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51.
2-Arylimino-3-aryl-thiazolidine-4-thiones were synthesized from the corresponding thiazolidine-4-ones using Lawesson's reagent (LR) and converted into 5-benzylidine-2-arylimino-3-aryl-thiazolidine-4-thiones by reaction with benzaldehyde, which were then used as heterodienes in the inverse-electron-demand hetero Diels–Alder cycloadditions with norbornene as a dienophile at 25 °C. The reactions with norbornene were found to proceed with 100% exo-selectivity as determined by NMR experiments. The hetero Diels–Alder reactions with axially chiral heterodienes with ΔG#>116 kJ/mol showed kinetic atroposelectivities up to 11:1. However, the products were found to equilibrate, as revealed by the 97.1 kJ/mol barrier to hindered rotation of the most sterically hindered product, to produce 2:1 diastereoselectivities after the 24 h reaction time. 相似文献
52.
Sevinc Kurbanoglu Burcu Dogan‐Topal Bengi Uslu Alp Can Sibel A. Ozkan 《Electroanalysis》2013,25(6):1473-1482
The effect of surface modifications on the electrochemical behavior of the anticancer drug idarubicin was studied at multiwalled carbon nanotubes modified glassy carbon and edge plane pyrolytic graphite electrodes. The surface morphology of the modified electrodes was characterized by scanning electron microscopy. The modified electrodes were constructed for the determination of idarubicin using adsorptive stripping differential pulse voltammetry. The experimental parameters such as supporting electrolyte, pH, accumulation time and potential, amount of carbon nanotubes for the sensitive assay of idarubicin were studied as details. Under the optimized conditions, idarubicin gave a linear response in the range 9.36×10?8–1.87×10?6 M for modified glassy carbon and 9.36×10?8–9.36×10?7 M for modified edge plane pyrolytic graphite electrodes. The detection limits were found as 1.87×10?8 M and 3.75×10?8 M based on modified glassy carbon and edge plane pyrolytic graphite electrodes, respectively. Interfering species such as ascorbic acid, dopamine, and aspirin showed no interference with the selective determination of idarubicin. The analyzing method was fully validated and successfully applied for the determination of idarubicin in its pharmaceutical dosage form. The possible oxidation mechanism of idarubicin was also discussed. The results revealed that the modified electrodes showed an obvious electrocatalytic activity toward the oxidation of idarubicin by a remarkable enhancement in the current response compared with bare electrodes. 相似文献
53.
54.
In this work, viscosities of ternary Au–Ag–Cu and Al–Cu–Si liquid alloys have been calculated as a function of gold, aluminium and copper compositions for the sections Au–Ag–Cu (xAg/xCu = 0.543 at 1373 K), Alx(Cu50–Si50)(1–x) and Cux(Al50–Si50)(1–x) at 1375 K using Chou’s general solution model, Muggianu, Kohler, Toop, Hillert, Budai et al., Kozlov et al., Schick et al. and Kaptay et al. models. The present study finds that a comparison of the predicted values of viscosities associated with the geometric and physical models indicate good mutual agreement. The Muggianu model indicates the best agreement with the results obtained for Au–Ag–Cu and Alx–Cu50–Si50 alloy systems and the Kaptay et al. model, which is a physical model, indicates the best agreement with the results obtained for Al50–Cux–Si50. 相似文献
55.
Axially chiral 2-arylimino-3-aryl-thiazolidine-4-ones have been synthesized as racemic mixtures, and each mixture with the exception of 2-(o-chlorophenyl)imino-3-(o-chlorophenyl)-thiazolidine-4-one has been converted to the corresponding 5-benzylidene-2-arylimino-3-aryl-thiazolidine-4-one racemates by reaction with benzaldehyde. The thermally interconvertible enantiomers of each compound have been obtained by enantioselective HPLC separation on columns Chiralpak AD-H and Chiralcel OD-H, and the barriers to racemization have been found to be 98.1-114.1 kJ/mol. The barriers determined were compared to those of structurally related compounds to provide evidence for the stereochemistry of the aryl imino bond. 相似文献
56.
This paper analyses the optimal timing of switching between alternative and consecutive regimes in optimal growth models. We derive the appropriate necessary conditions for such problems by means of standard techniques from the calculus of variations and some basic properties of Sobolev spaces. 相似文献
57.
The influence of the pore size of a chromatographic reversed phase material on the adsorption equilibria and diffusion of two industrially relevant peptides (i.e. a small synthetic peptide and insulin) has been studied using seven different reversed phase HPLC materials having pore sizes ranging from 90 Å to 300 Å. The stationary phase pore size distribution was obtained by inverse size exclusion measurement (iSEC). The effect of the pore size on the mass transfer properties of the materials was evaluated from Van Deemter experiments. It has been shown that the lumped mass transfer coefficient increases linearly with the average pore size. The Henry coefficient and the impurity selectivity were determined in diluted conditions. The saturation capacity of the main peptides was determined in overloaded conditions using the inverse method (i.e. peak fitting). It was shown that the adsorption equilibria of the peptides on the seven materials is well described by a surface-specific adsorption isotherm. Based on this a lumped kinetic model has been developed to model the elution profile of the two peptides in overloaded conditions and to simulate the purification of the peptide from its crude mixture. It has been found that the separation of insulin from its main impurity (i.e. desamido-insulin) was not affected by the pore size. On the other hand, in the case of the synthetic peptide, it was found that the adsorption of the most significant impurity decreases with the pore size. This decrease is probably due to an increase in silanol activity with decreasing pore size. 相似文献
58.
The physical and chemical characteristics of kaolinite (kaolin) may be variable, and minor amounts of other clay minerals, nonclay minerals, and other impurities may affect the properties of kaolinites. Thus specific technical properties of pharmaceutical grade kaolinites become very important because these clays are used in medical applications, e.g., as pharmaceutical excipients, and will be consumed by humans. Seven pharmaceutical grade kaolinite specimens were used in this study: K1004, KA105, 2242-01, K2-500, Acros, Acros-mono, and KX0007-1. In addition, two kaolinites from the Clay Minerals Society Source Clays, KGa-1b and KGa-2, were used for comparison purposes. The Acros-mono and 2242-01 kaolinites contained minor amounts of illite, which was demonstrated both compositionally and structurally by using inductively coupled plasma spectroscopy and powder X-ray diffraction. The KX0007-1 kaolinite powder was found to be heavily contaminated with quartz, cristobalite, and alunite. Crystal structure computations also showed excess Si in its tetrahedral site, and the mineral no longer has the typical kaolinite crystal structure. These widely-used industrial standards should be quantitatively characterized morphologically, compositionally, and structurally. Results of the mineralogical characteristics should be clearly labeled on the pharmaceutical grade kaolinites and reported to the relevant regulatory agencies. 相似文献
59.
Using the infinitesimal deformation approach, a crystallographic analysis of the austenite-martensite transformation from the cubic to orthorhombic phase - which predicts crystallographic parameters such as habit plane, orientation relationship between austenite and martensite, rotation matrix and total shape deformation matrix - is derived from a knowledge of the crystal structures of the initial and final phase only. The numerical values coming from orientation relationships obtained for Au-47.5 Cd Fe-Ni and In--Tl alloys are compared with predictions of the phenomenological crystallographic theory, infinitesimal deformation approach and experimental data. 相似文献
60.
Aziridines are highly useful compounds as building blocks for the synthesis of important organic compounds. Amino acid synthesis by aziridine ring opening reaction is a good example to the use of aziridines. Although this reaction is studied by many groups, the synthesis of amino phosphonic acids is less explored. In this study, we have carried out the ring opening reaction of aziridinyl phosphonates with a variety of alcohols including the more functional propargylic and allylic alcohols. These reactions provided functionalized α‐amino‐β‐alkoxyphosphonates in 40–91 % yield. 相似文献