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Mechanical properties of nanoparticle chain aggregates by combined AFM and SEM: isolated aggregates and networks.

Mechanical properties of nanoparticle chain aggregates (NCA) including tensile strength and Young's modulus were measured using an instrument incorporating an AFM tip under SEM imaging. The NCA were studied individually and as network films. Carbon NCA were made by laser ablation of graphite, and SnO2 NCA were made by oxidation of a tin compound. The films were deformable and showed elastic behavior. NCA serve as reinforcing fillers in rubber and films of SnO2 NCA for trace gas detection.

Carbon↗

Effect of tributyltin on Escherichia coli: role of modifying factors.

The effects of inorganic and organic tin compounds and various factors affecting the toxicity of the latter to Escherichia coli were studied. In comparison to stannous chloride, tributyltin chloride (TBTC) was more inhibitory to the growth of the test organism; this may be due to its greater liposolubility and ready absorption through the bacterial membrane. The toxicity of TBTC to E. coli was modulated by various factors, such as pH, sulfate and chloride ions, and the presence of glucose, succinate, and reducing agents like cysteine and dithiothreitol (DTT). TBTC was more toxic to cells in minimal than in complex media. Similarly, this compound was more inhibitory to the growth of E. coli at acid pH than at basic pH. Succinate in contrast to glucose, when used as a carbon source, made the bacterium more sensitive to TBTC. Cysteine and DTT (both at a final concentration of 0.5 mM) partially protected the cells against the inhibitory effect of this agent.

Chlorides↗

[Exposure to metal compounds in occupational galvanic processes].

BACKGROUND: Occupational galvanic processes are provided in more than 600 small and medium enterprises in Poland. Workers who deal with galvanic coating are exposed to heavy metal compounds: tin, silver, copper and zinc. Some of them are carcinogenic, for example, hexavalent chromium compounds, nickel and cadmium compounds. MATERIAL AND METHODS: Research covered several tens of workstations involved in chrome, nickel, zinc, tin, silver, copper and cadmium plating. Compounds of metals present in the air were determined: Cr, Ni, Cd, Sn, Ag--by atomic absorption spectrometry with electrothermal atomization (ET-AAS) and Zn--by atomic absorption spectrometry with flame atomization (F-AAS). RESULTS: The biggest metal concentrations--of silver and copper--were found at workstations of copper, brass, cadmium, nickel and chrome plating, conducted at the same time. Significant concentrations of copper were found at workstations of maintenance bathing and neutralizing of sewage. The concentrations of metals did not exceed Polish MAC values. MAC values were not exceeded for carcinogenic chromium(VI), nickel or cadmium, either. CONCLUSIONS: In galvanic processes there was no hazard related to single metals or their compounds, even carcinogenic ones. Combined exposure indicators for metals at each workstation did not exceed 1, either. However, if there are even small quantities of carcinogenic agents, health results should always be taken into consideration.

Air Pollutants, Occupational↗

Labelling of leucocytes with colloidal technetium-99m-SnF2: an investigation of the labelling process by autoradiography.

Autoradiography of smears and frozen sections of labelled cell suspensions was used to study the distribution of radioactivity in and among blood cells labelled in either whole blood or leucocyte-rich plasma (LRP) with technetium-99m-SnF2 colloid. The tracer proved selective for neutrophils: the labelling probability (relative to that for erythrocytes) for each cell type in LRP (mean of five samples) was: neutrophils, 9.4; lymphocytes, 3.7; monocytes, 3.0; eosinophils 1.4; erythrocytes, 1.0. When labelling was carried out in whole blood (five samples), 74.5% +/- 8.3% of the cell-bound radioactivity was bound to erythrocytes, 13.6% +/- 6.5% to neutrophils, and 11.9% +/- 2.1% to lymphocytes, whereas in LRP (in which the leucocytes were only slightly outnumbered by erythrocytes), 76.5% +/- 14.9% of radioactivity was neutrophil bound. Labelled cells in smear autoradiographs exhibited two distinct silver grain patterns, "diffuse", consistent with an intracellular radioactive particle (in neutrophils), and "focal", consistent with a cell surface-adhering particle in direct contact with the emulsion (in other leucocyte types and erythrocytes). The phagocytic inhibitor cytochalasin B neither reduced the proportion of labelled neutrophils nor altered the labelling pattern. Neutrophils were able to scavenge radioactivity from the surface of erythrocytes. It is concluded that neutrophils bind 99mTc-SnF2 intracellularly by phagocytosis, with high affinity; other cells become labelled at the cell surface reversibly and with lower affinity. This selectivity is high enough to permit predominantly leucocyte labelling in LRP but not in whole blood.

Autoradiography↗

Cytotoxicity of tin on human peripheral lymphocytes in vitro.

The comparative effects of inorganic and organic tin compounds on chromosomes were assessed in human peripheral blood lymphocytes of healthy donors 20-40 years of age. The endpoints observed were chromosomal abnormalities, sister-chromatid exchanges (SCEs) and cell cycle kinetics. The maximum concentrations which reduced the replicative index by about 50%, of stannic chloride and trimethyltin chloride were 40 micrograms and 2 micrograms per culture respectively. The tested doses were 20 micrograms and 10 micrograms of stannic chloride and 1 microgram and 0.5 microgram of trimethyltin chloride. Both doses of stannic chloride induced a much higher frequency of chromosomal abnormalities (P less than 0.05-P less than 0.001) and a greater reduction of cell cycle kinetics than the corresponding relative doses of trimethyltin chloride. The frequencies of SCEs/cell induced by the latter were, however, slightly higher than those induced by the former.

Cell Cycle↗

Action of inorganic tin and organotins on a hydrocarbon-using yeast, Candida maltosa.

Two inorganic tin compounds, as well as mono- and tri-substituted methyl-, butyl-, and phenyltins were examined for their interactions with a hydrocarbon-using strain of Candida maltosa. Neither of the inorganic tins (SnII and SnIV) inhibited growth at concentrations up to 0.8 mM while binding to the yeast cells occurred to levels of 0.3 and 0.23 mM Sn/g cells, respectively. Neither inorganic tin caused leakage of potassium from the yeast cells. Among the organotins, tributyl- and triphenyltins caused total viability loss and near maximum potassium loss at initial concentrations of 0.08 mM. For these compounds binding to the cells increased with increasing initial concentrations to maximum values of 0.51 and 0.65 mM Sn/g cells respectively. The other organotin compounds were not inhibitory and did not cause potassium leakage from the cells. Tin from them became cell associated only in the cases of monobutyl- and monophenyl tin, which were bound at markedly lower levels (<0.1 mM Sn/g cells). These results are consistent with the conclusion that the inhibitory compounds can act on the yeast cell membrane but, although binding to the cells is a prerequisite for growth inhibition and cell leakage, no simple correlation was established between binding levels and toxicity effects.

Candida↗

Speciation of butyl- and phenyltin compounds in sediments using pressurized liquid extraction and liquid chromatography-inductively coupled plasma mass spectrometry.

A liquid chromatographic method with inductively coupled plasma mass spectrometry is proposed for the speciation of butyl- (monobutyltin, dibutyltin, tributyltin) and phenyl- (monophenyltin, diphenyltin, triphenyltin) tin compounds in sediments. After evaluation of different additives in the mobile phase, the use of 0.075% (w/v) of tropolone and 0.1% (v/v) of triethylamine in a mobile phase of methanol-acetic acid-water (72.5:6:21.5) allowed the best chromatographic separation of the six compounds. Pressurized liquid extraction (PLE) with a methanolic mixture of 0.5 M acetic acid and 0.2% (w/v) of tropolone was suitable for the quantitative extraction of butyl- and phenyltin compounds with recovery values ranging from 72 to 102%. This analytical approach was compared to conventional solvent extraction methods making use of acids and/or organic solvent of medium polarity. The main advantages of PLE over conventional solvent extraction are: (i) the possibility to extract quantitatively DPhT and MPhT from sediments, which could not be done by a solvent extraction approach; (ii) to preserve the structural integrity of the organotin compounds; (iii) to reduce the extraction time from several hours in case of solvent extraction techniques to just 30 min. For spiked sediments, limits of detection ranged from 0.7 to 2 ng/g of tin according to the compound. The relative standard deviations were found to be between 8 and 15%. The developed analytical procedure was validated using a reference material and was applied to various environmental samples.

Chromatography, High Pressure Liquid↗

Chemical induction of nondisjunction in drosophila.

Tests for chemically induced nondisjunction and loss of the sex chromosomes in Drosophila were performed. Of 31 compounds tested four gave rise only to an increase of XO exceptions, indicating the induction of chromosome loss. Six compounds, all known spindle inhibitors (colchicine, organic mercury, lead, and tin compounds) gave rise to an increase both of XXY and XO or of only XXY. The effect by metalloorganic compounds of which methylmercury was studied particularly closely, follows a peculiar pattern. In females with structurally normal X chromosomes only an increase of XX gametes is obtained, while with X chromosomes heterozygous for long inversions only O gametes are increased. The data indicates that the effect of the metal compounds occurs at first meiosis and that the process is connected with a meiotic drive, giving rise to a preferential segregation of the two X chromosomes to the functioning pole. The increase only of O gametes with structurally heterozygous X chromosomes can tentatively be explained by a loss due to crossing over within the inversion. An increase of the effect of methyl mercury was obtained where the normal pairing of the X chromosomes was interfered with by means of autosomal inversions. Likewise a synergistic increase of nondisjunction was obtained when a temperature chock of 10 degrees C was applied together with treatment with methylmercury. It is concluded that chemical induction of nondisjunction can be studied in Drosophila, but the sensitivity of the test is rather low and large amount of material is required.

Animals↗

Application of experimental design in a method for screening sediments for global determination of organic tin by electrothermal atomic absorption spectrometry (ETAAS).

An experimental design was developed to obtain a simple procedure for global determination of organic tin compounds in sediment. Sediment was extracted by a two-phase method and tin was determined in the organic extract by electrothermal atomic absorption spectrometry (ETAAS), with palladium as chemical modifier. A Plackett-Burman design for screening and a fractional central composite design (CCD) for optimizing were used for evaluation of the effects of several variables. The results showed that sediment mass, volume and concentration of extracting acid, pyrolysis and atomization temperatures, and modifier concentration affect the determination. Reference material PACS-2 was analyzed to evaluate the procedure. It was possible to extract 82% of the organotin content certified in the reference sediment. The limit of detection (LOD) was 0.08 microg g(-1) and the relative standard deviation was 4%. The method was applied to the analysis of estuarine superficial sediments from Gipuzkoa (Spain). The organotin content of these samples ranged from 0.7 to 7.7 microg g(-1), as tin, on a dry-weight basis.

Acetic Acid↗

Direct Grignard pentylation of organotin-contaminated lard samples followed by capillary gas chromatography with flame photometric detection.

During a recent investigation of the organotin-contaminated lard samples, a simple method was developed by direct Grignard pentylation of lard samples and capillary gas chromatography with flame photometric detection using quartz surface-induced tin emission. Using HP-1 capillary column with temperature programming and FPD detector, pentylated tri-, di-, monometyltin, dioctyltin and Sn(IV) can be base-line separated and detected within 20 min. The analysis of pentylated tin compounds by GC-MS confirmed the existence of methyltins and inorganic tin in lard samples, which was agreeable with the results obtained by GC-FPD. The content of organotin compounds was calculated by internal standard method in which methyltripropyltin (MeSnPr3) acted as internal standard. The results showed that these samples were heavily contaminated with mg/g levels of dimethyltin, microg/g levels of tri- and monomethyltin. Among them, one sample contained mg/g level of dioctyltin and one contained a little of inorganic form of Sn(IV). The recoveries of tri-, di- and monomethyltin were 95.7%, 105.5% and 105.7%, respectively.

Chromatography, Gas↗

The neurotoxicology and pathology of organomercury, organolead, and organotin.

The toxicities of many metals, such as mercury and lead, are known to man since the dawn of civilization. Organic compounds of some heavy metals are known to have a particular toxic impact on the central nervous system. Organomercury, particularly alkyl-mercuric compounds (e.g. methylmercury), has a selective effect on the granule cells of the cerebellum, the nerve cells of the calcarine cortex, and the sensory neurons in the dorsal root ganglia. The well known Minamata Bay disease is the result of a massive epidemic episode of human exposure to alkylmercury contaminated food sources. Mental retardation and other developmental defects are also known to be a consequence of exposure to this toxic metal. Organic lead compounds have been employed as gasoline additives and in other industrial purposes. Unlike its inorganic counterpart, organolead compounds have a more prominent impact on the central nervous system. Pathological changes of the brain stem neurons have been described. Organotin compounds have been used in plastic industries and as agricultural chemicals. Both trimethyl and triethyl tin compounds are found to be extremely neurotoxic. Despite the similarity of their chemical structures, trimethyl and triethyl tins have a diversely different toxic property and effects. While triethyl tin is myelinotoxic, producing edematous and vacuolar changes in the central myelin, trimethyl tin is neurotoxic, producing prominent toxic changes in the neurons of the limbic system (hippocampus, entorhinal cortex, etc.). The factors which determine the specificity and selectivity of the neurotoxic impacts by various organometals are still unknown. In view that most of the organometals are still widely employed by many countries for industrial and for agricultural purposes, caution must be made for their proper handling and disposure to avoid undesirable exposures to workers and environmental contamination of water sources and food-chain for the common public. Since organometals are difficult to eliminate from the central nervous system, injuries usually lead to permanent neurological deficits, such tragedies are frequently long lasting and create not only a medical problem, but also a social economical problem for the society.

Animals↗

Organotin compounds enhance 17beta-hydroxysteroid dehydrogenase type I activity in human choriocarcinoma JAr cells: potential promotion of 17beta-estradiol biosynthesis in human placenta.

Organotin compounds, such as tributyltin (TBT) and triphenyltin (TPT), are typical environmental contaminants and suspected endocrine-disrupting chemicals because they cause masculinization in female mollusks. However, it remains unclear whether organotin compounds also cause crucial toxicities in human sexual development and reproductive functions. We investigated the effects of 17 tin compounds on the catalytic activity and mRNA expression of 17beta-hydroxysteroid dehydrogenase type I (17beta-HSD I) in human choriocarcinoma JAr cells. At nontoxic concentrations, both trialkyltins with propyl, butyl or cyclohexyl substituents on the tin atom and triphenyltin (TPT) enhanced 17beta-HSD I mRNA transcription and enzyme activity in a dose-dependent fashion. Although tetraalkyltin compounds such as tetrabutyltin and tributylvinyltin also increased the mRNA expression and enzyme activity of 17beta-HSD I, the concentrations necessary for activation were >30-100 times greater than those for trialkyltins. Inorganic tin had no effect on the catalytic activity and mRNA expression of 17beta-HSD I. Interestingly, diphenyltin and monophenyltin, which are metabolites of TPT, enhanced 17beta-HSD I activity with a concomitant increase in mRNA expression, whereas dibutyltin and monobutyltin, which are metabolites of tributyltin, enhanced 17beta-HSD I activity without a concomitant increase in mRNA expression. These results suggest that organotin compounds are potent stimulators of 17beta-estradiol biosynthesis to enhance 17beta-HSD I activity in the human placenta in vitro; the placenta represents a potential target organ for these compounds, whose endocrine-disrupting effects might be the result of local changes in 17beta-estradiol concentrations in pregnant women.

17-Hydroxysteroid Dehydrogenases↗

The behavioral toxicity of a tributyltin ester in the rat.

The behavioral toxicity of an organic tin compound under consideration for use in marine antifouling paint was assessed using a Sidman avoidance paradigm. The assessed compound, an organometallic polymer (tributyltin [methacrylic-CO-methylmethacrylate] ester), is from a group of alkyltin compounds of which triethyl and tributyltin are known to be toxic. Rats were tested under a free-operant avoidance procedure for 6 months while ingesting the polymer in their drinking water. At the beginning of the 5th month significant behavioral changes became evident, reflected in increases in shock rate, decreased responding, and a shifting of the interresponse time distribution. Performance improved upon withdrawal of the contaminant suggesting that limited exposure to the polymer may not result in permanent behavioral dysfunction.

Analysis of Variance↗

Determination of organotin compounds by headspace solid-phase microextraction-gas chromatography-pulsed flame-photometric detection (HS-SPME-GC-PFPD).

A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 mum PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L(-1) in water and close to ng (Sn) kg(-1) in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME-GC-PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices.

Chromatography, Gas↗

Pharmacodynamics of stannous chelates administered with 99mTc-labeled chelates.

The pharmacodynamics of several tin compounds were studied in healthy rabbits, rabbits with myocardial infarcts, and isolated myocardial tissue. The results showed that tin chelates of pyrophosphate, HEDP, DTPA, and glucoheptonate are very unstable in vivo, giving rise to free stannous ions. These ions localize mainly in bone, with the rest being primarily excreted in the urine. They also concentrate more in infarcted than in normal myocardium; there they enter the mitochondria. The supernatant of homogenates contains bound and free fractions, demonstrating a subcellular distribution pattern similar to that of calcium ions. Tin chelates have different pharmacodynamics from the corresponding 99mTc chelates.

Animals↗

Carcinogenesis Bioassay of Stannous Chloride (CAS No. 7772-99-8) in F344/N Rats and B6C3F1/N Mice (Feed Study).

Stannous chloride is an inorganic tin compound used as a food preservative, a stabilizer for colors, perfumes, and soaps, and as a reducing agent in tin plating. It is also used as a mordant in printing, a silvering agent for glass and plastics, a catalyst for curing phenolic resins, an additive to drilling muds, and an antisludge agent for oils. The chronic phase of a carcinogenesis bioassay for stannous chloride was conducted by feeding diets containing 1,000 or 2,000 ppm stannous chloride to groups of 50 F344/N rats and 50 B6C3F1/N mice of each sex for 105 weeks. Similar groups of untreated rats and mice served as controls. In this study, the concentrations of tin in bone, kidney, and liver were no higher than those attained in other lifetime studies utilizing 1/100 of the dose, suggesting that organ accumulation of tin was not dose dependent, but probably limited by absorption. Mean body weight gain and feed consumption of dosed and control rats and mice were comparable. Survival of high-dose male rats was somewhat lower than that of the control and low-dose groups (37/50, control; 39/50, low-dose; 30/50, high-dose). Survival of control male mice was less (P<0.05) than that of either dosed group (32/50, 42/50, 45/50); survival of the female mice appeared to be dose related (38/50, 33/50, 28/50). C-cell adenomas of the thyroid (2/50, 9/49, 5/50), C-cell adenomas or carcinomas combined (2/50, 13/49, 8/50), and adenomas of the lung (0/50, 0/50, 3/50) in male rats; and hepatocellular carcinomas or adenomas combined (3/49, 4/49, 8/49) and histiocytic malignant lymphomas (0/50, 0/49, 4/49) in female mice occurred with significant (P<0.05) positive trends and/or with significantly (P<0.05) increased incidences in the dosed groups when compared with the paired controls. However, when the lung adenomas in male rats are combined with lung carcinomas and when all lymphomas in female mice are considered, no statistical significance remains. For the thyroid C-cell tumors in male rats and for the liver tumors in female mice, the incidences in the high-dose groups were not significantly different from the historical control rates at that laboratory (C-cell tumors: 32/288, 11.1%; liver tumors: 24/297, 8%). When the historical control rate is used as a basis for comparison, the low-dose incidence of thyroid C-cell tumors remains significant (P<0.01). Under the conditions of this bioassay, stannous chloride was judged not to be carcinogenic for male or female F344/N rats or B6C3F1/N mice, although C-cell tumors of the thyroid gland in male rats may have been associated with the administration of the test chemical. Levels of Evidence of Carcinogenicity: Male Rats: Equivocal Female Rats: Negative Male Mice: Negative Female Mice: Negative

Journal Article↗

Synthesis and characterization of tin containing polyhedral oligometallasilsesquioxanes (POMSS).

Tin silicate species have shown good catalytic activity in various oxidation reactions. In an attempt to mimic surface tin species, several tin containing silsesquioxanes have been synthesized. Incompletely condensed silsesquioxanes (c-C5H9)7Si7O9(OH)3 and (c-C5H9)7Si7O9(OSiMe3)(OH)2 were reacted with common tin-precursors, which afforded several silsesquioxane ligated tin compounds. Divalent stannasilsesquioxanes form dimers of the type [(c-C5H9)7Si7O11(OX)Sn]2(X=H, SiMe3) with three-coordinated tin centers. The three-coordinated tin(II) are hydrolytically unstable whereas the octahedrally surrounded tetravalent stannasilsesquioxanes [(c-C5H9)7Si7O11(OX)]Sn(acac)2(X=H, OSiMe3) are hydrolytically robust. An unprecedented anionic trimeric cluster, [[(c-C5H9)7Si7O12Sn]3(mu2-OH)3(mu3-OH)]-[HNEt3]+, stabilized by bridging hydroxyl groups was formed when the product formed upon reacting (c-C5H9)7Si7O9(OH)3 with SnCl4 was slowly hydrolyzed. The stannasilsesquioxanes showed no catalytic activity in oxidation reactions.

Journal Article↗