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991.
A zwitterionic trichloroplatinum(II) complex PtCl3(4,4′-bpy-N-nBu) (1) was prepared by an aqueous reaction of [4,4′-bpy-N-nBu]Cl with K2PtCl4, and was characterized by 1H-n.m.r. and IR spectroscopy as well as elemental analysis. Dissolving (1) into dmso-d
6 at 25 °C yields a mixture of the complexes, cis-PtCl2(4,4′-bpy-N-nBu)(dmso-d
6) (2-cis), trans-PtCl2(4,4′-bpy-N-nBu)(dmso-d
6) (2-trans), [4,4′-bpy-N-nBu]Cl and PtCl2(dmso-d
6)2. Ratio of the products in the dmso-d
6 solution changed depending on the temperature and the total concentration of the complexes. These compounds are in equilibrium
via isomerization reaction between (2-cis) and (2-trans) and via displacement reaction of the alkylbipyridinium ligand of
(2-cis) and (2-trans) with dmso-d
6 to form [4,4′-bpy-N-nBu]Cl and PtCl2(dmso-d
6)2. 相似文献
992.
Satish M. Annigeri M. P. Sathisha Vidyanand K. Revankar 《Transition Metal Chemistry》2007,32(1):81-87
Binuclear cobalt(II), nickel(II), copper(II) and zinc(II) complexes of general composition [M2L1-2(μ-Cl)Cl2] · nH2O with the Schiff-base ligands (where L1H and L2H are the potential pentadentate ligands derived by condensing 2,6-diformyl-4-methylphenol with 4-amino-3-antipyrine and 2-hydroxy-3-hydrazinoquinoxiline,
respectively) have been synthesized and characterized. Analytical and spectral studies support the above formulation. 1H-NMR and IR spectra of the complexes suggest they have an endogenous phenoxide bridge, with chloride as the exogenous bridge
atom. The electronic spectra of all the complexes are well characterized by broad d–d and a high intensity charge-transfer
transitions. The complexes are chloro-bridged as evidenced by two intense far-IR bands centered around 270–280 cm−1. Magnetic susceptibility measurements show that complexes are antiferromagnetic in nature. The compounds show significant
growth inhibitory activity against fungi Aspergillus niger and Candida albicans and moderate activity against bacteria Bacillus cirroflagellosus and Pseudomonas auresenosa. 相似文献
993.
(2S)- and (2R)-2-Amino-4-bromobutanoic acid were prepared starting from N-Boc-glutamic acid α tert-butyl ester. The double tert-butyl protection was necessary to prevent a partial racemisation during Barton’s radical decarboxylation used to transform the γ-carboxylic group into a bromide. This bromide reacted with different nitrogen, oxygen and sulphur nucleophiles to give nonnatural amino acids characterised by basic or heterocyclic side chains. The title compound was also used to prepare a conformationally constrained peptidomimetic. 相似文献
994.
We show that the electronic and atomic structures of silicon carbide nanotubes (SiCNTs) undergo dramatic changes with hydrogenation from first-principles calculations based on density-functional theory. The exo-hydrogenation of a single C atom results in acceptor states close to the highest occupied valence band of pristine SiCNT, whereas donor states close to the lowest unoccupied conduction band appear as a Si atom being hydrogenated. Upon fully hydrogenating Si atoms, (8,0) and (6,6) SiCNTs become metallic with very high density of states at the Fermi level. The full hydrogenation of C atoms, on the other hand, increases the band gap to 2.6 eV for (8,0) SiCNT and decreases the band gap to 1.47 eV for (6,6) SiCNT, respectively. The band gap of SiCNTs can also be greatly increased through the hydrogenation of all the atoms. 相似文献
995.
Pekka Juusola Pentti Minkkinen Lasse Leino Jarmo K. Laihia 《Monatshefte für Chemie / Chemical Monthly》2007,138(10):951-965
Summary. (E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation
constants (pK
a1 and pK
a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation
(pK
a1 = 3.43 ± 0.12 and pK
a2 = 5.80 ± 0.04) and (pK
a1 = 2.7 ± 0.3 and pK
a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride
solutions up to the isotonic salt concentration (0.154 mol dm−3), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at
temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK
a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric
dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived.
The obtained pK
a1 and pK
a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature.
An erratum to this article is available at . 相似文献
996.
The molar conductivities (Λ) of solutions of n-tetrabutylammonium tetraphenylborate (NBu4BPh4) in 3-pentanone have been measured in the temperature range from 283.15 to 329.15 K. The conductance data have been analyzed
using the Lee-Wheaton conductivity equation with the distance parameter (a) set at Bjerrum’s pairing distance, and the limiting molar conductivities (Λo) and the association equilibrium constants (K
A) have been derived. The limiting ion conductivities (λ_±o) have been evaluated according to the method of Krumgalz. The λ+
o values have been compared with λ+
o values calculated from the empirical equation of Gill. The thermodynamic functions, Gibbs energy (Δ G
A
o), enthalpy (Δ H
A
o) and entropy (Δ S
A
o) for the process of ion-pair formation as well as the activation energy of the ionic movement (ΔH
∗) have been evaluated. The obtained results are discussed in terms of ion-ion and ion-solvent interactions. 相似文献
997.
以抑制型电导离子色谱法检测四甲基氢氧化铵溶液中痕量碱金属和碱土金属离子.色谱条件为:IonPac CS12A阳离子交换色谱柱,20mmol/L甲烷磺酸淋洗液等度淋洗,抑制型电导检测.稀释液样品通过Dionex OnGuardⅡ氢型聚苯乙烯基强酸性树脂柱和0.22μm微孔尼龙膜处理.该方法的检测限(S/N=3)在0.024μg/L~0.156μg/L之间,标准曲线在低ng/L到低μg/L范围内呈现良好线性,RSD在10%左右,回收率为88%~115%. 相似文献
998.
超音速气流中受热壁板的稳定性分析 总被引:3,自引:0,他引:3
采用Galerkin方法建立二维壁板的非线性气动弹性运动方程,用一阶活塞理论模拟壁板
受到的气动力. 基于李雅普诺夫间接法分析了平壁板的稳定性,得到了壁板失稳的边界
曲线;采用牛顿迭代法分析了壁板的屈曲变形,进而分析了后屈曲状态下壁板的稳定性;
在时域中分析了后屈曲状态下壁板的颤振边界. 分析结果表明,为了保证计算精度,
在二维壁板的静态失稳及过屈曲变形分析中,至少要取二阶谐波模态;在平壁板的超音速颤
振(动态失稳)边界分析中至少应取四阶模态. 还对壁板的温升,壁板长厚比、壁板密
度和气流马赫数作了无量纲变参分析,研究了这些参数的变化对壁板稳定性的影响规律. 研
究中发现,当气流速压较低时壁板一般会稳定在低阶谐波模态的屈曲变形位置,但是如果系
统出现多个渐近稳定的不动点,即使作用在壁板上的气流速压很低,壁板也有可能在较低速
压下发生二次失稳型颤振. 相似文献
999.
Cardiac pacing is a medical device to help human to overcome arrhythmia and to recover the regular beats of heart. A helical
configuration of electrode tip is a new type of cardiac pacing lead distal tip. The helical electrode attaches itself to the
desired site of heart by screwing its helical tip into the myocardium. In vivo experiments on anesthetized dogs were carried
out to measure the acute interactions between helical electrode and myocardium during screw-in and pull-out processes. These
data would be helpful for electrode tip design and electrode/myocardium adherence safety evaluation. They also provide reliability
data for clinical site choice of human heart to implant and to fix the pacing lead. A special design of the helical tip using
strain gauges is instrumented for the measurement of the screw-in and pull-out forces. We obtained the data of screw-in torques
and pull-out forces for five different types of helical electrodes at nine designed sites on ten canine hearts. The results
indicate that the screw-in torques increased steplike while the torque–time curves presente saw-tooth fashion. The maximum
torque has a range of 0.3–1.9 N mm. Obvious differences are observed for different types of helical tips and for different
test sites. Large pull-out forces are frequently obtained at epicardium of left ventricle and right ventricle lateral wall,
and the forces obtained at right ventricle apex and outflow tract of right ventricle are normally small. The differences in
pull-out forces are dictated by the geometrical configuration of helix and regional structures of heart muscle. 相似文献
1000.
The effects of relative density of metal foams on the stresses and deformation of beam under bending
The exact analytic solution of the pure bending beam of metallic foams is given. The effects of relative density of the material
on stresses and deformation are revealed with the Triantafillou and Gibson constitutive law (TG model) taken as the analysis
basis. Several examples for individual foams are discussed, showing the importance of compressibility of the cellular materials.
One of the objects of this study is to generalize Hill’s solution for incompressible plasticity to the case of compressible
plasticity, and a kinematics parameter is brought into the analysis so that the velocity field can be determined.
The English text was polished by Yunming Chen. 相似文献