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91.
Hitoshi Shimizu Kazuki Shimizu Atsuko Sugita Tsuyoshi Yamauchi Kazumi Morikawa 《Tetrahedron letters》2004,45(42):7837-7841
Two 21-nor-22-oxa-1α,25-dihydroxyvitamin D3 derivatives have been synthesized in quest of a drug with lower calcemic activity than Maxacalcitol, 22-oxa-1α,25-dihydroxyvitamin D3, being used as antihyperparathyroidism and antipsoriatic drug. Of two 21-nor products obtained, the product carrying one carbon elongated side chain with diethylcarbinol moiety has been found to exhibit comparable differentiation-inducing activity to Maxacalcitol with much lower exhibition of calcemic activity. 相似文献
92.
Y. M. Temerk 《Fresenius' Journal of Analytical Chemistry》1976,282(3):205-207
Summary The determination of some monoazo compounds by derivative pulse polarography has been investigated. The effect of pH is studied, and the optimum pH was determined to give the highest sensitivity. The detection limit is ca. 1×10–5 M. Response is linear up to 8×10–4 M.
Bestimmung einiger Monoazoverbindungen durch derivative Pulspolarographie
Zusammenfassung Die Bestimmungsmöglichkeiten für einige Monoazoverbindungen durch derivative Pulspolarographie wurden untersucht. Der Einfluß des pH-Wertes wurde getestet und der jeweils optimale Wert in Abhängigkeit von den Substituenten ermittelt. Die Nachweisgrenze liegt bei 1×10–5 M. Die Anzeige ist linear bis 8×10–4 M.相似文献
93.
通过紫外-可见光谱滴定法和圆二色光谱法,对手性锌卟啉化合物(ZnP)与4种咪唑类小分子的轴向配位反应的热力学性质进行了研究。测定的热力学数据和圆二色光谱的实验结果显示,配位常数按K(2-MeIm)>K(Im)>K(N-MeIm)>K(2-Et-4-MeIm)的顺序依次减弱,咪唑类配体的轴向配位能力按2-Et-4-MeIm<N-MeIm相似文献
94.
An explicit expression for the analytical first derivative of the Z-averaged perturbation theory taken to second order energy, due to Lee and Jayatilaka, is presented for application to high-spin
systems described by a restricted open-shell Hartree–Fock wavefunction. The use of frozen core orbitals is incorporated into
the derivation.
Received: 23 April 2001 / Accepted: 31 August 2001 / Published online: 9 January 2002 相似文献
95.
Changes in binding affinity to catalytic antibody 6D9 of chloramphenicol phosphonate derivatives (CPDs) containing H or F were investigated by performing free energy calculations based on molecular dynamics simulations. We calculated the binding free energy, enthalpy, and entropy changes (DeltaDeltaG, DeltaDeltaH, and -TDeltaDeltaS) attributable to H-->F substitution by comparing results for CPDs containing a trifluoroacetylamino group (CPD-F) or an acetylamino group (CPD-H). The calculated DeltaDeltaG, DeltaDeltaH, and -TDeltaDeltaS values were -2.9, -6.3, and 3.5 kcal mol(-1) and close to experimental values observed for a series of similar ligands, chloramphenicol phosphonates with F and H (-1.4, -3.5, and 2.1 kcal mol(-1)). Therefore, CPD-F binds more strongly to 6D9 than does CPD-H. To clarify the origin of the large difference in DeltaDeltaG, we apportioned the calculated values of DeltaDeltaG and DeltaG for the associated and dissociated states into contributions from various atomic interactions. We found that the H-->F substitution increased the binding affinity mainly by decreasing the hydration free energy and not by increasing favorable interactions with the antibody. The decreased hydration free energy of the ligand was mainly due to unfavorable coulombic interactions between the trifluoroacetylamino group and solvent waters, which increased the free energy of the dissociated state (by about 3.7 kcal mol(-1)). Also, the trifluoroacetylamino group slightly increased the free energy level of the associated state (about 0.8 kcal mol(-1)) because favorable van der Waals interactions compensated for unfavorable coulombic interactions with antibody atoms. In addition, the enthalpy and entropy changes, DeltaDeltaH and -TDeltaDeltaS (computationally -6.3 and 3.5 kcal mol(-1)), originated mainly from a decrease in hydration free energy in the dissociated state. The CPD-F and CPD-H ligands had substantially different structures in the dissociated and complexed states. 相似文献
96.
3-O-Acetyl-1,2-O-isopropylidene--D-allofuranose (2 b) was prepared from 1,2:5,6-di-O-isopropylidene--D-allofuranose (1 b). Treatment of2 b with triphenylphosphine-diethyl azodicarboxylate afforded regio- and stereospecifically the 5,6-epoxy--D-allo derivative (3). The other diastereomeric compound, 5,6-epoxy-1,2-O-isopropylidene--L-talofuranose (6) was also prepared stereoselectively from2 b
via the intermediates5 a and5 b. The epoxy sugars3 and6 were converted with lithium aluminum hydride to the corresponding 6-deoxy-1,2-O-isopropylidene--D-allofuranose (4 a) and --L-talofuranose (7 a) derivatives. Hydrolysis of4 a and7 a afforded 6-deoxy-D-allose and 6-deoxy-L-talose, respectively. The corresponding 3,5-di-O-acetyl- (4 b and7 b) and the 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) derivatives (4 c and7 c) are also described. Selective removal of the isopropylidene group and subsequent acetylation offers a convenient route to prepare sugar derivatives containing furanose ring, like8 b, as a suitable precursor for nucleoside analogs.Herrn Prof. Dr.K. Komarek mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
97.
A simple, sensitive and rapid derivative spectrophotometric method using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) has been developed for simultaneous determination of Co(II), Ni(II) and Fe(II) which have very similar chemical behavior and appear together in many real samples. The complexes of all these metal ions with 5-Br-PADAP were formed immediately at pH 7.0 ammonium acetate buffered solution and were stable for at least 24 h. Second derivative spectra were selected for evaluation, because working wavelength determination was more precise and spectral overlap was less than in the ordinary and first derivative spectra. Three wavelengths at which the complexes exhibit extremum 2D values for Co(II), Ni(II) and Fe(II) were selected as analytical wavelengths, i.e., 640, 600 and 740 nm, respectively. Calibration curves drawn with zero-to-peak values at mentioned wavelengths were linear between 80 and 2000 ng ml−1 for each metal ion. Concentrations of Co(II) and Ni(II) were calculated from the total 2D values and the sum of the linear equations for these three cations at 640 and 600 nm, after Fe(II) assay by making use of the 2D value at 740 nm. Limits of detection (LOD) for Co(II), Ni(II) and Fe(II) were 2.7, 13.9 and 3.0 ng ml−1, respectively. The method has been applied to tool steel and heater resistance wire samples successfully. 相似文献
98.
Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields. Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity. 相似文献
99.
稀土乙酰丙氨酸咪唑配合物的合成及光谱性质 总被引:22,自引:0,他引:22
稀土元素由于特殊的外层电子构型,在与不同类型配体配位时,呈现出丰富多彩的配位行为和结构,其配合物,特别是有机配合物,由于具有发光性强、选择性好的特点,在发光、激光材料创制、结构探针、荧光免疫分析及生物传感器等领域的研究和应用引起广泛关注.氨基酸、肽是各种生物大分子的基本组成单元,咪唑存在于组氨酸、羧肽酶、血红蛋白等生物分子中参与配位或"变构效应"成为活性部位结构,唑环有丰富的能级,其作为含N富电子体系可与稀土离子形成既有生物活性,又有优良光学性能的配合物. 相似文献
100.
Summary The development of a computer-aided rapid-scanning detector for HPLC based on the linear photodiode array UV-visible spectrophotometer is described. Chomatograms monitored at up to three wavelengths, with automatic capture of spectra for eluted peaks and post-run processing of spectral data to generate log10 (A) spectra, second derivative and fourth derivative spectra, are described. Methods are reported for the analysis of forensic samples of diacetylmorphine (heroin) in the presence of the degradation products and potential contaminants caffeine, papaverine, 6-acetylcodeine, thebaine, 6-acetyl-morphine, procaine and morphine separated by HPLC. The novel use of second and higher derivative spectra for the qualitative characterisation of drugs and contaminants separated by HPLC is described.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献