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81.
The crystal structure of SrAl2O4 at 1073 K was determined from conventional X-ray powder diffraction data using direct methods, and it was further refined by the Rietveld method. The structure was hexagonal (space group P63, Z=6) with a=0.89260(3) nm, c=0.84985(2) nm and V=0.58639(3) nm3. Final reliability indices were Rwp=7.87%, Rp=5.87% and RB=4.19%. The [AlO4] tetrahedra are linked to form trigonally distorted rings and they are joined in layers. These layers are stacked with a two-layer repeat and connected by the tetrahedral apices. All of the Sr atoms occupy the centers of the rings when viewed along the c-axis. The structure is described as a stuffed derivative of tridymite. 相似文献
82.
83.
A sensitive and selective method is described for the determination of neodymium in mixed rare earths using fourth-derivative spectrophotometry. The method is based on the absorption spectra of 4f electron transitions of the complex of neodymium with methyl thymol blue and cetylpyridinium chloride. The influence of various instrumental parameters and reaction conditions for maximum colour development are investigated. The calibration curve is linear over the range 0–3.5 g ml–1 neodymium. The relative standard deviation for determination of 1.4 g ml–1 neodymium (n = 7) is 1.6%. The detection limit (signal-to-noise ratio = 3) is 0.2 g ml–1. 相似文献
84.
《Electroanalysis》2004,16(11):938-948
The theory for an EC mechanism in chronopotentiometric techniques – reversal chronopotentiometry, cyclic chronopotentiometry and reciprocal derivative chronopotentiometry – is developed. The equations of this article are valid for spherical electrodes of any size and present a compact and easy‐to‐manage form. Methods for determining kinetic parameters of the chemical reaction are proposed and the influence of the electrode radius is discussed. We conclude that large errors in the determination of these parameters are committed if electrode sphericity is neglected. Reciprocal derivative chronopotentiometry has been applied in its traditional form (dt/dE vs. E), and in a more recently proposed modality consisting of plotting dt1/2/dE vs. E. These techniques are very convenient for studying an EC mechanism since the response is obtained in the form of peaks which are quantitatively related to the kinetic parameters of the chemical reaction. A comparison of the chronopotentiometric methods analyzed leads us to conclude that working curves based on the dt1/2/dE vs. E curves are more suitable to obtain accurate values of the rate constants of the chemical reaction. 相似文献
85.
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
86.
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
87.
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
88.
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
89.
于铂电极上修饰一层N-(3-二茂铁乙酰胺基)丙基吡咯聚合物膜,应用循环伏安法对聚合物的电化学性能进行研究,发现了N-位取代吡咯聚合物的电活性大大降低,聚合物中 二茂铁基团氧化还原性能稳定,制成酶电极后,在+0.2V以葡萄糖有一明显的催化峰,而对抗坏血酸,尿酸则几乎没有呼应,该葡萄糖电极性能稳定,连续工作十天,响应值基本不变。 相似文献
90.
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