The enthalpies of solution in water of L--methionine and its zinc complexes Zn(Met)Cl2, Zn(Met)2Cl2·2H2O, Zn(Met)(NO3)2·1/2H2O, Zn(Met)3(NO3)2·H2O and Zn(Met)SO4·H2O have been measured at 298.15 K. The standard enthalpy of formation of met(aq) has been calculated. The experimental results have been discussed.
Authors:B. Tong, Z. Tan, Q. Shi, Y. Li, and S. Wang
The low-temperature heat capacity Cp,m of sorbitol was precisely measured in the temperature range from 80 to 390 K by means of a small sample automated adiabatic
calorimeter. A solid-liquid phase transition was found at T=369.157 K from the experimental Cp-T curve. The dependence of heat capacity on the temperature was fitted to the following polynomial equations with least square
method. In the temperature range of 80 to 355 K, Cp,m/J K−1 mol−1=170.17+157.75x+128.03x2-146.44x3-335.66x4+177.71x5+306.15x6, x= [(T/K)−217.5]/137.5. In the temperature range of 375 to 390 K, Cp,m/J K−1 mol−1=518.13+3.2819x, x=[(T/K)-382.5]/7.5. The molar enthalpy and entropy of this transition were determined to be 30.35±0.15 kJ mol−1 and 82.22±0.41 J K−1 mol−1 respectively. The thermodynamic functions [HT-H298.15] and [ST-S298.15], were derived from the heat capacity data in the temperature range of 80 to 390 K with an interval of 5 K. DSC and TG measurements
were performed to study the thermostability of the compound. The results were in agreement with those obtained from heat capacity
A complex of neodymium perchloric acid coordinated with L-glutamic acid and imidazole, [Nd(Glu)(H2O)5(Im)3](ClO4)6·2H2O was synthesized and characterized by IR and elements analysis for the first time. The thermodynamic properties of the complex
were studied with an automatic adiabatic calorimeter and differential scanning calorimetry (DSC). Glass transition and phase
transition were discovered at 221.83 and 245.45 K, respectively. The glass transition was interpreted as a freezing-in phenomenon
of the reorientational motion of ClO4− ions and the phase transition was attributed to the orientational order/disorder process of ClO4− ions. The heat capacities of the complex were measured with the automatic adiabatic calorimeter and the thermodynamic functions
[HT-H298.15] and [ST-S298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior
of the complex in nitrogen atmosphere was studied by thermogravimetric (TG) analysis and differential scanning calorimetry
A fully automated adiabatic calorimeter controlled on line by a computer used for heat capacity measurements in the temperature
range from 80 to 400 K was constructed. The hardware of the calorimetric system consisted of a Data Acquisition/Switch Unit,
34970A Agilent, a 7 1/2 Digit Nano Volt /Micro Ohm Meter, 34420A Agilent, and a P4 computer. The software was developed according
to modern controlling theory. The adiabatic calorimeter consisted mainly of a sample cell equipped with a miniature platinum
resistance thermometer and an electric heater, two (inner and outer) adiabatic shields, two sets of six junction differential
thermocouple piles and a high vacuum can. A Lake Shore 340 Temperature Controller and the two sets of differential thermocouples
were used to control the adiabatic conditions between the cell and its surroundings. The reliability of the calorimeter was
verified by measuring the heat capacities of synthetic sapphire (α-Al2O3), Standard Reference Material 720. The deviation of the data obtained by this calorimeter from those published by NIST was
within ±0.1% in the temperature range from 80 to 400 K.
The thermal decomposition behaviour of the complexes of rare earth metals with histidine: RE(His)(NO3)3
H2O (RE=La—Nd, Sm—Lu and Y; His=histidine) was investigated by means of TG-DTG techniques. The results indicated that the thermal decomposition processes of the complexes can be divided into three steps. The first step is the loss of crystal water molecules or part of the histidine molecules from the complexes. The second step is the formation of alkaline salts or mixtures of nitrates with alkaline salts after the histidine has been completely lost from the complexes. The third step is the formation of oxides or mixtures of oxides with alkaline salts. The results relating to the three steps indicate that the stabilities of the complexes increase from La to Lu.
Authors:S. Dong, X. Shi, Q. Liu, Z. Zhang, and L. Zhao
A simple hydrolysis method has been developed for determination of phenylethanoid glycosides in Lamiophlomis rotata (L.R.). Different kinds of phenylethanoid glycosides were hydrolyzed in hydrochloric acid solution to produce corresponding phenethyl alcohols and cinnamic acids, mainly containing hydroxytyrosol, homovanillyl alcohol, 3,4-dimethoxyphenethyl alcohol, caffeic acid, fumalic acid and 3,4-dimethoxycinnamic acid. The six analytes could be determined simultaneously by high-performance liquid chromatography (HPLC). The effects of mobile phase, pH and concentration of running buffer, detection wavelength, flow rate and injection volume were also investigated. Under the optimum conditions, the six hydrolyzates could be perfectly separated within 45 min. The response was linear over four orders of magnitude with detection limits (S/N = 3) ranging from 1 × 10−8 to 1.5 × 10−4 mol L−1 for the analytes. The method has been successfully applied to the analysis of real sample Du-Yi-Wei capsule and Qi-Zheng-Yan-Tong patch, with satisfactory results.
Authors:S. Chen, X. Yang, Sh. Gao, R. Hu, and Q. Shi
The solid complexes of Cr(NO3)3 with L-α-amino acids (AA=Val, Leu, Thr, Arg, Phe and Try) have been prepared in 95% alcoholic, the compositions of which were identified as the general
formula Cr(AA)2(NO3)32H2O by elemental and chemical analyses. The bonding characteristics of the title complexes were characterized by IR, indicating
that nitrogen and oxygen atoms in the ligands coordinated to Cr3+ in a bidentate fashion. With the aid of TG-DTG and IR techniques, the complexes were subjected to thermal decomposition in
an atmosphere of oxygen, presuming that the decompositions of the complexes consist of two steps and the complexes were decomposed
into chromium hemitrioxide after undergoing dehydration and skeleton splitting of the complexes. The constant volume energies
of combustion of the complexes were determined by a RBC-P type rotating-bomb calorimeter. According to Hess's law, the standard
enthalpies of formation of the complexes were calculated as (-1831.404.40), (-2542.036.13), (-1723.813.99), (-2224.313.02),
(-2911.616.53) and (-659.327.42) kJ mol-1, respectively.
A reversed-phase high-performance liquid chromatographic method was developed for the first time to simultaneously determine salicin and eight flavonoids in leaves of Salix matsudana, that is salicin, luteolin-7-O-glucoside, myricetin, apigenin-3′-oxyethyl-7-O-glucoside, rutin, quercetin, luteolin, kaempferol and apigenin. The separation of these compounds was achieved on a reversed phase C18 column (250 × 4.6 mm, 5 μm), with linear gradient of methanol in 0.2% phosphoric acid solution with a flow rate of 1.0 mL/min with UV detection at 246 nm. The calibration curves for the determination of all analytes showed good linearity over the investigated ranges (r > 0.999). The % relative standard deviation (% RSD) values were less than 0.34%, and the recoveries were between 95.79% and 99.94%. The values of luteolin-7-O-glucoside, salicin, myricetin, apigenin-3′-oxyethyl-7-O-glucoside, rutin, quercetin, luteolin, kaempferol, and apigenin were 1.0 μg g−1, 20.0 μg g−1, 32.9 μg g−1, 2.0 μg g−1, 29.5 μg g−1, 6.0 μg g−1, 1.0 μg g−1, 3.5 μg g−1, and apigenin was not found in the sample. This developed method can be used for evaluating the quality of different plant materials.
Authors:S. Gao, S. Chen, G. Xie, G. Fan, and Q. Shi
Summary A ternary solid complex Gd(Et2dtc)3(phen) has been obtained from reactions of sodium diethyldithiocarbamate (NaEt2dtc), 1,10-phenanthroline (phen) and hydrated gadolinium chloride in absolute ethanol. The title complex was described by chemical and elemental analyses, TG-DTG and IR spectrum. The enthalpy change of liquid-phase reaction of formation of the complex, ΔrHΘm(l), was determined as (-11.628±0.0204) kJ mol-1 at 298.15 K by a RD-496 III heat conduction microcalorimeter. The enthalpy change of the solid-phase reaction of formation of the complex, ΔrHΘm(s), was calculated as (145.306±0.519) kJ mol-1 on the basis of a designed thermochemical cycle. The thermodynamics of reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A), the reaction order (n), the activation enthalpy (ΔrHΘ≠), the activation entropy (ΔrSΘ≠), the activation free energy (ΔrGΘ≠) and the enthalpy (ΔrHΘ≠), were obtained by combination of the thermodynamic and kinetic equations for the reaction with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, ΔcU, was determined as (-18673.71±8.15) kJ mol-1 by a RBC-II rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHΘm, and standard enthalpy of formation, ΔfHΘm, were calculated to be (-18692.92±8.15) kJ mol-1 and (-51.28±9.17) kJ mol-1, respectively.
Authors:S. Chen, Sh Gao, X. Yang, R. Hu, and Q. Shi
Solid complexes of M(His)2Cl2nH2O (M=Mn, Co, Ni, Cu) of MnCl26H2O, CoCl26H2O, NiCl26H2O, CuCl22H2O and L-α-histidine (His) have been prepared in 95% ethanol solution and characterized by elemental analyses, chemical analyses,
IR and TG-DTG. The constant-volume combustion energies of the complexes have been determined by a rotating-bomb calorimeter.
And the standard enthalpies of formation of the complexes have been calculated as well.