Heat-induced conformational transition of cytochrome c observed by temperature gradient gel electrophoresis at acidic pH

Temperature-gradient gel electrophoresis (TGGE) has been used to study the thermal unfolding of ferricytochrome c in low and high concentrations of acetic acid. It has been observed that the mobility of cytochrome c is a linear function of temperature when the system is characterized by a homogeneous population of conformation-state, single molecular species. Within the transition temperature range, the mobility clearly displays the characteristic sigmoidal shape describing the transitions of protein unfolding. The data obtained by TGGE were used to estimate the apparent thermodynamic parameters (enthalpy change deltaHvh and transition temperature Tm), associated with the transition of unfolding. The accuracy of the apparent thermodynamic parameters obtained by this method agrees within error limits with the values obtained by direct calorimetric measurements using differential scanning calorimetry (DSC).     

Determination of equilibrium constants by titration calorimetry : Part II. Data reduction and calculation techniques

Techniques of data reduction and methods of calculation have been given for the determination of equilibrium constants by titration calorimetry. It has been shown how, starting with typical titration calorimetry data, the apparent heat liberated in the reaction vessel can be calculated, corrected for extraneous heat effects, and used to solve for the equilibrium constant and enthalpy change value(s) for the reaction(s) under investigation. Equations are given for calculating the energy contributed to the overall heat effects measured in the reaction vessel by processes other than chemical reactions such as heat of stirring, heat losses, heat of dilution, etc., and by chemical reactions other than the one(s) for which equilibrium constant(s) are sought. Mathematical techniques and equations are presented for calculating equilibrium constants and enthalpy change values from titration data by least squares analysis.     

The cure of elastomers by dicumyl peroxide as observed in differential scanning calorimetry

Differential scanning calorimetry (DSC) has been used to determine the enthalpy changes accompanying the thermal homolysis and subsequent radical reactions occuring in the dicumyl peroxide (DCP) cure of elastomers (NR, EPDM, SBR, BR, NBR, and EPM). The thermal degradation of DCP alone, dispersed on kaolin clay in a hydrocarbon solvent, was also studied.The degradation of DCP alone results in an exothermic enthalpy change of ～ 215 kJ mole^?1. In elastomer systems, the observed enthalpy exchange can be ordered BR >; SBR ; NBR (34% ACN) > NBR (27% ACN) > NR > EPDM ～ EPM.Low enthalpy values are associated with systems containing predominantly secondary hydrogen atoms (EPDM, EPM). The high enthalpy of cure for BR appears associated with the known ability of the polybutadienyl radicals to propagate a limited chain reaction. The relative extent of cumyloxy radical disproportionation to hydrogen abstraction was determined in each system and this has no apparent effect on the observed enthalpy change.The method of Borchardt and Daniels was used for data reduction and calculation of apparent activation energies. For DCP degradation alone the calculated activation energy is in good agreement with literature values. In elastomer systems, the calculated activation energies must be treated with caution because, as pointed out by Borchardt and Daniels, their method does not apply to solid state reactions.     

多孔与平面硅电极界面的电化学行为

研究了重掺杂n-型单晶硅(CSi)在氢氟酸体系中生成多孔硅(PSi)的电化学行为,根据线性极化曲线,选取不同的电流密度,采用恒电流阳极极化法,制备了一系列多孔硅层。利用扫描电子显微镜对其进行了表面和断面形貌的表征,通过线性扫描极化技术和计时电位法,比较了单晶硅电极和多孔硅电极的电化学行为,分析了多孔硅形成前后的塔菲尔曲线和计时电位曲线,给出了多孔硅形成过程中的重要电化学参数,如腐蚀电流、开路电位、塔菲尔斜率等。并对其进行深入分析,根据实验结果,提出了单晶硅电极/电解质界面和多孔硅电极/电解质界面的结构模型,并利用该模型讨论了两种电极界面的电化学特性。     

Role of dissolved oxygen reduction in improvement inhibition performance of ascorbic acid during copper corrosion in 0.50 mol/L sulphuric acid

<正>The kinetics of dissolved O_2 reduction and hydrogen evolution reactions on copper surface was studied in naturally aerated and air and O_2-saturated 0.50 mol/L H_2SO_4 solutions using polarization measurements combined with the rotating disc electrode (RDE).The Koutecky-Levich plot indicated that the dissolved O_2 reduction at the copper electrode was an apparent four-electron process.A correlation between the presence of dissolved O_2 and the formation of Cu_2O,confirmed from XRD,was discussed. Ascorbic acid(AA) was tested as a safe inhibitor for copper corrosion in H_2SO_4 solutions at 25℃.Measurements were carried out as a function of dissolved oxygen concentration using Tafel polarization measurements.The addition of AA slowed down the reduction reaction of dissolved O_2 more effectively than the anodic reaction.Dissolved O_2 was found to enhance the inhibition performance of AA.Adsorption via hydrogen bonding was considered.     

热动力学的滴定量热发研究 I.一级反应的热动力学

用滴定量热法分别建立了滴定期和滴反应期一级反应热动力学的数学模型，根据这两种模型，均可由一次实验的滴定量热曲线同时解析出一级反应的速率常数和摩尔反应焓。用滴定量热法研究了去离子水溶剂中乙酸乙酯皂化反应的热动力学，实验结果验证了本文用滴定量热法研究一级反应热动力学的适用性。     

Microcalorimetric Investigations of K+- and Mg2+-Induced Polymerization of Actin at Temperatures from 293.15 K to 310.15 K

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 ΔH^owas fitted to ΔH^o(kJ mol^-1)=434.0-1.16 (T/K) and the change in heat capacity ΔC_p ^ocalculated from ΔH^owas -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. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural relaxation in poly(vinyl acetate)

Structural relaxation in poly(vinyl acetate) (PVAc) in and slightly above the glass-transition region has been studied by monitoring the time dependence of enthalpy using differential scanning calorimetry and the frequency dependence of electric polarization by dielectric loss measurements. The results have been analyzed to yield the kinetic parameters characterizing the structural relaxation and are compared with similar analyses of previously published shear compliance and volume relaxation experiments. Relaxation of enthalpy, electric polarization, volume, and shear stress in PVAc all appear to be characterized by somewhat different relaxation times. The difference between the volume and enthalpy relaxation times, coupled with the fact that PVAc exhibits a Prigogine–Defay ratio greater than unity, is evidence for a previously proposed connection between the thermodynamics and kinetics of structural relaxation in terms of an order parameter model.     

Actinomycin D binds to single stranded DNA oligomers which contain double GTC triplets

The present work carried out a study on the interactions between Actinomycin D (ActD) and some single-stranded DNA oligomers, which contain double GTC triplets separated by TTT sequence. The interactions of drugs with DNA oligomers were investigated by UV, circular dichroism (CD) spectroscopy and isothermal titration calorimetry (ITC). The results indicate that ActD binds to the single stranded DNA oligomers in the fold back binding model as supported by added A/T base at DNA strand terminal which facilitates the formation of hairpin. The apparent binding constant K_b, the apparent binding molar enthalpy ΔH⁰ and other thermodynamic data were obtained. The binding affinities are sequence dependent and related to the length of DNA strand. And the higher molar binding enthalpy indicates that the binding process is enthalpy driven.     

Reevaluation of donor number using titration calorimetry

Many empirical parameters have been suggested to measure solvent effects in chemical reactions. Gutmann's donor number has been a successful parameter to quantify the electron-donating property of the solvent molecule; it is defined as the enthalpy change of the addition reaction of solvent molecule to SbCl(5) in 1,2-dichloroethane. Calorimetric measurements can be applied to determine the quantity. Because the existence of water is critical for reactions in organic solvents, we have analyzed the enthalpy change using the titration calorimetry while considering the complexation with water. The determined donor numbers of formamide, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and 1,1,3,3-tetramethylurea (TMU) are 22.4, 26.5, 30.0, and 40.4, respectively. The values of DMF and DMSO are in perfect agreement with those of Gutmann. A reliable value for TMU is obtained for the first time on the basis of the enthalpy change for the addition reaction.     

Thermochemistry of complex salts of transition metal perchlorates with tetrazole ligands

Standard enthalpies of formation of transition metal (cobalt, nickel, and zinc) complex salts with an organic ligand 5-aminotetrazol-2-ylacetohydrazide (ATH-2) were obtained by combustion and solution calorimetry. The enthalpy of combustion of the ligand was determined using combustion calorimetry and the standard enthalpy of formation of the ligand was calculated. For calculations by reaction calorimetry, a thermochemical cycle was developed that allows determination of the standard enthalpy of formation of complex salts. The enthalpies of solution of the ligand and transition metal complex salts in water and in 0.1 M hydrochloric acid were determined. The data obtained allow calculations of the enthalpies of salts formation and the enthalpies of three new complex ions. The enthalpies of position isomerization in different compounds were analyzed.     

Etude thermodynamique des complexes de transfert de charge du type n-σ* en solution Complexes de la quinoléine et de quinoléines substituées avec I2, ICI et IBr

Thermodynamic study of charge transfert complexes (n-σ*) in solution Charge transfer complexes of quinoline and substituted quinolines (donors) with iodine, iodine chloride, and iodine bromide (acceptors) have been studied spectrophotometrically in CCl₄. The 1:1 stoechiometry of these complexes was verified by means of the continous variations method and the appearance of isosbestic points. Simultaneous determination of the equilibrium constant and enthalpy of adduct formation was carried out by calorimetry. It was observed for every donor that the equilibrium constants of the complexes studied increase with the strength of the acceptors. A linear correlation between enthalpy of adduct formation and donor strength was obtained only for the complexes Donor ICI.     

Ni-W-TiO2复合电极在碱性介质中的析氢电催化性能

具有较高的析氢电催化活性的镍基多元合金材料已广为报道。近年来通过复合电沉积技术在电极中掺入RuO2、ZrO2、WC等非溶性固体微粒制备的复合功能电极材料用于析氢方面的研究已有报道,这些复合电极对析氢反应都有明显的催化作用。但是用电沉积的方法在电极中掺入TiO2制备的复合功能材料的研究还未见报道,本文研究了Ni-W-TiO2复合电极的制备、形貌结构以及在碱性介质中的析氢电催化活性和电化学稳定性。     

Implementation of a Chloride‐selective Electrode Into a Closed Bipolar Electrode System with Fluorimetric Readout

Applicability of a bipolar electrode system was tested for arrangements containing a typical ion‐selective electrode (ISE) connected with an electrode coated by a conducting polymer characterized by electroluminescence. In this case a selective response of the ISE membrane at one pole of the bipolar electrode is transduced to a fluorimetric signal obtained by reduction of the conducting polymer at the second pole. This signal transformation mode was studied on example of a simple closed bipolar electrode system composed of all‐solid‐state chloride‐selective electrode with polypyrrole transducer as the sensing pole and the reporting pole represented by electrode coated by poly(3‐octylthiophene) (POT) layer characterized by fluorescence in the neutral state. In this system selective and linear dependences of fluorimetric signal on logarithm of chloride ions concentration in turn‐on mode were recorded for optimized external voltage applied. Alternatively, a concept of cascade bipolar electrode system with incorporation of additional bipolar electrode being a polarization source for the sensing bipolar electrode with ISE and POT layer was also tested. A significant advantage of the cascade system is its possibility to work spontaneously without external polarization. For this case also linear calibration plots of fluorimetric signal vs. logarithm of analyte concentration were recorded.     

Direct electrochemical redox of tyrosinase at silver electrodes

The direct electron transfer reactions between tyrosinase and silver electrode were investigated by using cyclic voltammetry and potential-step chronoamperometry as well as current-step chronopotentiometry techniques. The kinetics of these reactions is quasi-reversible with two electron transfer reactions and 0.030 s(-1) apparent electrode reaction rate constant. The results demonstrate that neither electrode surface modification nor the inclusion of mediators is necessary to study the electron transfer reactions of tyrosinase at silver electrodes. Moreover, both the anodic and the cathodic currents are linear relationship with the tyrosinase concentration in the range of 1 x 10(-9) approximately 5 x 10(-8)moll(-1). It is possible to be used as a method of analyzing tyrosinase concentration.     

Thermodynamic parameters for the complexation of water‐insoluble betulin derivatives with (2‐hydroxypropyl)‐γ‐cyclodextrin determined by phase‐solubility technique combined with capillary zone electrophoresis

The complexation of betulinic and betulonic acids (BIA and BOA) (pentacyclic lupane triterpenoids) with (2‐hydroxypropyl)‐γ‐cyclodextrin (HP‐γ‐CD) was studied at different temperatures using the method combining phase‐solubility technique and CZE. In contrast to mobility shift ACE utilizing the electrophoretic mobility, in this approach, the peak areas are used. The apparent binding (stability, formation) constants are obtained by the Higuchi and Connors method from the linear segment of compound solubility diagrams in CD solutions. It was found that the apparent binding constants of the HP‐γ‐CD complexes of BIA and BOA decrease with increasing temperature. The binding constants of BOA complexes are slightly higher than those of BIA complexes; this can be explained by difference in the hydration degrees of carbonyl and hydroxyl groups. On the basis of the binding constants obtained and their temperature dependences (van't Hoff plot), the enthalpy as well as entropy changes and Gibbs free energies were calculated. It was found that the complexation was characterized by negative changes of enthalpy and entropy, that is, it was controlled by enthalpy changes. The results obtained can be used for the optimization of microcapsulation processes of BOA and BIA with the HP‐γ‐CD application in order to increase solubility and bioavailability of these compounds.     

线性极化方法测量混凝土中钢筋的腐蚀速度(英文)

本文尝试用线性极化的方法对埋置于混凝土内部的钢筋的腐蚀速度进行测量 .自行设计了一组特殊结构的辅助电极 ,制备了不同尺寸和保护层厚度的混凝土试样 .通过改变辅助电极 ,调整电位的分布 ,使线性极化方法的测量误差降低到腐蚀速度测量允许的误差范围内 .确定了两种适用于混凝土中钢筋腐蚀速度测量的辅助电极 .     

Thermal behaviors of electrolytes in lithium-ion batteries determined by differential scanning calorimeter

Lithium-ion batteries have been widely used in daily electric appliance, but abusive accidents occurred from time to time. Lithium-ion batteries composed of various electrolytes (containing organic solvents, inorganic salts), binder, and electrode materials, which may be unstable under some abnormal conditions. The formulation or components of electrolytes played a crucial factor in affecting reactive hazards within the cell. In order to meet safety requirements of the lithium-ion batteries on electronic device, reseachers and scholars are continuing to do further studies on the important issues in relation to the lithium-ion batteries. This study aims to apply the differential scanning calorimeter for measuring the thermal or reactive hazards of the organic solvents related to the formulation of the electrolytes. Besides, thermal instabilities of lithiated graphite or deposited lithium with electrolytes were simulated by the reactions between metallic lithium (Li) and organic carbonates of linear and cyclic structures. Exothermic onset temperatures and enthalpy changes were measured and analyzed. Results showed that the thermal behaviors of these organic carbonates themselves or with lithium hexafluorophosphate liberated less enthalpy changes. However, violent exothermic reactions were detected between the linear or cyclic carbonates and lithium metal with larger enthalpy change larger than 1,000 J g^?1 of lithium. This can be observed by Li reacted with diethyl carbonate at surprisingly lower onset temperature about 46.6 °C.     

Thermochemistry of complex salts of transition metal perchlorates with tetrazole ligands

The combined use of combustion and solution calorimetry was proposed as a method for determining the standard enthalpy of formation of the complex salts of transition metals, viz., cobalt(II), nickel(II), and zinc, with the organic ligand (5-aminotetrazol-1-yl)acethydrazide. The enthalpies of solution in water and in a 0.1 M solution of hydrochloric acid were measured for the complex salts and ligand. The enthalpy of combustion of the ligand was determined by the combustion calorimetry method, and its standard enthalpy of formation was calculated. The thermochemical cycle was developed for determining the standard enthalpy of formation of the complex salts. The reliable values of the enthalpies of formation of the salts in the standard states were obtained, and the enthalpies of formation of the earlier unknown complex ions were determined.     

Cephalosporin antibiotics as new corrosion inhibitors for nickel in HCl solution

Inhibition of nickel corrosion in 1 M HCl solution in the absence and presence of some Cephalosporin antibiotics derivatives was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) techniques. The results obtained show that the inhibition efficiency of these compounds depends on their concentrations and chemical structures. The inhibitive action of these compounds was discussed in terms of blocking the electrode surface by adsorption of the molecules through the active centers contained in their structures following the Langmuir adsorption isotherm. The polarization measurement showed that these inhibitors are acting as mixed inhibitors for both anodic and cathodic reactions. The effect of temperature on the rate of corrosion in the absence and presence of these compounds was also studied. The efficiencies obtained from the potentiodynamic polarization technique were in good agreement with those obtained from EIS and EFM techniques. This proves the validity of these tools in the measurements of the investigated inhibitors.