Organometallic complexes with biological molecules II. Synthesis, solid-state characterization andin vivo Cytotoxicity of Diorganotin(IV)chloro and Triorganotin(IV)chloro derivatives of Penicillin G

Several new diorganotin(IV)chloro and triorganotin(IV)chloro penicillin G derivatives have been prepared. The isolated compounds showed 1:1 stoichiometry, with formulae R2SnClpenG and R3SnClpenGNa, respectively (penG− = penicillin G− = 4- thia - 1 - azabicyclo[3.2.0]heptane-2-carboxylate, 3,3-dimethyl-7-oxo-6-(2-phenylacet-amido) anion; R = Me, Bu, Ph). The coordination environment around the the tin(IV) atom, in all of the complexes, was trigonal bipyramidal. Penicillin G behaved as a monoanionic, bismonodentate ligand in R2SnClpenG through the β-lactamic carbonyl and unidentate ester-type carboxylate anion, and as unidentate through the β-lactamic carbonyl in R3SnClpenGNa, as inferred on …

Excess free energy, enthalpy and entropy of surfactant-surfactant mixed micelle formation

Enthalpies of dilution and osmotic coefficients of sodium decylsulfate (NaDeS)-dodecyldimethylamine oxide (DDAO) mixtures in water were determined at 298 and 310 K, respectively. From the enthalpies of dilution, the apparent and then the partial molar relative enthalpies of the surfactant mixtures were calculated. From the osmotic coefficients, calculated at 298 K, the non-ideal free energies were derived. The latter were combined with the partial molar relative enthalpies to obtain the non-ideal entropies. From the apparent molar properties, using a previously reported approach, the excess thermodynamic properties for the surfactant-surfactant mixed micelle formation in water were evaluate…

Organometallic Complexes with Biological Molecules: VIII. Synthesis, Solid State andin vivo Investigation of Triorganotin(IV) Derivatives ofL-Homocysteic Acid

Several new triorganotin(IV) derivatives of L-homocysteic acid (L-HCAH) with formula R3Sn(L-HCA) (R=Me, nBu, Ph) have been synthesized. Their solid-state configurations were determined by IR and Mossbauer spectroscopy. The tin(IV) atom is five-coordinated in all the complexes, with the L-homocysteic acid behaving as a monoanionic bidentate ligand coordinating the tin(IV) atom through a chelating or bridging carboxylate group. The sulfonate (SO3−) and NH3+ groups of L-homocysteic acid maintain their free acid configuration and hence do not participate to the coordination of the tin(IV) atom. Coordination hypotheses have been checked through the correlation between the Mossbauer parameter iso…

Thermodynamic Studies of Sodium Dodecyl Sulfate–Sodium Dodecanoate Mixtures in Water

Abstract Conductivity, density, heat capacity, enthalpy of dilution, and osmotic coefficient measurements of water–sodium dodecyl sulfate (NaDS)–sodium dodecanoate systems were carried out as functions of the surfactants total molality ( m t ) at different mole fractions ( X NaDS ). From conductivity data, the critical micelle concentration (cmc) and the degree of ionization of the micelles (β) were calculated. The cmc vs X NaDS profile deviates negatively from that predicted on the basis of the Clint approach, while the β vs X NaDS profile deviates positively from the line correlating the values for pure surfactants. At a given mole fraction, the profiles of all the investigated properties…

Organometallic complexes with biological molecules. I. Diorganotin(IV)chloro protoporphyrin IX complexes: Solid-state and solution-phase characterization

Protoporphyrin IX (H4PPIX) complexes of diorganotin(IV)chloro moieties with formula (R2SnCl)2H2PPIX (RMe, Bu and Ph) have been obtained and their solid-state and solution-phase configurations have been studied through spectroscopic investigations. Coordination of the side-chain carboxylates of H4PPIX to R2Sn(IV)Cl moieties, with bridging carboxylate (COO−) has been inferred by comparison of the free and coordinated H4PPIX IR spectra, while the occurrence of a five-coordinated tin(IV) atom in a cis-R2 trigonal bipyramidal structure has been deduced, for all of the synthesized complexes, by rationalization of the nuclear quadrupole splitting parameters, according to the point-charge model for…

Organometallic complexes with biological molecules. XI. Solid state and in vivo investigations of some diorganotin(IV)-chloramphenicol and cycloserine derivatives

Abstract Diorganotin(IV) derivatives of chloramphenicol, {=D-(-)threo-2,2-dichloro-N-[ β -hydroxy- α -(hydroxymethyl)- β -(4-nitrophenyl)ethyl]acetamide (=Hchloramph)}, and D-cycloserine, {=(R)-4-amino-3-isoxazolidone [=Hcyclos]} have been prepared. The stoichiometries of the obtained compounds were R 2 SnClantib and R 2 Snantib 2 (antib −1 =chloramph −1 , R=methyl and phenyl; antib −1 =cyclos −1 , R=methyl). The solid state configuration of the complexes was investigated by I.R. and Mossbauer spectroscopy, from which structural hypotheses were inferred. In particular, the experimental data suggested monomer structures both for R 2 Sn(IV)Clchloramph and R 2 Sn(IV)chloramph 2 , in which chlo…

Organometallic complexes with biological molecues, part 3.in vivo cytotoxicity of diorganotin (IV) chloro and triorganotin (IV) chloro derivatives of penicillin g on chromosomes ofaphanius fasciatus (pisces, cyprinodontiformes)

In order to obtain a continuous source of mitotic metaphases, gill tissue of Aphaius fasciatus (Pisces, Cyprinodontiformes) has been successfully employed. Results gathered after exposure of fish to R2SnClpenG, R3SnClpenGNa, to the parents R2SnCl2, R3SnCl and to penGNa (penGNa = penicillinGNa; R = methyl, butyl and phenyl) suggest that both the parent organotin (IV) chloride and organotin (IV) chloropenG derivatives are toxic while penGNa exerts no significant toxic activity. Essentially, all of the chromosome abnormalities are classifiable as irregularly staining of chromosomes, breakages, side-arm bridges or pseudochiasmata.

Organometallic complexes with biological molecules. X: dialkyltin(IV) and trialkyltin(IV) orotates: spectroscopic andin vivo investigations

Several novel diorgano- and triorgano-tin(IV) derivatives of orotic acid, (2,6-dihydroxypyrimidine-4-carboxylic acid; H 3 or) have been synthesized. In the diorganotin(IV) derivatives, the orotic acid behaved either as a monoanionic or as a dianionic ligand, yielding R 2 Sn(H 2 or) 2 and R 2 SnHor (R = Me, Bu) species, respectively, while in the triorganotin(IV) orotates only monodeprotonation of the orotic acid occurred, giving R 3 SnH 2 or (R = Me, Bu) derivatives. Structural hypotheses are proposed and discussed for the solid state based on Mossbauer and IR spectroscopic data, and for solution on 1 H and 1 C NMR results. Finally, investigations have been carried out in vivo, showing the …

Energetics of Water−Dodecyl Surfactant−Macrocyclic Compound Ternary Systems

Enthalpies of dilution and osmotic coefficients of sodium dodecyl sulfate (NaDS) and dodecyltrimethylammonium bromide (DTAB) in water + 18-crown-6 ether (CR) and water + β-cyclodextrin (CD) at a fixed cosolvent concentration were measured at 298 and 310 K, respectively, as functions of the surfactant concentration (mS). Enthalpies of transfer ΔH (W → W + S) of CR (0.03 m) from water to NaDS and DTAB aqueous solutions as functions of mS were also determined at 298 K. From the enthalpies of dilution the apparent (LΦ,S) and partial (L2,S) molar relative enthalpies of both surfactants were calculated. Despite CR forms inclusion complexes with the anionic surfactant only, the L2,S vs mS profiles…

Thermodynamic Properties of Sodium n-Alkanecarboxylates in Water and in Water + Cyclodextrins Mixtures

Densities and heat capacities of water−substrate, water−cyclodextrin, and water−substrate−cyclodextrin systems were determined at 298 K. The substrates studied are sodium n-alkanecarboxylates (CnCOONa) (from sodium acetate to sodium decanoate) and the cyclodextrins are hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin, (HP-β-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD). The apparent molar volumes and heat capacities of CnCOONa in water were calculated as functions of concentration. The standard partial molar properties agree with those obtained by using the additivity rule. HP-β-CD essentially does not affect the thermodynamic properties of C1COON…

Organometallic Complexes with Biological Molecules, VI. Diorganotin(IV) and Triorganotin(IV) Ampicillin and Methicillin Derivatives: Spectroscopic Investigations in the Solid State

Derivatives of D(-)-α-aminobenzylpenicillin (ampicillin) and of 2,6-dimethoxyphenylpenicillin (methicillin) with diorgano- and triorgano-tin(IV) moieties have been synthesized. The stoichiometries of the compounds obtained were of the type R 2 SnCIL.H 2 O, R 3 SnCILNa.H 2 O [L=ampicillin or methicillin monoanion; R=Me, Bu, Ph] and R 2 Snampic 2 . 2H 2 O (ampic=ampicillin; R=Me, Bu, Ph). For R 2 SnCIL.H 2 O and R 3 SnCILNa.-H 2 O, infrared (IR) data suggest five-coordination around the tin(IV) atom; in R 2 Snampic 2 .2H 2 O six-coordination is most likely to occur. Thermogravimetric (TG) analysis excludes any involvement in the coordination of tin(IV) by water molecules, in any of the compou…

Organometallic Complexes with Biological Molecules: VII. Dialkyl- and Trialkyl-tin (IV)[meso-tetra(4-carboxyphenyl)porphinate] Derivatives: Solid-state, Solution-phase Structural Aspects andIn Vivo Effects

The synthesis, the structural features and the in vivo biological activity of diorganotin(IV) and triorganotin(IV) derivatives of [meso-tetra(4-carboxyphenyl)porphine] (H 4 TPPC) are reported. Derivatives with general formula (R 2 Sn) 2 TPPC and (R 3 Sn) 4 TPPC (R=Me, Bu, and Ph) were obtained, and the main information extracted from the infrared and Mossbauer spectral data, in the solid state, was in favor of the occurrence of five-coordinated tin(IV) atoms, in a polymeric trigonal-bipyramidal configuration, attained through two differently coordinated, estertype and chelating respectively, carboxylate anions in [R 2 Sn] 2 TPPC, while in [Alk 3 Sn] 4 TPPC five-coordination of the tin(IV) a…

Organometallic complexes with biological molecules. IX. Diorgano- and triorgano-tin(IV)[meso-tetra (4-sulfonatophenyl)porphinate] derivatives: solid-state and solution-phase structural aspects andin vivo effects

Diorgano- and triorgano-tin(IV) derivatives of meso-tetra(4-sulfonatophenyl)porphine (H4TPPS) with general formula (R2Sn)2TPPS and (R3Sn)4TPPS (TPPS4−=[meso-tetra(4-sulfonatophenyl)porphinate]4−, R=Me, Bu, Ph) have been obtained and their solid-state configuration inferred on the basis of IR and Mossbauer spectroscopy, while solution-phase studies have been carried out by 1H and 13C NMR in DMSO-d6, together with determination of the in vivo cytotoxicity of the new derivatives towards embryonic development of Ciona intestinalis. In particular, octahedral and trigonal-bipyramidal eq-R3Sn polymeric configurations are proposed, in the solid state, respectively for (R2Sn)2TPPS and (R3Sn)4TPPS co…

Corrigendum: Organometallic complexes with biological molecules: VII. Diorgano- and triorgano-tin(IV)[meso-tetra(4-carboxyphenyl)porphinate] derivatives: solid-state, solution-phase structural aspects andin vivo effects

Organometallic complexes with biological molecules: V.In vivo cytotoxicity of diorganotin(IV)-amoxicillin derivatives in mitotic chromosomes ofrutilus rubilio (pisces, cyprinidae)

In order to test in vivo cytotoxicity of diorganotin(IV)-amoxicillin (amox) derivatives, mitotic chromosomes of Rutilus rubilio (Pisces, Cyprinidae) have been analyzed using two different chromosome-staining techniques. Results gathered after exposure of fish to the free amox.3H 2 O, R 2 SnClamox.2H 2 O, and R 2 Snamox 2 .2H 2 O (R = methyl, butyl and phenyl ; amox - = 6-[D(-)-β-amino-p-hydroxyphenylacetamido]penicillinate) suggest that methyl derivatives seem to exert a lower cytotoxicity than butyl and phenyl ones and that R 2 Snamox 2 .2H 2 O derivatives are more toxic than R 2 Snclamox.2H 2 O at both 10 -5 and 10 -7 mol dm -3 concentrations. The following structural lesions have been id…

Demixing of Mixed Micelles. Thermodynamics of Sodium Perfluorooctanoate−Sodium Dodecanoate Mixtures in Water

Conductivity, density, heat capacity, enthalpy of dilution, and osmotic coefficient measurements of water−sodium perfluorooctanoate (NaPFO)−sodium dodecanoate systems were carried out as functions of the surfactants' total molality (mt) at different mole fractions (XNaPFO). From conductivity data, the critical micelle concentration (cmc) and the degree of ionization (β) of the micelles were derived. The cmc's of the micelles are higher than those of the pure surfactants while β depends linearly on XNaPFO. At a given mole fraction, the apparent molar volume (VΦ) and heat capacity (CΦ) of the mixture increases and decreases monotonically with mt, respectively. From data in the premicellar reg…

Organometallic complexes with biological molecules, IV. Di- and tri-organotin(IV) amoxicillin derivatives: Solid-state and solution-phase spectroscopic investigations

Novel di- and tri-organotin(IV) derivatives of amoxicillin (amoxicillin - =Amox - =6-[D(-)-β-amino-p-hydroxyphenylacetamido] penicillinate) have been prepared. The isolated compounds showed stoichiometries of the type R 2 SnClAmox.2H 2 O, R 3 SnClAmoxNa.2H 2 O and R 2 SnAmox 2 .2H 2 O (R=Me, Bu, Ph). The infrared spectra suggest that Amox − , in both R 2 SnClAmox.2H 2 O and R 2 SnAmox 2 .2H 2 O, behaves as a monoanionic bidentate ligand, coordinating the tin(IV) atom through the ester-type carboxylate, as well as through the lactamic carbonyl. In R 3 SnClAmoxNa.2H 2 O, Amox - coordinates the organotin(IV) moieties through the lactamic carbonyl. In all of the compounds, water molecules are n…

CCDC 104672: Experimental Crystal Structure Determination

Related Article: E.V.Grigoriev, N.S.Yashina, V.S.Petrosyan, L.Pellerito, A.Pellerito, E.V.Avtomonov, J.Lorberth, A.A.Prischenko, M.V.Livantsov|1999|J.Organomet.Chem.|577|113|doi:10.1016/S0022-328X(98)01033-X