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991.
Polymorphism of paracetamol 总被引:1,自引:0,他引:1
G. L. Perlovich Tatyana V. Volkova Annette Bauer-Brandl 《Journal of Thermal Analysis and Calorimetry》2007,89(3):767-774
The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature
dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured
and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications
in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG
sub298=60.0 kJ mol−1; ΔH
sub298=117.9±0.7 kJ mol−1; ΔS
sub298=190±2 J mol−1 K−1. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition
enthalpy at 298 K, ΔH
tr298(I→II)=2.0±0.4 kJ mol−1, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based
on ΔH
tr298 (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value
of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification
II were also estimated (ΔG
sub298=56.1 kJ mol−1; ΔH
sub298=115.9±0.9 kJ mol−1; ΔS
sub298=200±3 J mol−1 K−1). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported
found by classical thermochemical methods. 相似文献
992.
Michael Plate Sigrid Wocadlo Werner Massa Kurt Dehnicke Harald Krautscheid 《无机化学与普通化学杂志》1995,621(3):388-392
Functionalized Alkyne Complexes of Tungsten(VI). Syntheses and Crystal Structures of [WCl4(Et? Se? C?C? Se? Et)(THF)] and [WCl4(Et? Te? C?C? Te? Et)(THF)] The title compounds have been prepared by reactions of [WCl4(SEt2)2] with the alkynes Et? X? C?C? X? Et (X = Se, Te) in CCl4 solution and subsequent addition of tetrahydrofurane. Both complexes were characterized by crystal structure determinations. [WCl4(Et? Se? C?C? Se? Et)(THF)]: Space group P21/n, Z = 4, structure determination with 2942 unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 934.2, b = 1639.5, c = 1189.5 pm, β = 96.497°. [WCl4(Et? Te? C?C? Te? Et)(THF)]: Space group P21/n, Z = 4, structure determination with 4097 unique reflections, R = 0.067, Lattice dimensions at ?70°C: a = 899.2, b = 1691.9, c = 1213.3 pm, β = 96.82°. The complexes have monomeric molecular structures with the oxygen atom of the THF molecules in trans-position to the side-on bound alkyne ligands. 相似文献
993.
Kurt Egger 《Fresenius' Journal of Analytical Chemistry》1961,182(3):161-166
Zusammenfassung 14 Glykoside der Aglykone Kaempferol, Quercetin und Myricetin werden auf ihr Verhalten im Perlon-Dünnschichtchromatogramm geprüft. Es wird gezeigt, daß 3-Monoside, 3-Bioside und 3,7-Glykoside scharf voneinander getrennt werden und an den stark verschiedenen Rf-Werten erkannt werden können. Der Einfluß des Aglykons ist gering; der entscheidende Faktor für den Rf-Wert ist die Glykosidierung.
Herrn Prof. Dr. L. Hörhammer, Herrn Doz. Dr. H. Wagner und Herrn Dr. W. Leeb, München, danke ich sehr für die freundlicherweise erteilte praktische Einführung in die Polyamid-Dünnschichtchromatographie, sowie für die Überlassung einer Probe von Kaempferol-3-rhamnoglucosid. Die Durchführung der hier dargestellten Versuche hielt sich eng an die in den Münchner Laboratorien entwickelten Verfahren.
Die Untersuchungen wurden von der Görres-Gesellschaft zur Pflege der Wissenschaften und von der Deutschen Forschungsgemeinschaft gefördert, wofür an dieser Stelle gedankt sei. Der BASF Ludwigshafen danke ich für die großzügige Überlassung des Polyamids. 相似文献
Summary 14 glycosides of the aglycons quercetin, kaempferol and myricetin were examined for their behaviour in chromatography with polyamide. The results show that the 3-monosides can be easily differentiated from the 3-biosides, as well as from both the 3,7-glycosides, by their sharply different Rf-values. The influence of the aglycon is small; the decisive factor for the Rf-value is the glycosidation.
Herrn Prof. Dr. L. Hörhammer, Herrn Doz. Dr. H. Wagner und Herrn Dr. W. Leeb, München, danke ich sehr für die freundlicherweise erteilte praktische Einführung in die Polyamid-Dünnschichtchromatographie, sowie für die Überlassung einer Probe von Kaempferol-3-rhamnoglucosid. Die Durchführung der hier dargestellten Versuche hielt sich eng an die in den Münchner Laboratorien entwickelten Verfahren.
Die Untersuchungen wurden von der Görres-Gesellschaft zur Pflege der Wissenschaften und von der Deutschen Forschungsgemeinschaft gefördert, wofür an dieser Stelle gedankt sei. Der BASF Ludwigshafen danke ich für die großzügige Überlassung des Polyamids. 相似文献
994.
Reversed-phase liquid chromatography and argentation chromatography of the minor capsaicinoids 总被引:1,自引:0,他引:1
Thompson RQ Phinney KW Sander LC Welch MJ 《Analytical and bioanalytical chemistry》2005,381(7):1432-1440
An investigation of the liquid chromatography of the minor capsaicinoids in a commercial capsaicinoid mixture is reported. Twelve stationary phases including C8, C18, C30, phenyl, and cation-exchange chemistries were examined in combination with isocratic aqueous methanol and aqueous acetonitrile mobile phases. A phenyl stationary phase and aqueous acetonitrile mobile phase baseline-resolved 7 of 11 capsaicinoids, and selected ion chromatograms (LC–ESI-MS) demonstrated this was the most effective reversed-phase separation. Argentation chromatography with an alkyl or phenyl column and aqueous silver nitrate–methanol mobile phase revealed the presence of the 6-ene-8-methyl and 6-ene-9-methyl homocapsaicin isomers and the absence of 7-ene-9-methyl homocapsaicin. A mixed phenyl–cation-exchange stationary phase (charged with silver ion) enabled unique and useful separations of the capsaicinoids. 相似文献
995.
When α,β-unsaturated γ-dimethoxymethyl cyclohexenones are excited to the S2(π,π*) state, certain unimolecular reactions can be observed to compete with S2 → S1 internal conversion. These reactions do not occur from the S1(n,π*) or the lowest T(π,π* and n,π*) states. They comprise the radical elimination of the formylacetal substituent (cf. 8 , 9 → 32 + 33 ), γ → α formylacetal migration (cf. 6 → 27 , 8 → 30 , 9 → 34 , 12 → 37 ), and a cyclization process involving the transfer of a methoxyl hydrogen to the α carbon and ring closure at the β position (cf. 6 → 28 , 8 → 31 , 12 → 38 , 20 → 40 + 41 ). The quantum yield of the ring closure 20a → 40a + 41a is 0.016 at ≤ 0.05M concentration. It is independent of the excitation wavelength within the π→π* absorption band (238–254 nm), but Φ ( 40a + 41a ) decreases at higher concentrations. According to the experimental data the reactive species of these specifically π→π*-induced transformations is placed energetically higher than the S1(n,π*) state, and it is either identical with the thermally equilibrated S2(n,π*) state, or reached via this latter state. The linear dienone 14 undergoes a similar π→π*-induced cyclization (→ 42 ) whereas the benzohomologue 26 proved unreactive, and the dienone 22 at both n → π and π→π* excitation only gives rise to rearrangements generally characteristic of cross-conjugated cyclohexadienones. 相似文献
996.
Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid are components of the trail pheromone of the ant species Lasius fuliginosus. The acids were extracted from the contents of the rectal ampullae and identified by the mass spectra and gas chromatographic retention times of the corresponding methyl esters. 相似文献
997.
Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition
metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities
for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex
catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition,
several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and
Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic
behavior with size-selective molecular recognition. 相似文献
998.
Krisztián Bogár 《Central European Journal of Chemistry》2005,3(1):63-71
(R, R)-(−)-N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II) was encapsulated into MCM-22 using the zeolite synthesis method. The
encapsulated catalyst proved to be active in the oxidation of α-methylstyrene with NaOCl with higher specific activity than
the homogeneous catalyst. At the same time, this encapsulated catalyst was completely inactive in the hydrolytic kinetic resolution
of racemic styrene oxide. This observation is in a good correlation with the assumption of the cooperative bimetallic mechanism
proposed by Annis and Jacobsen. 相似文献
999.
Jørgensen JM Erlacher K Pedersen JS Gothelf KV 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10320-10323
The influence of preparation temperature on the size and size distribution of dodecylthiol monolayer protected gold clusters was studied. The monolayer protected clusters (MPCs) were synthesized by two different variations of the Brust-Schiffrin procedure. In all of the experiments, the stoichiometry of the reactants dodecylthiol, HAuCl(4), and sodium borohydride was kept constant, while the temperature was varied in the range of -18 to +90 degrees C. Two series were performed in which an aqueous solution of NaBH(4) was either added over 30 s or all in one portion. The size and size distribution of the MPCs were determined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). It has been demonstrated that in general the MPC size increases with elevated preparation temperatures. 相似文献
1000.
A simplified approach was developed to estimate the vapor pressure of pure compounds from experimental data obtained by isothermal
thermogravimetric (TG) analysis. A numerical procedure was developed to estimate the Antoine parameters of the substance by
the analysis of isothermal TG data. The results of the experimental validations carried out evidenced that at least a preliminary
estimation of vapour pressures of pure substances by the analysis of TG data is possible. The limited time and the reduced
amounts of sample required for the experimental runs make the technique attractive with respect to the conventional and more
accurate techniques for vapor pressure assessment. 相似文献