Organotin Research Articles

Synthesis, structures, antioxidant, and antifungal activities of organotin(IV) complexes derived from 1-(3′-carboxyphenylhydrazono)naphthalene-2-one

In this study, the hydrazone ligand 1-(3′-carboxyphenylhydrazono)naphthalene-2-one (H2L) was employed to generate three new organotin(IV) compounds with the general formula of [R x SnIV(HL) y ] (where R = Me, x = y = 2 (1); R = n-Bu, x = 3, y = 1 (2), and R = Ph, x = 3, y = 1 (3)). The single-crystal structures of 1 and 3 were examined to establish the coordination environment about Sn(IV). Compound 1 possesses a hepta-coordinate homo-polymer with a chromophoric coordination environment of Me2SnIVO5. Compound 3, on the other hand, has monomeric distorted tetrahedral geometry with Ph3SnO chromophoric unit. The 119Sn-NMR signals in the spectra of 1–3 are found to be at 145.5, 120.1, and −104.4 ppm, respectively, indicating that they are isostructural and adopt four-coordinate tetrahedral geometry in solution. The bioactivities of 1 and 3 among the three are distinct. The antioxidant activity of 1 in ethanol is the highest, with a 45.64% DPPH-scavenging efficiency, whereas 3 shows excellent antifungal efficacy against Penicilium chrysogenum, with a 21 mm inhibited zone at 750 μg/mL, which is significantly higher than that of standard drug amphotericin-B. Thus, the compounds could be treated as potential antioxidant and antifungal agents.

Organotin compound as an inhibitor of nitric oxide formation

Organotin compound as an inhibitor of nitric oxide formation

Mobility of metal-organic pollutants in the emerging coastal-marine sediment of the Baltic Sea: The case-example of organotin compounds in sediments of the Gulf of Finland

Results of organotin and heavy metals pollution study of bottom sediment within three key areas in the Eastern Gulf of Finland (Baltic Sea) in the vicinity of Gogland and Moschny Islands and Vyborg Bay sampled during two seasons of 2017 and 2018 are presented.The studied bottom sediments contain organotin compounds in amounts (∑OTs from 5.7 to 123 ng/g) exceeding the permissible international standards, which can have a toxic effect and lead to pathological changes of aquatic organisms. The tributyltin was the prevail component of organotin compounds in bottom sediments in 2017, which high content (average 6.3 and 30 ng/g for Moschny and Gogland islands respectively) and low degradation coefficient (BDI: 0.1–0.8) indicate a permanent source of pollution. But the 2018 samples show an increase in BDI up to 1.7–3.3 that reveals the degradation of tributyltin over the annual period. But further monitoring of environmental pollution in the study areas is obviously necessary in view of the potential impact of these components on the irreversible change in the environmental situation for the entire Baltic region.

ВЛИЯНИЕ ГИБРИДНЫХ ОЛОВООРГАНИЧЕСКИХ СОЕДИНЕНИЙ В МАКСИМАЛЬНО ЭФФЕКТИВНОЙ ДОЗЕ НА РОСТ И АКТИВНОСТЬ МЕТАСТАЗИРОВАНИЯ МЕЛАНОМЫ В16 У МЫШЕЙ ЛИНИИ C57BL/6

Metastasis is a complex multicomponent process that largely determines the effect of the tumor process on the body. The study of indicators of changes in the activity of metastasis under the influence of new antitumor agents is one of the most important tasks of experimental pharmacology and oncology. The effect of the organotin compounds (OOS) bis (3,5-di-tert-butyl-4-hydroxyphenylthiolate) dimethylolol (Me3) and (3,5-di-tert-butyl-4-hydroxyphenylthiolate) triphenylolol (Me5) was studied at the maximum effective total doses of 375 mg/kg and 250 mg/kg, respectively, on a model of a spontaneously metastasizing transferable tumor melanoma B16. Both compounds showed a high antimeta- static effect, more pronounced for the dialkyl organic compound.

Acute Toxicity of a Novel anti-fouling Material Additive DCOIT to Marine Chlorella sp

DCOIT (4,5-dichloro-2-n-octyl-4-isothiazolin-3-one) is the main ingredient in SeaNine-211, a new antifouling agent that replaces organotin compounds to prevent the growth of fouling organisms on board. Biocides from antifoulants can cause problems for marine ecosystems by destroying non-target algal species. This study evaluated the potential adverse effects DCOIT using the Marine Chlorella sp. The concentration of DCOIT were set according to the semi-inhibitory concentrations for acute exposure experiments, and relevant oxidative stress indicators were measured to assess the acute toxic effects. The results showed that the inhibition concentrations (IC50) of DCOIT against Marine Chlorella sp was 2.522mg/L. The genes related to photosynthesis and antioxidant capacity showed the effect of promoting low concentration and inhibiting high concentration. In addition, based on the ultrastructural observation and the expression analysis of photosynthesis related genes, it was found that DCOIT had a significant effect on plant photosynthesis.

Occurrence and risk assessment of organotin compounds in the surface water of the upper Yangtze River Estuary

Organotin compounds (OTCs) are a category of persistent toxic substances with endocrine disrupting effects and may pose a risk to aquatic organisms and human health via water. This study collected 78 surface water samples from the drinking water source in the upper Yangtze River Estuary from July 2018 to November 2019. Out of the nine OTC targets, tributyltin (TBT), dimethyltin (DMT), trimethyltin (TMT), dibutyltin (DBT), and monobutyltin (MBT) were detected from more than 50% of the water samples, with cumulative concentrations of OTCs ranging from 42.5 ± 54.0 to 421 ± 176 ng Sn L−1. The composition and concentrations of OTCs in the stormy months were different from those in other months. The concentrations of OTCs with the ebbing tide exceeded those in the flooding tide and increased when the flooding tide transitioned to the ebbing tide. A pulsed trend in concentrations of OTCs in river water was evident due to the impact of rainfall runoff and tidal currents. Identified sources of OTCs included ship antifouling paints, agricultural pesticides, and plastic waste. TBT in water sources poses a low risk to human health and a risk to the ecosystem, particularly during the stormy months.

Use of GAL4 factor-based yeast assay to quantify the effects of xenobiotics on RXR homodimer and RXR/PPAR heterodimer in scallop Chlamys farreri

Retinoid X receptor (RXR) and peroxisome proliferators-activated receptors (PPAR) have been shown as important targets of endocrine disrupting effects caused by organotin compounds (OTCs). In vitro methods for non-model species are instrumental in revealing not only mechanism of toxicity but also basic biology. In the present study, we constructed the GAL4 factor-based recombinant yeast systems of RXRα/RXRα (RR), RXRα/PPARα (RPα) and RXRα/PPARγ (RPγ) of the scallop Chlamys farreri to investigate their transcriptional activity under the induction of OTCs (tributyltin chloride, triphenyltin chloride, tripropyltin chloride and bis(tributyltin)oxide), their spiked sediments and five other non‑tin compounds (Wy14643, rosiglitazone, benzyl butyl phthalate, dicyclohexyl phthalate and bis(2-ethylhexyl) phthalate). The results showed that the natural ligand of RXR, 9-cis-retinoic acid (9cRA), induces transcriptional activity in all three systems, while four OTCs induced the transcriptional activity of the RR and RPα systems. None of the five potential non‑tin endocrine disruptors induced effects on the RPα and RPγ systems. The spiked sediment experiment demonstrated the feasibility of the recombinant yeast systems constructed in this study for environmental sample detection. These results suggest that OTCs pose a threat to affect function of RXRα and PPARα of bivalve mollusks. The newly developed GAL4 factor-based yeast two-hybrid system can be used as a valuable tool for identification and quantification of compounds active in disturbing RXR and PPAR of bivalves.

Hollow-Fiber Liquid-Phase Micro-Extraction Method for the Simultaneous Derivatization, Extraction, and Pre-concentration of Organotin Compounds from Packed Fruit Juices

Organotin compounds are widely employed as pesticides and fungicides in agriculture and as stabilizers for the industrial manufacture of polyvinyl chloride and other polymers. Accordingly, these endocrine disruptors can be found in a variety of foods and beverages. In the present study, we describe the optimization of a hollow-fiber liquid-phase micro-extraction approach for the simultaneous derivatization, extraction, and pre-concentration of butyltin species from commercial fruit juices with the aim of investigating their migration from the packaging. The best extraction efficiencies were achieved by using hexane as the acceptor solvent and a polypropylene fiber length of 2 cm, whereas the agitation speed, extraction temperature, and total extraction time were set at 1100 rpm, 25 ºC, and 10 min, respectively. Using these optimal conditions, the method was satisfactorily validated in terms of linearity (5–1000 µg L−1), limits of detection (0.8–1.8 µg L−1), recovery (80.5–92.1%), intraday precision (10.2–13.1%), inter-day precision (11.0–15.5%), matrix effect (83.2–91.8%), accuracy (85.2–95.2%), specificity, and carryover. The application of this technique to commercial samples obtained from a local market demonstrated that levels of organotin species in packed fruit juices are negligible, in agreement with the limits established by the European Food Safety Authority (0.14 mg of total organotin compounds per kg of food).

Concentrations of organotin compounds in aquatic biota in coastal waters of Johor, Malaysia

AbstractThe concentrations of organotin (OT) compounds, butyltin (BT) and phenyltin (PT), in aquatic organisms from Merambong and Tinggi Island, Malaysia, which differ in industrial and economic activities, were measured. Tributyltin (TBT) compounds among BTs ranged from 2.9–28 and <0.1–21 ng g−1 ww in aquatic organisms from Merambong and Tinggi Island, respectively. Triphenyltin (TPT) compounds among PTs ranged from <0.1–25 ng g−1 ww and <0.1–61 ng g−1 ww in aquatic organisms from Merambong and Tinggi Island, respectively. A survey of OT concentrations among the species of OT compounds revealed that the concentrations of BTs and PTs in crabs and clams were high while those in fish were low. Correlation analysis with stable nitrogen isotopes suggest that OT compounds did not accumulate in aquatic organisms through the food web. The measurement of OT compounds in tissues and organs of fish revealed that BT concentrations in liver were higher than those in muscle and that BTs were detected in eggs of fish.

Effect of chain length on the cytotoxic activity of (alkyl-ω-ol)triphenyltin(IV) loaded into SBA-15 nanostructured silica and in vivo study of SBA-15~Cl|Ph3Sn(CH2)8OH.

A series of nanostructured SBA-15-based materials functionalized with the tetraorganotin(IV) metallodrugs Ph3Sn(CH2)nOH (n=3, 4, 6, 8 and 11) are synthesized and structurally characterized by different techniques used in solid-state chemistry. The cytotoxicity of both the organotin(IV) compounds and the tin-functionalized SBA-15 materials are studied against different cancer cell lines observing that the materials have similar cytotoxic activity in comparison with the free organotin compounds in terms of mass. However, considering that the percentage of active metal compound loaded into material is low, the utilization of mesoporous silica as drug vehicle clearly improves the cytotoxic effectiveness of metal-based drugs against cancer cells. One of the most potent between all tested systems is material SBA-15~Cl|Ph3Sn(CH2)8OH. Its cytotoxicity seems to come from additional mechanisms apart from apoptosis provoking cell reprogram in B16 melanoma into more mature and less aggressive phenotype. Moderated production of ROS/RNS is probably in the background of observed phenomenon. Obtained results are further confirmed in syngeneic mouse model of melanoma in C57BL6 mice. The in vivo results show that SBA-15 do not disturb tumor growth, while both Ph3Sn(CH2)8OH and SBA-15~Cl|Ph3Sn(CH2)8OH significantly decreases tumor volume with an enhancement of the antitumor potential of the tetraorganotin(IV) compound upon immobilization in SBA-15.

Novel Organotin-Loaded Plastic Scintillators Toward Gamma Spectroscopy Applications

In this work, we report polyvinyl toluene (PVT)-based plastic scintillators highly loaded with five different kinds of organotin compounds. The newly developed Sn-loaded plastic scintillators demonstrate the capability of gamma spectroscopy detection with fast decay characteristics. The maximum of organotin loading ratio of 33 wt% (10.8 wt% Sn) was achieved in tributyl(1-ethoxyvinyl) tin. PVT plastic scintillators containing 20 wt% tributyl(1-ethoxyvinyl) tin have optimal performance, providing gamma-ray spectroscopy with a light yield of 7100 photons/MeV and an energy resolution of 11.7% at 662 keV.

Comparative Analysis of the Pharmacological Activity of Bis(3,5-di-Tert-Butyl-4-Hydroxyphenylthiolate)Dimethylol in Different Modes of Administration on a Mouse Model of Melanoma B16 Tumor Growth.

We performed a comparative analysis of the pharmacological activity of the hybrid organotin compound bis(3,5-di-tert-butyl-4-hydroxyphenylthiolate)dimethylol (Me-3) administered in different modes to mice with transplanted melanoma B16 to identify the most effective dosage regimen. Three modes of administration were used: preventive (before transplantation of tumor cells), classical according to Z. P. Sof'ina (48 h after transplantation of tumor cells), and delayed (7 days after transplantation of tumor cells, after formation of nodules of the primary tumor node). Compound Me-3 was administered at a total dose of 375 mg/kg intraperitoneally once a day for 5 days. The classical mode of administration was identified as the most effective, which indicates the preventive antimetastatic activity of Me-3 on the model of the transplanted mouse tumor melanoma B16.

Catalysts in the Direct Synthesis of Organotin Compounds, Part III: Reactions between Carbofunctional Organohalides and Metallic Tin

Catalysts in the Direct Synthesis of Organotin Compounds, Part III: Reactions between Carbofunctional Organohalides and Metallic Tin

Organotins Remain a Serious Threat to the Indo-Pacific Humpback Dolphins in the Pearl River Estuary.

Marine mammals often accumulate high levels of environmental contaminants, even those that are globally regulated regarding usage, raising concerns about their health status. Here, we conducted the first investigation of tissue distribution, spatiotemporal trends, and potential risks of six organotin compounds (OTs) in Indo-Pacific humpback dolphins (n = 101) from the northern South China Sea during 2003-2021. We detected the highest level of hepatic triphenyltin in these humpback dolphins compared with the results reported in cetaceans globally, and the liver accumulated the highest OT concentrations than other analyzed tissues. Despite the downward trend of butyltins in humpback dolphins after the global ban on the use of OTs as antifouling paints, levels of phenyltins have continued to increase over the past 20 years, suggesting that the other applications of phenyltins in South China remain prevalent. In vitro and in vivo analyses revealed that tissue-relevant doses of OTs could induce agonistic effects on the dolphin peroxisome proliferator-activated receptor γ as a master regulator of lipid homeostasis and altered the dolphin fatty acid profiles. Our results highlight the lipid-disrupting effects of current OT exposure in humpback dolphins and emphasize the need for further efforts to eliminate OT contamination in South China.

Physiological responses in Nile tilapia (Oreochromis niloticus) induced by combined stress of environmental salinity and triphenyltin

Triphenyltin (TPT) has attracted considerable attention owing to its vitality, bioaccumulation, and lurking damage. TPT widely exists in complex salinity areas such as estuaries and coastal regions. However, there are few studies on the toxicological behavior of TPT under different salinity. In the study, juvenile Nile tilapia (Oreochromis niloticus) were utilized as model animals to investigate the effects of environmental relevant TPT exposure on the osmoregulation and energy metabolism in gill under different salinity. The results showed that salinity and TPT single or combined exposure affected the morphology of the gill tissue. After TPT exposure, Na+-K+-ATPase (NKA) activity significantly decreased at 0 ppt, while NKA and Ca2+-Mg2+-ATPase (CMA) activities significantly increased at 15 ppt. In addition, significantly higher succinate dehydrogenase (SDH) and lactate dehydrogenase (LDH) activities were found in the control fish compared to the TPT-exposed ones at 15 ppt. Quantitative real-time PCR results showed that TPT exposure affected the expression of osmoregulation and energy metabolism-related genes under different salinity. Overall, TPT exposure interfered with osmoregulation and energy metabolism under different salinity. The study will provide reference data for assessing the toxicity of organotin compounds in complex-salinity areas.

Organotin contamination in seafood from the Yucatán Peninsula, Mexico: Is there a potential risk for the health of consumers?

Since seafood is considered an important source of organotin compounds (OTCs), the present study assessed the potential risk to human health of ingesting butyltins (BTs) and phenyltins (PhTs) along with this type of food. Seafood samples were collected at five fishing sites in the Yucatán Peninsula (Mexico) during February and March 2018. In general, organotins were detected in all samples, suggesting a widespread occurrence of these compounds in the investigated region. The average concentration of total organotins in the muscle of demersal fish (Lutjanus synagris, Lutjanus campechanus, Calamus pennatula, Haemulon plumierii, Rhomboplites aurorubens), pelagic fish (Euthynnus alletteratus, and Opisthonema oglinum), gastropods (Melongena bispinosa and Strombus pugilis), oyster (Crassostrea virginica) and shrimp (Penaeus duorarum) was 146.7 ± 76.2, 93.1 ± 92.6, 61.0 ± 53.0, 76.7 ± 2.6, and 28.8 ± 2.7 ng Sn g−1 dry weight, respectively. Overall, MPhT among PhTs was the dominant compound in fish, while TBT among BTs was the dominant compound in shellfish. Regarding the toxic OTCs, TBT followed by DBT were the predominant compounds in all seafood species, while TPhT was below the quantification limit in most samples. The estimated daily intake values were lower than the tolerable daily intake (TDI) for the sum of organotins established by the European Food Safety Authority (EFSA). Furthermore, the hazard quotients (HQ) and hazard indices (HI) values were all lower than 1, suggesting that daily exposure to these levels of organotins is unlikely to cause any harm to the human health of seafood consumers at the Yucatán Peninsula. Thus, consumers may not be at risk through the inclusion of these investigated seafood species in their normal diet. However, due to the increasing coastal urbanization, maritime activities, and the likely illegal use of tin-based paints in Mexico, additional monitoring is needed to assess organotin levels in other regions along the Mexican coastal zone and using other seafood species.

Evaluation of female masculinization in Pomacea canaliculata (Caenogastropoda, Ampullariidae) induced by tributyltin, heavy metals, and uranium in culture water.

All female Pomacea canaliculata develop a small, male-like copulatory apparatus a few days after birth, which growths slowly until sexual maturity, and even further in older age. Previous studies have found trace elements like mercury (Hg), arsenic (As) and uranium (U) in tap water used for snail culture, and that these elements were accumulated in snail tissues. Here, we test whether the presence of these metals at maximum allowed concentrations (Environmental Protection Agency - EPA) in aquarium water could affect the development of the copulatory apparatus in mature females. Females of different ages were used as controls, grown in reconstituted metal-free water with or without the addition of Hg, As and U, as well as tributyltin (TBT), a compound used as masculinizing agent. Six and seven months old females cultured in tap water showed a longer penis and penile sheath, and a greater overall development of the copulatory apparatus, measured by an index (DI), as compared with same-age females cultured in reconstituted water. Moreover, when females were exposed to Hg, As or U at the maximum contaminant levels for human consumption allowed by EPA regulations, there was no further development of the copulatory apparatus, while there was a clearly positive effect in TBT-exposed females. This study confirms the masculinizing effect of organotin compounds on female copulatory apparatus and discusses the usefulness of the development of these organs as a bioindicator of environmental pollution.

Fit-for-Purpose Assessment of QuEChERS LC-MS/MS Methods for Environmental Monitoring of Organotin Compounds in the Bottom Sediments of the Odra River Estuary.

Organotin compounds (OTCs) are among the most hazardous substances found in the marine environment and can be determined by either the ISO 23161 method based on extraction with non-polar organic solvents and gas chromatography analysis or by the recently developed QuEChERS method coupled to liquid chromatography-mass spectrometry (LC-MS/MS). To date, the QuEChERS LC/MS and ISO 23161 methods have not been compared in terms of their fit-for-purpose and reliability in the determination of OTCs in bottom sediments. In the case of ISO 23161, due to a large number of interferences gas chromatography-mass spectrometry was not suitable for the determination of OTCs contrary to more selective determination by gas chromatography with an atomic emission detector. Moreover, it has been found that the derivatization of OTCs to volatile compounds, which required prior gas chromatography determination, was strongly affected by the sediments’ matrices. As a result, a large amount of reagent was needed for the complete derivatization of the compounds. Contrary to ISO 23161, the QuEChERS LC-MS/MS method did not require the derivatization of OTC and is less prone to interferences. Highly volatile and toxic solvents were not used in the QuEChERS LC-MS/MS method. This makes the method more environmentally friendly according to the principles of green analytical chemistry. QuEChERS LC-MS/MS is suitable for fast and reliable environmental monitoring of OTCs in bottom sediments from the Odra River estuary. However, determination of di- and monobutyltin by the QuEChERS LC-MS/MS method was not possible due to the constraints of the chromatographic system. Hence, further development of this method is needed for monitoring di- and monobutyltin in bottom sediments.

Speciation of organotin compounds in water and seafood samples by online hyphenation of porous polymer-based magnetism-enhanced in-tube solid phase microextraction and HPLC

A new strategy based on online hyphenation of magnetism-enhanced in-tube solid phase microextraction (ME-SPME) and HPLC was developed for speciation of organotin compounds (OTCs) in water and seafood samples. Task specific porous polymer embedded magnetic nanoparticles (TPM) was fabricated in capillary and utilized as the microextraction column (MEC) of ME-SPME. The implement of magnetic field during extraction duration obviously improved extraction efficiencies of prepared TPM/MEC towards studied TOCs from 48.0-77.0% to 84.2–99.7%. Under the optimized extraction parameters, sensitive and automatic approach for the quantification of TOCs was developed by online hyphenation of ME-SPME and HPLC with fluorescence detection. The limits of detection for water and seafood samples were in the ranges of 0.0030–1.5 μg/L and 0.71–14 μg/kg, respectively. The established method was employed to measure low contents of studied OTCs in actual samples, and the recoveries at different fortified contents varied from 80.2% to 116% with satisfactory reproducibility (RSDs below 10%). In addition, confirmation experiments were adopted to inspect the accuracy of introduced method.

Trans-Anethole Alleviates Trimethyltin Chloride-Induced Impairments in Long-Term Potentiation.

Trans-anethole is an aromatic compound that has been studied for its anti-inflammation, anticonvulsant, antinociceptive, and anticancer effects. A recent report found that trans-anethole exerted neuroprotective effects on the brain via multiple pathways. Since noxious stimuli may both induce neuronal cell injury and affect synaptic functions (e.g., synaptic transmission or plasticity), it is important to understand whether the neuroprotective effect of trans-anethole extends to synaptic plasticity. Here, the effects of trimethyltin (TMT), which is a neurotoxic organotin compound, was investigated using the field recording method on hippocampal slice of mice. The influence of trans-anethole on long-term potentiation (LTP) was also studied for both NMDA receptor-dependent and NMDA receptor–independent cases. The action of trans-anethole on TMT-induced LTP impairment was examined, too. These results revealed that trans-anethole enhances NMDA receptor-dependent and -independent LTP and alleviates TMT-induced LTP impairment. These results suggest that trans-anethole modulates hippocampal LTP induction, prompting us to speculate that it may be helpful for improving cognitive impairment arising from neurodegenerative diseases, including Alzheimer’s disease.