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51.
Fini P. Castagnolo M. Catucci L. Cosma P. Agostiano A. 《Journal of Thermal Analysis and Calorimetry》2003,73(2):653-659
Equilibrium constants and standard molar enthalpies of reaction were determined by titration calorimetry for the reaction
of 1-butanol with 2-hydroxypropyl-b-cyclodextrin (HP-b-CD) in aqueous solution at different concentrations of NaCl (0-1.9
M). The standard molar free energy and entropy changes associated to the complexation were calculated from the corresponding
equilibrium constants, K, and standard enthalpies determined experimentally. In NaCl solutions the inclusion complexes ButOH/HP-b-CD are more stable
than in water and their stability increases at increasing NaCl concentration; otherwise, the standard molar enthalpy associated
to the formation of the complexes does not change with the increasing of salt concentration. The dependence of K on NaCl concentration were used to evaluate the number of water molecules displaced from the hydration shells of HP-b-CD
and ButOH in forming complexes.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
52.
Gao F Ruan WJ Chen JM Zhang YH Zhu ZA 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):886-895
A barium-containing crown ether bridged chiral heterotrinuclear salen Zn(II) complex BaZn2L(ClO4)2, where L is a folded dinuclear chiral (R,R)-salen ligand, has been synthesized and characterized by elemental analysis, 1H NMR, UV-vis, IR, circular dichroism (CD) spectra, and mass spectra. As a folded dinuclear chiral host, its recognition with achiral guests (imidazole derivatives), rigid bidentate guest (1,4-diazobicyclo[2,2,2]octane, DABCO) and chiral guests (amino acid methyl esters) was investigated by means of UV-vis spectrophotometric titration, CD spectra. The association constants of D-amino acid methyl esters are found to be higher than those of their L-enantiomer. The sandwich-type binding of BaZn2L(ClO4)2-DABCO supramolecular assembly was specially studied via 1H NMR titration and 1H ROESY. To understand the recognition on molecular level, density functional theory (DFT) calculations on B3LYP/LanL2DZ were performed on the minimal energy conformations of host, guests, and host-guest complexes. The minimal energy conformations were obtained by molecular mechanics (MM) optimization and molecular dynamics (MD) simulation. The results of single point energy, HOMO energy, and charges transfer were analyzed. The results of theoretical calculations are in good agreement with the experimental data. 相似文献
53.
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
54.
Novel macrocyclic monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a were synthesized by the reaction of calix[4]arene dibromides 1-5 with the disodium salt of bis(2-selenylethyl)ether in the yields between 28% and 64%. Their structures were characterized by proton and carbon NMR spectra. X-Ray structure analysis of la further confirmed the cone conformation of compounds 1a-5a. An interesting host-guest complex of la with dichloromethane via CH/π and C1/π interactions was elucidated. Extraction experiments showed that these novel monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a had strong extraction ability towards mercury ion. The interaction of Hg^2+with the calix ligand has also been investigated by 1^H NMR titration. 相似文献
55.
本文通过化学分析的实验方法测定了第一过渡元素几种二价中心离子与EDTA配合形成的过渡金属配合物的稳定性顺序:Mn2+Zn2+,从实验数据得到证实,中心离子对配合物的稳定性影响与理论上的判断相吻合。 相似文献
56.
文中利用pH电位法,在25℃,0.1mol/L KCl存在的条件下,通过测定咪唑、苯并咪唑、2-甲基苯并咪唑、2-乙基苯并咪唑和2- 丙基苯并咪唑与二价铜离子络合反应时溶液酸度值的变化,分别求算出了五种物质的加质子常数及配位反应的各级稳定常数。 相似文献
57.
腐殖质与Ca~(2+)、Mg~(2+)、Co~(2+)、Ni~(2+)的络合作用及其在农业中的应用 总被引:2,自引:0,他引:2
杨春文 《西北民族学院学报》2003,24(3):67-73
用电位滴定法研究腐殖酸FA和HA与金属离子(Ca2+、Mg2+、Co2+、Ni2+)的络合作用,发现它们与金属离子形成的络合物比较稳定,在溶液中的络合形成常数可通过作图法获得 随着溶液中金属离子浓度的增大,络合形成常数减小,同时发现FA与金属离子的络合形成常数比HA的大 腐殖酸是土壤肥力高低的一个重要标志,在农业应用中具有重要作用 相似文献
58.
黄原酸钾的电位滴定法测定 总被引:1,自引:0,他引:1
报道了以银电极为指示电极,饱和甘汞电极为参比电极,在丙酮一氨水介质中,用硝酸银电位滴定法测定黄原酸钾的含量,滴定终点敏锐,方法简便、准确,相对标准偏差低于0.50%(n=5)。 相似文献
59.
对高锰酸钾测定双氧水含量的分析方法的研究和改进 总被引:1,自引:0,他引:1
研究KMnO4和双氧水在酸性条件下的自催化反应动力学,以及反应的诱导期与两种反应物浓度的关系,提出在各种浓度和KMnO4分析H2O2含量靠自身催化的分析方法,后的方法,适用浓度范围宽,反应速度快,滴定分析误差小。 相似文献
60.
林文如 《福州大学学报(自然科学版)》1996,(5):87-90
推导出电位双点滴定法通用的定量公式和相对误差公式,对方法的准确度进行了探讨,确定了ΔE值的最适宜范围 相似文献