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.     

Thermolysis of the phenyltin chlorides,PhxSnCl4–x, (x=1−3): Products and pathways

The thermal degradation of triphenyltin chloride, diphenyltin dichloride and phenyltin trichloride has been studied by pyrolysis at 375°C in sealed tubes for various time periods. In all cases, biphenyl and tin(II) chloride are produced. For both phenyltin trichloride and diphenyltin dichloride, ter- and poly-phenyls are also obtained. In some cases tin(IV) chloride or elemental tin are obtained. Pathways that account for all observed products are presented.     

GC FPD method for the simultaneous speciation of butyltin and phenyltin compounds in waters

A method is described for the simultaneous determination of nanogram amounts of mono-, di- and tri-butyltin compounds in water. The procedure is based on the conversion of tin compounds to volatile species by Grignard pentylation and analysis using GC with flame photometric detection (GC FPD). The ionic compounds are extracted from diluted acidified (HBr) aqueous solutions by using a pentane-tropolone solution. The extracted organotin compounds are pentylated by a Grignard reagent and purified on a Fluorisil column before analysis by GC FPD. The detection limits are 20 ng dm^?3 for butyltin compounds and 50 ng dm^?3 for phenyltin compounds. Recoveries from spiking experiments in tap-water and natural seawater matrices, in which no organotin compounds were detected, were greater than 90% for most of the alkyltin compounds.     

The effect of phenyltin chlorides on osmotically induced erythrocyte haemolysis

The toxicity of many amphiphilic compounds may result from their effect on the lipid phase of biological membranes. Upon incorporation such compounds may change the properties of membranes in general and in particular alter the organization of membrane lipids. These changes should affect, among other things, the mechanical properties of membranes. We selected two amphiphilic compounds, diphenyltin dichloride (Ph₂SnCl₂) and triphenyltin chloride (Ph₃SnCl), which are known to be located at different regions of the lipid bilayer and to be toxic. As a model biological membrane the erythrocyte plasma membrane was used. Analysis of the haemolysis kinetics showed differences between the effect of the compound studied on mechanical properties at so‐called non‐lytic concentrations. Diphenyltin dichloride showed a limited effect on erythrocyte haemolysis, whereas triphenyltin chloride affected all the parameters measured (extent of initial haemolysis, extent of final haemolysis and membrane mechanical strength). We correlated these effects with the location of the investigated compounds in liposomes. The presented data show that triphenyltin chloride reduces the erythrocyte plasma membrane mechanical strength and increases the extent of haemolysis under osmotic stress conditions. Copyright © 2005 John Wiley & Sons, Ltd.     

Crystallographic report: Diphenylbis(Hpiroxicam)tin(IV), [Ph2Sn(Hpir)2]

The crystal structure of complex [Ph₂Sn(Hpir)₂ ·CH₃CN] shows for the first time chelation to a metal atom of piroxicam through the keto‐enolate oxygen atoms. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis,spectral, theoretical studies and in vitro antimicrobial activities of novel diphenyltin(IV) complexes of Schiff bases derived from phenacylamine

A series of new diphenyltin(IV) complexes of the type Ph₂SnL (L¹: N‐phenacyl‐5‐bromosalicylideneimine, Ph₂SnL¹; L²: N‐phenacyl‐3,5‐dichlorosalicylideneimine, Ph₂SnL²; L³: N–phenacyl‐4‐methoxysalicylideneimine, Ph₂SnL³) were synthesized and characterized by elemental analysis, IR, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopy and mass spectrometry techniques. The C―Sn―C angles in the complexes were calculated using equations with the ¹J(^117/119Sn―¹³C) values from ¹³C NMR spectra. The possible structures, NMR and electronic properties of the studied molecules were calculated through density functional theory and results compared with experimental data. All the complexes were found to be mildly active against several microorganisms and some fungi. Copyright © 2014 John Wiley & Sons, Ltd.     

Environmental application of elemental speciation analysis based on liquid or gas chromatography hyphenated to inductively coupled plasma mass spectrometry—A review

In recent years the number of environmental applications of elemental speciation analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. The analytical characteristics, such as extremely low detection limits (LOD) for almost all elements, the wide linear range, the possibility for multi-elemental analysis and the possibility to apply isotope dilution mass spectrometry (IDMS) make ICP-MS an attractive tool for elemental speciation analysis. Two methodological approaches, i.e. the combination of ICP-MS with high performance liquid chromatography (HPLC) and gas chromatography (GC), dominate the field. Besides the investigation of metals and metalloids and their species (e.g. Sn, Hg, As), representing “classic” elements in environmental science, more recently other elements (e.g. P, S, Br, I) amenable to ICP-MS determination were addressed. In addition, the introduction of isotope dilution analysis and the development of isotopically labeled species-specific standards have contributed to the success of ICP-MS in the field. The aim of this review is to summarize these developments and to highlight recent trends in the environmental application of ICP-MS coupled to GC and HPLC.     

The effect of phenyltin chlorides on the phase polymorphism of dipalmitoylphosphatidylcholine

The effects of diphenyltin dichloride (DPhT) and triphenyltin chloride (TPhT) on polymorphic phase behaviour of aqueous dispersions of a dipalmitoylphosphatidylcholine (DPPC) bilayer were investigated by means of ³¹P NMR. It is suggested that DPhT induces interdigitated gel phase formation and TPhT induces hexagonal phase formation. The toxic activities of DPhT and TPhT seem to be connected with their ability to induce changes in the membrane structure. Copyright © 2001 John Wiley & Sons, Ltd.     

The effect of some phenyltin compounds on the thermotropic phase behaviour and the structure of model membranes

The effects of diphenyltin dichloride (DPhT), triphenyltin chloride (TPhT) and tetraphenyltin (TTPhT) on the thermotropic phase behaviour of phosphatidylcholine bilayers were studied. All the phenyltin compounds investigated affected phase transitions differently. TTPhT broadened the main phase transition but it left the transition temperatures and enthalpy unchanged. TPhT reduced the transition temperatures and the enthalpies while DPhT showed a dual effect on the pretransition and the main transition. At low concentrations DPhT reduced the temperatures of the transitions slightly and at higher concentrations it increased them. Based on differential scanning calorimetry (DSC) and also ¹H NMR and ³¹P NMR measurements, it is suggested that DPhT induces interdigitated gel phase formation and TPhT induces hexagonal phase formation. TTPhT seems to affect the structure only a little. The toxic activity of DPhT and TPhT seems to be connected with their ability to induce changes in the membrane structure. Copyright © 2000 John Wiley & Sons, Ltd.     

Di‐ and tri‐phenyltin chlorides transfer across a model lipid bilayer

A compound's ability to penetrate the plasma membrane of a cell is the critical parameter that determines its potential to become a biologically potent factor. A well‐known group of organotin compounds that exhibit toxic properties in relation to biological systems are phenyltins. There are as yet no studies that in a direct manner have established whether organotin compounds such as diphenyltin dichloride (DPhT) and triphenyltin chloride (TPhT) diffuse, or not, through the lipid bilayer, although we know that at least some organotins absorb in both liposome and biological membranes. In this paper we present a series of experiments that show transfer of these compounds across the lipid membrane using the stopped‐flow technique. The results obtained demonstrate that DPhT and TPhT first adsorb onto the lipid bilayer surface, in a diffusion‐controlled manner and within a very short time (0.05 s), whereas the membrane crossing was observed to be on the order of a minute. The adsorption process was easily fitted with a single exponential for both the compounds studied, indicating a single process phenomenon. The longer time kinetics (characteristic of membrane crossing) showed a complex dependence on compound concentration and the presence of cholesterol in the membrane. On passing from the outer to the inner surface of the bilayer, organotins undergo desorption and enter the liposome interior, which has been shown in lipid monolayer desorption studies. In conclusion, it can be stated that amphiphilic DPhT and TPhT permeate the liposome membrane. Copyright © 2005 John Wiley & Sons, Ltd.