Calorimetric investigations of the hydrolytic degradation for a series of β-sultams

The hydrolytic degradation of four β-sultams was investigated using isothermal microcalorimetry to determine kinetic and enthalpic data. Firstly, all four compounds were analysed in the solid-state at 310 K, with a significant substituent-based stabilising/destabilising effect being observed. Secondly, the four compounds were analysed in the presence of pH 4 acetate buffer, at three temperatures (298, 310 and 323 K). Under these conditions, the substituent choice affected the rate of hydrolysis and the associated change in enthalpy for each compound. Based on the calorimetric data presented in this work, no change in reaction mechanism for the hydrolytic degradation was observed over the temperature range considered.     

Measurement and estimation of rate constants for the reactions of hydroxyl radical with several alkanes and cycloalkanes

Relative rate experiments were used to measure ratios of chemical kinetics rate constants as a function of temperature for the reactions of OH with isobutane, isopentane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,3,4-trimethylpentane, n-heptane, n-octane, cyclopentane, cyclohexane, and cycloheptane. The results have been used to calibrate a structure-reactivity rate constant estimation method for k(298 K) which, when combined with previously determined relationships between k(298 K) and the Arrhenius parameters, is capable of determining the temperature dependence accurately. The estimation method reproduces most of the observed rate data within experimental accuracy but appears to fail for 2,3-dimethylbutane, which has an anomalously high rate constant. Curvature in the Arrhenius plots at low temperatures is not present for compounds with a single type of C-H bond and, for compounds with different C-H bonds, is shown to be consistent with effects due to different group sites on the molecule.     

Site-specific rate coefficients for reaction of OH with ethanol from 298 to 900 K

The rate coefficients for reactions of OH with ethanol and partially deuterated ethanols have been measured by laser flash photolysis/laser-induced fluorescence over the temperature range 298-523 K and 5-100 Torr of helium bath gas. The rate coefficient, k(1.1), for reaction of OH with C(2)H(5)OH is given by the expression k(1.1) = 1.06 × 10(-22)T(3.58)?exp(1126/T) cm(3) molecule(-1) s(-1), and the values are in good agreement with previous literature. Site-specific rate coefficients were determined from the measured kinetic isotope effects. Over the temperature region 298-523 K abstraction from the hydroxyl site is a minor channel. The reaction is dominated by abstraction of the α hydrogens (92 ± 8)% at 298 K decreasing to (76 ± 9)% with the balance being abstraction at the β position where the errors are 2σ. At higher temperatures decomposition of the CH(2)CH(2)OH product from β abstraction complicates the kinetics. From 575 to 650 K, biexponential decays were observed, allowing estimates to be made for k(1.1) and the fractional production of CH(2)CH(2)OH. Above 650 K, decomposition of the CH(2)CH(2)OH product was fast on the time scale of the measured kinetics and removal of OH corresponds to reaction at the α and OH sites. The kinetics agree (within ±20%) with previous measurements. Evidence suggests that reaction at the OH site is significant at our higher temperatures: 47-53% at 865 K.     

Not all G-quadruplexes exhibit ion-channel-like properties: NMR study of ammonium ion (non)movement within the d(G(3)T(4)G(4))(2) quadruplex

A solution-state NMR study on 15NH4(+) ion movement within d(G(3)T(4)G(4))(2), a dimeric G-quadruplex consisting of three G-quartets and two T(4) loops, rather unexpectedly demonstrated the absence of 15NH4(+) ion movement between the binding sites U and L along the central axis of the G-quadruplex. Distinct temperature dependences of autocorrelation signals for U and L binding sites have been observed in 15N-1H NzExHSQC spectra which correlate with the local stiffness of the G-quadruplex. The volumes of the cross-peaks, which are the result of 15NH4(+) ion movement, have been interpreted in terms of rate constants, T(1) relaxation, and proton exchange. 15NH4(+) ion movements from the binding sites U and L into the bulk solution are characterized by lifetimes of 139 ms and 1.7 s at 298 K, respectively. The 12 times faster movement from the binding site U demonstrates that 15NH4(+) ion movement is controlled by the structure of T4 loop residues, which through diagonal- vs edge-type orientations impose distinct steric restraints for cations to leave or enter the G-quadruplex. Arrhenius-type analysis has afforded an activation energy of 66 kJ mol(-)1 for the UB process, while it could not be determined for the LB process due to slow rates at temperatures below 298 K. We further the use of the 15NH4(+) ion as an NMR probe to gain insight into the occupancy of binding sites by cations and kinetics of ion movement which are intrinsically correlated with the structural details, dynamic fluctuations, and local flexibility of the DNA structure.     

Role of stress in the self-limiting oxidation of copper nanoparticles

The oxidation process of Cu nanoparticles has been investigated by means of an in-situ X-ray diffraction method. A self-limiting oxidation process involving an unusually drastic decrease (about 4 orders in magnitude) in the oxidation rate was observed at 298 K, whereas a non-self-limiting oxidation emerged at 323 K with a rate of at least 4 orders in magnitude faster than 298 K. The drastic slowing at 298 K and the big differences between the two close temperatures in the oxidation kinetics were found to be directly correlated to whether the compressive stress in the Cu(2)O(111) layers that commensurately formed on the Cu(111) surface is relaxed or not.     

金属离子对齐多夫定与牛血清白蛋白结合作用的影响

用荧光光谱法和紫外分光光度法研究了水溶液(Tris-HCl缓冲溶液, pH 7.1)中齐多夫定(ZDV)与牛血清白蛋白(BSA)的结合作用及三种金属离子(Cu2+, Mg2+, Zn2+)对其的影响. 结果表明: 齐多夫定及金属离子均导致BSA的内源荧光猝灭, 猝灭机制均为静态猝灭; 齐多夫定与BSA间存在较强结合作用, 热力学参数△H和△S分别为-10.2 kJ·mol-1和77.5 J·mol-1·K-1 (298 K), 表明其结合力以静电作用力为主; 298 K下结合常数、结合位点数和结合距离分别为6.92×105 L·mol-1、1.18和2.28 nm; 温度升高结合常数和结合位点数减小. 三种金属离子均导致ZDV与BSA的结合常数减小, 结合距离增大.     

Temperature dependence of oxygen evolution through catalase-like activity of horseradish peroxidase

By experimental investigations of the temperature dependence of catalase-like activity of horseradish peroxidase in the temperature range 278–328 K, different kinetic profiles for oxygen evolution were found below and above 298 K. Extension of the model is proposed to account for these observations. By numeric simulations of the reaction kinetics at different temperatures, it was found that enhanced evaporation of molecular oxygen from the reaction solution is the main root through which oxygen is lost at elevated temperatures in laboratory conditions. The text was submitted by the authors in English.     

Mechanism of the OH-initiated oxidation of hydroxyacetone over the temperature range 236-298 K

The mechanism of the gas-phase reaction of OH radicals with hydroxyacetone (CH3C(O)CH2OH) was studied at 200 Torr over the temperature range 236-298 K in a turbulent flow reactor coupled to a chemical ionization mass-spectrometer. The product yields and kinetics were measured in the presence of O2 to simulate the atmospheric conditions. The major stable product at all temperatures is methylglyoxal. However, its yield decreases from 82% at 298 K to 49% at 236 K. Conversely, the yields of formic and acetic acids increase from about 8% to about 20%. Other observed products were formaldehyde, CO2 and peroxy radicals HO2 and CH3C(O)O2. A partial re-formation of OH radicals (by approximately 10% at 298 K) was found in the OH + hydroxyacetone + O2 chemical system along with a noticeable inverse secondary kinetic isotope effect (k(OH)/k(OD) = 0.78 +/- 0.10 at 298 K). The observed product yields are explained by the increasing role of the complex formed between the primary radical CH3C(O)CHOH and O2 at low temperature. The rate constant of the reaction CH3C(O)CHOH + O2 --> CH3C(O)CHO + HO2 at 298 K, (3.0 +/- 0.6) x 10(-12) cm3 molecule(-1) s(-1), was estimated by computer simulation of the concentration-time profiles of the CH3C(O)CHO product. The detailed mechanism of the OH-initiated oxidation of hydroxyacetone can help to better describe the atmospheric oxidation of isoprene, in particular, in the upper troposphere.     

运用离子选择性电极研究氟离子与蛋白质的相互作用

摘要 在醋酸-醋酸钠缓冲溶液中（pH = 5.68）, 运用氟离子选择性电极研究了288 K～308 K时F–与牛血清蛋白（BSA）、牛血红蛋白（BHb）和卵清蛋白(OVA)的相互作用。F–和三种蛋白质相互作用体系的实验数据通过Klotz方程进行处理,得到了很好的线性关系,根据拟合的直线得到了F–在三种蛋白分子上的束缚位点数以及相应的束缚常数。结果表明,F–在BSA和BHb分子上的束缚位点数随着温度的升高而增大,而在OVA分子上的束缚位点数随着温度的升高而减小。另外,F–与BSA和BHb作用的束缚常数随着温度的升高,先减小后增大;而与OVA的束缚常数则表现出相反的规律,即先增大后减小。根据蛋白质分子二级结构的差别,对上述现象进行了合理的解释。运用热力学方程计算出了不同温度下每个束缚过程的热力学函数（△G,△H,△S）,说明F–和蛋白质分子之间主要依靠静电作用力相结合。     

Equilibrium and Kinetics of NO and CO Chemisorptions on Nonstoichiometric Nickel-Copper Manganites

The equilibrium and kinetics of adsorption of NO and CO on nonstoichiometric nickel-copper manganites have been investigated through volumetric measurements. The adsorption isotherms were satisfactorily fitted to the Freundlich equation. The equilibrium coverages at 298 K were found to depend closely on the chemical composition of the oxide; thus, a decrease in the coverage beyond a maximum copper extent was observed. The adsorption isotherms of NO at various temperatures in the range from 298 to 473 K showed that the equilibrium coverage decreases with increasing temperature. This behavior enabled us to follow the logarithmic decrease of the heat of adsorption of NO on such surfaces. The adsorptions of NO and CO on surfaces preadsorbed with CO and NO, respectively, were also studied. These experiments showed the ability of NO to displace CO preadsorbed molecules whereas the contrary did not hold, suggesting the existence of common adsorption sites as well as some specific CO adsorption sites. Finally, some kinetic data are reported showing that the experimental adsorption results fit the Elovich equation (with t(0) approximately 0), although two distinct rate processes could be identified. Copyright 2000 Academic Press.     

Fluorescence study on the interaction of human serum albumin with bromsulphalein

The binding of bromsulphalein (BSP) with human serum albumin was investigated at different temperatures, 298 and 308 K, by the fluorescence spectroscopy at pH 7.24. The binding constant was determined by Stern-Volmer equation based on the quenching of the fluorescence HSA in the presence of bromsulphalein. The effect of various metal ions on the binding constants of BSP with HSA was investigated. The thermodynamic parameters were calculated according to the dependence of enthalpy change on the temperature as follows: DeltaH and DeltaS possess small negative (9.3 kJ mol(-1)) and positive values (22.3 J K(-l)mol(-l)), respectively. The experimental results revealed that BSP has a strong ability to quench the intrinsic fluorescence of HSA through a static quenching procedure. The binding constants between BSP to HSA were remarkable and independent on temperature. The binding constants between HSA and BSP decreased in the presence of various ions, commonly decreased by 30-55%. The hydrophobic force played a major role in the interaction of BSP with HSA. All these experimental results and theoretical data clarified that BSP could bind to HSA and be effectively transported and eliminated in body, which could be a useful guideline for further drug design.     

A comparison study on the interaction of hyperoside and bovine serum albumin with Tachiya model and Stern–Volmer equation

The interaction between hyperoside and bovine serum albumin (BSA) was examined by fluorescence spectroscopy at 298, 304, and 310 K. The spectroscopic data were analyzed using Tachiya model and Stern–Volmer equation to determine the binding sites and apparent binding constant between hyperoside and BSA. For Tachiya model, both binding sites and apparent binding constants increased with the increasing of temperature, whereas for Stern–Volmer equation, the corresponding binding constants decreased as temperature increasing and the binding sites were independent of temperature. The positive sign of enthalpy change (ΔH) and entropy change (ΔS) suggested that hydrophobic forces played a major role in the interaction. Synchronous fluorescence spectra indicated that the conformation of protein was perturbed by the interaction of hyperoside with BSA. Moreover, the presence of metal ion affected the hyperoside-BSA binding.     

Kinetic (T = 201-298 K) and equilibrium (T = 320-420 K) measurements of the C3H5 + O2 ⇆ C3H5O2 reaction

The kinetics and equilibrium of the allyl radical reaction with molecular oxygen have been studied in direct measurements using temperature-controlled tubular flow reactor coupled to a laser photolysis/photoionization mass spectrometer. In low-temperature experiments (T = 201-298 K), association kinetics were observed, and the measured time-resolved C(3)H(5) radical signals decayed exponentially to the signal background. In this range, the determined rate coefficients exhibited a negative temperature dependence and were observed to depend on the carrier-gas (He) pressure {p = 0.4-36 Torr, [He] = (1.7-118.0) × 10(16) cm(-3)}. The bimolecular rate coefficients obtained vary in the range (0.88-11.6) × 10(-13) cm(3) s(-1). In higher-temperature experiments (T = 320-420 K), the C(3)H(5) radical signal did not decay to the signal background, indicating equilibration of the reaction. By measuring the radical decay rate under these conditions as a function of temperature and following typical second- and third-law procedures, plotting the resulting ln K(p) values versus 1/T in a modified van't Hoff plot, the thermochemical parameters of the reaction were extracted. The second-law treatment resulted in values of ΔH(298)° = -78.3 ± 1.1 kJ mol(-1) and ΔS(298)° = -129.9 ± 3.1 J mol(-1) K(-1), with the uncertainties given as one standard error. When results from a previous investigation were taken into account and the third-law method was applied, the reaction enthalpy was determined as ΔH(298)° = -75.6 ± 2.3 kJ mol(-1).     

Proton-transfer reactions between nitroalkanes and hydroxide ion under non-steady-state conditions. Apparent and real kinetic isotope effects.

The kinetics of the proton-transfer reactions between 1-nitro-1-(4-nitrophenyl)ethane (NNPE(H(D))) and hydroxide ion in water/acetonitrile (50/50 vol %) were studied at temperatures ranging from 289 to 319 K. The equilibrium constants for the reactions are large under these conditions, ensuring that the back reaction is not significant. The extent of reaction/time profiles during the first half-lives are compared with theoretical data for the simple single-step mechanism and a 2-step mechanism involving initial donor/acceptor complex formation followed by unimolecular proton transfer and dissociation of ions. In all cases, the profiles for the reactions of both NNPE(H) and NNPE(D) deviate significantly from those expected for the simple single-step mechanism. Excellent fits of experimental data with theoretical data for the complex mechanism, in the pre-steady-state time period, were observed in all cases. At all base concentrations (0.5 to 5.0 mM) and at all temperatures the apparent kinetic isotope effects (KIE(app)) were observed to increase with increasing extent of reaction. Resolution of the kinetics into microscopic rate constants at 298 K resulted in a real kinetic isotope effect (KIE(real)) for the proton-transfer step equal to 22. Significant proton tunneling was further indicated by the temperature dependence of the rate constants for proton and deuteron transfers: KIE(real) ranging from 17 to 26, E(a)(D) -- E(a)(H) equal 2.8 kcal/mol, and A(D)/A(H) equal to 4.95.     

Oxygen phase equilibria near 298 K

Raman spectra of fluid and solid oxygen have been measured at temperatures near 298 K to pressure greater than 180 kbar (18 GPa). At 298 K, fluid oxygen freezes at 59.1±0.5 kbar which is 2 kbar higher than the freezing pressure of n-H₂ at this temperature. Solid—solid phase transitions are observed near 96 and 99 kbar. The phase boundaries near room temperature and the intense visible absorption spectra of the very high pressure phase are described.     

High-Temperature Structural Disorder in R3NbO7

R₃NbO₇ (R = La, Nd, Gd, Y) niobates have been studied by Raman spectroscopy at 298-973 K. The temperature and composition effects on the structure of these compounds are considered. The changes observed in the Raman spectra at elevated temperatures are caused by a reversible structural disordering due to oxygen redistribution over anion sites.     

The influence of pressure on the structure of aqueous solutions of NaCl over the pressure range 0.1–1000 MPa according to the integral equation method

The influence of pressure (0.1–1000 MPa) on the structure of aqueous solutions of NaCl (1.91–3.08 m) at constant temperatures of 298 and 623 K was studied by the integral equation method. The most substantial structural rearrangement was found to occur at pressures exceeding 150 MPa. Solution structure formation at 298 K was characterized by a substantial decrease in interparticle distances and a baric distortion of the tetrahedral network of water, which resulted in an increase in the hydration of ions and a decrease in the fraction of ion pairs. Structure changes under compression conditions at 623 K were similar to those observed at 298 K, but the network of water H-bonds was already destroyed in solutions at the higher temperature, and hydration-separated ion pairs did not form over the whole pressure range studied. Ions partially dehydrated at 623 K virtually fully restored the hydration spheres they had at 298 K as the pressure increased to 1000 MPa.     

Ligand–Receptor Binding Affinities from Saturation Transfer Difference (STD) NMR Spectroscopy: The Binding Isotherm of STD Initial Growth Rates

The direct evaluation of dissociation constants (K_D) from the variation of saturation transfer difference (STD) NMR spectroscopy values with the receptor–ligand ratio is not feasible due to the complex dependence of STD intensities on the spectral properties of the observed signals. Indirect evaluation, by competition experiments, allows the determination of K_D, as long as a ligand of known affinity is available for the protein under study. Herein, we present a novel protocol based on STD NMR spectroscopy for the direct measurements of receptor–ligand dissociation constants (K_D) from single‐ligand titration experiments. The influence of several experimental factors on STD values has been studied in detail, confirming the marked impact on standard determinations of protein–ligand affinities by STD NMR spectroscopy. These factors, namely, STD saturation time, ligand residence time in the complex, and the intensity of the signal, affect the accumulation of saturation in the free ligand by processes closely related to fast protein–ligand rebinding and longitudinal relaxation of the ligand signals. The proposed method avoids the dependence of the magnitudes of ligand STD signals at a given saturation time on spurious factors by constructing the binding isotherms using the initial growth rates of the STD amplification factors, in a similar way to the use of NOE growing rates to estimate cross relaxation rates for distance evaluations. Herein, it is demonstrated that the effects of these factors are cancelled out by analyzing the protein–ligand association curve using STD values at the limit of zero saturation time, when virtually no ligand rebinding or relaxation takes place. The approach is validated for two well‐studied protein–ligand systems: the binding of the saccharides GlcNAc and GlcNAcβ1,4GlcNAc (chitobiose) to the wheat germ agglutinin (WGA) lectin, and the interaction of the amino acid L ‐tryptophan to bovine serum albumin (BSA). In all cases, the experimental K_D measured under different experimental conditions converged to the thermodynamic values. The proposed protocol allows accurate determinations of protein–ligand dissociation constants, extending the applicability of the STD NMR spectroscopy for affinity measurements, which is of particular relevance for those proteins for which a ligand of known affinity is not available.     

Temperature effects on femtosecond transient absorption kinetics of semiconducting single-walled carbon nanotubes

We report femtosecond transient absorption kinetics measured for selected semiconducting single-walled carbon nanotubes at different temperatures between 77 and 290 K. The nanotubes are embedded in a thin polymethylmethacrylate film, and the dominance of individual species enabled to probe selectively the kinetics associated with two desired tube types, the (6,5) and (7,5) tubes. A strikingly similar temperature dependence is found between the maximum change in the amplitude of transient absorption kinetics, the overall decay time and steady-state fluorescence emission intensity. The simplest explanation for our data is that the temperature dependence of the fluorescence intensity and the exciton decay kinetics are dominated by nonradiative decay and that the radiative decay rate is weakly temperature dependent.