibit a d-d band atca. 1600 cm–1. A dimeric structure with aminophenolic oxygen atoms as the bridging atoms is proposed on the basis of i.r. and magnetic data. 相似文献