Triphenyltin Research Articles

Performance Study of Organotin (IV) Complexes

Organotin(IV) complexes possess at least one covalent carbon to organotin bond as part of its structural characteristics [1]. It also contains tin in a +4 oxidation state bonded to donor atoms of a number of ligands. They have received a lot of research interests due to their structural diversity and numerous applications [2]. Organotins are the most widely used organometallic compounds globally (~ 50,000 t yr−1) [3] with applications in the stabilization of plastics, precursors in glass coating and as antifungal agents in textiles and other household items [4]. From the 1950s-2001, the major use of tributyltin (TBT) and triphenyltin (TPhT) was as a toxicant in antifoulant paints [4].

Triphenyltin exposition induces spermatic parameter alters of Calomys laucha species

The present study aims to evaluate the influence of triphenyltin (TPT) exposure on reproductive physiology on Calomys laucha species, since this species inhabits regions susceptible to exposure to this contaminant. Animals exposed to the highest dose (10.0 mg/kg) presented signs of severe intoxication in only 7 days of exposure, demonstrating a higher sensitivity of this species to triphenyltin. The 10.0 mg TPT/kg dose was analyzed separately for short-term exposure and results suggest that exposure to this dose was severely detrimental to sperm activity. Among the main results obtained in the evaluation of sperm kinetics, a reduction in total motility was observed from the 0.5 mg TPT/kg group, accentuated according to the increase in the doses of TPT. In progressive motility, there was a decrease from the dose of 0.5 mg TPT/kg and maintained the plateau until the dose of 5.0 mg TPT/kg. It was also observed an increase in the distances and velocities average path, rectilinear and curvilinear in doses of 2.5 and 5.0 mg/kg. From the flow cytometry, evaluation a decrease in mitochondrial functionality was observed as the dose increased. Increased membrane fluidity was also observed from the 5.0 mg TPT/kg dose and the acrosome reaction presented higher values at doses of 0.5 and 5.0 mg TPT/kg. We can conclude that TPT causes impairment of the sperm activity, reducing it in individuals exposed in the adult phase.

Abstract 688: Triphenylstannyl 2-(benzylcarbamoyl)benzoate (Ch-319) modulates AKT/FOXO3a signaling and inhibits progression of prostate cancer

Abstract Prostate cancer (PCa) is the most commonly diagnosed non-cutaneous malignancy in men in the United States. Moreover, its incidence is predicted to surge in many parts of the world due to increase in aging population and change in dietary habits. The PTEN/AKT axis plays a critical role in regulating PCa growth and survival. Synthetic and natural compounds have been explored in preclinical models as potential inhibitors of AKT pathway that can suppress proliferation or induce apoptosis in PCa cells. Triphenyltin compounds are complexes of tin with three phenyl groups attached to hydrocarbon ligands. Structural modifications have been attempted to yield organotins with enhanced cytotoxicity against cancer cells. Here, we synthesized a series of triphenyltin (IV) carboxylate derivatives and evaluated their efficacy against PCa. From this library, triphenylstannyl 2-(benzylcarbamoyl)benzoate (Ch-319) was selected for further studies on the basis of its selective cytotoxicity towards cancer cells. Treatment of PTEN-null PC3M and DU145 PCa cells with Ch-319 (250-500 nM) resulted in reduced viability and induction of cell cycle arrest associated with downregulation of PI3K and dephosphorylation of AKT and PRAS40. In parallel, elevation of FOXO3a expression, activation of pro-apoptotic Bax and downregulation of anti-apoptotic Bcl2 protein was observed. Flowcytometry revealed increased population of apoptotic cells in Ch-319 treated cells. Presensitization of PCa cells with Ch-319 augmented the effect of cabazitaxel, a commonly used taxane in patients with castration-resistant PCa. We next evaluated the effect of Ch-319 in a prostate-specific Pten-/- model where AKT activation is the major driving force for development of prostate adenocarcinoma. Mice treated with Ch-319 (5 µg/animal:intraperitoneally) for 6 weeks showed decreased tumor weights as compared to DMSO treated controls. Histological studies indicated a decrease in the number and size of foci in Ch-319 treated tumors. Consistently, reduced expression of androgen receptor, decreased phosphorylation of AKT and PRAS40 and increase in FOXO3a was observed in Ch-319 treated animals with no signs of organ toxicity. Our studies identify AKT/FOXO3a signaling as a target of triphenyltin (IV) carboxylate derivative Ch-319 and provide a molecular basis of its growth inhibitory effect in PCa cells. We propose that Ch-319 has potential to be developed as an anticancer agent against PCa. Citation Format: Durdana Waseem, Deeba N. Syed, Gul Majid Khan, Ihsan-ul Haq, Hasan Mukhtar. Triphenylstannyl 2-(benzylcarbamoyl)benzoate (Ch-319) modulates AKT/FOXO3a signaling and inhibits progression of prostate cancer [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2018; 2018 Apr 14-18; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2018;78(13 Suppl):Abstract nr 688.

Water quality criteria derivation and ecological risk assessment for triphenyltin in China

Triphenyltin (TPT) is one of the most toxic chemicals artificially discharged into aquatic environment with human activities. Due to its intensive use in antifouling paints and adverse effects on non-target species, TPT has aroused wide concern in both saltwater and freshwater environment. Nevertheless, the water quality criteria (WQC) are not available in China, which impedes the risk assessment for this emerging pollutant. This study aims to establish the WQC of TPT for both freshwater and saltwater ecosystems. With the derived WQC, a four-level tiered ecological risk assessment (ERA) approach was employed to assess the ecological risks of this emerging pollutant in Chinese waters. Through the species sensitivity distribution (SSD) methodology, the freshwater criterion maximum concentration (CMC) and criterion continuous concentration (CCC) were derived as 396 ng Sn L-1 and 5.60 ng Sn L-1, respectively, whereas the saltwater CMC and CCC were 66.5 ng Sn L-1 and 4.11 ng Sn L-1, respectively. The ecological risk assessment for TPT demonstrated that the acute risk was negligible whereas the chronic risk was significant with HQ (Hazard Quotient) values of up to 5.669 and 57.1% of coastal waters in China facing clear risk. TPT contamination in coastal environment, therefore, warrants further concern.

Plasma biomarkers in juvenile marine fish provide evidence for endocrine modulation potential of organotin compounds

Organotin compounds, such as tributyltin (TBT) and triphenyltin (TPT), have been widely used to control marine fouling. Here, we show that organotin stimulation reduces the hormone levels in the plasma of two economically important aquaculture fish. Blood plasma samples were collected from juvenile red seabream and black rockfish exposed to environmentally realistic concentrations of TBT and TPT for 14 days. The levels of two plasma biomarkers, namely the yolk protein precursor vitellogenin (VTG) and the sex steroid 17β-estradiol (E2), were measured to determine the endocrine disrupting potential of the organotin compounds. Both organotin compounds were dose-dependently accumulated in the blood of two fish. Exposure to waterborne TBT and TBT significantly decreased the plasma VTG levels in both the juvenile fish in a dose-dependent manner. In contrast, the treatment with E2, a well-known VTG inducer, significantly increased the plasma VTG levels in both the fish. In addition, the mRNA levels of vtg were also downregulated in the liver tissues of both the fish at 100 and/or 1000 ng L−1 of TBT or TPT exposure. The plasma E2 titers were significantly suppressed at 100 and/or 1000 ng L−1 of TBT or TPT exposure for 14 days compared to their titer in the control. Since estrogen directly regulates vtg gene expression and VTG synthesis, our results reveal the endocrine disrupting potential of organotin compounds, and subsequently the endocrine modulation at early stage of fish can trigger further fluctuations in sexual differentiation, maturation, sex ration or egg production. In addition, the results demonstrate their effects on non-target organisms, particularly on animals reared in aquaculture and fisheries.

The role of pparγ in embryonic development of Xenopus tropicalis under triphenyltin-induced teratogenicity

Evidence has shown that triphenyltin (TPT) triggers severe malformations in Xenopus tropicalis embryos, partly due to activation of PPARγ (peroxisome proliferator activated receptor γ) protein. In the present study, we investigated how abundance of pparγ and TPT exposure interact and affect X. tropicalis embryonic development. We observed pparγ expression signals appeared in the neural crest and neural fold, as well as in the brain, eyes and spinal cord organs. Both pparγ overexpression and its Morpholino (MO) knockdown inhibited pax6 (paired box 6) expression, a marker of eye development, and significantly up- and down-regulated lipid and glucose homeostasis related genes, such as lpl (lipoprotein lipase), slc2a4 (solute carrier family 2 (facilitated glucose transporter), member 4) and pck1 (phosphoenolpyruvate carboxykinase 1, cytosolic), thus inducing eye phenotypes. Overexpression of pparγ induced small eye phenotype, while pparγ MO induced small eye plus turbid eye lens microencephaly and enlarged trunk. In contrast, 5–20μgSn/L (stannum/L) TPT exposure reversed some impacts induced by pparγ overexpression, i.e., no small eye, up-regulation of pax6 and down-regulation of pparγ, lpl, slc2a4 and pck1. Meanwhile, microinjection of pparγ MO combined with exposure to 20μgSn/L TPT caused 85% mortality. In brief, our work clearly indicates that pparγ is essential to eye development and inhibition of its expression combined with TPT exposure can be extremely harmful to X. tropicalis embryo.

Characterization and comparison of transcriptional activities of the retinoid X receptors by various organotin compounds in three prosobranch gastropods; Thais clavigera, Nucella lapillus and Babylonia japonica

Two cDNAs of RXR were isolated, for the first time, from the ivory shell, Babylonia japonica, and the transcriptional activities were tested in vitro to compare with other gastropod (Thais clavigera and Nucella lapillus) RXR isoforms. The transcriptional activities of all of these RXR isoforms were significantly induced by mammalian RXR agonist, 9-cis retinoic acid (9cRA). The transcriptional activity of T. clavigera RXR-1 was also examined by using 9cRA and 16 organotin compounds, and significant ligand-dependent transactivations were observed by 9cRA and 5 organotins (tributyltin (TBT), tetrabutyltin (TeBT), tripropyltin (TPrT), tricyclohexyltin (TcHT) and triphenyltin (TPhT)). These 5 organotins also induced significant transcriptional activities in N. lapillus and B. japonica RXR isoforms. These 4 organotins, except for TeBT, have been reported to promote the development of imposex after a month of a single injection each, using female T. clavigera. To investigate the function of gastropod RXR isoforms, the effects of mammalian specific pan-agonist, PA024, and pan-antagonist, HX531, were examined, and significant induction of transcriptional activity by PA024 was demonstrated in these gastropod RXR isoforms. The additions of HX531 significantly suppressed the transcriptional activities of these gastropod RXR isoforms by 9cRA and 5 organotins. Using the mammalian two retinoic acid response elements, the transcriptional activities by 2 agonists, 9cRA and PA024, were different among the RXR isoforms of each gastropod species. With retinoid X response element (RXRE), transcriptional activities of TcRXR-1, BjRXR-1, and NlRXRa were significantly higher than those of TcRXR-2, BjRXR-2, and NlRXRb. Transcriptional activities of TcRXR-2, BjRXR-2, and NlRXRb, however, were significantly higher than those of TcRXR-1, BjRXR-1, and NlRXRa with thyroid hormone response element, TREpal. Thus, induction of imposex in prosobranch gastropods is strongly suggested to be triggered by 9cRA and certain organotins, such as TBT and TPhT through the activation of RXRs. These gastropod RXRs might control the different gene transcription by forming homo- or heterodimer complex with their own isoforms. These findings will contribute to our understanding of the fundamentals of the endocrine system in molluscs, particularly on RXR signaling pathway.

Organotin exposure stimulates steroidogenesis in H295R Cell via cAMP pathway

Organotin compounds (OTs) are used in a range of industrial products, such as antifouling paints, agricultural pesticides and stabilizers. Owing to potential endocrine-disrupting effects, human exposure to such compounds is a concern. Nevertheless, little is known about the adverse effect of OTs on adrenocortical function in organisms. In this study, the human adrenocortical carcinoma cell (H295R) model was used to investigate effects of OTs on steroidogenesis and potential causes for such endocrine disruption was examined. H295R cells were exposed to several commonly used OTs, including triphenyltin (TPT), tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT), and the production level of steroid hormones were quantified. TPT and TBT decreased the production levels of 17β-estradiol, aldosterone, and cortisol, but increased that of testosterone. Furthermore, the expression levels of ten major steroidogenic genes (HMGR, StAR, CYP11A1, 3βHSD2, CYP17, CYP19A1, CYP21, CYP11B1, CYP11B2, and 17βHSD) were examined and both up-regulation of CYP11B2 and down-regulation of StAR, 3βHSD2, CYP19A1, CYP21 and CYP11B1 by TPT and TBT were observed. Intracellular levels of ATP and cyclic adenosine monophosphate (cAMP) and the activity of adenylate cyclase (AC) decreased in the H295R cells treated with TPT and TBT. No obvious changes in H295R were found with the treatment of DBT and MBT. These results suggest that OTs may stimulate steroidogenesis in vitro via inhibition of cAMP signaling pathway.

Occurrence and health risk assessment of organotins in waterworks and the source water of the Three Gorges Reservoir Region, China.

The occurrence and health risks of organotins (OTs) in the waterworks and source water in the Three Gorges Reservoir Region (TGRR), China were assessed in this study. Water samples were collected at four waterworks (A, B, C, and D) in March and July 2012 to analyze butyltins (BTs) and phenyltins (PTs) using a gas chromatography-mass spectrometry (GC-MS) system. Our results showed that both the waterworks and their nearby water sources were polluted by OTs, with PTs being the most dominant species. Monobutyltin (MBT), monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) were detected in most of the analyzed water samples. The highest concentrations of OTs in influents, effluents, and source water in March were 52.81, 17.93, and 55.32ngSnL-1, respectively. Furthermore, significant seasonal changes in OTs pollution were observed in all samples, showing pollution worse in spring compared with summer. The removal of OTs by the conventional treatment processes was not stable among the waterworks. The removal efficiency of OTs in July reached 100% at plant B, while that at plant C was only 38.8%. The source water and influents shared similar composition profiles, concentrations, and seasonal change of OTs, which indicated that OTs in the waterworks were derived from the source water. A health risk assessment indicated that the presence of OTs in the waterworks would not pose a significant health risk to the population, yet their presence should not be ignored.

Ursolic Acid Hydrazide Based Organometallic Complexes: Synthesis, Characterization, Antibacterial, Antioxidant, and Docking Studies.

In thecurrent research work,eleven metal complexes were synthesized from the hydrazide derivative of ursolic acid. Metal complexes of tin, antimony and iron were synthesized and characterized by FT-IR and NMR spectroscopy. The antibacterial and antioxidant activities were performed for these complexes, which revealed that the metal complexes synthesized are more potent than their parent compounds. We observed that antioxidant activity showed by triphenyltin complex was significant and least activity have been shown by antimony trichloride complex. The synthesized metal complexes were then evaluated against two Gram-negative and two Gram-positive bacterial strains. Triphenyl tin complex emerged as potent antibacterial agent with MIC value of 8 μg/ml each against Shigellaspp, Salmonella typhi and Staphylococcus aureus. While, the MIC value against Streptococcus pneumoniae is 4 μg/ml. Computational docking studies were carried out on molecular targets to interpret the results of antioxidant and antibacterial activities. Based on the results, it may be inferred that the metal complexes of ursolic acid are more active as compared to the parent drug and may be proved for some other pharmacological potential by further analysis.

Effects of triphenyltin on glycinergic transmission on rat spinal neurons

Glycine is a fast inhibitory transmitter like γ-aminobutyric acid in the mammalian spinal cord and brainstem, and it is involved in motor reflex, nociception, and neuronal development. Triphenyltin (TPT) is an organometallic compound causing environmental hazard to many wild creatures. Our previous findings show that TPT ultimately induces a drain and/or exhaustion of glutamate in excitatory presynaptic nerve terminals, resulted in blockage of neurotransmission as well as methylmercury. Therefore, we have investigated the neurotoxic mechanism how TPT modulates inhibitory glycinergic transmission in the synaptic bouton preparation of rat isolated spinal neurons using a patch clamp technique. TPT at environmentally relevant concentrations (3–300 nM) significantly increased the number of frequency of glycinergic spontaneous and miniature inhibitory postsynaptic currents (sIPSC and mIPSC) without affecting the current amplitude and decay time. The TPT effects were also observed in external Ca2+-free solution containing tetrodotoxin (TTX) but removed in Ca2+-free solution with both TTX and BAPTA-AM (Ca2+ chelator). On the other hand, the amplitude of glycinergic evoked inhibitory postsynaptic currents (eIPSCs) increased with decreasing failure rate (Rf) and paired pulse ratio (PPR) in the presence of 300 nM TPT. At a high concentration (1 µM), TPT completely blocked eIPSCs after a transient facilitation. Overall, these results suggest that TPT directly acts transmitter-releasing machinery in glycinergic nerve terminals. Effects of TPT on the nerve terminals releasing fast transmitters were greater in the order of glycinergic > glutamatergic > GABAergic ones. Thus, TPT is supposed to cause a strong synaptic modulations on glycinergic neurotransmission in wild creatures.

The Evidence of Imposex in Turbo sp. from Ujungpiring Waters of Jepara

Imposex is an endocrine disruption syndrome, in which females of marine gastropods develop sexual characteristics of males (penis and/or vas deferens). This syndrome is caused by tributyltin (TBT) or triphenyltin (TPT), toxic organotin compounds found in naval paints used as antifouling system in boats and artificial structures. The main objective of this study was to assess the incidence and severity of imposex in Turbosp.A hundred individus of Turbo sp was collected from Ujung Piring waters of Jepara, and observed for their sex and imposex. The results showed that the ratio male and female was 1.13 : 1, and the frequency of imposex females was 64.58%. The relative penis size were longer in imposex female than in male. The possibility of pollution was clearly shown from high evidence of imposex female.

Stability studies of endocrine disrupting tributyltin and triphenyltin compounds in an artificial sea water model.

Triorganotins belong to toxic components present predominantly in antifouling paints for marine vessels. Tributyltin/triphenyltin at pico- or nanomolar concentrations in sea water are known to induce an irreversible sexual abnormality in females of over 190 marine species, an "imposex" phenomenon - the superimposition of male genitalia on a female. Moreover, trialkyltins and triaryltins function as potent nuclear retinoid X receptors (RXR) agonists. In mammals, triorganotin compounds induce immunosuppressive, metabolic, reproductive or developmental effects. Toxic effects of triorganotins warrant the need for monitoring of their long-lasting presence in the environment. This study brings novel data on the stability of two triorganotin compounds in artificial sea water model obtained by applying ultra-pressure liquid chromatography (UPLC) and gas chromatography-mass spectrometry (GC-MS) methods. Stability of tributyltin and triphenyltin chlorides was studied for 180 days and the degradation kinetic parameters were obtained. Tributyltin chloride was the less stable with the degradation kinetic parameters Kdeg = 0.00014 day-1 and t1/2 = 4950 days (13.6 years). Kdeg of the more stable triphenyltin chloride was determined to be Kdeg = 0.00006 day-1 with t1/2 = 11550 days (31.6 years). Since similar stability data of triorganotin compounds were not published previously, we report high stability for both tested compounds, which indicates a significant environmental problem when these substances enter sea water and later coastal sediments.

Development and evaluation of a new diffusive gradients in thin-films technique for measuring organotin compounds in coastal sediment pore water

Organotins present a toxicological risk to biota in the aquatic environment. Understanding the behaviour of these compounds in sediment is challenging, with sophisticated analytical techniques required for their measurement. We investigated the use of silica-bound sorbents for diffusive gradients in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic strength ranges typical of coastal waters. Recoveries from adsorption gels deployed in filtered sea water were MBT = 123 ± 20%, DBT = 75 ± 12%, TBT = 81 ± 16%, DPhT = 72 ± 30%, TPhT = 58 ± 10% respectively. Devices were used to investigate DGT fluxes and pore water concentrations of organotins in coastal sediment collected from a contaminated site. DGT fluxes measured in sediment cores for the five organotins ranged between 4.3 × 10−8 and 1.6 ×10−5ngcm2s−1. The depletion of organotin species within pore waters at the interface with DGT devices was measured over a series of deployment times (2, 7, 14, 21 and 28 days) and provided estimates of the concentration of organotins in pore waters at Langstone Harbour, UK, prior to depletion by the DGT device and information on their spatial heterogeneity. The novel in situ DGT device developed can pre-concentrate organotins from pore waters in coastal sediment core samples and allows their detection at low environmental concentrations using conventional gas chromatographic/mass spectrometric instrumentation. Use of the DGT device overcomes many problems associated with the conventional pore water sampling of organotins. Our preliminary data suggests it has potential in the future to be a useful tool in investigating the environmental fate of these pollutants. The use of the C8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water.

Simultaneous Cell Disruption Extraction and Purification Followed by Two-phase Derivatization Procedure for the Determination of Organotin Compounds in Wet Biological Samples by GC–MS

Freeze-dried biological samples used for the determination of organotin compounds (OTCs) involve complicated or tedious pretreatment (e.g., freeze-drying) that may result in loss of analyst or contamination. In the present study, a rapid and accurate method for determination of five kinds of OTCs—monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT) and triphenyltin (TPhT) in fresh biota samples—was developed and further compared with freeze-dried tissues. It involved a sample preparation method of simultaneous extraction and purification of OTCs in fresh biological samples, which was developed with ultrasonic cell disruption and primary secondary amine (PSA) adsorption, and followed by two-phase (organic solvent and cell membrane phases) derivatization before the analysis by gas chromatography–mass spectrometry. The extraction efficiency from biota matrices was relatively better with the acetate/acetic acid and tropolone into methanol as extraction agents and primary secondary amine as grease-removing agents. The retention of cell membrane-like materials as well as 25% of ethyl acetate as co-extraction reagents used after centrifugation improved the targeted OTCs’ recoveries. The proposed method, under the optimal condition, has shown satisfactory performance in wet biological samples. The limits of detection obtained were less than 10 ng Sn g−1 ww (wet weight) for all analytes. Spiked recoveries were within the range 89–118% and the relative standard deviations were less than 7% (n = 5) when quantified by matrix-matched calibration curves. Finally, the applicability of this new method was further verified by comparing the results from wet and freeze-dried oyster tissues collected from two coastal cities in China.

Effects of triphenyltin on reproduction in Japanese medaka (Oryzias latipes) across two generations

Triphenyltin (TPT) is an organotin compound used in marine anti-fouling coatings to prevent the attachment and growth of marine organisms, and it has negative effects on aquatic organisms. TPT is still detected at low concentrations, although its use has been prohibited at least in the European Community and is restricted in Japan as well. Studies using Japanese medaka (Oryzias latipes) indicate that TPT has the potential to inhibit reproduction. Although TPT is detected in many aquatic ecosystems, the multi-generational impact of TPT remains unknown. We investigated the two-generational effects of TPT on Japanese medaka and examined the relationships of several such effects between the F0 and F1 generations. Suppression of fecundity was observed in both generations, and fertility and growth were inhibited in the F1 generation. Moreover, delayed hatching and lower hatchability were observed in F1 embryos. Importantly, the value of the lowest observed effect concentration (LOEC) for these influences in F1 was lower than that in F0: that is, the LOEC values of fecundity and mortality were 3.2μg/L in the F0 generation and 1.0μg/L in the F1 generation. Fertility was not affected by TPT in F0, whereas it was significantly suppressed in the 1.0μg/L-exposure group of the F1 generation. Our results provide the first evidence of the effects of TPT on reproduction in a teleost fish across two generations, highlighting the concern that TPT could affect reproduction and mortality at decreasing concentrations in temporally overlapping generations.

Differences in bioaccumulation and transfer ability between tributyltin and triphenyltin from parental female to offspring in viviparous surfperch Ditrema temmincki

To examine the risk of transgenerational transfer of organotin compounds (OTs) in fish, tributyltin (TBT) and triphenyltin (TPT) compounds and their breakdown products were determined in both parental females and offspring of viviparous surfperch Ditrema temmincki collected from Japanese coastal waters. TBT concentrations (Mean ± SD) in the offspring (34 ± 5.7 ng Sn g−1 wet wt) were significantly higher (10–17 times) than in the parental females (2.8 ± 1.0 ng Sn g−1 wet wt). In the offspring, TBT was the predominant butyltin compound (82 ± 1.6% ∑BTs = TBT + DBT + MBT), and represented a greater proportion than in the parental females (51 ± 9.3% as TBT). TPT concentrations were significantly lower than TBT, and the ratio of TPT in parental females, relative to offspring, was different from TBT. TPT concentrations in the offspring (0.8 ± 0.3 ng Sn g−1 wet wt) were almost identical to those in the parental females (1.0 ± 0.5 ng Sn g−1 wet wt). TPT was the predominant phenyltin (∑PTs = TPT + DPT + MPT) in both offspring (73 ± 12% as TPT) and parental females (72 ± 18% as TPT). Results suggest that the transfer rate of TBT from parent to offspring could be much faster than its degradation rate in the offspring, accounting for higher accumulation of TBT in the latter. In contrast, the transfer rate of TPT is slower than its biodegradation, leading to a lower concentration of TPT in the offspring. It is therefore likely that the offspring might be at a higher risk from TBT than the parental females during their early growth stage in ovary in the viviparous surfperch whereas exposure to TPT is comparable in both generations.

Biomonitoring of metals by aquatic mosses in a mining region

The aim of this work is to estimate background concentrations of organometallic compounds, such as tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT), monophenyltin (MPhT), methylmercury (MeHg), inorganic mercury (iHg) and diethyllead (Et2Pb) in the aquatic environment at the French national scale.Both water and sediment samples were collected all over the country, resulting in 152 water samples and 123 sediment samples collected at 181 sampling points. Three types of surface water bodies were investigated: rivers (140 sites), lakes (19 sites) and coastal water (42 sites), spread along the 11 French river basins. The choice of sites was made on the basis of previous investigation results and the following target criteria: reference, urban sites, agricultural and industrial areas. The analytical method was properly validated for both matrices prior to analysis, resulting in low limits of quantification (LOQ), good precision and linearity in agreement with the Water Framework Directive demands. The results were first evaluated as a function of their river basins, type of surrounding pressure and water bodies. Later, background concentrations at the French national scale were established for both water and sediment matrices, as well as their threshold, i.e., the concentration that distinguishes background from anomalies or contaminations. Background concentrations in water are ranging between <0.04–0.14 ng Hg. L−1 for MeHg, <0.14–2.10 ng Hg. L−1 for iHg, <1.0–8.43 ng Pb. L−1 for Et2Pb and 0.49–151 ng Sn. L−1, <0.08–3.04 ng Sn. L−1 and <0.08–0.25 ng Sn. L−1 for MBT, DBT and TBT, respectively. For sediments, background concentrations were set as <0.09–1.11 ng Hg. g−1 for MeHg, <0.06–24.3 ng Pb. g−1 for Et2Pb and <1.4–13.4 ng Sn. g−1, <0.82–8.54 ng Sn. g−1, <0.25–1.16 ng Sn. g−1 and <0.08–0.61 ng Sn. g−1 for MBT, DBT, TBT and DPhT, respectively. TBT occurs in higher concentrations than the available environmental protection values in 24 and 38 sampling sites for both water and sediment samples, respectively. Other phenyltins (MPhT and TPhT) did not occur above their LOQ and therefore no background was possible to establish. Throughout this work, which is the first assessment of background concentrations for organometallic compounds at the French national level ever being published, it was possible to conclude that over the last 10–20 years organotin concentrations in French river basins have decreased while MeHg concentration remained stable.

Triphenyltin recognition by primary structures of effector proteins and the protein network of Bacillus thuringiensis during the triphenyltin degradation process

Herein, triphenyltin (TPT) biodegradation efficiency and its transformation pathway have been elucidated. To better understand the molecular mechanism of TPT degradation, the interactions between amino acids, primary structures, and quaternary conformations of effector proteins and TPT were studied. The results verified that TPT recognition and binding depended on amino acid sequences but not on secondary, tertiary or quaternary protein structure. During this process, TPT could change the molecular weight and isoelectric point of effector proteins, induce their methylation or demethylation, and alter their conformation. The effector proteins, alkyl hydroperoxide reductase and acetyl-CoA acetyltransferase, recognizing TPT were crucial to TPT degradation. Electron transfer flavoprotein subunit alpha, phosphoenolpyruvate carboxykinase, aconitate hydratase, branched-chain alpha-keto acid dehydrogenase E1 component, biotin carboxylase and superoxide dismutase were related to energy and carbon metabolism, which was consistent with the results in vivo. The current findings develop a new approach for investigating the interactions between proteins and target compounds.

Toxicity of triphenyltin on the development of retinal axons in zebrafish at low dose

The impacts of triphenyltin (TPT) on ecological health are of particular concern due to the unexpectedly high levels found in wild fish around the world. Here, zebrafish embryos were exposed to TPT via in ovo nano-injection to study its toxicity on the development of retinal axons in fish. Lipophilic dye labeling revealed obvious defects in retinal axon development in larvae with normally shaped eyes, with incidences of 0, 1.08%, 2.66%, 4.26%, and 6.85% observed in the control, 0.8, 4.0, 20.0, and 100ng TPT-Cl/g wet weight (ww) exposure groups, respectively, showing a dose-dependent increase. Since the lowest observable effective concentration of TPT to induce retinal axon development defects was 0.8ng TPT-Cl/g ww, which is lower than the concentrations in wild fish eggs, this defect would occur in wild fish larvae. Alterations in the expressions of pax6 and ephrinBs, which regulate the establishment of retinal polarity, were correlated with defect incidence. Expression levels of the CYP26A1 gene and protein were significantly up-regulated in all exposure groups compared with the control, which may lead to significant decreases in concentrations of all-trans retinoic acid (atRA). Such a disruption of RA metabolism would, at least partly, contribute to the incidence of developmental defects in retinal axons. This study is the first to report that TPT can interfere with development of retinal axons in fish at low dose.