Organometallic complexes with biological molecules

Novel triorganotin(IV) complexes of two beta-lactamic antibiotics, 6-[D-(-)-beta-amino-p-hydroxyphenyl-acetamido]penicillin (=amoxicillin) and 6-[D-(-)-alpha-aminobenzyl]penicillin (=ampicillin), have been synthesized and investigated both in solid and solution states. The complexes corresponded to the general formula R(3)Sn(IV)antib*H(2)O (R=Me, n-Bu, Ph; antib=amox=amoxicillinate or amp=ampicillinate). Structural investigations about configuration in the solid state have been carried out by interpreting experimental IR and 119Sn Mossbauer data. In particular, IR results suggested polymeric structures both for R(3)Sn(IV)amox.H(2)O and R(3)Sn(IV)amp*H(2)O. Moreover, both antibiotics appear …

Hetero {N} donoratomot és hidroxilcsoportot tartalmazó ligandumok ónorganikus komplexeinek előállítása és szerkezet-vizsgálata

Sintesi e caratterizzazione allo stato solido ed in soluzione di derivati chinolonici di organostagno(IV)

I chinoloni sono antibiotici, recentemente usati anche come chemioterapici. Tra i derivati dell’acido nalidixico, precursore di tutte le classi di chinoloni, sono stati scelti chinoloni di I e II generazione per la sintesi di derivati di diorganostagno(IV). Questi composti sono stati caratterizzati sia allo stato solido che in soluzione con spettroscopia FT-IR, Mössbauer, 1H NMR, e con spettrometria di massa (ES-MS).

Interaction of Dimethyltin(IV)2+ Cation with Gly-Gly, Gly-His, and Some Related Ligands. A New Case of a Metal Ion Able To Promote Peptide Nitrogen Deprotonation in Aqueous Solution

Equilibrium (pH-metric) and spectroscopic (1H,13C, and 119Sn NMR and 119Sn Mossbauer) studies were performed to characterize the interaction of the dimethyltin(IV) cation with glycine, glycyl-glycine (Gly-Gly), imidazole-4-acetic acid, histamine, histidine, glycyl-histamine, glycyl-histidine (Gly-His), and β-alanyl-histidine (carnosine). For histamine and glycyl-histamine (having only nitrogen donor atoms) no complex formation was detected. The hydrolyzed species of the dimethyltin(IV) cation are always dominant over the complexes formed with the other ligands, except with Gly-Gly and Gly-His. For these two ligands, {COO-,N-,NH2} coordinated complexes are dominant in the neutral pH range wi…

Diorganotin(IV) and triorganotin(IV) complexes of meso-tetra(4-sulfonatophenyl) porphine induce apoptosis in A375 human melanoma cells

The cytotoxic effect of several diorganotin(IV) and triorganotin(IV)-meso-tetra(4-sulfonatophenyl)porphine derivatives was tested and only the (Bu(2)Sn)(2)TPPS and the (Bu(3)Sn)(4)TPPS showed cytotoxicity on A375 human melanoma cells. To examine the pathway of (Bu(2)Sn)(2)TPPS or (Bu(3)Sn)(4)TPPS induced A375 cell death, DNA fragmentation analysis, Annexin V binding and PI uptake as well as caspases activation analysis by Western blot were carried out. A375 cells treated exhibited several typical characteristics of apoptosis. Both the (Bu(2)Sn)(2)TPPS and the (Bu(3)Sn)(4)TPPS compounds activate caspase-8 and caspase-9 leading to caspase-3 activation. Thus, we propose that these two porphiri…

Preparation and structural studies on dibutyltin(IV) complexes with pyridine mono- and dicarboxylic acids

Abstract A number of organotin(IV) complexes with pyridine mono- and dicarboxylic acids (containing ligating –COOH group(s) and aromatic {N} atoms) were prepared in the solid state. The bonding sites of the ligands were determined by means of FT-IR spectroscopic measurements. It was found that in most cases the –COO− groups form bridges between two central {Sn} atoms, thereby leading to polymeric (oligomeric) complexes. On this basis, the experimental 119Sn Mossbauer spectroscopic data were treated with partial quadrupole splitting approximations. The calculations predicted the existence of complexes with octahedral (oh) and trigonal-bipyramidal (tbp) structures, but the formation of comple…

Syntesis, characterization and electrochemistry of Ru(III) complexes with several aminoacid ligands

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 …

Effects of Tributyltin(IV) Chloride Exposure on Larvae ofCiona intestinalis (Urochordata): An Ultrastructural Study

The effects of tributyltin(IV) chloride (TBT chloride) have been tested on embryos of the ascidian Ciona intestinalis, at two different stages of development: (1) before hatching (coiled larval stage) and (2) 2 h after hatching (swimming larval stage). In vivo observations carried out with a light microscope showed that embryos at the coiled larval stage did not hatch following exposure to TBT chloride. Severe anomalies in the swimming larva, mainly concerning the morphology of the tail, which appeared twisted and squatter than in the controls, were observed. Such anomalies were also found at a functional level, i.e. contractile movements were poor so that the larvae appeared motionless. Ul…

Coordination properties of adenosine-5'-monophosphate and related ligands towards Me2Sn(IV)2+ in aqueous solution.

Abstract The coordination of Me 2 Sn(IV) 2+ to adenosine-5′-monophosphate (AMP) and the related compounds d -ribose-5-phosphate (R5P), d -glucose-1-phosphate (G1P) and d -glucose-6-phosphate (G6P) in aqueous solution was investigated by means of potentiometric titration, and 1 H-, 31 P-NMR and Mossbauer spectroscopic methods in the pH range 2–11 ( I =0.1 M NaClO 4 , 298 K). The complex of AMP and Me 2 Sn(IV) 2+ precipitated at low pH was characterised by elemental analysis, FT-IR and Mossbauer spectroscopic methods. From a comparison of the p K values obtained in the presence and absence of metal ion and the stability constants for the different systems, the coordination of {N} is excluded,…

Organotin IV-Quinilone Antibiotic Derivatives: Solid State Investigations

Structural characterization of triorganotin(IV) complexes with sodium fusidate and DFT calculations

Abstract Three new complexes of the steroid sodium fusidate (sodium 2-[(1 S ,2 S ,5 R ,6 S ,7 S ,10 S ,11 S ,13 S , 14 Z ,15 R ,17 R )-13-(acetyloxy)-5,17-dihydroxy-2,6,10,11-tetramethyl tetracyclo[8.7.0.0 2,7 .0 11,15 ] heptadecan-14-ylidene]-6-methylhept-5-enoate = (NaFusidate, Na FA )]), with triorganotin(IV) moieties have been prepared and investigated by conventional techniques as FTIR, Mossbauer, ESI-MS and NMR spectroscopy. The isolated compounds showed stoichiometries organotin(IV)/fusidate 1/1, R 3 Sn(IV) FA (R = Me, FA1 ; Bu, FA2 ; Ph, FA3 ). The ligand coordination sites were determined by FTIR spectroscopic measurements. In the complexes, the carboxylate group of the fusidate li…

Equilibria involved in the diorganotin(IV) and triorganotin(IV) phosphomycin interaction in aqueous solution

Four new diorganotin(IV), (R = Me, Bu), and triorganotin(IV), (R = Me, Ph), derivatives of the phosphomycin disodium salt antibiotic[(1R,2S)-1,2-epoxypropylphosphonate]Na2 have been synthesized and their solid state configuration studied by X-ray crystallography, FT-IR, Mossbauer, UV–Vis spectroscopies. The X-ray diffraction investigation, performed on the bis[trimethyltin(IV)]- phosphomycin, showed that the coordination geometry at all the Sn atoms is trigonal bipyramidal. The structure of the complex forms an unusual polymeric zig-zag planar network. The FT-IR and the 119Sn Mo¨ssbauer studies supported the formation of trigonal bipyramidal (Tbp) molecular structures, both in the diorganot…

Piridin-karbonsavak és hidroxi-piridinek Ph3Sn(IV)komplexeinek előállítása és szerkezet-vizsgálata

Preparation and XAFS studies of organotin(IV) complexes with adenosine and related compounds and calf thymus DNA

Complexes of adenosine and related compounds (adenosine-5’-monophosphate, adenosine-5’-triphosphate and pyridoxal-5-phosphate) with Bu2SnO and/or BuSnCl2 were prepared in the solid state. The compositions of the complexes were determined by standard analytical methods. It was found that the complexes contain the organotin(IV) moiety and the ligand in a ratio of 1:1. The FT-IR spectra demonstrated that Bu2SnO reacts with the D-ribose moiety of the ligands, while Bu2SnCl2 is coordinated to the deprotonated phosphate group. The basic part of the ligands does not participate directly in complex formation. Comparison of the experimental Mossbauer Δ (quadrupole splitting) values with those calcul…

Spermatocyte chromosome alterations intruncatella subcylindrica (L., 1767) (Mollusca, Mesogastropoda) following exposure to dibutyltin(IV) and tributyltin(IV) chlorides

In order to analyze chromosomes for possible numerical and structural alterations in response to exposure to organotin(IV) compounds, gastropod Truncatella subcylindrica specimens were treated with dibutyltin(IV) and tributyltin(IV) chloride solutions with different exposure times. Experimental evidence suggests that tributyltin(IV) chloride is more toxic to this organism than dibutyltin(IV) dichloride at low concentrations. Furthermore, the toxicity responses to these organotin(IV) derivatives seem to be proportional to both concentration and exposure time. The following structural lesions have been identified by comparative analysis of spermatocyte chromosomes from untreated specimens and…

Synthesis, structure and electrochemistry of ruthenium(III) complexes whith potential biological activity

Synthesis of polymeric alkoxides from dialkyltin(IV) oxides and chloral, and their characterization by mössbauer and infrared spectroscopy

Abstract The reaction of (Alk2SnO)n with OCH·CCl3 gives compounds of elemental formula Alk2SnOCH- (CCI3)O (Alk = Bun, Octn), probably by addition of the Sn-O bond to the carbonyl group. Mossbauer parameters suggest the occurrence of five-coordinated Sn, and polymeric structures with bridging three- coordinating oxygens are proposed. The assumption that C2SnO3 units with trigonal bipyramidal type structures are present is consistent with point-charge model rationalization of the quadrupole splitting. Infrared spectra are in keeping with the proposed structures, suggesting, inter alia, bent C Sn C skeletons, but the analysis of possible ν(Sn-O) modes does not provide conclusive evidence for t…

Complexes of Tin(IV) with Tridentate Ligands M�SSBAUER, Infrared, and Solution Phase Studies

The configuration in the solid state and in solution phase of complexes of SuIV wit,li tridentate “planar” ligands, Sn(trid)2 and HNEt3Cl3 Sntrid, have been investigated by infrared and MOSSBAUER spectroscopy, as well as by osmometry, conductivity, and electronic and PMR spectroscopy. The presence of monomeric Sn(trid)2 and ionic [HNEt] [Cl3Sn trid−] species has been inferred. Octahedral type configurations are advanced for both classes of compounds. Komplexe des Zinn (IV) mit dreizahigen Liganden. Mossbauer- und IR-Spektren sowie Untersuchungen von Losungen Die Struktur von SnIV-Komplexen mit dreizahnigen “planaren” Liganden, Sn(trid)2 und HNEt3Cl2Sntrid, wurde in fester Phase und in Losun…

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…

Mössbauer Spectroscopy and Organotin Polymers

Mössbauer spectroscopy allows the structural analysis of certain metal atoms situated in complex structures. Briefly, Mössbauer spectroscopy is a resonant absorption spectroscopy that is observed best in isotopes having long lived, low-lying excited nuclear energy states. The largest recoil-free resonant cross-section is found for 57Fe. Currently, Mössbauer spectroscopy is being used on Mars to identify iron compounds that are present in the Martian landscape. There are over 20,000 entries in SciFinder for Mössbauer spectroscopy, of which the two largest entries are for iron and tin containing compounds. There are only about 100 entries for organotin compounds, with only a handful related t…

Potentiometric studies on azido complexes of the aquodimethyltin(IV) cation in aqueous solution

Summary Mono and polynuclear azide complexes of the aquodimethyltin(IV) cation have been studied in solution at [ClO 4 − ]=3.00 M , by e.m.f. measurements of [H + ], using the competitive reaction method. Throughout the entire range of data, 2.5≤−log[N 3 − ] free ≤4.9, the results are interpreted by assuming that the complexes {[(CH 3 ) 2 Sn] 3 [N 3 ] 3 } 3+ and [(CH 3 ) 2 Sn(N 3 ) 4 ] 2− predominate; the cumulative equilibrium constants for their formation are log β 33 =12.98±0.03 and log β 14 =2.45±0.02.

Infrared and M�SSBAUER spectroscopic studies on complexes of Hal2SnIV moieties with tridentate ligands

Novel complexes hal2Sntrid, where hal Cl, Br, and trid2− are dianions of „planar” tridentate ligands with ONO and SNO donor basic atoms, were synthesized and structurally investigated in the solid state mainly by far infrared and MOSSBAUER spectroscopy. Possible configurations were advanced and discussed, and it was concluded that the most probable is a monomeric trigonal bipyramidal structure for all compounds, although polymers, or dimers with O or Cl bridges, were not a priori excluded, in a special way for Br2Sntrid. Infrarot- und MOSSBAUER-spektroskopische Untersuchungen an Komplexen von Hal2SnIV mit dreizahnigen Liganden Neue Komplexverbindungen von Typ hal2Sntrid werden dargestellt (…

Solution structure of R2Sn(IV)-β-N-Acetyl-Neuraminate (R=Me, Bu) complexes in D2O and DMSO-d6: experimental NMR and DFT computational study.

Two diorganotin(IV)-NANA complexes (NANA (1) = beta-N-acetyl-Neuraminic Acid = 5-amino-3,5-dideoxy-D-glycero-beta-D-galactononulosic acid) with formula Me(2)Sn(iv)NANA (2) and Bu(2)Sn(IV)NANA (3) were synthesized and characterized by (1)H, (13)C and (119)Sn NMR spectroscopy, both in D(2)O and DMSO-d(6) solutions. The experimental data in DMSO suggested the monosaccharide bidentate chelation via O1 carboxylate and vicinal O2 alkoxide atoms, which, in D(2)O, can be dynamically extended to a third binding site (O8 atom) of the pendant chain. Coordination at the tin atom is discussed on the basis of experimental NMR data and DFT calculation.

Organometallic complexes with biological molecules: XII. Solid-state and solution studies on dialkyltin(IV)- and trialkyltin(IV)-thiaminepyrophosphate derivatives

Dialkyltin(IV) and trialkyltin(IV) derivatives of the coenzyme thiaminepyrophosphate (H2TPP) have been synthesized with general formula R2Sn(HTPP)2·nH2O (Alk = Me, n = 2; Alk = Bu, n = 4) and R3SnHTPP·nH2O (R=Me, n = 2; R = Bu, n = 1), respectively. The solid-state structure of the complexes has been investigated through infrared and Mossbauer spectroscopy. The infrared data suggest the involvement of only phosphate oxygen atoms in the coordination of both dialkyl- and trialkyl-tin(IV) moieties, with phosphate anions behaving as monoanionic bidentate bridging or chelating groups, with the tin(IV) involved in six- and five-fold coordination geometries, respectively, in R2Sn(HTPP)2·nH2O (R = …

New Ruthenium complexes with antitumoral activity

Complexes of organometallic compounds

Abstract Novel 1/1 adducts have been obtained from the complex N , N ′-ethylenebis(salicylideneiminato)nickel(II) (NiSalen) with di- and mono-organotin(IV) chlorides, and their solid state configuration investigated by Mossbauer , IR and electronic spectroscopy and magnetic measurements. In coordinated NiSalen the square planar structure is maintained around Ni II , and the coordination to tin involves three-coordinate phenolic oxygens. The environment of Sn IV is judged to be octahedral in both types of compounds. A trans -R 2 , cis -Cl 2 configuration is advanced for R 2 SnCl 2 NiSalen.

Effects of two organotin(IV)(sulfonato phenyl)porphynates on the MAPKs and on the growth of A375 human melanoma cells

Previously we showed apoptotic induction in A375 human melanoma cells using two complexes of the meso-tetra(4-sulfonatophenyl)porphinate (TPPS), (Bu 2 Sn) 2 TPPS and (Bu 3 Sn) 4 TPPS. To understand how these compounds activate apoptosis in melanoma cells we studied MAPKs and the (Bu 2 Sn) 2 TPPS and (Bu 3 Sn) 4 TPPS cellular uptake. Western blotting experiments showed activated protein kinases ERK 1/2, JNK and p38 in 10 μM (Bu 2 Sn) 2 TPPS- and 1 μM (Bu 3 Sn) 4 TPPS-treated melanoma cells, which suggests that the three MAP kinases are involved in the apoptotic death of A375-treated cells. By taking advantage of the porphyrin fluorescence, we found a fast concentration of (Bu 2 Sn) 2 TPPS an…

Synthesis, Structural characterization and Exafs investigations of new ruthenium(III) complexes.

Two new complexs of Ru(III) with glucosaminic acid and 1-Methyluracil, [RuCl2(Glun-N,O)2]H (I), (Glun-= glucosaminate); [RuCl4(1-MeU-N3)(DMSO)]H2.H2O (II), (1-MeU-= 1-Methyluracilate) were prepared from the same Ru(III) precursors, RuCl3•3H2O and [(DMSO)2H][trans-RuCl4(DMSO)2]. The characterization of the complexes have been carried out by elemental analysis, FT-IR, ES-MS, NMR and EXAFS.

Preparation and structural studies on the tBu2Sn(IV) complexes with aromatic mono- and dicarboxylic acids containing hetero {N} donor atom

Nine complexes of 'Bu2Sn(IV)(2+) were obtained in the solid state with ligands containing -COOH group(s) and aromatic (N) donor atom. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. It was found that in most cases the -COO- groups are co-ordinated in monodentate manner. Nevertheless, in some of our complexes, the -COO- group forms bridges between two central {Sn} atoms resulting in the formation of an oligomeric structure, a motif that is characteristic only to the nicotinate compound. These pieces of information and the rationalisation of the experimental Sn-119 Mossbauer nuclear quadrupole splittings, Delta, - according to the point charge model forma…

119Sn NMR Ccomputational study of Dimethyltin(IV) - D-ribonic Acid and Dimethyltin(IV) - N-Acetylneuraminic acid complexes

Synthesis and structures of some diorganotin bis(hydroxamate)s

Analysis of literature data on the antitumor activity of organotin compounds reveals that R2SnX2 and their complexes containing SnO, SnN or SnS bonds often exhibit biological activity, especially if such bonds are formed by means of intramolecular coordination. Furthermore, a wide range of biological activities, from fungicidal, bactericidal and antiseptic to psychotropic and antitumor, is found to be characteristic for some organic hydroxamic acids (N-acylhydroxylamines). From this point of view the diorgantion bis-hydroxamates in this paper are of particular interest as potential biologically active antitumor drugs. Di-n-butyltin bis(N-methyl-N-p-bromobenzoylhydroxylamine) is being screen…

Characterization of diorganotin(IV) complexes with captopril. The first crystallographically authenticated metal complex of this anti-hypertensive agent

Abstract Diorganotin(IV) complexes R 2 Sn(cap) (capH 2 = N -[( S )-3-mercapto-2-methylpropionyl]- l -proline; R=Me, Et, n -Bu and t -Bu) were prepared and characterised. The FTIR and Raman spectra demonstrated that the organotin(IV) moieties interact with the {S} atom of the ligand, while the other coordination sites are the carboxylate and the amide –CO groups. Mossbauer Δ data showed that the diorganotin(IV) compounds adopt slightly distorted trigonal-bipyramidal (tbp) geometry. A single-crystal X-ray study was performed on the compound Me 2 Sn(cap): the Sn atom is five-coordinated in a distorted tbp environment, with two {O} atoms in the axial positions and the {S} and two {C} atoms in t…

Vibrational Assignments for Organotin Dihalides and the Organotin Polyester Amines Containing Ciprofloxacin

ChemInform Abstract: Organoelement Derivatives of Steroids: Synthesis and Structural Characterization of Diorganotin Chloride Adducts of Hormones.

Abstract Ten new diorganotin dichloride adducts of hormones of the type R 2 SnCl 2 ·2L [where R = Me, Et, n-Bu, Oct and Ph; L = 4-androsten-17s-ol-3-one ( A ); 5-androsten-3s-ol-17-one ( B ); 4-androsten-17α- methyl-17s-ol-3-one ( C ) and 3,17-dihydroxy-5- pregnene-20-one ( D )] have been prepared and characterized at 297 K and 223 K. Spectroscopic measurements (IR; Raman; 1 H, 13 C, 119 Sn NMR) suggest the dissociation or fast ligand exchange in solution at 297 K. Hexa-coordinated adducts with bonding through carbonyl oxygen and trans -R groups in octahedral geometry are formulated at 223 K.

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…

Complexes of organometallic compounds. XLVII. Synthesis of dimethyltin(IV) adenosinate and its characterization by Mössbauer and infrared spectroscopy

Chelating behaviour of diacetylbisbenzoylhydrazone with SnIV, PbII and PbIV

Organotin(IV) derivatives of fatty acids: Solid state and solution phase investigations

How organotin(IV)(sulfonatophenyl) porphynate may activate the apoptotic pathways in melanoma cells?

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.

Interference of tri-n-butyltin(IV)chloride (TBTCl) on the vascular plant cells

119Sn mössbauer, IR, 1H NMR spectroscopic and thermal decomposition studies on organotin(IV) adducts with glycylglycine

Abstract The complexes R2SnCl2·(H2glygly), (H2glygly = glycylglycine) (R = Me, Bun, Octn, Ph) and RSnCl3·(H2glygly)

Supramolecular Assemblies Based on Complexes of Nonionic Amphiphilic Cyclodextrins and a meso-Tetra(4- sulfonatophenyl)porphine Tributyltin(IV) Derivative: Potential Nanotherapeutics against Melanoma

Amphiphilic cyclodextrin (ACyD) provides water-soluble and adaptable nanovectors by modulating the balance between the hydrophobic and hydrophilic chains at both CyD sides. This work aimed to design nanoassemblies based on nonionic and hydrophilic ACyD (SC6OH) for the delivery of a poor-water-soluble organotin(IV)-porphyrin derivative [(Bu3Sn)4TPPS] to melanoma cancer cells. To characterize the porphyrin derivatives under simulated physiological conditions, a speciation was performed using complementary techniques. In aqueous solution (≤ 20 μM), (Bu3Sn)4TPPS primarily exists as a monomer (2 in Figure 1), as suggested by the low static anisotropy (ρ ≈ 0.02) with a negligible formation of por…

Hidroxi-piridinek és piridinkarbonsavak Ph3Sn(IV)komplexeinek előállítása és szerkezetvizsgálata

Négy potenciális biopolimer karboxi-metil-cellulóz származék Me2Sn(IV)komplexének előállítása és szerkezetvizsgálata.

Bu2Sn(N-acetyl-L-cysteinate) antitumor activity on HepG2 cells

Diorganotin(IV) N-acetyl-L-cysteinate complexes: synthesis, solid state, solution phase, DFT and biological investigations.

Diorganotin(IV) complexes of N-acetyl-L-cysteine (H(2)NAC; (R)-2-acetamido-3-sulfanylpropanoic acid) have been synthesized and their solid and solution-phase structural configurations investigated by FTIR, Mössbauer, (1)H, (13)C and (119)Sn NMR spectroscopy. FTIR results suggested that in R(2)Sn(IV)NAC (R = Me, Bu, Ph) complexes NAC(2-) behaves as dianionic tridentate ligand coordinating the tin(IV) atom, through ester-type carboxylate, acetate carbonyl oxygen atom and the deprotonated thiolate group. From (119)Sn Mössbauer spectroscopy it could be inferred that the tin atom is pentacoordinated, with equatorial R(2)Sn(IV) trigonal bipyramidal configuration. In DMSO-d(6) solution, NMR spectr…

Diorganotin(IV) dipeptide complexes with potential antitumour activity

A series of complexes of the dimethylltin(IV) moiety with dipeptides has been synthesized. The dipeptides are L-alanyl-L-histidine (H2AlaHis), L-methionyl-L-methionine (H2MetMet), L-glycyl-L-histidine (H2GlyHis) and L-histidyl-L-glycine (H2HisGly). The complexes have been characterized by IR and 119Sn Mossbauer spectroscopy in the solid state and by 1H NMR in CD3OD and D2O solutions. They consist of monomeric entities, with the tin atom arranged in a pentacoordinated trigonal bipyramidal structure. The dipeptides are coordinated via the amino group, deprotonated peptide nitrogen and carboxylate group. Neither imidazole in histidine-containing dipetides, nor the thioether group in MetMet, is…

Organotin(IV) chloride complexes with phosphocholine and dimyristoyl-L-?-phosphatidylcholine

Several complexes of R n SnCl 4-n (R = Me, Ph, n = 1-3; R = nBu, n = 2, 3) with phosphocholine and dimyristoyl-L-α-phosphatidylcholine (phospholipid) have been synthesized and characterized by means of Mossbauer spectroscopy and NMR. Triorganotin chlorides form complexes of (R 3 SnCl) 2 .L stoichiometry with a trigonal bipyramidal pentacoordinate tin environment, while the others form 1:1 complexes with an octahedral hexacoordinate tin environment, with the ligands coordinating through anionic phosphodiester moieties in all cases.

Dibutyltin(IV) complexes containing arylazobenzoate ligands: chemistry, in vitro cytotoxic effects on human tumor cell lines and mode of interaction with some enzymes.

Dibutyltin(IV) complexes of composition Bu2Sn (LH)2, where LH is a carboxylate residue derived from 2-[(E)- (5-tert-butyl-2- hydroxyphenyl)diazenyl]benzoate (L1H) with water molecule (1), 4-[(E)-(5-tert-butyl-2-hydroxyphenyl) diazenyl]benzoate (L2H) (2) and 4-[(E)-(4-hydroxy-5- methylphenyl)diazenyl]benzoate (L3H) (3), were synthesized and characterized by spectroscopic (1H, 13C and 119Sn NMR, IR, 119Sn Mössbauer) techniques. A full characterization was accomplished from the crystal structure of complex 1. The molecular structures and geometries of the complexes (1a i.e. 1 without water molecule and 3) were fully optimized using the quantum mechanical method (PM6). Complexes 1 and 3 were fo…

Organometallic complexes with biological molecules. XVIII. Alkyltin(IV) cephalexinate complexes: synthesis, solid state and solution phase investigations

Abstract Dialkyltin(IV) and trialkyltin(IV) complexes of the deacetoxycephalo-sporin-antibiotic cephalexin [7-( d -2-amino-2-phenylacetamido)-3-methyl-3-cephem-4-carboxylic acid] (Hceph) have been synthesized and investigated both in solid and solution phase. Analytical and thermogravimetric data supported the general formula Alk 2 SnOHceph · H 2 O and Alk 3 Snceph · H 2 O (Alk=Me, n -Bu), while structural information has been gained by FT-IR, 119 Sn Mossbauer and 1 H, 13 C, 119 Sn NMR data. In particular, IR results suggested polymeric structures both for Alk 2 SnOHceph · H 2 O and Alk 3 Snceph · H 2 O. Moreover, cephalexin appears to behave as monoanionic tridentate ligand coordinating th…

Solid State Analysis of Metal-Containing Polymers Employing Mossbauer Spectroscopy, Solid State NMR and F EI TOF MALDI MS

Polymers in general and metal-containing polymers in particular are often sparingly soluble or insoluble, in contrast to small molecules. Thus, special significance is attached to characterization techniques that can be applied to the materials as solids. Here, three techniques are discussed that give structural information gained from the solid material. Mossbauer spectroscopy is a powerful technique that may give information on the structure about the metal-containing moiety for about 44 different nuclei. Its use in describing the structure of the product obtained from organotin dichlorides and the unsymmetrical ciprofloxacin is presented along with the reaction implications of the result…

Apoptosis and cell growth arrest in A375 human melanoma cells by diorganotin(IV) and triorganotin(IV) complexes of [meso-Tetra(4-sulfonatophenyl)porphine] manganese(III)chloride

In previous studies we have demonstrated that two derivatives of meso-Tetra(4-sulfonatophenyl)porphine (TPPS), (Bu2Sn)2TPPS and (Bu3Sn)4TPPS, cause apoptotic death of A375 melanoma cells and, at lower concentrations, arrest of cell proliferation. In the present study, we examined if the manganese metal inside the porphyrin cavity could improve the efficacy of this class of compounds. Thus, [meso- Tetra(4-sulfonatophenyl)porphine]Mn(III)Cl (=MnTPPS) derivatives, namely (Me2Sn)2MnTPPS, (Bu2Sn)2MnTPPS, (Me3Sn)4MnTPPS and (Bu3Sn)4MnTPPS, were tested on the A375 human melanoma cell line. A cytotoxicity assay showed that (Bu2Sn)2MnTPPS and (Bu3Sn)4MnTPPS were highly cytotoxic by inducing apoptosi…

Thermodynamic and spectroscopic study of the binding of dimethyltin(IV) by citrate at 25°C

Thermodynamic (potentiometric and calorimetric) and spectroscopic ( 1 H NMR, 119 Sn Mossbauer) studies were performed in aqueous solution in order to characterize the interaction of dimethyltin(IV) cation with citrate ligand. Six species {(CH 3 ) 2 Sn(cit) - ; [(CH 3 ) 2 Sn] 2 (cit) 2 2- ; (CH 3 ) 2 Sn(cit)H 0 ; (CH 3 ) 2 Sn(cit)OH 2- ; [(CH 3 ) 2 Sn] 2 (cit)OH 0 ; [(CH 3 ) 2 Sn] 2 (cit)(OH) 2 - } were found. All the species formed in this system are quite stable and formation percentages are fairly high. For example, at pH = 7.5 and C (CH3)2Sn = C cit = 10 mmol l -1 , E% for [(CH 3 ) 2 Sn] 2 (cit)(OH) 2 - and (CH 3 ) 2 Sn(cit)OH 2- species reaches 65%. Overall thermodynamic parameters obta…

Complexes of organometallic compounds XXVIII. The solution chemistry of bis(acetylacetone)ethylenediimine adducts of organotin(IV) halides

Abstract The nature of methanol solutions of a series of bis(acetylacetone)ethylenediimine adducts of organotin(IV) halides has been studied by electronic and PMR spectroscopy and by osmometry and conductivity. Effectively complete dissociation to the free ligand and solvated organotin(IV) halide moieties is inferred.

ChemInform Abstract: COMPLEXES OF ORGANOMETALLIC COMPOUNDS PART 42, SPECTROSCOPIC STUDIES OF N,N′-ETHYLENEBIS(ACETYLACETONEIMINE) AND N,N′-ETHYLENEBIS(SALICYLIDENEIMINE) ADDUCTS OF ORGANOLEAD(IV) AND ORGANOTHALLIUM(III)

Abstract The nature of the 1 1 adducts formed from the ligands N,N′-ethylenebis(acetylacetonemine) and N,N′-ethylenebis(salicylideneimine) with Ph2PbCl2 and PhTlCl2 was investigated in the solid state and in methanol solution by IR, electronic and PMR spectroscopy, and by osmometry and conductivity. The adducts exist only in the solid state and dissociate fully into the parent compounds in solution. Polymeric structures are proposed for the solids, in which bis-monodentate ligands bridge the organometallic moieties.

Synthesis, structural investigations on organotin(IV) chlorin-e6 complexes, their effect on sea urchin embryonic development and induced apoptosis

Four new organotin(IV) chlorin derivatives, [chlorin=chlorin-e(6)=21H,23H-porphine-2-propanoic acid, 18-carboxy-20-(carboxymethyl)-8-ethenyl-13-ethyl-2,3-di-hydro-3,7,12,17-tetramethyl-(2S-trans)-], with formula (R(2)Sn)(3)(chlorin)(2).2H(2)O (R=Me, n-Bu) and (R(3)Sn)(3)chlorin.2H(2)O (R=Me, Ph) have been synthesized. The solid state and solution phase structures have been investigated by FT-IR, (119)Sn Mössbauer, (1)H and (13)C NMR spectroscopy. In the solid state, (R(2)Sn)(3)(chlorin)(2).2H(2)O complexes contain six coordinated Sn(IV), in a skew trapezoidal environment by forming trans-R(2)SnO(4) polymeric units. As far as (R(3)Sn)(3)chlorin.2H(2)O complexes are concerned, Sn(IV) is five …

Négy karboxi-metil-cellulóz (CMC) származék Me2Sn(IV)komplexeinek FT-IR és Mössbauer-spektroszkópiai vizsgálata

Organoelement derivatives of steroids: Synthesis and structural features of organosilicon, -tin and -lead derivatives of cholesterol and desoxycholic acid

Some organo-Main-Group-IV-element compounds of steroids of the type R3M(COL), R2Sn(COL)2 and (R3M)2(HDCA) (where R = Me or Ph; M = Si, Sn and Pb; HCOL = cholest-5-en-3β-ol; H3DCA = 3α, 12α-dihydroxy-5β-cholan-24-oic acid), have been synthesized. The structures of these compounds have been investigated by vibrational, mass, NMR (1H, 13C, 29Si, 119Sn and 207Pb) and 119Sn Mossbauer spectroscopy. For Me3Sn(COL) both in solution and in the solid state an associated structure with distorted trigonal bipyramidal geometry around tin and three-coordinated oxygen atoms is postulated. Discrete tetrahedral geometries are assigned to Ph3M(COL) complexes and to R2Sn(COL)2 complexes in solution. The latte…

Organotin(IV) and simple fatty acids: preliminary assessments

Our group has a long researching tradition in the field of organotin(IV) complexes, usually proposed and tested as potential anti-tumor drugs. The leitmotif has usually been the modulation of the intrinsic toxicity/cytotoxicity of the organometallic moiety and a modulation of the toxic effect by means of biologically related molecules (synthetic or natural). Such a modulation is usually achieved by two (often overlapping) routes: dampen the damaging effects of the metal core, and serving as a carrier for specific tissue districts. Since a too tight binding on the organotin moiety is not always desirable – a too much stable complex could be a non-active one – carboxylates have always played …

Organic derivatives of mercury and tin as promoters of membrane lipid peroxidation.

The toxicity mechanisms of mercury and tin organic derivatives are still under debate. Generally the presence of organic moieties in their molecules makes these compounds lipophilic and membrane active species. The recent results suggest that Hg and Sn compounds deplete HS-groups in proteins, glutathione and glutathione-dependent enzymatic systems; this process also results in the production of reactive oxygen species (ROS), the enhancement of membrane lipids peroxidation and damage of the antioxidative defence system. The goal of this review is to present recent results in the studies oriented towards the role of organomercury and organotin compounds in the xenobiotic-mediated enhancement …

Organotin(IV)(sulfonatophenyl)porphynate effects on survival and apoptotic signalling pathways in melanoma cells

Syntheses and Solid-State Structures of Some Dialkyltin Derivatives of ?-Methoxy- and ?-Acetoxy-phenylacetic Acids

Several di-n-butyltin and diethyltin biscarboxylates and distannoxanes of α-methoxy- and α-acetoxy-phenylacetic acids were synthesized and (two of) their structures were studied by means of X-ray diffraction analysis as well as by means of IR and Mossbauer spectroscopies. It was shown for {[(n-Bu) 2 - SnOC(O)CH(OMe)Ph] 2 O} 2 that there is an interaction between the OMe group and one of the endocyclic tin atoms, resulting in a distorted pentagonal-bipyramidal geometry with the pentagonal plane defined by five O atoms and an uncommon seven coordination number for this tin atom. Spectral data indicate that biscarboxylates have trans-octahedral structures.

Chromosomes of the Parasitic Isopod Anilocra Physodes

AbstractCounts of mitotic chromosomes have allowed to determine 2n = 12 as the modal diploid number of Anilocra physodes. Application of the C-banding technique reveals that two hetero-chromatic blocks bordering the centromeric region occur in each chromosome. This supports the notion that the actual low chromosome number of A. physodes may have been derived through a process of Robertsonian fusion.

Effects of sublethal levels of tributyltin chloride on a new toxicity test organism,Liza saliens (osteichthyes, mugilidae): a histological study

The histopathological effects of 10−7 and 10−9M tributyltin(IV)chloride,TBTCl, solutions on different Liza saliens organs have been studied by light microscope. The fish were sacrificed after 3–4 h incubation in 10−7M TBTCl solution or after 15 days incubation in 10−9M solution. The observed histopathological changes were dose- and time-dependent. The 10−7M TBTCl concentration resulted in major damage to the gill epithelium, indicating that TBTCl primarily interfered with the respiration, osmoregulation, acid balance and nitrogenous waste excretion processes. After incubation in 10−9M TBTCl solution the fish lived 20 or more days, but many of the organs were altered. Thymus atrophy, reduced…

Structural investigations on diorgano- and triorganotin(IV) derivatives of [meso-tetra(4-sulfonatophenyl)porphine]metal chlorides.

Abstract Several new complexes of organotin(IV) moieties with MCln[meso-tetra(4-sulfonatophenyl)porphine], (R2Sn)2MCln[meso-tetra(4-sulfonatophenyl)-porphinate]s and (R3Sn)4MCln [meso-tetra(4-sulfonatophenyl)porphinate]s, [M = Fe(III), Mn(III): n = 1, R = Me, n-Bu; Ph; M = Sn(IV): n = 2, R = Me, n-Bu] have been synthesized and their solid state configuration investigated by infrared (IR) and Mossbauer spectroscopy, and by 1H and 13C NMR in D2O. The electron density on the metal ion coordinated inside the porphyrin ring is not influenced by the organotin(IV) moieties bonded to the oxygen atoms of the side chain sulfonatophenyl groups, as it has been inferred on the basis of Mossbauer spectro…

Ciprofloxacin Polymers Derived from Diallyltin and Divinyltin Dihalides

The initial synthesis of condensation polymers from newly available divinyltin dichloride and diallyltin dichloride and ciprofloxacin is accomplished employing a modified interfacial polycondensation process. The polymeric (DP are about 2,000) products are rapidly (less than 15 seconds) formed in good yield. Infrared spectroscopy shows the formation of Sn-O and Sn-N bonds as predicted from the proposed structure. F-MALDI MS also shows ion fragments containing organotin in the predicted isotopic abundances as well as ion fragments containing both organotin and ciprofloxacin. The polymers exhibit low toxicity towards healthy WI-38 cells with variable toxicities towards a variety of cancer cel…

Mössbauer studies on tin(IV) and organotin(IV) diacetylbis(benzoylhydrazone) complexes

Abstract The Mossbauer parameters of Ph 2 SnDB, PhClSnDB and Sn(DB) 2 were determined, where DB 2− is the dianion of the multidentate ligand diacetylbis(benzoylhydrazone). According also to data treatment with the point charge model formalism, the configurations of Ph 2 Sn IV and PhSn IV derivatives appear to be essentially octahedral, with linear CSnC and CSnCl skeletons. As to Sn(DB) 2 , it appears that the electrical charge density at the Sn IV nucleus has a cubic symmetry, which is consistent with both tetrahedral and octahedral configurations around Sn IV .

Adducts of organolead(IV) and organothallium(III) chlorides with N,N′-ethylenebis(salicylideneiminato)nickel(II) and bis(β-mercaptoethylamine)nickel(II)

Abstract Novel 1/1 adducts of organolead(IV) and organothallium(III) chlorides with the complexes N,N′-ethylenebis(salicylideneiminato)nickel(II) and bis(β-mercaptoethylamine)nickel(II) have been synthesized. Their configurations have been investigated in the solid state by IR and electronic spectroscopy and by magnetic measurements.

Lipid and fatty acid variations inCiona intestinalis ovary after tri-n-butyltin(IV)chloride exposure

Reduction of total lipids (TL) content and significant variations of triglyceride (TG) and phospholipid (PL) fractions were observed as a consequence of exposure of Ciona intestinalis ovaries to tributyltin chloride (TBTCL) solutions. In particular, an evident TG decrease and a PL increase were observed, which probably provoked an increment in membrane fluidity, because of the high concentration of long chain fatty acids and, as a consequence, PL. This could be a cell adaptive standing mechanism towards the pollutants, as observed in Saccharomyces cerevisiae. Also the increase in the content of the polyunsaturated fatty acids (PUFA), important in the synthesis of compounds such as prostagla…

ChemInform Abstract: Chemically Induced Chromosome Damage in Early-Developing Embryos of Anilocra Physodes L. (Crustacea, Isopoda) Following Exposure to Bis( dimethyltin(IV)chloro)protoporphyrin IX.

In order to obtain chromosome preparations from early-developing embryos of Anilocra physodes, a squash technique has been successfully employed. Results gathered after exposure of this material to bis[dimethyltin(IV)chloro]protoporphyrin IX {[(CH3)2SnCl]2 - Protoporphyrin IX} solutions at different exposure times suggest that this chemical complex is capable of producing abnormal metaphase and anaphase figures in proportion to its concentration and not to exposure length. Essentially, all of the chromosome abnormalities are classifiable as chromosome fragments mainly observed at the metaphase stage; chromosome bridges; and large decondensed chromosome regions.

Synthesis, characterization and in vitro antimicrobial activity of triorganotin(IV)fusidate complexes

Synthesis, structural investigations on organotin(IV) chlorin-e6 complexes, their effect on sea urchin embryonic development and induced apoptotic changes

Preparation and structural characterization of organotin(IV) complexes with ligands containing a hetero {N} atom and a hydroxy group or hydroxy and carboxyl groups

AbstractTwenty-two n-butyltin(IV) and t-butyltin(IV) complexes of ligands containing an –OH (–C@O) group or –OH and –COOHgroups and an aromatic {N} donor atom were prepared by metathetical reactions. On the basis of the FT-IR and Mo¨ssbauer spec-troscopic data, molecular structures were assigned to these compounds. The binding sites of the ligands were identified by means ofFT-IR spectroscopic measurements, and it was found that in most cases the organotin(IV) moiety reacts with the phenolic form ofthese ligands. In the complexes with –OH and –COOH functions, the –COOH group is coordinated to the organotin(IV) centres in amonodentate manner. The 119 Sn Mo¨ssbauer and the FT-IR studies suppor…

Triphenyltin(IV) 2-[(E)-2-(aryl)-1-diazenyl]benzoates as anticancer drugs: Synthesis, structural characterization, in vitro cytotoxicity and study of its influence towards the mechanistic role of some key enzymes

Summary: Triphenyltin(IV) complexes of composition [Ph3SnL 1H]n (1) and [Ph3SnL2H]n (2) (where L1H=2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl] benzoate and L2H = 2-[(E)-2-(4-Hydroxy-5-methylphenyl)-1-diazenyl] benzoate) were synthesized and characterized by spectroscopic (1H, 13C and 119Sn NMR, IR, 119Sn Mössbauer) techniques in combination with elemental analysis. The molecular structures and geometries of the complexes (1 and 2) were fully optimized using the quantum mechanical method (PM3). Complexes (1 and 2) were found to exhibit stronger cytotoxic activity in vitro across a panel of human tumour cell lines viz., A498, EVSA-T, H226, IGROV, M19 MEL, MCF-7 and WIDR. The test compound…

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 …

Effects of tri-n-butyltin(IV) chloride on neurulation of Ciona intestinalis (Tunicata, Ascidiacea): an ultrastructural study

This paper reports the cytotoxic effects of tri-n-butyltin (IV) chloride, TBTCl, on the neurulation process of the ascidian Ciona intestinalis. Exposure of the embryos at early neurula stage in 10−5 and 10−7M TBT (IV) chloride solutions for 1–2 h provoked the irreversible arrest of their development. Morphological and ultrastructural observations suggested that most probably there are two principal causes determining the neurulation process block. The first is due to the TBT effects of inhibiting the polymerization and/or degradation of microfilaments and microtubules, proteins that constitute the cytoskeleton. The lack of orientation and extension of both microtubules and microfilaments of…

Effects of tributyltin(IV) chloride on the gametes and fertilization ofAscidia malaca (Ascidiacea: Tunicata)

Ascidia malaca gametes before fertilization incubated in 10-5 or 10-7 M solutions of tributyltin(IV) chloride, TBTCl, for 3 h appear highly damaged under transmission electron microscopy observation. Also, the fertilization process is affected by the compound: the damaged spermatozoa are present in the vitelline coat and the egg does not cleave. An increase of microbodies, structurally similar to peroxisomes, have been detected in the egg peripheral cytoplasm, probably in relation to their role in alleviating damage to some cellular components. The results have shown that the reproduction of ascidians under unfavourable environmental conditions is prevented. Copyright © 2003 John Wiley &amp…

Synthesis and Characterization of organotin (IV) derivates of nalidixic acid

Organotin(IV)n+ complexes formed with biologically active ligands: equilibrium and structural studies, and some biological aspects

Abstract The organotin(IV) cations form complexes with ligands containing {O}, {N}, {S}, or {phosphorus(O)} donor atoms with various composition and stability. The emergence of new experimental techniques (EXAFS, multinuclear 1 H-, 13 C-, 119 Sn-NMR, 119 Sn Mossbauer, etc., spectroscopic techniques) provided useful information about the structure and stabilities of the complexes formed. We reviewed the literature on these type of complexes taking into account the biological aspects of the complexes discussed.

TPPS derivatives induce apoptosis on A375 human melanoma cells

Effects of sublethal levels of tributyltin chloride on a new toxicity test organism, Liza saliens (Osteichthyes, Mugilidae)

The histopathological effects of 10−7 and 10−9 M tributyltin(IV)chloride,TBTCl, solutions on different Liza saliens organs have been studied by light microscope. The fish were sacrificed after 3–4 h incubation in 10−7 M TBTCl solution or after 15 days incubation in 10−9 M solution. The observed histopathological changes were dose- and time-dependent. The 10−7 M TBTCl concentration resulted in major damage to the gill epithelium, indicating that TBTCl primarily interferedwith the respiration, osmoregulation, acid balance and nitrogenous waste excretion processes. After incubation in 10−9 M TBTCl solution the fish lived 20 or more days, but many of the organs were altered. Thymus atrophy, red…

Organotin(IV) complexes with tetraethyl ethylene- and propylene-diphosphonates

The series of organotin halide complexes with tetraethyl ethylene- and propylene-diphosphonates R n SnX 4-n .L [n=0, X=Cl; n=1, R=Me, X=Cl, Br; n=1, R=Ph, X=Cl; n=2 R=Me, Et, Bu, X=Cl, Br; n=2, R=Ph, X=Cl; L=(EtO) 2 P(O)CH 2 CHR'P(O)(OEt) 2 , R'=H, Me] were synthesized and characterized by means of NMR and Mossbauer spectroscopy. The crystal structure of the complex of diphenyltin dichloride with propylenediphosphonate was determined. The complex consists of polymer chains with bridging bidentate ligands and an octahedral tin environment containing two types of phosphoryl fragments. All of the R 2 SnX 2 adducts have trans-R 2 SnX 4 geometries of tin coordination octahedra according to the q…

Effects of organotin(IV)(metal-sulfonatophenyl)porphinates on the growth of A375 human melanoma cells

Carbocysteine degradation catalyzed by organotin(IV) compounds.

Toxic Effects of Organometallic Compounds towards Marine Biota

Organometallic derivatives are compounds containing a direct σ or π carbon metal linkage. Furthermore, the concept of the metallic atom must be extended to all the elements that are less negative than the carbon atom. As a consequence, taking into account all elements that are less negative than carbon and the number of existing organic compounds, it is possible to synthesize millions of organometallic derivatives. Several of these are extensively used in organic syntheses; others may find application in agriculture and in many other fields as pesticides, fire retardants, wood preservatives, antifouling agents, etc. In general, the organic derivatives of the metals are more toxic than the p…

Tin(IV) complexes with O-ethyl(N-ethyl-N,N-dimethylammoniomethyl)phosphonate

Abstract O,O-Diethyl-(N,N-dimethylaminomethyl)phosphonate undergoes ethyl migration leading to O-ethyl-(N-ethyl-N,N-dimethylammoniomethyl)phosphonate (L). Several new complexes of tin(IV) and organotin(IV) chlorides with the title ligand have been synthesized. The stoichiometry of the obtained complexes is as follows: (R3SnCl)2 · L (R=Me, Bu, Ph), R2SnCl2 · L (R=Me, Bu, Ph), RSnCl3 L (R=Me, Ph) and SnCl4 · L. All the complexes have been studied in solution by means of 1H-, 13C-, 31P- and 119Sn-NMR spectroscopy. Their solid state structures have been investigated by means of Mossbauer spectroscopy and the molecular structure of the complex (Ph3SnCl)2 · L has been determined by X-ray crystall…

Novel metallic and organometallic based antiproliferative complexes: Integrated methodologies of evaluation

Complexes of organometallic compounds. XLIX. A Mössbauer-zeeman spectroscopic study of glycylglycinato-O,N,N(2−) diphenyltin(IV), and the point-charge model rationalization of the quadrupole splittings of some glycylglycinato-O,N,N(2−) diorganotin(IV) complexes

Synthesis and structural investigations on R2Sn(IV)-D-aldonic acid complexes (R = methyl; butyl). Their effect on a new toxicity test organism,Liza saliens(Osteichthyes, Mugilidae): a histological study

Eight R2Sn(IV)-D-aldonate complexes [(R = Me, Bu; D-aldonate = D-galactonate2− (Galn), D-Gluconate2− (Glun), D-Gulonate2− (Guln), D-Ribonate2− (Ribn)], five of which are new derivatives, have been synthesized and structurally characterized both in solid and solution state by IR, 119Sn Mossbauer and 1H, 13C, 119Sn NMR spectroscopies, showing that ligands act as dianonic chelating agents. In solution phase, NMR data suggest that the bidentate chelation is attained by the O1 carboxylate and the vicinal O2 alkoxide atoms, which can be dynamically extended to a third binding site (O4) competing with O2. In Me2Sn(IV)-D-gluconate complex the occurrence of a self-association process leading to a di…

Complexes of organometallic compounds

Abstract Tetraphenylarsonium and tetramethylammonium salts of the complex anions Ph 3 Pb(N 3 ) − 2 , Ph 3 Pb(N 3 )(NCS) − , Ph 2 Pb(N 3 ( 2 − 4 )) and Ph 2 Pb(N 3 )(NCS) − 2 have been prepared and characterized. Infrared spectra and solution conductance data are reported. Possible configurations of the complex anions are discussed.

ATTIVITÀ CITOTOSSICA DEI COMPLESSI DIORGANOSTAGNO(IV)-N-ACETILCISTEINA SU CELLULE DI MELANOMA A-375.

Effects of tributyltin(IV) chloride on fertilization ofStyela plicata(Ascidiacea: Tunicata): II. Scanning and transmission electron microscopy studies

The morphological aspects of Styela plicata fertilization after treatment with tributyltin(IV) chloride are described by means of scanning and transmission electron microscopy investigations. Alterations have been shown both on female and male gametes; spermatozoa, all the egg envelopes and the mitochondria of the egg cortical cytoplasm are modified in relation to incubation time. As a consequence, the damage to gametes blocks sperm–egg interaction and fertilization does not occur. Copyright © 2003 John Wiley & Sons, Ltd.

Structural investigations on diorganotin and triorganotin(IV) phosphomycin derivatives.

Abstract Four new diorganotin(IV), (R = Me, Bu), and triorganotin(IV), (R = Me, Ph), derivatives of the phosphomycin disodium salt antibiotic[(1R,2S)-1,2-epoxypropylphosphonate]Na2 have been synthesized and their solid state configuration studied by X-ray crystallography, FT-IR, Mossbauer, UV–Vis spectroscopies. The X-ray diffraction investigation, performed on the bis[trimethyltin(IV)]phosphomycin, showed that the coordination geometry at all the Sn atoms is trigonal bipyramidal. The structure of the complex forms an unusual polymeric zig-zag planar network. The FT-IR and the 119Sn Mossbauer studies supported the formation of trigonal bipyramidal (Tbp) molecular structures, both in the dio…

Preparation and structural studies on diorganotin(IV) complexes of N-nitroso-N-phenylhydroxylaminates

Abstract Diorganotin(IV)-complexes of the N -nitroso- N -phenylhydroxylaminates (hereinafter cupf), Et 2 Sn(cupf) 2 ( 1 ), Bu 2 Sn(cupf) 2 ( 2 ), {[Bu 2 Sn(cupf)] 2 O} 2 ( 3 ), t -Bu 2 Sn(cupf) 2 ( 4 ) and Oc 2 Sn(cupf) 2 ( 5 , 6 ) were prepared and characterised by FT-IR and Mossbauer spectroscopic measurements. The binding modes of the ligand were identified by FT-IR spectroscopy, and it was found that the ligand is coordinated in chelating or bridging mode to the organotin(IV) center. The 119 Sn Mossbauer and FT-IR studies support the formation of trans -O h ( 1 – 6 ) structures. The X-ray diffraction analysis of 4 revealed that the tin centre is in a skew-trapezoidal geometry defined by…

Equilibrium, Structural and Biological Activity Studies on [Organotin(IV)]n+ Complexes

Organotin(IV) compounds are characterized by the presence of at least one covalent C–Sn bond. The compounds contain tetravalent {Sn} centers and are classified as mono-, di-, tri-, and tetraorganotin(IV), depending on the number of alkyl (R) or aryl (Ar) moieties bound. The anions are usually Cl, F, O2, OH,–COO, or –S. It seems that the nature of the anionic group has only secondary importance in biological activity. The rapid rise in the industrial (catalyst in PVC and foam production), agricultural (fungicides and acaricides), and biological applications (wood, stone, and glass preservatives) of organotin(IV) compounds during the last few decades has led to their accumulation in the envir…

Synthesis, structural investigation and biological activity of metal ions complexes of N-acetylcysteine and carbocysteine

Complexes of organometallic compounds XXXIII. The coordination chemistry of dimethyl and diphenylthallium(III) ith tridentate ligands

Summary Several novel complexes Na[Me 2 TIL] and Na[Ph 2 TIL] (L 2− =dianion tridentate ligands with S, N, and O donor atoms) were synthesized, and investigated by infrared spectroscopy in the solid state, and by electronic and PMR spectroscopy in solution. Suggestions for the configuration of the complex anions are advanced and the nature of species present in solution is discussed.

Organometallic complexes with biological molecules: XVI. Endocrine disruption effects of tributyltin(IV)chloride on metamorphosis of the ascidian larva

The effects of tributyltin(IV)chloride (TBT) on the metamorphosis of ascidian larvae of Ciona intestinalis, 2 h after hatching, were investigated. Ascidians are protochordates that lack thyroid follicles and possess thyroid hormones (THs) and their precursors, 3-monoiodo-tyrosine (MIT) and 3,5-diiodo-tyrosine (DIT), in their endostyle. According to recent findings, these hormones are also present at larval stages, localize in mesenchymal cells and their function seems to be mainly related to larval transformations. Here, we investigate the effects of TBT on thyroxine (T4) content and localization by exposing larvae of C. intestinalis for different times to TBT concentrations known to block …

Complessi di nuova sintesi di derivati della cisteina con ioni metallici

Electrochemotherapy for "in vivo" experimental trial of new promising anti-melanoma therapy

Interference of tributyltin(IV)chloride on the vascular plant cells

In the recent past years, interest in the environmental impact of organotin(IV) compounds has risen markedly. Considering that most data in the scientific literature refers to the animal kingdom and not to higher plants cells, we tested the effects of organotin compounds on vascular plant cells, by studying the interaction of tributyltin chloride (TBTCl) with Allium cepa, Solanun tuberosum and Solanum melongena, vascular plants that are directly involved in the human food chain. The TBTCl effects on mitotic metaphase plates, on pollen grains and on both microtubers and adult tuber parenchymatic cells were investigated and the concentrations of TBTCl inside the treated parenchymatic cells we…

Characterization of complexes formed between [Me2Sn(IV)]2+ and carboxymethylcelluloses.

Complexes formed between carboxymethylcellulose (CMC) and the [Me(2)Sn(IV)]2+ cation have been prepared in the solid state and characterized by FTIR and Mossbauer spectroscopy. The complexes contained CMC with varying molar weight and degree of carboxylation, and the complexes were isolated both from acidic and from neutral solutions at varying metal-to-ligand ratios. The characteristic vibration bands of the ligands were identified from their pH-dependent FTIR spectra. In the organotin(IV) complexes obtained at pH approximately 2, the -COO- moieties were found to be coordinated in a monodentate manner, and the band characteristic of the protonated (unbound) -COO- group(s) was also identifi…

Nanoassemblies of Amphiphilic Cyclodextrin and Tributyltin(IV)Complexes of meso-Tetra (4-sulfonatophenyl)porphine: Spectroscopy, Release and Cytotoxicity on Human Melanoma Cells

Organometallic complexes in ascidian embryonic development: II. Effects on different stages and larvae

The effects of the organometallic compounds Bu2Sn-D-(−;)sorbitol, Bu2Sn-D-(+)glucose, Bu2Sn-D-(−)fructose and Bu2Sn-D-(+)glyceraldehyde were tested in vivo on different stages of Ascidian development, larval movement and metamorphosis. Organotin(IV) complexes are organometallic compounds widely used as industrial biocides, antifouling agents and agricultural fungicides and are toxic to a range of organisms. Two-cell stage embryos, if incubated for one hour in the organotin (IV) solutions, stopped the cleavage, which was restored when they were transferred into normal sea water. The gastrula stage was seriously affected in 10−4mol dm−3 solutions of the above-mentioned complexes: 85% of the e…

Synthesis of Ru(III) complexes with several N and S donor ligands

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…

Coordination properties of the ACE inhibitor captopril towards Me2Sn(IV)2+ in aqueous solution, and biological aspects of some dialkyltin(IV) derivatives of this ligand

Abstract The coordination of Me 2 Sn(IV) 2+ (M) to captopril { N -[( S )-3-mercapto-2-methylpropionyl]- l -proline, H 2 (cap), H 2 L} in aqueous solution was studied by means of potentiometric titration, electrospray mass spectrometry, 1 H-NMR spectroscopy and Mossbauer spectroscopy in the pH range 2–11 ( I =0.1 mol dm −3 NaClO 4 , 298 K). The results obtained with these methods proved that only monomeric complexes are formed in solution. In the acidic pH range, species with a metal-to-ligand ratio of 1:1 exist. The neutral complex ML, similarly to the complex Me 2 Sn(cap) crystallized in the same pH range, adopts a tbp structure with eq S − and ax COO − , while, instead of the coordina…

Embryotoxicity studies of tri-n-butyltin(IV) complexes of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acid and 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl] benzoic acid on sea urchin development

The toxicity studies of free 5-[(E)-2-(aryl)-1-diazenyll-2-hydroxybenzoic acid and 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyllbenzoic acid and their tri-n-butyltin(IV) complexes were evaluated by using sea urchin early developmental stages as recommended model organisms for toxicity tests. The novel complexes, as the parent tri-n-butyltin(IV) chloride (TBTCl), caused mitosis block and induced high embryonic mortality in sea urchin. Copyright (c) 2005 John Wiley & Sons, Ltd.

Synthesis, Structural Analysis, Fiber Formation and Preliminary Anticancer Characterization of the Organotin Polyether from Dibutyltin Dichloride and 2,5-Dimethyl-3-hexyne-2,5-diol

The organotin polyether derived from reaction of dibutyltin dichloride and 2,5-dimethyl-3-hexyne-2,5-diol was rapidly synthesized employing classical interfacial polymerization in 65% yield and a chain length of 360 units. IR results are consistent with the polyether structure. Bands characteristic of the formation of the Sn-O are present and bands characteristic of the Sn-Cl are absent. F MALDI MS results in the low mass range gives ion fragment clusters to five units. Isotopic abundance matches for tin are consistent with its presence in these ion fragment clusters. In the high mass range ion fragment clusters to greater than 300 units are found. The products offer outstanding inhibition …

Mono- and polynuclear hydroxo complexes of monophenylthallium(III)

Summary The hydrolysis of PhTl(OH)ClO4 has been studied in a medium 0.3 M in NaClO4 by a potentiometric technique. The complexes formed by the hydrolysis reactions together with their formation constants have been determined by the general minimizing computer programme LETAGROP. The hydrolysis species observed in the pH range 3–5 are the mononuclear [(PhTlOH)(OH)], the dinuclear [(PhTlOH)2(OH)]+ and the dimer [(PhTlOH)2(OH)2]. The formation constants are log *β11=−4.92±0.2, log *β21=−1.52±0.03 and log *β22=−6.11±0.05. Stepwise reactions are then postulated whose formation constants are respectively log (*β21/*β11)=3.40±0.25, log (*β22/*β21)=−4.59±0.08 and log (*β22/*β112)=3.73±0.09.

Az N-nitrozo-N-fenil-hidroxil-amin (kupferron) ón(IV)organikus komplexeinek előállítása és szerkezetvizsgálata

Synthesis and characterization of diorganotin(IV)complexes with Phenothiazine class Drugs. Biological and Theoretical studies on cytotoxic activity

Organometallic complexes with biological molecules. XIV. Biological activity of dialkyl and trialkyltin(IV) [meso-tetra(4-carboxy- phenyl)porphinate] derivatives

Molecules. XIV. Biological Activity of Dialkyl and Trialkyltin(IV) [Meso-tetra(4-carboxyphenyl)porphinate] Derivatives C. Mansueto, E. Puccia, F. Maggio, R. Di Stefano, T. Fiore, C. Pellerito, F. Triolo and L. Pellerito* Dipartimento di Biologia Animale, Universita di Palermo, Via Archirafi 18, 90123 Palermo, Italy Dipartimento di Chimica Inorganica, Universita di Palermo, Viale delle Scienze, Parco d’Orleans, 90128 Palermo, Italy

Mössbauer spectroscopic studies on compounds containing tin-cadmium and tin-zinc bonds

The Mossbauer parameters of compounds Ph3Sn MCl · TMED (M = Cd, Zn; TMED = N,N,N′,N′-tetramethylethylenediamine), (Ph3Sn)2CdL2 (L2 = TMED, 2,2′-bipyridine and o-phenanthroline) and (Ph3Sn)2 Zn · TMED have been determined and are discussed in connection with Mossbauer data concerning Ph3SnIV derivatives with other Sn-metal bonds. The isomer shift values suggest a high s character in SnCd and SnZn bonds resulting in deviations from regular tetrahedral environments around tin. Experimental quadrupole splittings and calculated partial quadrupole splitting values indicate reduced donor abilities towards the tin atom of an individual Ph3SnIV moiety by Cd-and Zn(Ph3Sn)1−nClnL2 (i.e., the remaini…

Preparation and structural characterization of Ph3Sn(IV)+ complexes with pyridinecarboxylic acids or hydroxypyridene, -pyrimidine and –quinoline.

A number of [Ph3Sn(IV)](+) complexes formed with ligands containing -OH (-C=O), or -COOH group(s) and aromatic IN) donor atom have been prepared. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. In the complexes containing hydroxy and carboxylate functions, the carboxylato group is coordinated to the organotin(IV) centres in monodentate or bridging bidentate manner. It was also found that in the hydroxypyridine and -pyrimidine complexes the [Ph3Sn(IV)]+ moiety in most cases reacts with the phenolic form of the ligands. The rationalisation of the experimental Sn-119 Mossbauer nuclear quadrupole splittings, vertical bar Delta(exp)vertical bar - according t…

Studi strutturali e indagini biologiche di nuovi complessi di rutenio(III) con 1- tioglucosio e 1-metiluracile

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…

Mossbauer spectroscopic studies on the molecular dynamics of organotin(IV) polymers

Abstract Linear organotin(IV) polymers with tin appended to the polymer chain or inserted into the polymer backbone have been characterized by Mossbauer spectroscopy. The lattice dynamics of three representative examples of these classes, as well as of a cross-linked organotin(IV) polymer, have been investigated by temperature-dependent Mossbauer spectroscopy. It has been shown that parameters associated with polymers having low interchain interactions practically correspond to those of molecular, non-coupled, solids.

Organotin(IV) derivatives of the ambidentate ligand 2-thiouracil. Infrared, Mössbauer, 1H and 13C NMR studies

Abstract Complexes Bu 2 n Sn(s 2 UraH −2 and [Me 2 SnOH] 2 (s 2 UraH −2 have been synthesized. Comparison of infrared spectra of the solid complexes with spectra of s 2 Ura and (PhHg) 2 (s 2 UraH −2 complex and point charge calculations (Mossbauer spectra) allow assignment of structures for the complexes of this ambivalent ligand. Polymeric structures are proposed for the complexes in the solid state, where the organometallic moieties are bonded to exocyclic S and N(3) atoms of the dianionic base, with formation of a four-membered chelate ring for Bu 2 n Sn(s 2 UraH −2 ). For [Me 2 SnOH] 2 (s 2 UraH −2 , 1 H and 13 C NMR data suggest retention of penta-coordination in trifluoacetic acid sol…

Diorganotin(IV) complexes with aldonic acids. Synthesis and structural study in solid state and in solution phase and biological activity

Computational studies of new metallic ions complexes of antioxidant dipeptides

Effects of tributyltin(IV) chloride exposure on early embryonic stages ofCiona intestinalis:In vivo and ultrastructural investigations

The effects of tributyltin(IV) chloride (TBT chloride) solutions on ascidian embryos of Ciona intestinalis have been tested at different stages of development. It has been observed, in vivo, that TBT chooride inhibited cleavage of fertilized eggs and of embryo blastomeres giving rise to cellular masses that are not delimited by plasma membrane. Electron-dense precipitates of TBT chloride, probably as inorganic tin, have been observed by transmission electron microscopy in the egg cytoplasm of cellular masses. The same type of precipitate was present also inside the mitochondria, whose structure appeared to be highly modified. These ultrastructure aspects are indicative of a degenerative pro…

Complexes of tryptophan dipeptides with the R2Sn(IV)2+ ion (R=Me, Ph): Spectroscopic studies, solution properties and structural implications

Tryptophan dipeptides such as L-tryptophyl-L-alanine (H 2 TrpAla), L-tryptophyl-L-tyrosine (H 2 TrpTyr), L-tryptophyl-L-tryptophan (H 2 TrpTrp), along with L-histidyl-L-tyrosine (H 2 HisTyr), were reacted with R 2 SnO (R=Me, Ph) yielding the corresponding complexes. The complexes have been characterized by IR and 119 Sn Mossbauer spectroscopy in the solid state and by 1 H and 13 C NMR in CD 3 OD solutions. Monomeric species were detected, with the tin atom arranged in a pentacoordinated trigonal-bipyramidal structure. The dipeptides are coordinated via the terminal amino group, deprotonated peptide nitrogen and terminal carboxylate group. No side-chain appears to be involved in bonding. Det…

Diorganotin(IV) complexes ofD-galacturonic acid: solid-state and solution-phase structural study

Three diorganotin(IV) complexes of D-galacturonic acid (H2GalA; R = Me, n-Bu, Ph), two of which are new derivatives (R = Me, Ph), have been synthesized and their solid-state and solution-phase investigated by IR, Mossbauer, 1H, 13C and 119Sn NMR spectroscopy. The FTIR data suggest that H2GalA, in the dialkyltin derivatives, behaves as a dianionic ligand, coordinating the tin(IV) atom through an ester-type carboxylate and deprotonated alcoholic hydroxo groups, whereas a bridging carboxylate occurs in the diphenyltin(IV) complex. Octahedral and trigonal bipyramidal local geometries on tin(IV) atoms are proposed for dialkyltin(IV)GalA and diphenyltin(IV)GalA complexes respectively on the basis…

Computational study of dimethyl- and trimethyl-tin(IV) complexes of porphyrin derivatives

The molecular geometry, energetics and electronic charge distribution of diorgano- and triorgano-tin(IV) complexes of [protoporphyrin-IX] and [meso-tetra(4-carboxyphenyl)porphine] derivatives were determined at semi-empirical and ab initio levels. To study the molecular details of the complexes, simpler molecule models were calculated by the ab initio pseudo-potential method. The molecular properties of these complexes are essentially independent of the presence of the peripheral tin atoms. Agreement was always found among the results of the different computational approaches, as well as between the theoretical and the experimental findings on the molecular geometry of the hypothesized comp…

Complexes of organometallic compounds

Abstract Novel complexes RClSntrid, where R is Me, Ph, n-Oct, and trid 2− are dianions of tridentate “planar” ligands with ONO and SNO donor atoms, were synthesized and investigated in the solid state by infrared and Mossbauer spectroscopy. Possible configurations are discussed; polymeric trigonal bipyramidal structures seem to occur, although five-coordinated monomers as well as octahedral dimers (via oxygen or sulfur bridges) are not excluded.

Biological activity studies on organotin(IV)n+ complexes and parent compounds

This review summarized the literature and own data on the parent organotin(IV) compounds and complexes formed with biologically active ligands.

Molecular basis of the interaction of novel tributyltin(IV) 2/4-[(E)-2-(aryl)-1-diazenyl] benzoates endowed with an improved cytotoxic profile: Synthesis, structure, biological efficacy and QSAR studies

A series of tributyltin(IV) complexes based on 2/4-[(E)-2-(aryl)-1-diazenyl]benzoate ligands was synthesized, wherein the position of the carboxylate and aryl substituents (methyl, tert-butyl and hydroxyl) varies. The complexes, Bu(3)SnL(1-4)H (1-4), have been structurally characterized by elemental analysis and IR, NMR ((1)H, (13)C, and (119)Sn) and (119)Sn Mossbauer spectroscopy. All have a tetrahedral geometry in solution and a trigonal bipyramidal geometry in the solid-state, except for Bu(3)SnL(4)H (4) that was ascertained to have tetrahedral coordination by X-ray crystallography. Cytotoxicity studies were carried out on human tumor cell lines A498 (renal cancer), EVSA-T (mammary cance…

Porphyrin tributyltin(IV) complexes for a novel approach in the tratment of human melanoma

Melanoma is the most deadly form of skin cancer, largely refractory to existing therapies. The study of porphyrin derivatives as potential anti-tumor drugs has been an interesting field of investigation in the last years. Recently, a photo-independent cytotoxic effect of (Bu3Sn)4TPPS in the blocking melanoma cell proliferation an inducing a morphology cell change was investigated.[1] Amphiphilic CD (ACyD) provides more water soluble and adaptable nanovectors through modulation of the balance between hydrophobic and hydrophilic chains at both CD sides. ACyD can be conveniently tailored by covalently appending fluorescent label or receptor-targeting glycosyl- groups and can encapsulate conven…

Synthesis and characterization of some new ruthenium complexes with ligands of biological interest

Organometallic complexes with biological molecules: XIII. Organotin(IV)[meso-tetra (4-carboxyphenyl)porphinate]s and the cell cycle: a flow-cytometric approach

The cytotoxic derivatives diorganotin(IV) and triorganotin(IV) [meso-tetra(4-carboxyphenyl)porphinates, with stoichiometries [R2Sn]2TPPC and [R3Sn]4TPPC [R = Me, Bu, Ph; TPPC4−­= meso-tetra(4-carboxyphenyl)porphinate4−], namely bis[dimethyltin(IV)], bis[dibutyltin(IV)], bis[diphenyltin(IV)], tetra[trimethyltin(IV)], tetra[tributyltin(IV)] and tetra[triphenyltin(IV)] [meso-tetra(4-carboxyphenyl)porphinate]s, have been used to investigate their effects on the cultured human kidney cell cycle in order to understand further the origin of cell-growth inhibition induced by the above-mentioned chemicals. The cell-cycle-dependent DNA content distribution of cultured cells exposed to these compounds…

Chemically induced chromosome damage in early-developing embryos ofAnilocra physodes L. (Crustacea, Isopoda) following exposure to bis[Dimethyltin(IV)Chloro]protoporphyrin IX

In order to obtain chromosome preparations from early-developing embryos of Anilocra physodes, a squash technique has been successfully employed. Results gathered after exposure of this material to bis[dimethyltin(IV)chloro]protoporphyrin IX {[(CH3)2SnCl]2 - Protoporphyrin IX} solutions at different exposure times suggest that this chemical complex is capable of producing abnormal metaphase and anaphase figures in proportion to its concentration and not to exposure length. Essentially, all of the chromosome abnormalities are classifiable as chromosome fragments mainly observed at the metaphase stage; chromosome bridges; and large decondensed chromosome regions.

Mössbauer spectroscopy of mono-organotin(IV) derivatives

Abstract The Mossbauer parameters isomer shift, δ, and quadrupole splitting, ΔE, of mono-organotin compounds insofar investigated have been collected and tabulated. It is demonstrated that isomer shifts consistently depend on ligand electronegativities and coordination numbers, from which it is deduced that RSn IV behave much more as Sn IV rather than R 2 Sn IV and R 3 Sn IV derivatives. The changes of δ for RSn IV are then interpreted by hypotheses analogous to those advanced for Sn IV and its adducts and complexes. It is also inferred that in RSn IV compounds there is a consistent s-character in all tin-ligand atom bonds.

SYNTHESIS, LASER-RAMAN, INFRARED AND PROTON MAGNETIC RESONANCE SPECTRA OF (CH3)3PtX2- 3 IONS (X = Cl−, Br−) AND (CH3)3Ptiv ISOCYANIDE COMPLEXES

Abstract The novel ionic complexes [(C6H5)4As]2 [(CH3)3PtX3](X = Cl− and Br−) and [(CH3)3Pt(bipy)L]+[B(C6H5)4]− (bipy = 2,2′-bipyridine, L = aliphatic and aromatic isocyanide) have been prepared. The structure of the complex ions has been inferred from Laser-Raman and infrared spectra in the solid state and 1H NMR in solution. These data are consistent with a facial configuration of the organometallic moiety. Trends in vibrational frequencies ν(Pt-C) and ν(Pt-X) indicate a “trans” influence sequence for the ligands, which in the case of (CH3)3PtX2- 3 is related with that found for (CH3)2AuX− 2 ions.

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…

Equilibrium and spectroscopic studies of diethyltin(iv) complexes formed with hydroxymono- and di-carboxylic acids and their thioanalogues

The complex formation of diethyltin(IV) cation with glycolic (GA), lactic (LA), succinic (SA), malic (MA), tartaric (TA), mercaptoacetic (MAA), 2-mercaptopropionic (MPA), mercaptosuccinic (MSA) and dimercaptosuccinic acid (DMSA) has been investigated by potentiometric, spectrophotometric, 1H NMR and Mossbauer spectroscopic methods. The mercaptocarboxylic acids yielded much more stable complexes than the corresponding hydroxy acids. Below pH 3, the carboxylate and the still protonated hydroxyl group of hydroxy acids are co-ordinated to the metal ion, while in the case of their thio analogues, {COO−, S−} co-ordinated species are dominant. With increasing pH, the metal promoted deprotonation o…

An infrared study of organothallium thiocyanates

Abstract Some structural aspects of the organothallium(III) thiocyanates R 2 TlCNS (R = Me, Ph).[Ph 4 As][Me 2 Tl(CNS) 2 ] and Phtl(CNS) 2 have been studied by IR spectroscopy. From the frequencies of the NCS group vibrations in the solids, and the integrated intensity of the C≡N stretching absorption in solution, it was ascertained that the diorganothallium derivatives are isothiocyanates with a certain amount of ionic character in the TlNCS bonds, whereas PhTl(CNS), is essentially a TlSCN bonded compound. Apparently both solid Me 2 TlCNS and [Ph 4 As][Me 2 Tl(CNS) 2 ] do not show IR active ν s (TlC 2 )bands. The compound Me 2 TlCNS displays a double ν as (TlC 2 band, from which the pres…

Synthesis, chemical characterization and biological activity of new histone acetylation/deacetylation specific inhibitors: a novel and potential approach to cancer therapy

Three new triorganotin(IV) complexes of valproic acid (vp1, Me3Sn-valproate; vp2, Bu3Sn-valproate; vp3, Ph3Sn-valproate) have been synthesized and investigated by spectroscopic and biological methods. An anionic, monodentate valproate ligand was observed, ester-like coordinating the tin atom on a tetra-coordinated, monomeric environment. The structures, though, can distort towards a penta-coordination, as a consequence of a long range O center dot center dot center dot Sn interaction. Crystallographic and NMR findings confirm this situation both in solid state and solution. Biological finding evidenced a clear cytotoxic action of the complexes in hepatocellular carcinoma cell cultures: one …

Tributyltin affects phagocytic activity of Ciona intestinalis hemocytes

Organotin compounds have been used in marine anti-fouling paints as biocides. Because tunicates are vulnerable to these compounds in their natural habitats, we used Ciona intestinalis to establish an assay for phagocytosis in vitro of yeast by hemocytes after exposure to different concentrations (0.0015, 0.015, 0.15 and 1.5 microM) of four organotin compounds: tributyltin (TBT), triphenyltin (TPT), dibutyltin (DBT) and diphenyltin (DPT). To evaluate the phagocytic activity, we used a method based on fluorescence excitation of yeast pre-treated with eosin-Y. The percentage of phagocytosis decreased from 45.1 +/- 3.49 to 22.4 +/- 5.14 at 1.5 microM of TBT (P0.001); it was significantly reduce…

Synthesis, structural investigation and biological activity of new diorganotin(IV) N-acetylcysteine Complexes.

Organoelement derivatives of steroids: synthesis and structural characterization of diorganotin chloride adducts of hormones

Abstract Ten new diorganotin dichloride adducts of hormones of the type R 2 SnCl 2 ·2L [where R = Me, Et, n-Bu, Oct and Ph; L = 4-androsten-17s-ol-3-one ( A ); 5-androsten-3s-ol-17-one ( B ); 4-androsten-17α- methyl-17s-ol-3-one ( C ) and 3,17-dihydroxy-5- pregnene-20-one ( D )] have been prepared and characterized at 297 K and 223 K. Spectroscopic measurements (IR; Raman; 1 H, 13 C, 119 Sn NMR) suggest the dissociation or fast ligand exchange in solution at 297 K. Hexa-coordinated adducts with bonding through carbonyl oxygen and trans -R groups in octahedral geometry are formulated at 223 K.

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…

Organometallic complexes with biological molecules. XV. Effects of tributyltin(IV)chloride on enzyme activity, Ca2+, and biomolecule and synthesis inCiona intestinalis (Urochordata) ovary

Considerable attention has been given in recent years to the possibility that xenobiotics in the environment may affect reproduction in animals. In this study, the relative impact of tributyltin(IV) (TBT) chloride, one of the most toxic environmental pollutants, was investigated using Ciona intestinalis ovary as a model system. The pleiotropic effects of TBT exposure are concentration dependent and include a decrease of ATP levels, lipid content and nucleic acid content and synthesis. In contrast, a marked increase in calcium (Ca2+) and glucose content is observed. Furthermore, TBT alters enzymatic activity, inhibiting creatine kinase and stimulating alkaline phosphatase and cholinesterase …

Abnormal Expression of the major Histocompatibility Complex Class II (MHC Class II) Molecules in melanoma and cytotoxic effect of meso-tetra-(4-sulfonatophenyl)porphynate (=TPPS) derivatives.

Mössbauer Investigation on Organotin Polyester Amines Containing Ciprofloxacin.

Syntheses, Mössbauer and infrared spectroscopic investigations on tin(II) chloride adducts with purine and pyrimidine bases and nucleosides

Abstract The synthesis of two types of tin(II) complex SnCl2·L·CH3OH (L = adenosine, cytidine and inosine) and SnCl2·L2·CH3OH (L = adenine and cytosine) are described. The complexes are characterised by their infrared and 119Sn Mossbauer data. The Mossbauer shift data suggest that the bonds between tin(II) chloride and the donor atoms of the ligands are relatively weak.

Crystal structure of the molecular adduct of dimethyltin(IV) chloride with N,N′-ethylenebis(salicylideneiminato) nickel(II)

Abstract N,N′-Ethylenebis(salicylideneiminato)nickel(II) behaves as a neutral bidentate ligand through its oxygen atoms forming binuclear complexes with organotin(IV) chlorides. The crystal structure of the dimethyl derivative is reported.

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…

An in vitro comparative assessment with a series of new triphenyltin(IV) 2-/4-[(E)-2-(aryl)-1-diazenyl]benzoates endowed with anticancer activities: Structural modifications, analysis of efficacy and cytotoxicity involving human tumor cell lines

Four new triphenyltin(IV) complexes of composition Ph 3SnLH (where LH = 2-/4-[(E)-2-(aryl)-1-diazenyl]benzoate) (1-4) were synthesized and characterized by spectroscopic ( 1H, 13C and 119Sn NMR, IR, 119Sn Mössbauer) techniques in combination with elemental analysis. The 119Sn NMR spectroscopic data indicate a tetrahedral coordination geometry in non-coordinating solvents. The crystal structures of three complexes, Ph 3SnL 1H (1), Ph 3SnL 3H (3), Ph 3SnL 4H (4), were determined. All display an essentially tetrahedral geometry with angles ranging from 93.50(8) to 124.5(2)°; 119Sn Mössbauer spectral data support this assignment. The cytotoxicity studies were performed with complexes 1-4, along…

New histone acetylation/deacetylation specific inhibitors: a novel and potential approach to cancer therapy

The acetylation status of histones is regulated in eukaryotes by two kinds of enzymes, histone acetyltransferases (HATs) and histone deacetylases (HDACs), which are responsible for acetylation and deacetylation of lysines residues in N-terminal tails of histone.[1] Thus acetylation, together with phosphorylation and methylation of N-terminal tail of histones, are involved in regulating fundamental processes, such as proliferation and cell death.[2-3] Sodium butyrate, which belongs together with valproic acid to the class of short chain fatty acids, was the first HDAC inhibitor (HDACI) to be identified.[1] Organotin compounds have various influences on physical function including the hormone…

Complexes of (CH3)2AuIII: synthesis, PMR and IR spectra

Abstract The syntheses and reactivity of dimethylgold(III) complexes with multidentate ligands as TRIPHOS (i.e., 1,1,1-tris(diphenylphosphinomethyl)ethane) and TREN (i.e. 2,2′,2″-triaminotriethylamine) have been examined. I.r. spectra for the compounds in the solid state, conductivity and PMR data for solutions, lead to the assignment of an ionic formula [CH 3 ) 2 Au TRIPHOS] + [(CH 3 ) 2 AuCl 2 ] − where the gold(III) atoms are presumably four-coordinate. The complex (CH 3 ) 2 AuCl TREN in DMSO solution undergoes a reductive elimination reaction, as found for analogous dimethylgold(III) derivatives.

Organometallic Complexes with Biological Molecules. Structural investigation of cis-diammineplatinum(II)-Porphyrin derivatives.

Complexes of diorganotin(IV) dihalides with diphosphoryl compounds and their Mössbauer spectra

Synthesis of diorganotin(IV) complexes with nucleosides and their Characterization by Mössbauer and infrared spectroscopy

Abstract A number of new complexes of R 2 Sn IV with adenosine, guanosine, inosine, cytidine and uridine were synthesized by reaction of ribonucleosides with diorganotin oxide in hot methanol. The complexes were characterized by infrared and 119 Sn Mossbauer spectroscopy as O(2′), O(3′) (diorganostannylene) nucleosides; the occurence of dimers with three-co-ordinate oxygen atoms is inferred on the basis of spectroscopic data.

CCDC 830010: Experimental Crystal Structure Determination

Related Article: Ornella Pellerito, Cristina Prinzivalli, Elisabetta Foresti, Piera Sabatino, Michele Abbate, Girolamo Casella, Tiziana Fiore, Michelangelo Scopelliti, Claudia Pellerito, Michela Giuliano, Giulia Grasso, Lorenzo Pellerito|2013|J.Inorg.Biochem.|125|16|doi:10.1016/j.jinorgbio.2013.04.008