The synthesis and crystal structures of triphenyl(1,2,3-trimethylallyl)tin and triphenyl( 1,1,2-trimethylallyl)tin

In an attempt to isolate new allylating reagents, two new tin compounds, triphenyl(1,2,3-trimethylallyl)tin (3) and triphenyl(1,1,2-trimethylallyl)tin (4) have been prepared and their crystal structures determined. Both compounds are examples of σ-bound allyl complexes. However, the infrared spectra of both compounds do not show the absorptions characteristic of other σ-bound allyl complexes. The chemistry of these new compounds also differs significantly from that of similar triphenyltin(allyl) reagents.     

Tests of dibutyltin compounds as potato blight fungicides

Dibutyltin dicarboxylates were about one-tenth as effective as fentin acetate in controlling potato haulm blight (Phytophthora infestans) in laboratory tests on detached leaflets, but were less phytotoxic. Tributyltin acetate was no more effective than dibutyltin diacetate; dioctyltin dichloride was ineffective.     

Comparison of fungicides for control of leaf spot (Septoria apiicola) of celery

Of twenty-one fungicides tested at recommended rates of application for their effectiveness in controlling leaf spot of celery grown in Ireland on peat and on a clay-loam soil, three formulations containing fentin acetate with maneb and formulations of fentin hydroxide and fentin chloride were most effective. Benomyl was superior to the other non-tin fungicides tested and, at moderate disease levels, it resulted in marketable yields of celery equal to those recorded after treatment with the organotin compounds. Generally, the organotin compounds and benomyl were followed in descending order of effectiveness by copper oxychloride, captafol, Daconil 2787 and maneb. None of the fungicides tested in the three seasons caused visible symptoms of phytotoxicity and, on disease-free celery in 1969, none had a significant effect on yield.     

On the fungicidal properties of thioaceto-hydroxamic acids and related compounds

Summary A number of (phenylthio)alkanoyl hydroxamic acids have been assessed for their fungicidal activity against Rhizoctonia solani and Fusarium sp. Of the compounds tested (3,4,5-tribromo phenylthio) and (2,3,5-tribromophenylthio)acetohydroxamic acids as well as (-phenylthio)butyryl hydroxamic acid are the most effective in inhibiting the mycelial growth of the fungi tested.     

Organotin-induced hemolysis,shape transformation and intramembranous aggregates in human erythrocytes

Organotin compounds examined in this study exhibited a relative order of potency for induction of in vitro hemolysis in human erythrocytes as follows: tri-n-butyltin > tri-n propyltin > tetra-n-butyltin > triphenyltin chloride > tri-n-ethyltin bromide > dibutyltin dichloride > stannous chloride > tri-n-methyltin chloride = butyltin chloride dihydroxide. All of the organotin compounds induced erythrocyte shape transformation from the normal discocyte to an echinocyte and, in addition, triphenyltin chloride, tetra-n-butyltin and tri-n-ethyltin bromide also elicited stomatocyte formation at higher concentrations. Select organotin compounds also formed tin-containing aggregates within the plasma membrane. The relative order of effectiveness for organotin induction of intramembranous aggregates was tri-n-butyltin > tri-npropyltin > tetra-n-butyltin > tri-n-ethyltin bromide, which was based upon the lowest concentration at which they were observed. These results support the previously suggested theory that organotins are membrane effectors because of their comparatively high hydrophobic, lipid partitioning properties. The relatively lipophilic compound, triphenyltin chloride, appeared to be anomalous because it did not readily promote hemolysis or induce the formation of intramembranous aggregates in human erythrocytes. A log-linear statistical model demonstrated an association of hemolysis with both tri-n-butyltin aggregate formation and shape transformation. Select organotin compounds should be useful probes in membrane studies because of their numerous effects.Abbreviations DBT dibutylin dichloride - MBT butyltinchloride dihydroxide - SnCl₂ stannous chloride - TBT tri-n-butyltin - TET tri-n-ethyltin bromide - TMT tri-n-methyltin chloride - TPhT triphenyltin chloride - TPT tri-n-propyltin - TTBT tetra-n-butyltin     

Analyses of the acetate-producing pathways in <Emphasis Type="Italic">Corynebacterium glutamicum</Emphasis> under oxygen-deprived conditions

Corynebacterium glutamicum R efficiently produces valuable chemicals from glucose under oxygen-deprived conditions. In an effort to reduce acetate as a byproduct, acetate productivity of several mutant-disrupted genes encoding possible key enzymes for acetate formation was determined. Disruption of the aceE gene that encodes the E1 enzyme of the pyruvate dehydrogenase complex resulted in almost complete elimination of acetate formation under oxygen-deprived conditions, implying that acetate synthesis under these conditions was essentially via acetyl-coenzyme A (CoA). Simultaneous disruption of pta, encoding phosphotransacetylase, and ack, encoding acetate kinase, resulted in no measurable change in acetate productivity. A mutant strain with disruptions in pta, ack and as-yet uncharacterized gene (cgR2472) exhibited 65% reduced acetate productivity compared to the parental strain, although a single disruption of cgR2472 exhibited no effect on acetate productivity. The gene cgR2472 was shown to encode a CoA-transferase (CTF) that catalyzes the formation of acetate from acetyl-CoA. These results indicate that PTA-ACK as well as CTF is involved in acetate production in C. glutamicum. This study provided basic information to reduce acetate production under oxygen-deprived conditions. An erratum to this article can be found at     

A Mössbauer spectroscopic study of [phthalocyaninato tin(IV) tetracarbonyl iron(0)]

The action of Na₂Fe(CO)₄ and bis(chloro)phthalocyaninato tin(IV) yields phthalocyaninato tin(IV) tetracarbonyl iron(0). Mössbauer spectroscopic studies on the product indicate no change in formal oxidation state need be invoked to account for the formation of the metal-metal bond.     

Synthesis of triphenyltin(IV) hydrosulfide

Compounds of the type R₃SnSH are believed to be unstable (unless sterically protected by very bulky R groups) because of their facile condensation into the corresponding sulfide, (R₃Sn)₂S. One such compound, Ph₃SnSH has been synthesized by an one pot reaction of triphenyltin hydroxide with thiophosgene followed by the hydrolysis of the intermediate triphenyltin chlorothioformate. The product, triphenyltin hydrosulfide has been characterized by IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectral techniques. Single crystal X-ray analysis revealed that the molecule is a discrete monomer containing tin atom at the centre of a distorted tetrahedron. Plausible reaction mechanism for the formation of the molecule has also been reported.     

Effect of bis(acetato)tetrakis(imidazole) copper(II) in delaying the onset and reducing the mortality rate of strychnine- and thiosemicarbazide—Induced convulsions

The anticonvulsant activity of bis(acetato)tetrakis(imidazole) copper(II), Cu(OAc)₂(Im)₄, was studied in normal mice using chemical convulsions induced by strychnine, thiosemicarbazide, picrotoxin, and pentelenetetrazol. Intraperitoneal administration of Cu(OAc) ₂(Im)₄, 50 mg/kg body mass, has delayed the onset of strychnine (3 mg/kg)-induced convulsion by 204% (p≤0.005) and thiosemicarbazide (20 mg/kg)-induced convulsant by 61% (p≤0.005). The changes in the onset of picrotoxin-(6 mg/kg) and pentelenetetrazol (50 mg/kg)-induced convulsions were not significant. The same dosage of the copper compound was effective in delaying the lethal time and reducing the mortality rate of treated animals. The anticonvulsant activity of Cu(OAc) ₂(Im)₄ complex against strychnine was not related to its constituents because the inorganic form of copper such as copper chloride, copper acetate, and the parent imidazole has no anticonvulsant activity. Other copper(II) complexes like copper(II)aspirinate and bis(acetato)bis(2-methyl imidazole) copper(II) were less effective.     

Dothistroma needle blight of pines

In laboratory and field tests against Dothistroma pini of thirty-eight commercially available or experimental fungicides several showed high contact activity (notably Blasticidin M), indicating potential eradicant properties. Only triphenyl tin or copper-based compounds gave good field protection. For protection, two widely spaced annual applications are recommended for an area with two heavy rainfall periods.     

Highly enantioselective kinetic resolution of trans-2-(phenylthio)cyclohexanol derivatives by immobilized Candida antartica B lipase

Candida antartica B (immobilized CAL-B) mediated resolutions of trans-2-(phenylthio)cyclohexanol derivatives using vinyl acetate as acylating agent and MTBE as solvent provide excellent enantioselectivity (up to >99%) and high yield of both the enantiomers in short reaction time.     

Studies on the Mechanisms of the Monofluoroacetanilides Poisoning to Mammals

Organophosphates, phosphorothioates, phosphorodithioates, phosphites, and phosphonates were found to inhibit the fluoroacetanilide amidohydrolase of chicken liver. Above all, the inhibition by triphenyl phosphate, tri-n-butyl phosphorothioate, triphenyl phosphite, Dipterex, and DDVP were extremely remarkable. Their concentrations for 50% inhibition were about 10^?8 m or 10^?7 m, and the inhibition of triphenyl phosphate was non-competitive to the substrate. These compounds were slightly or moderately toxic to mice even when administered intraperitoneally. The specificity of the inhibition was also discussed.

The effects of the fluoroacetanilide amidohydrolase (fluoroacetanilidase) inhibitors on the fluoroaceto-p-bromoanilide (FBA) poisoning to mammals and insects were studied. Triphenyl phosphate (TPP) and tri-n-butyl phosphorothioate (TBT) were mainly used as the inhibitors. TPP was effective for reducing the oral and cutaneous toxicities of FBA to mice and rats only when applied prior to the FBA application. However, in cases of the inhaled toxicity and the combined inhaled-cutaneous toxicity, TPP or TBT were effective even when they were applied simultaneously with FBA. When TPP and TBT were administered to mice by the combined inhaled-cutaneous application, the activity of fluoroacetanilidase in liver and kidney was rapidly decreased, but it recovered within 4 to 6 days after the application. The insecticidal and miticidal activities of FBA were not affected at all both in the previous and simultaneous applications of the inhibitors. However, it was found that the fluoroacetanilides hydrolyzing enzyme of Mealy plum aphid was not inhibited by TPP even in the concentration of 10^?4 m. The mechanisms of the fluoroacetanilides poisoning to mammals and insects were discussed.     

Utilization of the tricarboxylic acid cycle intermediates and symbiotic effectiveness inRhizobium meliloti

Summary The utilization of the tricarboxylic acid cycle intermediates and related compounds was studied in strains ofRhizobium meliloti having different symbiotic effectiveness. In general, the very effective (VE) strains used these compounds as sole carbon source better than the ineffective (I) strains. However, a significant different was observed between VE and I strains in their ability to use acetate or oxaloacetate for growth. In fact, at a concentration of 2 mM, 80% of the VE strains used acetate or oxaloacetate white 50% of the I strains used acetate and none was able to grow on oxaloacetate. No correlation was found between the symbiotic effectiveness of the strains and their ATP content, when grown on mannitol. The highest ATP content (9.21 nM×g protein^–1) was found in the I strain S₂₀ and the lowest (0.69 nM×g protein^–1 was found in the effective strain S₈. Numerical analysis of the patterns of utilization of the TCA cycle intermediates and related compounds indicated that the 49 strains tested formed 11 distinct groups at 86% similarity, according to Jaccard's coefficient. Several strains showed unique patterns of utilization and can be clearly identified under laboratory conditions.Contribution no.225 Station de Recherches, Agriculture Canada.     

Effect of wax and lanolin emulsions on the efficiency of potato-blight fungicides in laboratory tests

Four potato-blight fungicides (copper oxychloride, tetrachloroisophthalo-nitrile, zineb and fentin acetate) were formulated either by adding emulsions of paraffin wax or lanolin to solid fungicide dispersed in water, or by dissolving the fungicide in wax or lanolin and then emulsifying the solution; all emulsions were non-creaming and extremely stable. These formulations were compared in the laboratory with commercial wettable powders of the same fungicides for their ability to protect detached potato leaflets against infection by Phytophthora infestans (Mont.) de Bary; in these and in other laboratory tests, the quality of rain-fastness, or tenacity, was involved directly or indirectly. Most of the wax or lanolin formulations gave better protection than the wettable powders. It is suggested that the wax and lanolin acted as viscous stickers, suitably increasing the rain-fastness of deposits on leaflets; and that when the fungicide was dissolved in the wax or lanolin before emulsification, the particle size of the dispersed fungicide was extremely small, a quality that increases biological action.     

Synthesis and characterization of a novel spring-like organotin complex containing guest benzene molecules

A novel spring-like organotin complex [(Ph₃Sn)(C₇H₅ClNO₂)]_n·3C₆H₆ (1), has been synthesized by treatment of 6-chloro-3-pyridineacetic acid bis(triphenyltin)oxide on the condition of reflux. The complex was characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy, and X-ray crystallography diffraction analysis. The structure analyses reveals that complex 1 is an 1D infinite chain linked by intermolecular Sn-O bonds, in which the guest benzene molecules are established in the cavity of this helical chain; all the tin atoms of complex 1 are five-coordinated.     

On the bioreactivity of triorganotin aminobenzoates. Investigation of trialkyl and triarylyltin(IV) esters of 3-amino and 4-aminobenzoic acids

The synthesis and study of trimethyl-, tributyl- and triphenyltin esters of the 3- and 4-aminobenzoic acids are reported. The triorganotin derivatives are characterized by elemental analyses, FT-IR and solution ¹H and ¹³C NMR spectra. The structure of the trimethyltin 4-aminobenzoate is solved by X-ray diffraction and proves to be polymeric in nature with bridging carboxylates and trigonal bipyramidal tin(IV) environment. However, all the compounds become monomeric in solution with a tetrahedral tin coordination environment in chloroform and trigonal bipyramidal in DMSO due to coordination of the solvent as the NMR spectra have revealed. The compounds exhibit variable cytotoxic activity when tested against Κ562 myelogenous leukaemia, HeLa cervical cancer and HepG2 hepatocellular carcinoma cell lines, with the butyl derivatives being the more effective and the methyl ones the less. Interestingly, their antibacterial action was significantly lower when tested against Escherichia coli, while not appreciable direct interaction with DNA has been observed. The above observations account for a mode of action that may be related to their potential interaction with cell membranes and the subsequent inhibition of various signaling processes.     

Detection of novel syntrophic acetate‐oxidizing bacteria from biogas processes by continuous acetate enrichment approaches

To enrich syntrophic acetate‐oxidizing bacteria (SAOB), duplicate chemostats were inoculated with sludge from syntrophic acetate oxidation (SAO)‐dominated systems and continuously supplied with acetate (0.4 or 7.5 g l^?1) at high‐ammonia levels. The chemostats were operated under mesophilic (37°C) or thermophilic (52°C) temperature for about six hydraulic retention times (HRT 28 days) and were sampled over time. Irrespective of temperature, a methane content of 64–69% and effluent acetate level of 0.4–1.0 g l^?1 were recorded in chemostats fed high acetate. Low methane production in the low‐acetate chemostats indicated that the substrate supply was below the threshold for methanization of acetate via SAO. Novel representatives within the family Clostridiales and genus Syntrophaceticus (class Clostridia) were identified to represent putative SAOB candidates in mesophilic and thermophilic conditions respectively. Known SAOB persisted at low relative abundance in all chemostats. The hydrogenotrophic methanogens Methanoculleus bourgensis (mesophilic) and Methanothermobacter thermautotrophicus (thermophilic) dominated archaeal communities in the high‐acetate chemostats. In line with the restricted methane production in the low‐acetate chemostats, methanogens persisted at considerably lower abundance in these chemostats. These findings strongly indicate involvement in SAO and tolerance to high ammonia levels of the species identified here, and have implications for understanding community function in stressed anaerobic processes.     

Electron microscopy of the marine microalga Dunaliella tertiolecta exposed to triphenyltin

Chemostat-grown cells of the chlorophyte Dunaliella tertiolecta (Butcher) exposed to triphenyltin were examined using transmission electron microscopy. Following a 1-h exposure to 21 and 84μM triphenyltin, mitochondria underwent structural damage and the thylakoid membranes of a small proportion of cells spread from the usual compact arrangement. Prolonging the exposure time resulted in significant cell lysis in cultures exposed to 84μM triphenyltin. Received 05 May 1997/ Accepted in revised form 28 January 1998     

Crosslinkable Amino‐Functionalized Conjugated Polymer as Cathode Interlayer for Efficient Inverted Polymer Solar Cells

A novel crosslinkable aminoalkyl‐functionalized polymer, poly[9,9‐bis(6‐(N,N‐diethylamino)propyl)fluorene‐alt‐9,9‐bis(hex‐5‐en‐1‐yl)‐fluorene] (PFN‐V), is designed and synthesized. The resulting polymer can be rapidly crosslinked by UV‐curing within 5 s in a nearly quantitative yield based on the “click” chemistry of alkyene end‐groups of the PFN‐V side chains and the addition of 1,8‐octanedithiol. The crosslinked PFN‐V film exhibits excellent solvent resistance property and can act as effective cathode interlayer to modify the indium tin oxide (ITO) electrode, which can thus facilitate the formation of Ohmic contact between cathode and active layer. The surface energy of PFN‐V is quite comparable to that of PC₇₁BM, which is favorable for the formation of vertical phase separation in the bulk heterojunction film that can facilitate extraction of charges as verified by transient photocurrent measurements. Based on the resulting PFN‐V as the cathode interlayer, the fabricated polymer solar cells with inverted device structure show a remarkable enhancement of power conversion efficiency from 3.11% for the control device to 9.18% for PFN‐V based device. These observations indicate that the synthesized PFN‐V can be a promising crosslinked copolymer as the cathode interlayer for high performance polymer solar cells.     

The effects of triphenyltin chloride on respiration and photosynthesis in the green algae Enteromorpha intestinalis and Ulothrix pseudoflacca

Abstract Respiration and photosynthesis in zoospores of Enteromorpha intestinalis (L.) Link and Ulothrix pseudoflacca Wille showed greater sensitivity to inhibition by triphenyltin chloride than in vegetative tissue. Photosynthesis in zoospores and vegetative tissue of U. pseudoflacca was more resistant to triphenyltin chloride inhibition than in zoospores and vegetative tissue of E. intestinalis. Respiration in zoospores and vegetative tissue of both species was equally sensitive to triphenyltin chloride.