Studies on the reaction between Laccase ando-methoxyphenol by microcalorimetry

The reaction between Laccase ando-methoxyphenol have been studied by LKB-2107 batch microcalorimetry system. Thermodynamic parameters Δ _r H _m , ΔG _o , ΔG _T ^≠ and kinetic parameters (K _m ,k ₂) have been determined. The process of the reaction has been analyzed from changes in energy by using the transition state theory. Two methods for enhancing catalytic power of Laccase are proposed. The results shown that formation of an enzyme-substrate complex is “anticatalytic”. The enter and sole source of catalytic power is the stabilization of transition state; reactant-state interactions are by nature inhibitory and only waste catalytic power. Supported by the National Natural Science Foundation of China Wang Tianzhi: born in 1968. Ph D     

RAgSb2金属间化合物的第一性原理研究

本文从理论计算的角度研究RAgSb_2(R=La-Sm,Gd-Er)合金的部分物理性质,为解释这些化合物的奇特物理性质提供理论依据。采用第一性原理计算方法研究RAgSb_2化合物的结构、机械性能、声子以及热力学性质。根据Birch-Murnagha方程拟合结果,发现LaAgSb_2无磁性,其余合金均表现磁有序,其中除了CeAgSb_2和GdAgSb_2外,其余的RAgSb_2合金的反铁磁态能量低于铁磁态。这些化合物的结合能计算数值均为负值,说明它们具有稳定的结构。而弹性模量的计算结果表明这些化合物具有稳定的机械性能。根据泊松比和B/G值,可以证实GdAgSb_2合金和TbAgSb_2合金具有韧性,而其余的合金表现为脆性。声子谱的计算结果显示这些合金具有稳定的热力学性质,其热容CV随着温度的升高,在低温下急剧增加并与T~3成正比,在较高温度下缓慢增加并趋向于Dulong-Petit极限,高温下的热容接近47.5cal·cell~(-1)·K~(-1)。     

Standard molar enthalpy of formation of morin studied by rotating-bomb combustion calorimetry

Flavonols are plant pigments that are ubiquitous in nature. Morin and other related plant flavonols have come into recent prominence because of their usefulness as anticancer, anti-tumor, anti-AIDS, and other important therapeutic activities of significant potency and low systemic toxicity. The heat of combustion of morin (molecular formula, C₁₅H₁₀O₇·H₂O) in oxygen was measured by a rotating-bomb type combustion calorimeter, the standard molar enthalpy of combustion of morin at T = 298.15 K was determined to be Δ_c H _m^⦵ (C₁₅H₁₀O₇·H₂O, s) = −(5 937.99 ± 2.99) kJ · mol⁻¹. The derived standard molar enthalpy of the formation of morin in solid powder state at T = 298.15 K, Δ_f H _m^⦵ (C₁₅H₁₀O₇·H₂O, s), was −(1 682.12 ± 3.58) kJ · mol⁻¹, which provide an accurate data of the stability of morin to the pharmacy and pharmacology. Biography: HOU Hanna(1956–), female, Visiting researcher, Associate professor of Hubei University of Education, research direction: thermochemistry.     

Directional solidification and physical properties measurements of the zinc-aluminum eutectic alloy

Zn-5wt% Al eutectic alloy was directionally solidified with different growth rates (5.32–250.0 μm/s) at a constant temperature gradient of 8.50 K/mm using a Bridgman-type growth apparatus. The values of eutectic spacing were measured from transverse sections of the samples. The dependences of the eutectic spacing and undercooling on growth rate are determined as λ=9.21V-0.53 and ΔT=0.0245V0.53, respectively. The results obtained in this work were compared with the Jackson-Hunt eutectic theory and the similar experimental results in the literature. Microhardness of directionally solidified samples was also measured by using a microhardness test device. The dependency of the microhardness on growth rate is found as Hv=115.64V0.13. Afterwards, the electrical resistivity (r) of the casting alloy changes from 40×10-9 to 108×10-9 Ω·m with the temperature rising in the range of 300–630 K. The enthalpy of fusion (ΔH) and specific heat (C_p) for the Zn-Al eutectic alloy are calculated to be 113.37 J/g and 0.309 J/(g·K), respectively by means of differential scanning calorimetry (DSC) from heating trace during the transformation from liquid to solid.     

Determination of the solubility parameter of cellulose acrylate using inverse gas chromatography

The solubility parameters of cellulose acrylate substituted degree 2.12(CEA) have been calculated from the measured retention data by inverse gas chromatography at various temperatures. The weight frac-tion activity coefficients of the solvents at infinite dilution(Ω1∞),the Flory-Huggins thermodynamic in-teraction parameters between CEA and solvents(χ 1∞2),the excess molar heats of mixing(△H1s),the par-tial molar heats of mixing at infinite dilution(△H1∞),the solubility parameters of solvent(δ1),and the solubility parameters of CEA(δ2),were calculated at various temperatures. The δ2 of the CEA was 17.32,18.00,18.13,18.54,19.39 at 55,60,65,70 and 75℃,respectively.     

QSPR between Physical-Chemical Properties and Molecule Parameters of Alkanes

A set of molecule parameters, namely, N, N′, p, q, n, were used to express the structures of alkanes. A correlative model was established between certain physical-chemical properties and molecular parameters of alkanes by regression method. Eight physical-chemical properties, such as evaporation heat （△vHm^20）, density（D^20 ）, capacity （C^20）, surface tension （δ^20）, boiling point （Tb）, critical temperature（Tc）, critical pressure（Pc） and critical volume（Vc）, of fifty-six C3-C16 alkanes were calculated directly from the model in this paper. The calculated values are in good accordance with the literature ones reported for alkanes, and the correlation coefficients （R） equal or exceed 0.99 . The research results indicate that the principle of the method is simple and clear, the method is practical, the correlativity is excellent, and the predicted data are credible.     

Itinerant-electron metamagnetic transition and giant magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6 compound

Iron-based rare-earth intermetallic compounds LaFe13?xSix (1.2≤x≤2.6) and CeFe13?xSix (2.4≤x≤2.6) both have the cubic NaZn13-type structure with Fm3c(Oh6) space-group symmetry[1―3]. Fujita et al. [4] demonstrated that the cubic NaZn13-type LaFe13?xSi     

Thermodynamic study on elimination of platinum inclusions in phosphate laser glasses for inertial confinement fusion applications

A new method to calculate the formation enthalpies and free energies of compounds based on standard electromotive force of cation, φ0, and free energies of formation, ΔG2980, or formation enthalpies, ΔH2980, of chloride was proposed. A linear relationship between φ0 and ΔG2980, φ0 and ΔH2980, and ΔG2980 and ΔH2980 was found respectively. The parameters used for thermodynamic calculation were calculated. The calculated values of the formation enthalpies and the free energies of formation of platinum compounds, such as Pt3(PO4)2 and Pt(PO3)2, were given for the first time. The mechanism of eliminating platinum inclusions in phosphate laser glass by POCI3 gas bubbling was interpreted from thermodynamic aspect.     

Studies on reduced extent method for inhibited thermokinetics of enzyme-catalyzed reaction

The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distinguishing inhibition type was given and the methods for calculating kinetic parameters,K _M,K _i andv _m were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation ofo-dihydroxybenzene bym-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type,K _M=6.224×10⁻³ mol·L⁻¹,K _i=2.363×10⁻² mol·L⁻¹. Xiong Ya: born Sep. 1961, Ph. D. graduate student. Curent research interest is in biothermochemistry research Supported by the National Natural Science Foundation of China     

The Total Irredundance Numbers on Graphs

This paper discusses the total irredundance relations between the graph G and its clone-contraction graph H, that is, let H be the clone-contraction graph of G and v1,v2,...,vk be all contraction vertices ofH. IfS is a maximal total irredundant set of H such that A = S ∩ {V1,V2,…,Vk} contains as few vertices as possible, then S＇= S-A is the maximal total irredundant set of G. Furthermore, we obtain the bound of the total irredundance A（G） number： irt ≤△（G）/2△（G）＋1 n, which n is the order of graph G, and △（G） is maximum degree in G.     

Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol

The reaction of a typical unsaturated alcohol, 3-methyl-3-buten-1-ol （MBO331）, with Cl atoms, was investigated for the first time. The reaction was investigated using discharged flow-tube coupled with electron impact mass spectrometer. The experiments were performed over the temperature range of 248 K-298 K and at pressure of 1 torr in He as the bath gas. The obtained kinetic data were used to derive the Arrhenius expression： k1 = （3.47 ± 1.21） × 10^-11 exp[（ 599 ±69）/7] cm^3 molecule^-1 s^-1. Finally, atmospheric lifetimes of the MBO331 with respect to OH radicals, NO3 radicals and CI atoms have been calculated and the atmospheric implications are considered briefly.     

Surface tension and specific heat of liquid Ni<Subscript>70.2</Subscript>Si<Subscript>29.8</Subscript> alloy

The thermophysical properties of liquid alloys in me-tastable state are of importance for liquid-solid phase transformation under nonequilibrium conditions[1―10]. Sur-face tension and specific heat, two of the most important thermophysical properties, have significant influences on the process of crystal nucleation and growth. Furthermore, it is necessary to obtain these data so as to perform quan-titative research on rapid solidification[3―10]. The tradi-tional measurement methods, however,…     

Spectroscopic investigation of the interaction between human serum albumins and 10-hydroxycamptothecin

The binding reaction between 10-hydroxycamptothecin (10-HCPT) and human serum albumins (HSA) is studied by means of fluorescence spectroscopy, UV-Vis absorption spectrum, 1H NMR spectrum, and molecular simulation. The results indicate that the binding reaction of 10-HCPT and HSA is a single static quenching process, and the binding equilibrium constant for 10-HCPT binding with HSA is estimated K ₀= 4.93×10⁴ L · mol⁻¹ at 25 °C with the molar ratio of 1:1. The distance (r) and energy transfer efficiency (E) between donor (HSA) and acceptor (10-HCPT) are obtained as follows, r =3.51 nm; E =0.27. The enthalpy change (ΔH ^⦵) and entropy change (ΔS ^⦵) are calculated at different temperatures, and the hydrophobic force and shidipole force are the functions in the reaction. The results show that 10-HCPT binds within the subdomain II A of HSA by the hydrophobic force, and the 10-OH and 20-OH of 10-HCPT bind with both residue Leu-238 of HSA and Ala 291 of HSA by hydrogen bonds. Biography: LI Guizhi(1962–), female, Associate professor, research direction: organic analysis.     

茜素黄R-γ-环糊精包合物与鲱鱼精DNA的作用机制

  在生理pH=7.4环境下,用摩尔比法测定γ-环糊精(γ-CD)与茜素黄R(AYR)的包合比(摩尔比)n_γ-CD ∶n_AYR =1∶1,确定包合常数K^Θ_f ,_288.15K=1.69×10⁵ L/mol。以吖啶橙(AO)作为分子探针,用紫外光谱法、荧光光谱法、化学热力学法和黏度法等研究包合物γ-CD-AYR与鲱鱼精DNA(hsDNA)的作用,得到γ-CD-AYR包合物与hsDNA作用的结合比n_DNA ∶n_γ-CD-AYR=1∶2,结合常数为K _288.15K=3.10×10⁴ L/mol,K _310.15K =4.02×10⁴ L/mol。热力学函数Δ_rH_m^Θ=8.78×10³ J/mol,Δ_rG_m^Θ=-2.59×10⁴ J/mol, Δ_rS_m^Θ=116.45 J/(mol·K) ,说明γ-CD-AYR包合物与DNA作用为熵驱动。确定γ-CD-AYR与hsDNA的作用方式为静电和部分嵌插的作用方式。     

碱土金属卤化物理化性质QSPR的研究

根据无机物成键原子的结构特征,提出用新的方法：δi^S=（mizi＋ziEi）/2ninj来计算无机分子中原子特征值δi^S,构建新的拓扑指数^mS.用^0S、^1S作为分子结构特征描述符,通过Statistica5.0软件进行多元线性回归,按照标准偏差取最小,相关系数取最大的原则,建立碱土金属卤化物的物理化学性质Pi与分子结构描述符（^0S、^1S）之间的定量相关方程,并对相关关系进行显著性检验.结果表明,新的拓扑指数对分子结构选择区分性高,具有比较高的相关性和精度,并且计算简便,物理意义明确,建立的各种方程得出的各种物理化学性质预测值与实验值之间能很好地吻合,比其他文献方法更具有广泛性.     

Plasma structures inside boundary layers of magnetic clouds

Magnetic cloud is an important interplanetary dis-turbance structure generated by the coronal mass ejections(CMEs), it has been widely investigated[1—5] since it wassuggested by Burlaga et al[1]. However, the boundary ofthe magnetic cloud has no objective definition yet. Manyobservational signatures have been used to identify thecloud boundary[6—13], as Burlaga[14] indicated, there is noconsistency among these various approaches. The problemof the BLs was not been solved because of its co…     

Vegetation effects on mean daily maximum and minimum surface air temperatures over China

Changes in the daily maximum (Tmax) and minimum (Tmin) surface air temperatures and the associated temperature extremes have severe consequences on human society and the natural environment. In this study, we assess vegetation effects on mean Tmax and Tmin over China by computing a vegetation feedback parameter using the satellite-sensed Normalized Difference Vegetation Index (NDVI) and observed temperatures for the period 1982–2002. In all seasons, vegetation exerts a much stronger forcing on Tmax than on Tmin, and thus has a substantial effect on the diurnal temperature range (DTR) over China. Significant positive feedbacks on Tmax and the DTR occupy many areas of China with the feedback parameters exceeding 1°C (0.1 NDVI)–1, while significant negative effects only appear over the summertime climatic and ecological transition zone of northern China and some other isolated areas. Also, the vegetation feedbacks are found to vary with season. In areas where significant feedbacks occur, vegetation contributes to typically 10%–30% of the total variances in Tmax, Tmin, and the DTR. These findings suggest that vegetation memory offers the potential for improving monthly-to-seasonal forecasting of Tmax and Tmin, and the associated temperature extremes over China. Meanwhile, the limitations and uncertainties of the study should be recognized.     

Kinetic study of the hydrocarbon generation from marine carbonate source rocks characterization of products of gas and liquid hydrocarbon

The kinetic parameters of hydrocarbon generation from the marine carbonate source rocks were determined and calibrated through kinetic simulating experiment. The kinetic parameters of hydrocarbon generation then were extrapolated to geological condition by using the relative software. The result shows that gaseous hydrocarbons (C_1, C_2, C_3, C_(4-5)) were generated in condition of 150℃相似文献   

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Hamilton-Jacobi-Bellman equations and dynamic programming for power-optimization of a multistage heat engine system with generalized convective heat transfer law

A multistage endoreversible Carnot heat engine system operating between a finite thermal capacity high-temperature fluid reservoir and an infinite thermal capacity low-temperature environment with generalized convective heat transfer law [q∝(ΔT) m ] is investigated in this paper.Optimal control theory is applied to derive the continuous Hamilton-Jacobi-Bellman (HJB) equations,which determine the optimal fluid temperature configurations for maximum power output under the conditions of fixed initial time and fixed initial temperature of the driving fluid.Based on the universal optimization results,the analytical solution for the Newtonian heat transfer law (m=1) is also obtained.Since there are no analytical solutions for the other heat transfer laws (m≠1),the continuous HJB equations are discretized and dynamic programming algorithm is performed to obtain the complete numerical solutions of the optimization problem.The relationships among the maximum power output of the system,the process period and the fluid temperature are discussed in detail.The results obtained provide some theoretical guidelines for the optimal design and operation of practical energy conversion systems.