The Impact of Implementing the International Convention on the Control of Harmful Anti-fouling Systems in Ships （AFS Convention） on the Marine Environment

Marine fouling is the settlement and growth of a variety of marine organisms, such as bacteria, diatoms, protozoa and algae spores on structures immersed in seawater, such as ship＇s hulls, navigation buoys, and sonar equipment. Anti-fouling refers to material or systems used to prevent the accumulation of biological material on submerged surfaces. Bio-fouling results in higher fuel consumption and can also facilitate the transport of harmful NIS （Non-Indigenous Species）. Antifouling technologies incorporating biocides （e.g., Tributyltin） have been developed to prevent fouling. Their widespread use, however, raised concerns about their toxic effects on marine communities. The AFS Convention （International Convention on the Control of Harmful Anti-fouling Systems in Ships） is a 2001 IMO （International Maritime Organization） treaty, whereby states agree to ban the use of harmful anti-fouling paints and other anti-fouling systems that contain harmful substances. Particularly, the use of the organotinTributyltin is prohibited, since leaching of that chemical from the hulls of ships has been shown to cause deleterious effects on some sea creatures. Although the AFS Convention has entered into force, its full implementation has not yet been appropriately achieved. Most of the ratifying States have delegated the Classification Society to inspect their ships to ensure the implementation of the provisions of the Convention. Since painting ships takes place in dry docks, the full control falls in the hands of Classification Societies.

Investigation on the Antitumor Activity of Organotin Compound

Changes in the surface structure of cell membrane and the contents of membrane pro- teins and nuclear DNA of human gastric cancer (BGC-823) cells treated with organotin compound (Et_2SnCl_2phen) were studied with a scanning electron microscope (SEM),a scanning tunneling,micro- scope (STM),and a cytofluorophotometer.It was found that Et_2SnCl_2Phen not only inhibited the cell growth but also remarkably changed the surface structure of the membrane of cancer cells.The surface of Et_2SnCl_2phen treated cancer cells was relatively smooth and showed fewer microvilli under SEM. STM images showed an uneven and loose distribution of the surface of the cell.In comparison with the untreated cancer cells,there was an evident decrease in the content of membrane proteins and nuclear DNA in Et_2SnCl_2phen treated cells.

Synthesis, Crystal Structure and Luminescent Property of the One-dimensional Chain Chlorodibenzyltin 2-Quininate

A one-dimensional chain chlorodibenzyltin 2-quininate has been synthesized and characterized by IR, NMR spectra and elemental analysis. The crystal structure has been determined by X-ray diffraction. The crystal belongs to the monoclinic system, space group I4（—） with a = 19.1171（10）, b = 19.1171（10）, c = 12.5158（6） , Z = 8, V = 4574.1（4） 3, Dc = 1.477 g·cm-3, μ（MoKα） = 1.252 mm-1, F（000） = 2032, R = 0.0259 and wR = 0.0723. In the complex, the tin atom is six-coordinated to adopt a distorted octahedral configuration with bridging carboxyl of quinoline-2-carboxylic acid. The result of fluorescence spectrum analysis shows that the title complex at room temperature exhibits an intense photoluminescence with maximum emission at 364.2 nm （λex = 303.0 nm）.

Synthesis,Spectroscopic Properties and Crystal Structural Characterization of a Triphenyltin(IV) Complex with 5-Bromonicotinic Acid

A novel organotin complex [Ph3Sn（C2H5OH）（OCOC5H3NBr）SnPh3（OCOC5H3NBr）] has been synthesized by the reaction of 5-bromonicotinic acid with triphenyltin hydroxide in ethanol and characterized by elemental analysis, IR and ^1H NMR. The crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 15.564（2）, b = 24.975（4）, c = 12.2973（19）°A, β = 92.224（2）°, Z = 4, V = 4776.5（13）°A^3, Dc = 1.596 g/cm^3, μ（MoKα） = 2.765 mm^-1, F（000） = 2264, R = 0.0385 and wR = 0.0667. In the molecular structure of the title complex, the tin atoms are five-coordinated in a trigonal bipyramidal geometry.

Application of Neomysis awatschensis as a standard marine toxicity test organism in China

The small mysid crustacean Neomysis awatschensis was collected in the west coast of Jiaozhou Bay, Qingdao, China in 1992 and acclimated and cultured in laboratory conditions since then. Standard acute toxicity tests using 4—6 d juvenile mysids of this species were conducted and the results were compared with Mysidopsis bahia, a standard toxicity test organism used in the US in terms of their sensitivities to reference toxins, as well as their taxonomy, morphology and geographic distributions. Because of its wide distribution along the Chinese coast, similar sensitivity to pollutants as M. bahia, short life history, small size and the ease of handling, this study intended to use N. awatschensis as one of the standard marine organisms for toxicity testing in China. The species were applied to acute toxicity evaluations of drilling fluid and its additives, organotin TPT and toxic algae, and to chronic(life cycle) toxicity assays of organotin TPT and a toxic dinofalgellate Alexandrium tamarense, respectively. Using N. awatschensis as a standard toxicity testing organism in marine pollution assessment in China is suggested.

Synthesis, Crystal Structure and Quantum Chemical Study of the Ladder Organotin Compound {[(C_6H_5CH_2)2Sn]_2(O)(Cl_2)}_2

The title compound {[（C6H5CH2）2Sn]2（O）（Cl2）}2 has been synthesized by the reaction of bisbenzyltin dichloride with NaOH dilute solution, and its structure was determined by X-ray diffraction. The crystal belongs to monoclinic, space group C2/c, with a = 2.5081（17）, b = 1.0089（7）, c = 2.0909（14） nm, β = 94.267（8）°, V= 5.276（6） nm^3, Z = 4, De= 1.734 g/cm^3,μ（MoKa） = 21.55 cm^-1, F（000） = 2704, R = 0.0398 and Rw = 0.1024. According to structural analysis, the tin atom adopts a distorted five-coordinate trigonal bipyramidal geometry, and the ladder-like structure is shaped by one planar four-membered Sn2O2 ring together with two planar four-membered Sn2OCl rings.

Synthesis,Crystal Structure and Properties of A Triphenyltin Schiff Complex with Salicylidene-2-aminophenol

The triphenyltin complex with salicylidene-2-aminophenol （C31H24NO2Sn, 1） has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and X-ray single-crystal diffraction. The complex crystallizes in monoclinic system, P21/c space group with a = 1.09515（8）, b = 1.17739（8）, c = 2.29075（14） nm, β = 117.070（4）°, V = 2.6302（3） nm3, Z = 4, Dc = 1.417 g/cm3, ？ = 0.999 mm–1, F（000） = 1123, R = 0.0472 and wR = 0.1169. X-ray single-crystal diffraction showed that 1 demonstrates a one-dimensional chain structure. The quantum chemical calculation of 1 has been investigated. Complex 1 emits fluo- rescence at 558 nm and exhibits certain inhibitory activity against NCI-H460, A549 and MCF-7.

Syntheses, Crystal Structures and Biological Activities of the 2-Oxo-3-phenylpropionic Acid Arylformylhydrazone Dibenzyltin Complexes

Two 2-oxo-3-phenylpropionic acid arylformylhydrazone dibenzyltin(IV)complexes{[C4H3O(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅰ)and{[t-Bu-C6H4(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅱ)have been synthesized and characterized by IR,1H,13C and 119Sn NMR spectra,HRMS,and elemental,thermal stability and single-crystal X-ray diffraction analyses.Complex I crystallizes in the triclinic system,space group P1 with a=9.0392(9),b=10.249(1),c=15.5762(15)?,α=98.605(1)°,β=103.765(1)°,γ=104.056(1)°,Z=2,V=1326.3(2)?3,Dc=1.511 Mg·m^–3,m(MoKa)=1.005 mm–1,F(000)=612,R=0.0206 and wR=0.0524.Complex Ⅱ belongs to triclinic system,space group P1,a=11.4643(3),b=11.8885(3),c=13.0362(4)?,α=73.800(1)°,β=71.679(1)°,γ=79.006(1)°,Z=2,V=1609.34(8)?3,Dc=1.381 Mg·m^–3,m(MoKa)=0.833 mm–1,F(000)=688,R=0.0244 and wR=0.0244.In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines(NCI-H460,HepG2 and MCF7)and human cell lines(HL7702).Both complexes exhibit better antitumor activity.Furthermore,the interaction between both complexes and calf thymus DNA was studied with EB fluorescent probe.

Synthesis,Structure and Biological Activities of a Novel Anionic Organotin(Ⅳ)Complex{[(pClC6H4CH2)Sn(H2O)(Cl)2OCOCH(O)CH(O)CO2Sn(H2O)(Cl)2(p-ClC6H4CH2)]·2(HNEt3)}

A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.

Synthesis and Crystal Structure of a One-dimensional Infinite Chain Organotin Complex [(n-Bu)_3Sn(OCOC_5H_4NO)]_n

A novel organotin complex [（n-Bu）3Sn（OCOC5H4NO）]n has been synthesized and characterized by elemental analysis, IR and ^1H NMR. The crystal structure has been determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P2 1/c with a = 8.982（2）, b = 17.908（4）, c = 13.219（3） A, β= 96.981（4）°, Z = 4, V= 2110.6（8） A^3, Dc = 1.347 g/cm^3, μ（MoKa） = 12.23 cm^-1, F（000） = 880, R = 0.0497 and wR = 0.1263. In the molecular structure of the title complex, the tin atoms are five-coordinated in a distorted trigonal bipyramidal geometry. A one-dimensional linear polymer is formed through an interaction between the O atoms of pyridine-3-carboxylic acid N-oxide and tin atoms of an adjacent molecule.

Synthesis of Five-coordinated Anionic Tin(Ⅳ) Complexes and Crystal Structure of [(i-Pr)_2NH_2][PhSn( μ~2-SCH_2COO)_2]

Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.

Synthesis, Characterization and Antibacterial Activity of Cyclohexyltin Complexes of N-(3,5-Dibromosalicylidene)valine

Three cyclohexyltin complexes of N-（3,5-dibromosalicylidene）valine（H_2L）, Cy_3Sn（HL）（1）, Cy_2SnL（2）, and Cy2 SnL ·Cy_3Sn Cl（3）（Cy = cyclohexyl）, have been synthesized and characterized by elemental analysis, IR, and ~1H and ^（13） C NMR spectra. The crystal structures of 2 and 3 have been determined. Complex 2 belongs to the monoclinic system, space group P21/n with a = 21.250（8）, b = 10.837（4）, c = 23.050（8） ？, b = 93.193（9）°, V = 5300（3） ？~3, Z = 8, D_c = 1.659 g/cm^3, m = 4.004 mm^（-1）, F（000） = 2624, R = 0.0471 and wR = 0.1015. Complex 3 belongs to the monoclinic system, space group P21 with a = 10.3452（10）, b = 18.7665（18）, c = 12.1483（12） ？, b = 103.374（2）°, V = 2294.5（4） ？3, Z = 2, D_c = 1.542 g/cm^3, m = 2.923 mm^（-1）, F（000） = 1072, R = 0.0428 and wR = 0.0936. Complex 2 has a distorted trigonal bipyramidal geometry with the axial locations occupied by one carboxylate oxygen and a phenolic oxygen of the ligand, and 3 reveals that the two tin atoms are joined via the carbonyl atom of the ligand to form a mixed organotin binuclear complex. Bioassay results show that 1 and 2 have good in vitro antibacterial activity against Escherichia coli.

Syntheses and Structural Characterization of Dimethyltin Complexs of N-(3-Methoxysalicylidene)-α-amino Acid

Three new dimethyltin complexes of N-（3-methoxysalicylidene）-α-amino acid,（CH3）2Sn（3-CH3O-2-OC6H3CH=NCHRCOO）（R = H,1;CH3,2;（CH3）2CH,3）,have been synthe-sized by treating dimethyltin dichloride with the potassium salt of the ligand and characterized by elemental analysis,IR and 1H NMR spectra.The crystal structure of [（CH3）2Sn（3-CH3O-2-OC6H3CH=NCH2COO）（CH3OH）]2 H2O（1a）,formed from methanol solution of 1,has been deter-mined.The crystal belongs to the monoclinic system,space group C/2c with a = 20.636（3）,b = 7.8854（9）,c = 20.668（2） ,β= 113.265（2）°,V = 3089.7（6） 3,Z = 4,Dc = 1.707 g/cm3,= 1.675 mm-1,F（000） = 1592,R = 0.0301 and wR = 0.0841.In complex 1a,the tin atom is six-coordinate and possesses a distorted [SnC2NO3] octahedral geometry with the two methyl groups occupying the trans positions.The weak Sn O interactions and intermolecular hydrogen bonds connected the molecules into an infinite chain.

Diorganotin Complexes of N-[4-(Diethylamino)salicylidene]-(L)-tryptophane: Syntheses, Structures and Properties

Four chiral diorganotin complexes of N-[4-(diethylamino)salicylidene]-(L)-tryptophane,R2Sn[4-(Et2N)-2-OC6H3CH=NCH(CH2Ind)COO](Ind=3-indolyl;R=Me(1);Et,(2);n-Bu(3);Cy(cyclohexyl)(4)),have been synthesized and characterized by elemental analysis,IR,and 1H and 13C NMR spectra.The crystal structures of 1-CH3OH-CHCl3,2,3-CH3OH and 4-CH3CH2OH have been determined by single-crystal X-ray diffraction.The complexes crystallize in orthorhombic system with P212121 space group,and the tin atoms are in distorted trigonal bipyramidal geometry and form five-and six-membered chelate rings with the chiral ONO tridentate ligand N-[4-(diethylamino)salicylidene]-(L)-tryptophane.In the complexes,the molecules are connected into one-dimensional supramolecular chain by intermolecular N–H…O–H…O=C or N–H…O–C hydrogen bonds.The fluorescence spectrum indicates that the complexes may be explored for potential blue luminescent materials.Bioassay results show that 3 and 4 belong to the efficient cytostatic agents against A549 human tumor cell.

Synthesis,Characterization and Crystal Structure of the Dimeric Organotin Compound:{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NC_(4)H_(8))]_(2)O}_(2)

The title compound,{[n-Bu_(2)Sn(O_(2)CCH_(2)CS_(2)NC_(4)H_(8))]_(2)O}_(2),has been synthesized by the reaction of(tetrahydro-pyrrodithiolocarbamoylthio)acetic acid with the di-n-bubyltin oxide in1∶1molar ratio.The complex has been characterized by elemental analysis,IR and NMR.The crystal structure of it has been determined by X-ray single crystal diffraction.And the results showed that the crystal belongs to triclinic system with space group P1and some crystal parameters:a=1.2202(9)nm,b=1.3158(10)nm,c=1.3804(10)nm,α=111.215(9)°,β=99.357(9)°,γ=96.075(10)°,V=2.006(2)nm 3,Z=1,F(000)=908,μ=1.489mm^(-1),D c=1.474g·cm^(-3),R_(1)=0.0375,wR_(2)=0.0839.The complex has a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn_(2)O_(2)unit in which two bridged oxygen atoms both connect with an exo-cyclic tin atom which has a distorted octahedron.Each of the endo-cyclic tin atoms exhibits a distorted trigonal bipyramid coordination geometry with an additional weak coordination carboxylate oxygen.Four carboxylate ligands are divided into two types.And two of them are bidentate and connecting to each of exo-cyclic tin atoms by using both oxygen atoms,whereas the others bridge to each pair of exo-and endo-cyclic tin atoms utilizing one oxygen atom only.CCDC:220513.

Synthesis and Crystal Structure of the Organotin Complex [(o-Cl-PhCH_2)_3SnOCOC_(10)H_8N]·0.5C_6H_6

A novel organotin complex [(o-Cl-PhCH2)3SnOCOC10H8N]?0.5C6H6 has been syn- thesized, and its crystal structure was determined by X-ray diffraction. The crystal belongs to mo- noclinic, space group C2/c with a = 1.6214(5), b = 1.2033(3), c = 3.2873(10) nm, β = 91.467(5)°, V = 6.411(3) nm3, Mr = 1441.26, Z = 4, Dc = 1.493 g/cm3, μ(MoKα) = 10.79 cm-1, F(000) = 2904, R = 0.0500 and Rw = 0.0884. The bond lengths of Sn–C are 0.2150(5), 0.2157(4) and 0.2164(4) nm, and that of Sn–O is 0.2043(3) nm. The tin atom adopts a distorted tetrahedral geometry.

Structure and Transesterification Reaction of Methyl 3-(Phenyldihalostannyl)propionates

The title compounds, PhX2SnCHECHECO2Me （X = C1, 1a; Br, 1b; I, 1c）, readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features of these compounds were described, and the possible mechanism of the novel transesterification was suggested.

Synthesis, Structural Investigations and Biological Screening of Diorganotin(IV) Complexes Derived from 5,5-Diethyl Sodium Barbital

Some biologically important tin（Ⅳ） complexes derived from 5,5-diethyl sodium barbital have been synthesized and characterized through various analytical and spectroscopic techniques such as IR, ^1H-, ^13C-NMR and ^119mSn mossbauer. On the basis of these spectroscopic techniques, octahedral geometry has been assigned to all the novel compounds. These complexes, soluble in DMSO and DMF, were screened against a wide range of microorganisms. The results proved that the diphenyltin（Ⅳ） and dibutyltin（Ⅳ） complexes exhibit excellent activity against all types of microorganisms, while the rest of the compounds show significant activity that can be used during the biological study.

Syntheses,Crystal Structures and Biological Activities of the 2-Oxo-butyric Acid Salicylacylhydrazone Dibenzyltin Complexes

2-Oxo-butyric acid salicylacylhydrazone dibenzyltin（IV） complexes 1 {[o-OHC6H4（O）C=N-N=C（Et）COO]（CH3OH）[（C6H5CH2）2Sn]}2 and 2 {[o-OH-C6H4（O）C=N-N=C（Et）-COO]（CH3OH）[（2,4-Cl2C6H3CH2）2Sn]}2 have been synthesized. The complexes were characterized by IR, 1H, 13C and 119Sn NMR spectra, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex 1 belongs to triclinic system, space group P1 with a = 8.9121（6）, b = 10.3875（7）, c = 14.5658（10） ？, α = 89.534（5）, β = 86.790（5）, γ = 70.103（6）°, Z = 1, V = 1265.85（15） ？3, Dc = 1.488 Mg·m^（-3）, m（Mo Kα） = 1.047 mm-1, F（000） = 576, R = 0.0466 and w R = 0.1054. The crystal of complex 2 belongs to monoclinic system, space group P21/n, a = 12.7165（10）, b = 17.8466（14）, c = 12.8538（10） ？, β = 95.1310（10）°, Z = 2, V = 2905.4（4） ？~3, Dc = 1.612 Mg·m^（-3）, m（Mo Kα） = 1.286 mm-1, F（000） = 1408, R = 0.0369 and w R = 0.0958. In vitro antitumor activities of both complexes were evaluated by the 3-（4,5-dimethylthiazoly-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay against three human cancer cell lines（NCI-H460, HepG2, MCF7） and one human cell line（HL7702）. Two complexes exhibited strong antitumor activity, and then they were expected after further chemical optimization of candidate compounds as anti-cancer drugs. The interaction between complexes and calf thymus DNA were studied by EB fluorescent probe. The interactions of the two complexes with calf thymus DNA were intercalation.