Organotin concentrations in the Rivers Bure and Yare,Norfolk Broads,England

Butyltin concentrations have been measured at eight freshwater sites (rivers and lakes) in the Norfolk Broads, UK, during 1986 and 1987. Tributyltin (TBT) was found in water samples from seven of the sites. Wherever TBT was present, dibutyltin and (usually) monobutyltin occurred. Levels of TBT exceeded 100 ng dm^?3 in open stretches of both the Rivers Bure and Yare in 1986 and 1987. The highest concentration of TBT recorded for Wroxham Broad (a shallow lake) was 898 ng dm^?3. Values of up to 3.26 μg dm^?3 were measured in water samples taken from a marina. A depth profile for Wroxham Broad showed TBT to be uniformly distributed throughout the shallow water column. The results are discussed in relation to toxicity of TBT to freshwater organisms. Laboratory measurements of the degradation of TBT in freshwater from a marina gave a half-life of six days at 20°C in the light.     

17O NMR spectra of some butyltin(IV) acetates

The ¹⁷O NMR spectra of ¹⁷O isotope‐enriched tributyltin(IV) acetate (1) and dibutyltin(IV) diacetate (2) were recorded in various solvents over wide temperature ranges. Only a single ¹⁷O signal was observed for both oxygen atoms of the —COOSn—groups under these experimental conditions, in both non‐coordinating and coordinating solvents. The ¹⁷O NMR spectra of tert‐butyl acetate (3) were obtained for comparison. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis, Crystal Structure and Quantum Chemistry of Dibutyltin 3, 4-Dimethoxybenzotate Compound

The dibutyltin 3,4-dimethoxybenzotate compound {[(3,4-(CH3O)2C6H3COO) Sn(Bu-n)2]2O}2 has been synthesized by the reaction of dibutyltin oxide with 3,4-dimethoxybenzoic acid. Its structure was determined by X-ray single-crystal diffraction. The crystal belongs to the triclinic system,space group P1 with a = 1.2003(2),b = 1.2821(3),c = 1.3666(3) nm,α = 80.50(3),β = 65.56(3),γ = 73.36(3)°,Z = 2,V = 1.8318(6) nm3,Dc = 1.530 Mg·m-3,μ(MoKa) = 1.413 mm-1,F(000) = 860,R = 0.0554 and wR = 0.1092. In the complex,each tin atom adopts a distorted tigonal bipyramidal structure,and the dimer structure is shaped by one Sn2O2 planar four-membered ring. The stabilities of the title complex,along with its orbital energies and composition characteristics of some frontier molecular orbitals have been investigated by means of quantum chemistry calculation methods.     

Acid extraction treatment of sediment samples for organotin speciation; occurrence of butyltin and phenyltin compounds on the cadiz coast,south-west spain

A method is described for leaching of nanogram amounts of mono-, di and tri-butyltin compounds and mono-, di- and tri-phenyltin compounds from sediments. The procedure is based on soaking the sediments in a water–hydrogen bromide mixture (2:3) with magnetic stirring for 1 h followed by extraction with 0.02% (w/v) tropolone solution in pentane for 2 h. Organotins are determined by GF FPD after clean-up through a Florisil column and derivatization by Grignard pentylation. The method has been applied to the study of water and sediments in different areas of south-west Spain. Predominant species are butyltins, especially tributyltin (TBT), which has high values in waters and sediments of Puerto de Santa Maria and Cadiz Bay, as well as in sediments of the Sancti Petri Channel, which suggests a harmful action on biota. A direct relation has been found beween organotin levels and distance of potential focus determined by boating activities. In addition, the relative occurrence of dibutyltin (DBT) and monobutyltin (MBT) together with TBT has been noted, possibly as a result of a degractation process, and the influence of grain size of sediment and presence of organic matter on organotin accumulation has been studied.     

π–π stacking motifs in dialkylbis{5‐[(E)‐2‐aryldiazen‐1‐yl]‐2‐hydroxybenzoato}tin(IV) complexes

The diorganotin(IV) complexes of 5‐[(E)‐2‐aryldiazen‐1‐yl]‐2‐hydroxybenzoic acid are of interest because of their structural diversity in the crystalline state and their interesting biological activity. The structures of dimethylbis{2‐hydroxy‐5‐[(E)‐2‐(4‐methylphenyl)diazen‐1‐yl]benzoato}tin(IV), [Sn(CH₃)₂(C₁₄H₁₁N₂O₃)₂], and di‐n‐butylbis{2‐hydroxy‐5‐[(E)‐2‐(4‐methylphenyl)diazen‐1‐yl]benzoato}tin(IV) benzene hemisolvate, [Sn(C₄H₉)₂(C₁₄H₁₁N₂O₃)₂]·0.5C₆H₆, exhibit the usual skew‐trapezoidal bipyramidal coordination geometry observed for related complexes of this class. Each structure has two independent molecules of the Sn^IV complex in the asymmetric unit. In the dimethyltin structure, intermolecular O—H…O hydrogen bonds and a very weak Sn…O interaction link the independent molecules into dimers. The planar carboxylate ligands lend themselves to π–π stacking interactions and the diversity of supramolecular structural motifs formed by these interactions has been examined in detail for these two structures and four closely related analogues. While there are some recurring basic motifs amongst the observed stacking arrangements, such as dimers and step‐like chains, variations through longitudinal slipping and inversion of the direction of the overlay add complexity. The π–π stacking motifs in the two title complexes are combinations of some of those observed in the other structures and are the most complex of the structures examined.     

二丁基氧化锡在糖苷类化合物脱乙酰保护基中的应用

发展了在中性条件下选择性脱乙酰保护基的新方法。该方法以催化剂量的二丁 基氧化锡作催化剂，用甲醇作溶剂，对糖苷类化合物脱乙酰保护基进行了研究。文 中对该反应结果、应用范围与反应机理进行了讨论，本研究表明糖苷类化合物采用 该方法可以顺利得到脱乙酰保护基产物，所得到产物的结构经~1H NMR，IR，元素 分析证实。脱保护基的反应在有机合成中具有很重要的意义，该方法属于首次将二 丁基氧化锡用于脱乙酰保护基的反应中。     

Effects of exposure to dibutyltin dichloride on sperm density,viability and morphology in male mice

Experiments on the effects of 0.025–0.40 µg of dibutyltin dichloride (DBTCl) per kilogram body weight (kg bw), on sperm density, viability and morphology in mature mice were conducted by daily intraperitoneal injection for 7 days at 22 ± 2 °C and 12 h light–dark cycle conditions. The results demonstrated that DBTCl exhibited strong toxicity on sperm quality. Dosed with ≥ 0.05 µg DBTCl/kg bw groups, the testes weight, sperm density and the rate of survival of sperm decreased, whereas the rate of sperm abnormalities increased significantly. In addition, treatment with 0.05 µg DBTCl/kg bw resulted in increasing rate of sperm head abnormalities, whereas administration at 0.20 and 0.40 µg DBTCl/kg bw significantly increased the rate of sperm tail abnormalities. In the group treated at ≥ 0.10 µg DBTCl/kg bw, the mice body weights decreased. It appeared there was a noticeable dose–response relationship between DBTCl and the parameters studied. ED₅₀ values (7 days) of DBTCl for survival rate of sperm and density were 0.17 µg/kg bw and 0.19 µg/kg bw respectively. The present study provides a possibility for early diagnostic indicators and methods for sperm quality induced by organotin compounds (DBTCl) in mammals. Copyright © 2001 John Wiley & Sons, Ltd.     

Degradation of tributyltin chloride in water photoinduced by iron(III)

The degradation of tributyltin chloride (TBT) photoinduced by iron(III) was investigated. Upon irradiation at λ_excitation >300 nm a photoredox process was observed, yielding iron(II) and ^·2OH radicals. The disappearance of TBT was proved to involve only an attack by ^·2OH radicals: the quantum yield of TBT disappearance was determined. A wavelength effect was observed; the shorter the excitation wavelength, the higher the rate of TBT disappearance. Most of the photoproducts were identified and the mechanism of degradation was elucidated. The main route to degradation is a stepwise debutylation of TBT to di‐ and mono‐butyltin with final formation of inorganic tin. The complete mineralization of TBT was achieved with long irradiation times, leading to innocuous inorganic tin. Copyright © 1999 John Wiley & Sons, Ltd.     

Immunotoxicity of butyltins in tunicates

This study was designed to investigate the effects of butyltins on yeast phagocytosis in vitro by haemocytes of the colonial ascidian Botryllus schlosseri. This species has been reported to be very sensitive to organotins. Results show that, in analogy to reports on mammalian leukocyte re-activity, butyltins exert inhibitory effects on phagocytosis in a concentration-dependent manner, mainly by influencing cellular calcium homeostasis by interacting with the calcium pump. As the immunosuppressant activity of organotins described in mammals and teleosteans also occurs in an invertebrate marine species, the latter may assume a role as a sensitive biosensor of butyltins as immunotoxins in aqueous ecosystems.     

Optimization of butyltin measurements for seawater,tissue, and marine sediment samples

Optimized techniques for measuring butyltins at the sub-part-per-trillion (ppb; 1:10¹²) level in seawater and at the part-per-billion (ppb; 1:10⁹) level in tissues and sediments are presented. Purge and trap/hydride derivatization followed by atomic absorption (AA) detection was optimized to give better sensitivity than was previously attained for seawater, yielding environmental detection limits of 0.08–0.2 ng dm^?3. Improvement in precision and reproducibility in measurement of butyltins in tissues and sediments was attained by adjustment of the concentration in an organic extract to minimize matrix effects and by use of internal standards. The tissues and sediments were homogenized and extracted with methylene chloride (CH₂Cl₂) after acidification. The butyltins in the organic layer were derivatized with hexylmagnesium bromide and analyzed by gas chromatography (GC) with a flame photometric detector (FPD). The absolute detection limits in tissues and sedimets were 0.1 ng for tributyltin (TBT), 0.12 ng for dibutyltin (DBT) and 0.29 ng for monobutyltin (MBT).