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A new copper(II) complex, [Cu(naph-leu)phen]CH3OH·0.5H2O, in which naph-leu is the tridentate Schiff base ligand derived from the condensation of 2-hydroxy-1-naphthaldehyde and L-leucine, phen is phenanthroline, has been synthesized and characterized by elemental analyses, IR spectra and single crystal X-ray diffraction. The DNA-binding properties of this complex have been investigated by absorption spectra, fluorescence spectra and circular dichroism (CD) spectra, as well as viscosity measurement. Results show that this copper(II) complex binds to calf thymus DNA (CT-DNA) in an intercalative mode and its intrinsic binding constant Kb is 4.87×103 L·mol−1. Furthermore, the DNA cleavage activity of this copper(II) complex has also been investigated by submarine gel electrophoresis. Interestingly, it was found that this complex can cleave the supercoiled plasmid pBR322 DNA to both nicked and linear forms.

The enthalpies of dilution of matrine (MAT) in pure water and aqueous sodium chloride solutions were determined by isothermal titration microcalorimetry at 298.15 K, and the corresponding homogeneous enthalpic interaction coefficients were calculated according to the modified McMillan–Mayer model. The values of enthalpic pair-wise interaction coefficients, h 2, are all positive and become more positive with increasing concentration of sodium chloride.

The low-temperature heat capacities of berberine hydrochloride were measured over the temperature range from 78 to 350 K by an adiabatic calorimeter. The thermodynamic functions H T − H 298.15 and S T − S 298.15 were derived from the heat capacity data. The results showed that the structure of berberine hydrochloride was stable over the temperature range from 78 to 350 K. The thermal stability of the compound was further tested by DSC and TG measurements. The results were in agreement with those obtained from adiabatic calorimetry experiment. The standard molar enthalpy of formation in the crystalline state of berberine hydrochloride was obtained from the standard molar energies of combustion in oxygen at T = 298.15 K, measured by a rotating-bomb combustion calorimeter.

The dilution enthalpies of D-mannitol and D-sorbitol in aqueous sodium chloride solution at various concentrations have been determined by isothermal microcalorimetry at 298.15 K. The homogeneous enthalpic interaction coefficients over a quite large range of concentration of aqueous sodium chloride solutions have been calculated according to the excess enthalpy concept. The results show that enthalpic pairwise interaction coefficients (h 2) of D-mannitol and D-sorbitol are positive in aqueous sodium chloride solution and become more positive with increase of the concentration of sodium chloride. The results are interpreted in terms of the different conformations of the two polyols, solute-solute and solute-solvent interactions involved by solvent effects.

A series of organotin (IV) compounds of the type [R3SnL]2, R is Me (1), Bu (2), [R2SnL]2, R is Ph (3), Me (4), Bu (5), L is pyruvic acid thiophene-2-carboxylic hydrazone, and R2SnL, R is Me (6), Bu (7), Ph (8), L is salicylaldehyde thiophene-2-carboxylic hydrazone have been synthesized in 1:1 molar ratio. All compounds were characterized by elemental analysis, IR, 1H NMR, 13C NMR and 119Sn NMR spectra. The crystal structure of compounds 1, 3, 4, 8 have been determined by X-ray single crystal diffraction analyses, study found that the compounds 1 and 3 are rendered one-dimensional chain structure and the tin atoms are five-coordinated in a distorted trigonal-bipyramidal geometry. The compound 4 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. While the compound 8 is a monomer in which the tin atom adopts five-coordinated in distorted trigonal-bipyramidal geometry.

A series of diorganotin(IV) and triorganotin(IV) compounds of the type [R2Sn(pca)2ClSnR3]2 (R PhCH2 1, 2-ClC6H4CH2 2, 2-FC6H4CH2 3, 4-FC6H4CH2 4, 4-CNC6H4CH2 5, 4-ClC6H4CH2 6, 2,4-Cl2C6H3CH2 7; Hpca 2-methylpyrazine-5-acid), [(nBu)3Sn(pca)]∞ 8, [(CH3)2Cl2Sn(pca)Sn(CH3)2(pca)]∞ 9, {[(nBu)2Sn(pca)]2O}2 10 and {[Ph2Sn(pca)]3O2[Ph2Sn(OCH3)]} 11 have been obtained by reactions of 2-methylpyrazine-5-acid with triorganotin(IV) chloride, diorganotin(IV) dichloride, and diorganotin(IV) oxide. All compounds were characterized by elemental, IR, and NMR spectra analyses. The crystal structure of compounds 1, 8–11 were determined by X-ray single crystal diffraction, which revealed that compound 1 was tetranuclear macrocyclic structures with seven-coordinate and five-coordinate tin atoms, compounds 8 and 9 were polymeric chain structures with five-coordinate and seven-coordinate tin atoms, compounds 10 and 11 were monomeric structures with six-coordinate and five-coordinate tin atoms.

Low-temperature heat capacities of a solid complex Zn(Val)SO4·H2O(s) were measured by a precision automated adiabatic calorimeter over the temperature range between 78 and 373 K. The initial dehydration temperature of the coordination compound was determined to be, TD=327.05 K, by analysis of the heat-capacity curve. The experimental values of molar heat capacities were fitted to a polynomial equation of heat capacities (Cp,m) with the reduced temperatures (x), [x=f (T)], by least square method. The polynomial fitted values of the molar heat capacities and fundamental thermodynamic functions of the complex relative to the standard reference temperature 298.15 K were given with the interval of 5 K. Enthalpies of dissolution of the [ZnSO4·7H2O(s)+Val(s)] (Δsol Hm,l0) and the Zn(Val)SO4·H2O(s) (Δsol Hm,20) in 100.00 mL of 2 mol dm−3 HCl(aq) at T=298.15 K were determined to be, Δsol Hm,l0=(94.588±0.025) kJ mol−1 and Δsol Hm,20=–(46.118±0.055) kJ mol−1, by means of a homemade isoperibol solution–react...

Low-temperature heat capacities of the solid coordination compound Zn(Leu)SO(4)center dot 1/2H(2)O(s) were measured by a precision automated adiabatic calorimeter over the temperature range between T = 78 K and T = 371 K. The initial dehydration temperature of the coordination compound was determined to be T-D = 326.50 K by analysis of the heat-capacity curve. The experimental values of molar heat capacities were fitted to a polynomial equation of heat capacities (C-p,C-m) with the reduced temperatures (x), [x = f (T)] by least-squares method. Enthalpies of dissolution of the [ZnSO(4)center dot 7H(2)O(s) + Leu(s)] ( Delta(sol)H degrees(m,1)) and the Zn(Leu)SO(4)center dot 1/2H(2)O(s) (Delta(sol)H degrees(m,2)) in 100.00 mL of 2 mol center dot dm(-3) HCl(aq) at T = 298.15 K were determined to be Delta solH degrees(m,1) = -(85.80 +/- 0.09) kJ center dot mol(-1) and Delta solH(m,2) = (55.97 +/- 0.06) kJ center dot mol(-1) by means of a homemade isoperibol solution-reaction calorimeter. The standard molar enthalpy of formation of the compound was determined as Delta H degrees(m)(Zn(Leu)SO(4)center dot 1/2H(2)O, s, 298.15 K) = -(1999.0 +/- 0.9) kJ center dot mol(-1) from the enthalpies of dissolution and other auxiliary thermodynamic data through a Hess thermochemical cycle. Furthermore, the reliability of the Hess thermochemical cycle was verified by comparing UV/Vis spectra and the refractive indexes of solution A (from dissolution of the [ZnSO(4)center dot 7H(2)O(s) + Leu(s)] mixture in 2 mol center dot dm(-3) hydrochloric acid) and solution A' (from dissolution of the complex Zn(Leu)SO(4)center dot 1/2H(2)O(S) in 2 mol center dot dm(-3) hydrochloric acid).

The two solid-state coordination reactions (1) CuAc 2 · H 2 O ( s )+2 Ala ( s )→trans- Cu ( Ala ) 2 ( s )+2 HAc ( l )+ H 2 O ( l ) (2) CuAc 2 · H 2 O ( s )+2 Gly ( s )→trans- Cu ( Gly ) 2 · H 2 O ( s )+2 HAc ( l ) have been studied by solution calorimetry. The molar dissolution enthalpies of the reactants and the products in some solvents (such as 2 mol l−1 HCl or its solutions) of these solid–solid coordination reactions have been measured by an isoperibol solution calorimeter. The standard molar formation enthalpies of [trans-Cu(Ala)2(s), 298.15 K] and [trans-Cu(Gly)2(s), 298.15 K] have been determined to be −1015.42 ± 0.06 and 1252.36 ± 0.05 kJ mol−1, respectively, from the results of the molar dissolution enthalpies and other auxiliary thermodynamic data.

The solid-state coordination reactions: 2 HQ ( s )+ Co ( Ac ) 2 ·4 H 2 O ( s )→ Co ( HQ ) 2 ·2 H 2 O ( s )+2 HAc ( l )+2 H 2 O ( l ) 2 HQ ( s )+ Zn ( Ac ) 2 ·2 H 2 O ( s )→ Zn ( HQ ) 2 · H 2 O ( s )+2 HAc ( l )+ H 2 O ( l ) have been studied by solution calorimetry. The molar dissolution enthalpies of the reactants and the products in a certain solvent, 4 mol l −1 HCl, of this solid–solid coordination reaction have been measured using an isoperibol calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies of [Co(HQ) 2 ·2H 2 O(s), 298.15 K], [Zn(HQ) 2 ·H 2 O(s), 298.15 K] and have been determined to be Δ f H m Θ (Co(HQ) 2 ·2H 2 O(s), 298.15 K)=−766.9±3.0 kJ mol −1 , Δ f H m Θ (Zn(HQ) 2 ·H 2 O(s), 298.15 K)=−580.7±3.0 kJ mol −1 .

Solubilities of potassium tetraphenylborate in water, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-octanol at 15, 25, 35, 45, 55°C have been determined by spectrophotometry. The standard Gibbs energy of transfer of potassium tetraphenylborate form water to straightchain n-alkanols and the medium effect of potassium tetraphenylborate from 15 to 55°C have been calculated. Furthermore, the contribution of microscopic interactions to the standard Gibbs energy of transfer of potassium tetraphenylborate is calculated and discussed.