Synthesis, structures, and cytotoxicity insights of organotin(IV) complexes with thiazole-appended pincer ligand.

Diorganotin complexes of the compositions [Me2Sn(L)] (1), [n-Bu2Sn(L)] (2), [Ph2Sn(L)]⋅C6H6 (3), [Bz2Sn(L)]⋅C6H6 (4) and [n-Oct2Sn(L)] (5) were synthesized by reacting R2SnO (R = Me, n-Bu, Ph, Bz or n-Oct) with the N2,N6-di(thiazol-2-yl)pyridine-2,6-dicarboxamide (H2L, where H2 denotes the two acidic protons) in refluxing toluene. Additionally, the mono-n-butyltin complex [n-BuSn(HL)Cl2]·H2O (6) was synthesized from n-BuSnCl3 and H2L in acetonitrile. Compounds were characterized by FT-IR, 1H, 13C and 119Sn NMR spectroscopy, while their solid-state structures were examined using single-crystal X-ray diffraction studies. In diorganotin compounds 1-5, the dianionic tridentate ligands (Npy, N-, N-) act as κ-N3 chelators. In 6, the L moiety (O, Npy, N-) acts as a κ-ON2 tridentate chelator, with involvement of one of the carboxamide oxygen atoms. The coordination polyhedron around the Sn(IV) ion is completed either by two axial Sn-R ligands in compounds 1-5 or by n-Bu and Cl ligands in compound 6, giving rise to distorted trigonal bipyramid or octahedral structures, respectively. The tin NMR results show that the penta-coordinated structures of compounds 1-5 and the hexacoordinated structure of compound 6, observed in the solid-state, are retained in solution. The in vitro antitumor activities of 1-5 were tested on T-47D breast cancer cells. Of these, diphenyltin compound 3 showed the highest anti-proliferative effect, with an IC50 of 10 ± 1.60 µM. Compound 3 exhibited selective toxicity, potentially inducing apoptosis via reactive oxygen species generation and nuclear changes, indicating promise as a breast cancer treatment. This study is the first to explore thiazole-appended organotin compounds for cytotoxicity.

An alternative silicone-based passive sampling device to derive organotin concentrations in the aqueous phase.

Organotin compounds (OTs) are well studied in various environmental compartments, with a critical focus on the water column as their primary entry point into aquatic ecosystems. In this context, a method for the analysis of organotin (OTs) in water using silicone rubber-based passive sampling was optimized, validated, and field-tested. Validation covered crucial parameters, including the limit of detection (LOD), limit of quantification (LOQ), accuracy, precision, linearity, and matrix effect. The method was shown to be robust (R2 ≥ 0.99), with recoveries between 70.2 and 114.6%, and precise (CV < 12.8%) (N = 3). LODCw and LOQCw were ≤15 and ≤ 48 pg Sn L-1, respectively, for TBT and TPhT. The matrix effect showed to be low (>-20% ME < 20%) for all OTs but TPhT (69.4%). The silicone rubber-water partition coefficients (Log Ksr,w) were estimated at 3.37 for MBT, 3.77 for DBT, 4.17 for TBT, 3.49 for MPhT, 3.83 for DPhT, and 4.22 for TPhT. During the field study carried out between October 2021 and February 2022 at the entrance of the Port of Santos navigation channel (Southeastern Brazil), sampling rates ranged between 4.1 and 4.6 L d-1, and the equilibrium was achieved for MBT, DBT, MPhT, and DPhT after ∼45 days of deployment. The freely dissolved concentrations varied between 134 and 165 pg Sn L-1 for TBT, 388 and 610 pg Sn L-1 for DBT, and 1114 and 1509 pg Sn L-1 for MBT, while MPhT, DPhT, and TPhT were below the limit of detection. Results pointed out that J-FLEX® rubber-based passive sampling is a suitable and reliable alternative method for the continuous monitoring of OTs in the water column.

Structure-activity relationship and mechanistic study of organotins as inhibitors of human, pig, and rat gonadal 3ß-hydroxysteroid dehydrogenases.

Organotins have been widely used in various industrial applications. This study investigated the structure-activity relationship as inhibitors of human, pig, and rat gonadal 3ß-hydroxysteroid dehydrogenases (3ß-HSD). Human KGN cell, pig, and rat testis microsomes were utilized to assess the inhibitory effects of 18 organotins on the conversion of pregnenolone to progesterone. Among them, diphenyltin, triethyltin, and triphenyltin exhibited significant inhibitory activity against human 3ß-HSD2 with IC50 values of 114.79, 106.98, and 5.40 µM, respectively. For pig 3ß-HSD, dipropyltin, diphenyltin, triethyltin, tributyltin, and triphenyltin demonstrated inhibitory effects with IC50 values of 172.00, 100.19, 87.00, 5.75, and 1.65 µM, respectively. Similarly, for rat 3ß-HSD1, dipropyltin, diphenyltin, triethyltin, tributyltin, and triphenyltin displayed inhibitory activity with IC50 values of 81.35, 43.56, 55.55, 4.09, and 0.035 µM, respectively. They were mixed inhibitors of pig and rat 3ß-HSD, while triphenyltin was identified as a competitive inhibitor of human 3ß-HSD2. The mechanism underlying the inhibition of organotins on 3ß-HSD was explored, revealing that they may disrupt the enzyme activity by binding to cysteine residues in the catalytic sites. This proposition was supported by the observation that the addition of dithiothreitol reversed the inhibition caused by all organotins except for triethyltin, which was partially reversed. In conclusion, this study provides valuable insights into the structure-activity relationship of organotins as inhibitors of human, pig, and rat gonadal 3ß-HSD. The mechanistic investigation suggests that these compounds likely exert their inhibitory effects through binding to cysteine residues in the catalytic sites.

Organotins in fish, shrimp, and cephalopods from the Pearl River Estuary, China: Dietary exposure risk to Indo-Pacific humpback dolphin and human.

Food has regularly been proven to be a key source of exposure to environmental pollutants, drawing attention to the dietary exposure risks of contaminants to mammals with significant daily food intake. Here, the levels of six organotin compounds (OTs) in 18 fish (n = 310), three cephalopods (n = 50), and one shrimp (n = 34) from the Lingdingyang (LDY) and west four region (WFR) of the Pearl River Estuary (PRE) and their dietary exposure risks to Indo-Pacific humpback dolphins and humans were first investigated. Total OT levels ranged from 3.84 to 901. 48 ng/g wet weight (ww) in 22 prey species from the LDY, and from 14.37 to 1364.64 ng/g ww in 19 species from the WFR. The LDY marine species generally accumulated higher butyltin levels but lower phentyltin levels than those in the WFR. All species have a phenyltin degradation index <1 and over 60 % of the sampled species have a butyltin degradation index <1, suggesting the PRE marine species might be exposed to the fresh discharge of OTs. A total of nine marine species exceeded the threshold levels of OT intake for adverse health effects on human juveniles by consumption, all 22 marine species posed high dietary risks to the PRE humpback dolphins. Moreover, probabilistic risk assessment using Monte Carlo simulation revealed that the probabilities of RQ values associated with WFR OT exposure higher than 1 were 18.87 % for human adults, 40.55 % for human juveniles, 100 % for both humpback dolphin adults and humpback dolphin juveniles. Our results highlighted the potentially high dietary exposure risks of OTs to marine mammals and residents in the PRE.

Assessing the ecotoxicity of combined exposure to triphenyltin and norfloxacin at environmental levels: A case study of immunotoxicity and metabolic regulation in carp (Cyprinus carpio).

This paper evaluates the coexistence risks of triphenyltin (TPT) and norfloxacin (NOR) to aquatic organisms in the aquatic environment. Carp (Cyprinus carpio) was used as the test organism, the control and exposure groups (1 µg/L TPT), 1 mg/L (NOR), 1 µg/LTPT+1 mg/LNOR (TPT_NOR)) were set up according to the environmental concentration in the severely polluted area for 42 days. The single/combined toxic effects of TPT and NOR on aquatic organisms were evaluated by analyzing carp brain transcriptome sequencing, gut microbiota structure, and detection of biochemical indicators and RT-qPCR. Our results show that TPT and NOR induce lipid metabolism disorder in carp brain tissue, affecting the metabolism of cytochrome P450 to exogenous substances, and NOR also induces immunosuppression in carp. Long-term exposure to TPT combined with NOR amplifies the monotoxicity of TPT or NOR on lipid metabolism and immunosuppression in carp, induces immune dysfunction in brain tissue and changes in gut microbiota structure. However, TPT_NOR has no obvious neurotoxicity on the brain, but it can inhibit the level of intestinal MDA. This highlights that co-exposure of TPT and NOR amplifies metabolic disorders and immunosuppressive functions in carp.

Effects of tributyltin (TBT) on the intermediate metabolism of the crab Callinectes sapidus.

This study investigated if the exposure to tributyltin (TBT), a chemical used worldwide in boat antifouling paints, could result in metabolic disturbances in the blue crab Callinectes sapidus. After the exposure to TBT 100 or 1000 ng.L-1 for 48 and 96 h, hemolymph and tissues were collected to determine the concentration of metabolites and lipid peroxidation. The levels of glucose, lactate, cholesterol, and triglycerides in the hemolymph were not affected by TBT exposure. Hemolymph protein and heart glycogen increased in the crabs exposed to TBT 1000 for 96 h. Anterior gills protein and lipoperoxidation decreased after 96 h in all groups. These results suggest that C. sapidus can maintain energy homeostasis when challenged by the TBT exposure for 48 h and that metabolic alterations initiate after 96 h.

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.

Synthesis, Characterization, Biological Activity and Molecular Docking Studies of Novel Organotin(IV) Carboxylates.

Four new carboxylates complexes with general formula R2SnL2 and R3SnL, where R = n-butyl (1, 3), methyl (2, 4) and L = 4-Chlorophenoxyacetate, were synthesized in significant yields. FT-IR analysis revealed a chelating (1 and 2) and a bridging bidentate (3 and 4) coordination modes for the carboxylate ligand in solid state which was further confirmed by the single crystal X-ray analysis of complex 4. The NMR data (1H, 13C and 119Sn) revealed a higher coordination number around the tin center in R2SnL2 (1 and 2) compared to R3SnL (3 and 4). A close matching was observed between the experimental and calculated structures (obtained at B3LYP/6-31G* + LANL2DZ basis set). Quantum chemical analysis indicates that the carboxylate moiety has the major contribution in the formation of filled and unfilled orbitals as well as in ligand to ligand intramolecular charge transfer during the electronic transitions. The cytotoxicity data of the screened compounds evaluated against lung cancer cell line (A549) and normal lung fibroblast cell line (MRC-5) revealed that 1, 3 and 4 have shown dose dependent cytotoxic effects while HL and 2 have shown steady and low cytotoxic activities. The antibacterial activity of complexes 1-4 is higher than that of HL. Molecular docking study showed an intercalation binding mode for complex 3 with DNA (docking score = -3.6005) involving four polar interactions. Complex 3 docking with tubulin (PDB ID 1SA0) with colchicine as a target protein resulted in three polar interactions (docking score -5.2957). Further, the docking analysis of the HL and 1-4 has shown an adequate interactions with the coronavirus SARS-CoV-2 spike protein, nucleocapsid protein and human angiotensin converting enzyme (ACE2).

Organotin compounds (OTs) in surface sediments, bivalves and algae from the Russian coast of the Barents Sea (Kola Peninsula) and the Fram Strait (Svalbard Archipelago).

Organotin pollution in components of benthic ecosystems was investigated in 2019 in the Barents Sea (South shore, Kola Peninsula) and the Fram Strait (Icefjord, Svalbard Archipelago). Six species of organotin compounds (OTs), including monobutyltin, dibutyltin, tributyltin, tetrabutyltin, triphenyltin and tricyclohexyltin, were measured in the surface sediments, bivalve molluscs (Ciliatocardium ciliatum, Macoma calcarea, Chlamys islandica) and macrophyte algae (Saccharina latissima, Palmaria palmata, Ulvaria obscura, Fucus serratus, Fucus distichus). The results obtained showed moderate contamination of the studied samples with OTs. The total content of six tin compounds was in the ranges 35-139 ng g-1, 13-108 ng g-1 and 2.9-75 ng g-1 (dry weight) in the samples of sediments, bivalves and algae, respectively. In most cases, the concentrations of tributyltin in bottom sediments and mollusc tissues did not exceed the established international regulations. The degradation indices analysis of butyl tin derivatives indicated the active transformation of tributyltin and tetrabutyltin in bottom sediments and macrophyte algae and the accumulation of these compounds in the soft tissues of molluscs. The sediment and mollusc concentrations of OTs measured in this study were comparable to those reported for other areas of the Arctic region.

Mexican paradise under threat: The impact of antifouling biocides along the Yucatán Peninsula.

Levels of booster biocides (Irgarol, diuron, chlorothalonil, dichlofluanid and DCOIT), organotins (TBT, DBT, MBT, TPhT, DPhT and MPhT) and antifouling paint particles (APPs) were assessed in sediments of sites under the influence of maritime activities along the coastal zone of the Yucatán Peninsula, Mexico. Imposex incidence and organotin levels were also evaluated in seven caenogastropod species. The incidence of imposex was detected in five species from sites nearby fishing harbors and marinas, including the first reports to Gemophos tinctus and Melongena bispinosa. Butyltins levels were higher than phenyltins in gastropod tissues, sediments, and APPs. Regarding booster biocides, chlorothalonil was the most frequently detected compound and DCOIT was the most abundant biocide in sediments. DCOIT levels were registered in APPs from fishing harbors and marina areas. In addition, the highest levels of TBT, Irgarol, diuron and DCOIT exceeded the threshold limits set by international sediment quality guidelines, indicating that toxic effects could be expected in some of the studied areas, thus being a potential threat to marine life. Based on such outputs, Mexico urgently needs to adopt restrictive actions aiming at conserving the rich biological heritage of the Yucatán Peninsula.

The Preservation of PPARγ Genome Duplicates in Some Teleost Lineages: Insights into Lipid Metabolism and Xenobiotic Exploitation.

Three peroxisome proliferator-activated receptor paralogues (PPARα, -ß and -γ) are currently recognized in vertebrate genomes. PPARγ is known to modulate nutrition, adipogenesis and immunity in vertebrates. Natural ligands of PPARγ have been proposed; however, the receptor also binds synthetic ligands such as endocrine disruptors. Two paralogues of PPARα and PPARß have been documented in teleost species, a consequence of the 3R WGD. Recently, two PPARγ paralogue genes were also identified in Astyanax mexicanus. We aimed to determine whether the presence of two PPARγ paralogues is prevalent in other teleost genomes, through genomic and phylogenetic analysis. Our results showed that besides Characiformes, two PPARγ paralogous genes were also identified in other teleost taxa, coinciding with the teleost-specific, whole-genome duplication and with the retention of both genes prior to the separation of the Clupeocephala. To functionally characterize these genes, we used the European sardine (Sardina pilchardus) as a model. PPARγA and PPARγB display a different tissue distribution, despite the similarity of their functional profiles: they are unresponsive to tested fatty acids and other human PPARγ ligands yet yield a transcriptional response in the presence of tributyltin (TBT). This observation puts forward the relevance of comparative analysis to decipher alternative binding architectures and broadens the disruptive potential of man-made chemicals for aquatic species.

Organotin Antifouling Compounds and Sex-Steroid Nuclear Receptor Perturbation: Some Structural Insights.

Organotin compounds (OTCs) are a commercially important group of organometallic compounds of tin used globally as polyvinyl chloride stabilizers and marine antifouling biocides. Worldwide use of OTCs has resulted in their ubiquitous presence in ecosystems across all the continents. OTCs have metabolic and endocrine disrupting effects in marine and terrestrial organisms. Thus, harmful OTCs (tributyltin) have been banned by the International Convention on the Control of Harmful Antifouling Systems since 2008. However, continued manufacturing by non-member countries poses a substantial risk for animal and human health. In this study, structural binding of common commercial OTCs, tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT), monophenyltin (MPT), and azocyclotin (ACT) against sex-steroid nuclear receptors, androgen receptor (AR), and estrogen receptors (ERα, ERß) was performed using molecular docking and MD simulation. TBT, DBT, DPT, and MPT bound deep within the binding sites of AR, ERα, and Erß, showing good dock score, binding energy and dissociation constants that were comparable to bound native ligands, testosterone and estradiol. The stability of docking complex was shown by MD simulation of organotin/receptor complex with RMSD, RMSF, Rg, and SASA plots showing stable interaction, low deviation, and compactness of the complex. A high commonality (50-100%) of interacting residues of ERα and ERß for the docked ligands and bound native ligand (estradiol) indicated that the organotin compounds bound in the same binding site of the receptor as the native ligand. The results suggested that organotins may interfere with the natural steroid/receptor binding and perturb steroid signaling.

Bone Disruption and Environmental Pollutants.

BACKGROUND: Endocrine Disrupting Chemicals (EDCs) are ubiquitous and may significantly contribute to environmental pollution and contamination in humans and wildlife. Ecological pollutants could interfere with bone homeostasis through different mechanisms, including hormonal imbalance, direct osteoblast toxicity, and enhancement of osteoclasts activity, leading to either osteopenia or osteoporosis. Among these chemicals, bisphenols, dioxins, polycyclic aromatic hydrocarbons, polychlorobiphenyls, poly- and perfluoroalkyl, phthalates, parabens, organotins, and cadmium may play a role in the bone disruption. METHODS: Authors searched PubMed/MEDLINE, ISI-web of knowledge, and Google scholar databases for medical subject headings terms and free-text words related to the classes mentioned above of chemicals and bone metabolism and remodeling for better clarifying and understanding the main mechanisms of bone disruption. RESULTS: Several EDCs act as xeno-estrogens. Considering that estrogens play a significant role in regulating bone remodeling, most of these chemicals generate hormonal imbalance with possible detrimental consequences on bone tissue structure and its mechanical and non-mechanical properties. DISCUSSION: Much evidence about bone disruptors was obtained from in vitro studies or animal models with equivocal results. Besides, a few data have been acquired from humans, and most of these data focused on the impact of EDCs on bone mineral density without considering their influence on long-term fracture risk. Moreover, humans may be exposed to a mixture of EDCs, and the final effect on bone metabolism might be attributable to either synergistic or antagonist effects. Age of first exposure, cumulative exposure over time, and the usually observed non-monotonic dose-response curve for EDCs should be considered as other essential variables influencing bone metabolism's final effect. CONCLUSION: Given these variables, observational studies are needed to analyze this issue for ecological purposes better and preserve bone health.

An ancestral nuclear receptor couple, PPAR-RXR, is exploited by organotins.

Environmental chemicals have been reported to greatly disturb the endocrine and metabolic systems of multiple animal species. A recent example involves the exploitation of the nuclear receptor (NR) heterodimeric pair composed by PPAR/RXR (peroxisome proliferator-activated receptor/retinoid X receptor), which shows lipid perturbation in mammalian species. While gene orthologues of both of these receptors have been described outside vertebrates, no functional characterization of PPAR has been carried in protostome lineages. We provide the first functional analysis of PPAR in Patella sp. (Mollusca), using model obesogens such as tributyltin (TBT), triphenyltin (TPT), and proposed natural ligands (fatty acid molecules). To gain further insights, we used site-directed mutagenesis to PPAR and replaced the tyrosine 277 by a cysteine (the human homologous amino acid and TBT anchor residue) and an alanine. Additionally, we explored the alterations in the fatty acid profiles after an exposure to the model obesogen TBT, in vivo. Our results show that TBT and TPT behave as an antagonist of Patella sp. PPAR/RXR and that the tyrosine 277 is important, but not essential in the response to TBT. Overall, these results suggest a relation between the response of the mollusc PPAR-RXR to TBT and the lipid profile alterations reported at environmentally relevant concentrations. Our findings highlight the importance of comparative analysis between protostome and deuterostome lineages to decipher the differential impact of environmental chemicals.

Hazardous substances in the sediments and their pathways from potential sources in the eastern Gulf of Finland.

Contamination by hazardous substances is one of the main environmental problems in the eastern Gulf of Finland, Baltic Sea. A trilateral effort to sample and analyse heavy metals (HMs), polycyclic aromatic hydrocarbons (PAHs), and organotins from bottom sediments in 2019-2020 were conducted along with harvesting historical data in Russian, Estonian and Finnish waters. We suggest that the input of organotins still occurs along the ship traffic routes. The tributyltin content exceeded the established quality criteria up to more than 300 times. High contamination by PAHs found near the ports, most likely originate from incomplete fuel incineration processes. The Neva River Estuary and Luga Bay might potentially suffer from severe cadmium contamination. The high ecological risk attributed to the HMs was detected at deep offshore areas. The simulated accumulation pattern qualitatively agrees with field observations of HMs in sediments, demonstrating the potential of numerical tools to tackle the hazardous substances problems.

Organotin Compounds (OTCs) in Saccharina latissima (Phaeophyceae) from the Barents Sea.

The degree of contamination of Saccharina latissima, the dominant species among macrophyte algae in the sublittoral zones of the Kola Bay and Eastern Murman of the Barents Sea, with organotin compounds (monobutyltin, dibutyltin, tributyltin, tetrabutyltin, triphenyltin, and tricyclohexyltin) has been assessed. The results show a moderate degree of contamination of the studied samples with organotin compounds. The total concentration of six tin compounds was 17-74 ng/g (dry weight) in algal samples. Analysis of the indices of degradation of butyl tin derivatives showed active processes of tributyltin and tetrabutyltin transformation in algae.

Long-term monitoring of Nucella lapillus imposex in Ria de Aveiro (Portugal): When will a full recovery happen?

Nucella lapillus imposex has been monitored in Ria de Aveiro (Portugal) in order to understand the evolution of organotin (OT) pollution after the EU ban on OT-based antifouling systems (OT-AFS). A rapid decrease of imposex occurred, but a countercurrent tendency upsurged recently (2018-2019) with a slight increase of imposex at some sites, instead of a continuous decline towards a complete recovery. In 2018 the vas deferens sequence index ranged between 0.6 and 1.0 across stations and the percentage of females with imposex varied from 63 to 100%. In 2019 these parameters varied between 0.4 and 1.0 and 37-100%, while the concentration of butyltins (TBT, DBT, MBT) in the dogwhelk tissues were < 1 ng Sn g-1 dw. Although N. lapillus imposex levels are low they are indicative of OT pollution. The full recovery of N. lapillus imposex in the future is uncertain and a cause for concern.

Organotin derivatives of cholic acid induce apoptosis into breast cancer cells and interfere with mitochondrion; Synthesis, characterization and biological evaluation.

Organotin(IV) derivatives of cholic acid (CAH) with the formulae R3Sn(CA) (R = Ph- (1), n-Bu- (2)) and R2Sn(CA)2 (R = Ph- (3), n-Bu- (4) and Me- (5)) were synthesized. The compounds were characterized in solid state by melting point, FT-IR, 119Sn Mössbauer, X-ray fluorescence (XRF) spectroscopy and in solution by 1H NMR, UV-Vis spectral data and by Electrospray Ionisation Mass spectrometry (ESI-MS), High Resolution Mass spectrometry (HRMS), and atomic absorption analysis. The in vitro bioactivity of 1-5 against human breast adenocarcinoma cancer cells MCF-7 (positive to hormone receptors) and MDA-MB-231 (negative to hormone receptors) reveal that triorganotin derivatives 1-2 exhibit significantly stronger activity than the corresponding diorganotin ones. Compound 5 is inactive against both cell lines at the concentrations tested. Triorganotins 1-2 inhibit selectively MCF-7 than MDA-MB-231 cells, suggesting hormone mimetic behavior of them. Organotins 1-4 inhibit both cancerous cell lines, stronger than cisplatin which rise up to 55-fold against MCF-7 and 170-fold against MDA-MB-231. The in vitro toxicity of 1-4 was evaluated on normal human fetal lung fibroblast cells (MRC-5), while their genotoxicity in vitro by micronucleus assay (MN). Moreover, the in vivo toxicity of 1-4 was tested by Artemia salina assay and their in vivo genotoxicity with Allium cepa test. The mechanism of action of 1-4 against MCF-7 was clarified in vitro by the means of cell morphology studies, cell cycle arrest, Acridine Orange/Ethidium Bromide (AO/EB) Staining, mitochondrial membrane permeabilization test and by their binding affinity toward the calf thymus (CT) DNA.

Tissue distribution of triphenyltin compounds in marine teleost fishes.

Continuous release of the highly toxic triphenyltin compounds (TPT) from antifouling paints and fungicides has caused serious pollution to urbanized coastal marine environments worldwide since the 1960s. Using gas-chromatography mass-spectrometry (GC-MS), this study investigated the distribution profile of TPT in 15 types of tissues of four marine teleost fish species collected from Hong Kong waters. Concentrations of TPT in various tissues had a significant positive correlation with protein contents in the tissues (r = 0.346, p < 0.001) and, to a lesser extent with lipid contents (r = 0.169, p = 0.020). Highest concentrations of TPT were consistently found in liver, ranging from 1074.9 to 3443.7 ng/g wet weight; whereas fish scales always contained the least concentration of TPT in all species, ranging from 10.4 to 48.5 ng/g wet weight. Through mass balance models and regression analyses, muscle tissues were found to contribute most to the total TPT body burden, and the average TPT concentration of both dorsal and ventral muscles was identified as the best predictor for estimating TPT burden in the entire fish. Hence, further investigations of bioaccumulation and biomagnification of TPT in fishes should adopt this modelling approach in estimating its total body burden in individual fish.

Impacts of microplastics on organotins' photodegradation in aquatic environments.

Microplastics are ubiquitous in natural waters and affect the environmental fate of hydrophobic organic micropollutants. This study evaluated the impacts of four microplastics, polypropylene (PP), polyethylene (PE), polystyrene (PS) and polymethyl methacrylate (PMMA), on the photodegradation of organotin compounds (OTCs) under UV365 irradiation (2.3 ± 0.1 W m-2). The experiments were performed by mixing PP, PE, PS or PMMA microparticles with tri-organotins in artificial seawater. The photodegradation of OTCs in microplastic suspensions was influenced by the absorptivity onto microplastics. The decomposition rate of tributyltin (TBT) in UV-irradiated PP suspensions was greater than trimethyltin (TMT) and triphenyltin (TPhT) (p < 0.01). The adsorption capacities of OTCs (e.g., TBT) on PP particle surfaces were significantly lower than those on PE surfaces (p < 0.05) but similar with those on PMMA due to the different surface areas, shapes, and surface hydrophobicity of microplastics. TBT degraded faster (9.1%) in PS than in PMMA suspension (11.2%) within 240 min, respectively. However, only less than 5.4% was photodegraded in PP suspension due to the light scattering or absorption of the large sized PP particles. This study provided new insight into the impacts of microplastics on photodegradation of micropollutants in natural waters.