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Abstract  

By substututing99Mo for the Mo in the reconstituted MoFe protein, the nuclear quadrupole interactions (NQI) of99Mo have been measured using the perturbed angular correlations (PAC). Two well-defined electric quadrupole interaction parameters have been observed. The configuration of the M-Center of the MoFe protein is identified by the quadrupole couplign constant Q1(412(9)MHz) and the asymmetry parameter 1(0.49(5)). Other parameters, VQ2(1939(13)MHz) and 1(0.90(1)), may correspond to a deformation M—Center of MoFe protein.

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Abstract  

A ternary binuclear complex of dysprosium chloride hexahydrate with m-nitrobenzoic acid and 1,10-phenanthroline, [Dy(m-NBA)3phen]2·4H2O (m-NBA: m-nitrobenzoate; phen: 1,10-phenanthroline) was synthesized. The dissolution enthalpies of [2phen·H2O(s)], [6m-HNBA(s)], [2DyCl3·6H2O(s)], and [Dy(m-NBA)3phen]2·4H2O(s) in the calorimetric solvent (VDMSO:VMeOH = 3:2) were determined by the solution–reaction isoperibol calorimeter at 298.15 K to be
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[2phen·H2O(s), 298.15 K] = 21.7367 ± 0.3150 kJ·mol−1,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[6m-HNBA(s), 298.15 K] = 15.3635 ± 0.2235 kJ·mol−1,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[2DyCl3·6H2O(s), 298.15 K] = −203.5331 ± 0.2200 kJ·mol−1, and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[[Dy(m-NBA)3phen]2·4H2O(s), 298.15 K] = 53.5965 ± 0.2367 kJ·mol−1, respectively. The enthalpy change of the reaction was determined to be
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{r}} H_{\text{m}}^{\theta } = 3 6 9. 4 9 \pm 0. 5 6 \;{\text{kJ}}\cdot {\text{mol}}^{ - 1} .$$ \end{document}
According to the above results and the relevant data in the literature, through Hess’ law, the standard molar enthalpy of formation of [Dy(m-NBA)3phen]2·4H2O(s) was estimated to be
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{f}} H_{\text{m}}^{\theta }$$ \end{document}
[[Dy(m-NBA)3phen]2·4H2O(s), 298.15 K] = −5525 ± 6 kJ·mol−1.
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Abstract  

The complex of [Nd(BA)3bipy]2 (BA = benzoic acid; bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, and TG/DTG techniques. The crystal is monoclinic with space group P2(1)/n. The two–eight coordinated Nd3+ ions are linked together by four bridged BA ligands and each Nd3+ ion is further bonded to one chelated bidentate BA ligand and one 2,2′-bipyridine molecule. The thermal decomposition process of the title complex was discussed by TG/DTG and IR techniques. The non-isothermal kinetics was investigated by using double equal-double step method. The kinetic equation for the first stage can be expressed as dα/dt = A exp(−E/RT)(1 − α). The thermodynamic parameters (ΔH , ΔG , and ΔS ) and kinetic parameters (activation energy E and pre-exponential factor A) were also calculated.

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Abstract  

Positron annihilation lifetime measurement and Fourier transform infrared spectrometry were applied to the study of temperature dependencies of free volume parameters and hydrogen bonds in segmented polyurethane, specially fabricated as a shape memory polymer. The variation of free volumes in amorphous region were correlated to that of hydrogen bonding and the shape memory mechanism of polyurethane is elucidated from a microscopic point of view. The relationship between free volume contents and the formation of hydrogen bonds significantly suggests that the shape memory occurs due to the configurational recovery of the microscopic regulation around urethane bundles of hard segment and consequent restoration of soft-segment in polyurethane.

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Abstract  

The power–time curves of a biological oscillation system were determined for different temperatures, acidities and carbon sources, by using a 2277 thermal activity monitor. The apparent activation energy and order of the oscillation reaction were calculated from the induction period (t in) and the first oscillation period (t p). The regularity of the biological oscillation system is discussed.

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Abstract  

Microcalorimetric measurements of the polymerization of actin in the presence of 100 mM KCl and 2 mM MgCl2were carried out with a Calvet MS-80 microcalorimeter at temperatures from 293.15 to 310.15 K. It was observed that the polymerization of actin was endothermic and the enthalpy change for actin polymerization was temperature-dependent. The enthalpy change ΔHowas fitted to ΔHo(kJ mol-1)=434.0-1.16 (T/K) and the change in heat capacity ΔCp ocalculated from ΔHowas -1.16 kJ (mol K)-1in the above range of temperatures. The direct calorimetry results showed that the enthalpy and entropy change for actin polymerization could not be obtained from measurements of the critical concentration and the only way to assess the enthalpy change for the polymerization of actin and similar reactions lies in the use of calorimetry.

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Abstract  

The inclusion complex of benzaldehyde (BA) with β-cyclodextrin (β-CD) was prepared and was studied by thermal analysis and X-ray diffractometry. The composition of the complex was identified by TG and elemental analysis as β-CDBA9H2O. TG and DSC studies showed that the thermal dissociation of β-CDBA9H2O took place in three stages: dehydration in the range 70-120C; dissociation of β-CDBA in the range 235-270C; and decomposition of β-CD above 280C. The kinetics of dissociation of β-CDBA in flowing dry nitrogen was studied by means of TG both at constant temperature and at linearly increasing temperature. The results showed that the dissociation of β-CDBA was dominated by a one-dimensional random nucleation and subsequent growth process (A2). The activation energy E was 124. 8 kJ mol-1, and the pre-exponential factor A 5.041011 min-1.

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Abstract  

The acidity of mesoporous materials FeSiMCM-41, LaSiMCM-41, SiMCM-41, AlSiMCM-41 and HAlSiMCM-41 has been investigated by microcalorimetric studies of the adsorption of ammonia and temperature programmed ammonia desorption method. In the initial stage, the acid strength sequence is SiMCM-41>HAlSiMCM-41>AlSiMCM-41>FeSiMCM-41>LaSiMCM-41, in agreement with that found for microporous molecular sieves materials. A small number of strong acid sites of SiMCM-41 may result from the aluminum impurity contained in the silica source material. The acid density sequence is HAlSiMCM-41>AlSiMCM-41>FeSiMCM-41>LaSiMCM-41SiMCM-41 and can be explained by the studies of existing states of trivalent atoms in these samples reported in previous work. Since some NH3-TPD plots of these samples show the profiles that could not be back to baseline at elevated temperature, the technique of microcalorimetric adsorption is preferable in studying these samples.

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