Synthesis, characterization, crystal structures and in vitro antistaphylococcal activity of organotin(IV) derivatives with 5,7-disubstituted-1,2,4-triazolo[1,5-a]pyrimidine.

New organotin(IV) complexes of 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) and 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine (dptp) with 1:1 and/or 1:2 stoichiometry were synthesized and investigated by X-ray diffraction, FT-IR and (119)Sn Mössbauer in the solid state and by (1)H and (13)C NMR spectroscopy, in solution. Moreover, the crystal and molecular structures of Et(2)SnCl(2)(dbtp)(2) and Ph(2)SnCl(2)(EtOH)(2)(dptp)(2) are reported. The complexes contain hexacoordinated tin atoms: in Et(2)SnCl(2)(dbtp)(2) two 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine molecules coordinate classically the tin atom through N(3) atom and the coordination around the tin atom shows a skew trapezoidal structure with axial ethyl groups.

(S)-2-[(2-Hy-droxy-benz-yl)aza-nium-yl]-4-(methyl-sulfan-yl)butano-ate.

The zwitterionic title compound, C(12)H(17)NO(3)S, is a reduced Schiff base derived from (S)-N-(2-hy-droxy-benzyl-idene)methio-nine. An intra-molecular inter-action between the N-H and carboxyl-ate groups forms a roughly planar (r.m.

7-Amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid as the dimethylformamide and water monosolvates at 293 K.

The molecular structure of 7-amino-2-methylsulfanyl-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylic acid is reported in two crystal environments, viz. as the dimethylformamide (DMF) monosolvate, C(7)H(7)N(5)O(2)S·C(3)H(7)NO, (I), and as the monohydrate, C(7)H(7)N(5)O(2)S·H(2)O, (II), both at 293 (2) K. The triazolo[1,5-a]pyrimidine molecule is of interest with respect to the possible biological activity of its coordination compounds.

The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine.

The interaction of native calf thymus DNA with the Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine (ZnL(2+) and CuL(2+)), in 1 mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectrophotometry, circular dichroism (CD) and fluorescence spectroscopy. The results support for an intercalative interaction of both ZnL(2+) and CuL(2+) with DNA, showing CuL(2+) an affinity of approximately 10 times higher than ZnL(2+). In particular, the values of the binding constant, determined by UV spectrophotometric titration, equal to 7.

DFT calculations of the electric field gradient at the tin nucleus as a support of structural interpretation by 119Sn Mössbauer spectroscopy.

DFT calculations, using an all-electron basis set and with full geometry optimization, were performed on 34 Sn(II) and Sn(IV) compounds of known structure and (119)Sn Mössbauer parameters, to obtain the theoretical values of the electric field gradient components, V(xx), V(yy), and V(zz), at the tin nucleus. These were used to determine the quantity V = V(zz)[1+ 1/3((V(xx) - V(yy))/((V(zz))(2)](1/2), for each investigated compound, which is related to the quadrupole splitting (DeltaE) parameter according to DeltaE = 1/2eQV, where e is the electronic charge and Q is the quadrupole moment of the tin nucleus. The linear fitting of the correlation plot of the experimental DeltaE, versus the corresponding calculated V values, produced a slope that is equal to 0.

The interaction of native DNA with iron(III)- N ,N'-ethylene-bis(salicylideneiminato)-chloride.

The interaction between native calf thymus deoxyribonucleic acid (DNA) and Fe(III)- N ,N'-ethylene-bis (salicylideneiminato)-chloride, Fe(Salen)Cl, was investigated in aqueous solutions by UV-visible (UV-vis) absorption, circular dichroism (CD), thermal denaturation and viscosity measurements. The results obtained from CD, UV-vis and viscosity measurements exclude DNA intercalation and can be interpreted in terms of an electrostatic binding between the Fe(Salen)(+) cation and the phosphate groups of DNA. The trend of the UV-vis absorption band of the Fe(Salen)Cl complex at different ratios [DNA(phosphate)]/[Fe(Salen)Cl] and the large increase of the melting temperature of DNA in the presence of Fe(Salen)Cl, support the hypothesis of an external electrostatic interaction between the negatively charged DNA double helix and the axially stacked positively charged Fe(Salen)(+) moieties, analogously to what reported for a number of porphyrazines and metal-porphyrazine complexes interacting with DNA.

The dynamics of 57Fe nuclei in Fe(II)-DNA and [Fe(II)(1-methyl-2-mercaptoimidazole)2]-DNA condensates.

Alcoholic solutions of FeCl(2) and Fe(II)(Hmmi)(2)Cl(2) (Hmmi=1-methyl-2-mercaptoimidazole) induce calf thymus DNA condensation from aqueous solutions buffered at pH 7.4. A 1:1 Fe(II)-(DNA monomer) stoichiometry is assumed.

The dynamics of (57)Fe nuclei in Fe(III)-DNA condensates.

The dynamics of iron nuclei in the condensates obtained by interaction of Fe(III) with DNA, Fe(III)(DNA monomer)(2), have been investigated by variable temperature (57)Fe Mössbauer spectroscopy. Studies were effected on gel and freeze-dried samples, obtaining nearly coincident values of the parameters isomer shift and nuclear quadrupole splitting in T ranges 20-260 K. Functions ln(A(T)/A(77.