Synthesis, characterization and high in vitro antitumour activity of novel triphenyltin carboxylates

The synthesis and spectral characterization of six novel triphenyltin compounds are described. The in vitro antitumour activity of three of these compounds against two human tumour cell lines, MCF-7, a mammary tumour, and WiDr, a colon carcinoma, was determined. All three compounds are more active than cis-platin, etoposide and doxorubicin against both tumour cell lines. They are as active as mitomycin C against WiDr, but less active against MCF-7.     

Evaluation of antibacterial properties of triorganotin carboxylates containing functionalised ester groups in tests against some pathogenic bacteria

Bacterial screening employing the agar diffusion test on triphenyltin carboxylates containing various functional residues in the ester moiety revealed appreciable differences in their activities relative to triphenyltin acetate. Among these, [3-(Diethylphosphono)propionato] triphenyltin (1) and [N-cyclohexylcarbamoyl) glycinato] triphenyltin displayed activities comparable to tri-n-butyltin cinnamate (2) towards both Gram-positive and Gram-negative bacteria; the latter compound was the most active among the eleven triorganotin compounds tested, which included cyclopentyldiphenyltin hydroxide (3) and its methacrylate derivative. Applying the more quantitative plate count and optical density tests on compounds 1-3, it was shown that their inhibitory activity ranked in the order 2 > 3 >1. Significantly, 3 caused around 90% inhibition of both Eschechia coli (-) and Pseudomonas aeruginosa (-) when incubated for 24 h at 37+/-1 at the 10.0 mug/ mL concentration level. Compound 2 was less effective against P.aeruginosa than against E.coli. While the Gram-positive bacteria were all readily inhibited, Bacillus subtilis (+) appeared to the most susceptible among them towards the test compounds.     

Di-n-Butyl-, Tri-n-Butyl- and Triphenyltin dl-Terebates: Synthesis, Characterization and In Vitro Antitumour Activity

Di-n-butyltin, tri-n-butyltin and triphenyltin terebates were screened against several human tumour cell lines and found comparably or more active than carboplatin, cis-platin, 5-fluorouracil, methotrexate and doxorubicin, some reference compounds used clinically.     

Triphenyltin ortho-aminophenyl- and 2-pyridyl-thiolates: synthesis and in vitro antitumour activity

The synthesis, spectroscopic characterization and in vitro antitumour activity of two triorganotin compounds, triphenyltin ortho-aminophenylthiolate (1) and triphenyltin 2-pyridylthiolate, compound (2) are reported. The structure of 1 is confirmed by X-ray diffraction, with the tin atom in a distorted tetrahedral geometry because of monodentate coordination, as a thiolate (Sn-S 2.431(2) A), of the ortho-aminophenylthiolate ligand. The in vitro antitumour activities of 1 and 2, against a number of cell lines, are comparable to those exhibited by methotrexate and doxorubicin, and higher than those of carboplatin and cisplatin.     

O-三苯基锡不饱和烃基膦酸的合成与性质

通过三苯基锡不饱和烃基膦酸反应,合成了8种新的O－三苯基锡不饱和烃基膦酸Ph3SnOP(O)(OH)R.。利用元素分析、IR、^1HNMR和MS确定了这些化合物的结构。     

Concentration of Antifouling Biocides and Metals in Sediment Core Samples in the Northern Part of Hiroshima Bay

Accumulation of Ot alternative antifoulants in sediment is the focus of this research. Much research had been done on surface sediment, but in this report, the accumulation in the sediment core was studied. The Ot alternative antifoulants, Diuron, Sea-Nine211, and Irgarol 1051, and the latter’s degradation product, M1, were investigated in five samples from the northern part of Hiroshima Bay. Ot compounds (tributyltin (TBT) and triphenyltin (TPT)) were also investigated for comparison. In addition, metal (Pb, Cu, Zn, Fe and Mn) levels and chronology were measured to better understand what happens after accumulation on the sea floor. It was discovered that Ot alternative antifoulant accumulation characteristics in sediment were like Ot compounds, with the concentration in the sediment core being much higher than surface sediment. The concentration in sediment seems to have been affected by the regulation of Ot compounds in 1990, due to the concentration of Ot alternative antifoulants and Ot compounds at the survey point in front of the dock, showing an increase from almost the same layer after the regulation.     

Toxicity profiles in vivo in mice and antitumour activity in tumour-bearing mice of di- and triorganotin compounds

The in vivo toxicity profiles in mice and the antitumour activity in tumour bearing mice were screened for four di-n-butyltin and five triorganotin carboxylates, di-n-butyltin diterebate (5), bis(phenylacetate) (6), bis(deoxycholate) (7), bis(lithocholate) (8), tri-n-butyltin terebate (9), cinnamate (10), and triphenyltin terebate (11).At their maximum tolerated dosis (MTD), no antitumour effect (T/C ~1) was observed for the compounds 5, 7, 9, 10 and 11. The compounds 6 (T/C = 0.51) and 8 (T/C = 0.42) showed clear antitumour activity after single dose administration and might therefore be of interest for further antitumour activity studies.     

A one-year survey of organotin compounds in the reservoirs supplying the drinking water treatment plants of Athens, Greece

Organotin compounds belong to the priority list of substances regulated by 76/464/EEC Directive, as well as by 2000/60/EC Water Framework Directive, because they pose considerable risks to the environment and human health. They are the most commonly used organometallic compounds with estimated global amount produced 50,000 tons per year. Therefore, they have been detected worldwide in surface waters, drinking water, sediments and biota. The objective of the present investigation was the determination of these compounds in the water sources supplying the drinking water treatment plants of Athens, Greece, in particular at the reservoirs Mornos, Marathonas, Yliki and Evinos. The quality of water of those reservoirs could be affected from human activities, such as industry and agriculture, as well as from settlements in the area nearby. The surface water sampling campaigns executed were seasonal, during the period March 2004–May 2005, while finished drinking water samples from the distribution network of Athens were also analyzed. Six organotin species (monobutyltin, dibutyltin, tributyltin, monophenyltin, diphenyltin and triphenyltin) were determined by a gas chromatography — flame photometric detector (GC-FPD) method, after sample pretreatment with simultaneous liquid–liquid extraction with hexane and derivatization with tetraethyl borate. The results showed that the waters studied are free from organotin compounds, except for a limited number of samples, where the occurrence of some organotin species at low concentrations was observed.     

Bioactivity of antifouling paints based on organotin toxicants

This paper discusses the bioactivity of antifouling paints based on organotin toxicants, such as tributyltin fluoride (TBTF) and triphenyltin fluoride (TPTF). These compounds were used alone or mixed as the main toxicant in formulations. The use of TPTF or mixtures of TPTF and TBTF, with vinyl binders, led to paints with satisfactory bioactivity during a 24 months immersion period. With the same binders, TBTF alone provided only 12 months of antifouling protection. The correlation coefficients calculated from the fouling attachment values and the rosin content in the binder showed that the bioactivity of the tested formulations depended on the solubility of the toxicant in sea water and on the composition and solubility of the binders.     

Triphenyltin (IV) derivatives of N-acetyl amino acids,N-acetyl dipeptides and tripeptides: Preparation,NMR investigations and NMR spectroscopic resolution of the enantiomeric composition

Triphenyltin(IV) derivatives of N-acetyl amino acids ( 1a–g ) and N-acetyl di- ( 2a–f ) or tripeptides ( 3 ) mostly in the (L )- and the racemic (DL )-form have been prepared from bis(triphenyltin)oxide and the appropriate N-acetyl amino acid or N-acetyl peptide using various dehydrating agents. The compounds were characterized by NMR spectroscopy and elemental analysis. These compounds were studied at different concentrations and temperatures, revealing a strong self-association tendency. NMR investigations were undertaken in order to highlight preferred conformations of the peptide derivatives due to possible strong intramolecular associations between tin and nucleophilic donor atoms of the peptide moiety in weakly polar solvents. No preferred conformation was found which was in accordance with the underivatized peptides. The enantiomeric composition was determined by means of ¹H NMR spectroscopy using (−)-quinine hydrochloride and S-(−)-1-phenylethylamine as chiral solvating agents.     

气相色谱-质谱联用法测定PVC塑料制品中的微量有机锡

建立了一种可同时测定聚氯乙烯(PVC)塑料制品中一丁基锡、二丁基锡、三丁基锡、四丁基锡、一辛基锡、二苯基锡和三苯基锡等7种有机锡化合物的气相色谱-质谱(GC-MS)检测方法。利用三水合二乙基二硫代氨基甲酸钠(NaDDTC)与有机锡的螯合作用,以甲醇-NaDDTC水溶液(2%,m/v)的混合溶液浸取PVC样品中的有机锡,经四乙基硼酸钠(NaBEt4)水溶液衍生化后,用正己烷萃取分离,再进行GC-MS的定性定量分析。对样品前处理过程、衍生化条件、色谱条件等进行了优化,并考察了方法的线性关系、检出限、回收率和精密度等。方法的线性范围为0.1～50.0 mg/L,线性相关系数为0.999 0～0.999 8。有机锡化合物的检出限为0.005～0.025 mg/L,样品加标回收率为87.64%～110.16%,相对标准偏差皆小于10%。结果表明,该法简便、灵敏,能很好地应用于PVC制品中微量有机锡的测定。     

Organotin polymers. VII. Copolymerization of triphenyltin methacrylate with some acrylic and methacrylic acid esters

The monomer reactivity ratios for the copolymerization of triphenyltin methacrylate with methyl acrylate, ethyl acrylate, and butyl acrylate have been found to be r₁ = 2.58, r₂ = 0.66, r₁ = 2.37, r₂ = 0.43, and r₁ = 1.27, r_0.39 = 0.39, respectively. also, the copolymerization parameters of triphenyltin methacrylate with methyl methacrylate and butyl methacrylate were as follows: r₁ = 0.94, r₂ = 0.99, and r₁ = 0.68, r₂ = 0.83, respectively. Copolymerization reactions were carried out in solution at 70°C using 1 mol % AIBN, and the copolymer compositions were determined by tin analysis. The sequence distribution of the alternating diad fractions for the systems studied were calculated at various feed compositions. The structure of the triphenyltin methacrylate monomer as well as its azeotropic copolymer with butyl methacrylate were investigated by IR spectroscopy.     

利用微生物燃料电池同步降解沼液和三苯基氯化锡

微生物燃料电池(MFC)作为一种同步产电和除污的新型电化学装置,为有效处理难降解有机污染物提供了一种途径。基于阴极Fenton反应,提出了一种耦合典型双室MFC中阳极沼液产电及阴极降解有机锡的新方法。结果表明,阳极产电生物膜经驯化后MFC的最高电压提高了50.32%,而且电压稳定时间延长了1倍。MFC运行结束后,阳极沼液COD、总氮、总磷的去除率分别为85.35%±1.53%、59.20%±5.24%、44.98%±3.57%。阴极三苯基氯化锡(TPTC)的降解率随其初始浓度增加而降低。在添加100 μmol·L^-1 TPTC时,MFC的最高输出电压为280.2 mV,最大功率密度为145.62 mW·m^-2。TPTC在14 d后完全降解,降解效率为91.88%,降解速率约为0.273 μmol·L^-1·h^-1。研究结果可为利用MFC同步处理阳极有机废水和阴极有机污染物的实际应用提供基础支持。     

3,5-二溴水杨醛类缩氨基硫脲的合成和抑菌活性研究

设计合成了3种3,5－二溴水杨醛的缩氨基硫脲衍生物,经元素分析,红光谱确证了其结构,并对化合物的抑制活性进行了测试。     

三唑硫酮类化合物的合成与生物活性

[方法]三唑硫酮类化合物具有广谱的生物活性。以2-氯烟酸为起始原料,经6步反应,设计并合成了一系列三唑硫酮类化合物,通过核磁等分析手段确定了其结构,并进行了生物活性测试。[结论]共合成8个化合物,生测结果表明:该类化合物对白粉病具有较好的防治效果,并对其进行了初步的构效关系研究。构效关系表明:R2为吸电子取代基的化合物活性大于R2为给电子基取代的化合物。通过比较R1的不同取代位置,发现对位取代的化合物活性>邻位取代的化合物的活性>间位取代的化合物的活性。     

A comparison of the predictive values of the Salmonella/microsome mutation and BHK21 cell transformation assays in relation to dyestuffs and similar materials

A group of 22 dye-related compounds were selected for testing in two short-term predictive tests for carcinogenicity. The group of compounds was made up of nine established animal carcinogens and 13 chemicals for which there was substantial evidence of non-carcinogenicity. The materials were coded and used to assess the predictive value of the Salmonella/microsome reverse mutation assay and the BHK21 cell transformation test. The overall predictive value with these compounds obtained for the Salmonella microsome reverse mutation assay was 86% and it is concluded that because of the good predictive value and the relative ease of experimental procedure, the Salmonella mutation assay is a useful first step in any proposed series of toxicological bioassays for the identification of genotoxic agents in the dyestuffs industry.The cell transformation test on the other hand was difficult to conduct and interpret. The interpretation of the coded data as judged by the IRI scientists was that of the 22 'unknown' compounds, eight results were judged to be correct, six were wrong and seven were doubtful. However, when the same data were re-evaluated uncoded by ICI staff, 15 results were judged to be correct and six were wrong. These results serve to exemplify the difficulties encountered with cell transformation assays and it is concluded that the system should not be used as a routine test for dyestuffs and related compounds.     

Synthesis and Structure Characterization of Some Triorganotin Esters of Heteroaromatic Carboxylic Acid and Crystal Structure of Triphenyltin Esters of 6-Hydroxynicotinic Acid and 5-Chloro-6-hydroxynicotinic Acid

Reactions of (R₃Sn)₂O (R=Ph, 2-ClC₆H₄CH₂, 2-FC₆H₄CH₂, 4-CNC₆H₄CH₂) with 6-hydroxynicotinic acid and 5-chloro-6-hydroxynicotinic acid in 1:2 stoichiometry yielded eight triorganotin compounds. These compounds have been characterized by elemental analysis, IR and ¹H NMR spectroscopy. The crystal structures of triphenyltin esters of 6-hydroxynicotinic acid (1) and 5-chloro-6-hydroxynicotinic acid (2) were determined by single crystal X-ray diffraction. In these two compounds the tin atoms are rendered five-coordinate in a trigonal bipyramidal structure by coordination though the three phenyl carbon atoms and two oxygen atoms, one from carboxylate and other from the phenolic hydroxide. The resulting structures are two one-dimensional linear polymers through an interaction between the O atoms of phenolic hydroxide and tin atoms of an adjacent molecule.     

Aggregation pheromone system of adult gregarious desert locust schistocerca gregaria (forskal)

Six electrophysiologically active aromatic compounds, viz., anisole, benzaldehyde, veratrole, guaiacol, phenylacetonitrile, and phenol, were identified in the volatiles of older-adult male desert locust. Young adults and females of all age groups produced none or only trace quantities of these compounds. Comparison of the aggregation responses of young and older adults to the crude, older-adult, volatile extract and different synthetic blends of the six compounds showed that the aggregation pheromone system of the adult gregarious locust consists of phenylacetonitrile, guaiacol, phenol, and benzaldehyde. Like the crude volatile extract of older males, neither the synthetic blend of the six compounds nor the adult pheromone blend evoked any significant aggregation responses from nymphs. These results confirm our previous report of sexual differentiation in the production of adult aggregation pheromone in the desert locust and of the evidence of two distinct aggregation pheromone systems in the two stages of the insect.     

Synthesis, Characterization and Transesterification Activity of Cross-Linked Styrenic Resins Containing the Triphenyltincarboxylate Moiety Spaced by a Dimethylene from the Aromatic Ring

An organotin monomer, triphenyltin 3-(4-styryl)-propionate (TPTSPr) has been synthesized and copolymerized in different ratios with styrene and 1,4-divinylbenzene in order to obtain resins with catalytic activity in transesterification reactions. The resins and a low molecular weight model compound, triphenyltin 3-(4-ethylphenyl)-propionate (TPT-C2-Pr), mimicking the catalytic co-unit, have been characterized by FT-IR and NMR spectroscopy, with particular attention paid to the coordination at tin and how it correlates to the catalytic activity. The activity of both the resins and of the model compound have been tested in a transesterification model reaction between ethyl acetate and primary alcohol. All the resins show catalytic activity that decreases with increasing content of the active co-unit in the resins, owing to the interaction of the active sites among themselves.