Proton NMR and infrared investigations of secondary dithiocarbamate ester: molecular conformation and vibrational assignment of S-methyl N-methyl dithiocarbamate

Rotational isomerism of S-methyl N-methyl dithiocarbamate (MMDTC) has been investigated by means of variable temperature proton NMR and i.r. spectroscopy. The i.r. spectra of MMDTC as neat, solution and at sub-ambient temperatures have been examined. Normal vibrational analysis of all the fundamentals of MMDTC has been carried out, the vibrational assignment has been compared with those of related secondary thioamides to note the consistency in the assignments and to obtain the pattern characteristic of the secondary thioamide vibrations.

N-Acetylglycyl-L-lysine methyl ester acetate

C llH22 N 30 + . C2H302, orthorhombic, P2~2~2~, a = 5.511(2), b = 14.588(4), c = 21.109 (4)A, Z = 4. The structure has been solved using MULTAN and refined to R = 0.079 for 993 observed reflections. The fully extended lysine side chain in the molecule is staggered between the main-chain amino and carbonyl groups. The dipeptide molecules in the crystal structure are arranged in twofold helices centred on 21 screw axes. These helices are interconnected through interactions involving the acetate and the side-chain amino groups. Each acetate group bridges two adjacent side-chain amino groups, related by an a translation, giving rise to an infinitely long chain of alternating negatively charged carboxylate and positively charged amino groups.

Efficacy of acibenzolar-S-methyl (Bion®) treatment of Australian commercial passionfruit, Passiflora edulis f. sp. flavicarpa, on resistance to Passionfruit woodiness virus (PWV) and activities of chitinase & β-1,3-glucanase

This greenhouse study investigated the efficacy of acibenzolar-S-methyl (Bion®) treatment of lower leaves of passionfruit, (Passiflora edulis f. sp. flavicarpa), on Passionfruit woodiness disease and activities of two pathogenesis-related proteins, chitinase and β-1,3-glucanase after inoculation with passionfruit woodiness virus (PWV). All Bion® concentrations reduced disease symptoms, but the concentration of 0.025 g active ingredient (a.i.)/l was the most effective, reducing disease severity in systemic leaves by 23, 29 and 30 compared with water-treated controls at 30, 40 and 50 days post inoculation (dpi) with PWV, respectively. Correspondingly, relative virus concentration as determined by DAS-ELISA in the upper, untreated leaves (new growth) above the site of inoculation at 50 dpi was reduced by 17 and 22 in plants treated with 0.025 and 0.05 g a.i./l, respectively. Bion® treatment and subsequent inoculation with PWV increased chitinase and β-1,3-glucanase activities in the new leaves above the site of inoculation at 30 dpi with PWV. It was concluded that optimal protective Bion® treatment concentrations were 0.025 and 0.05 g a.i./l.

Halosulfuron-methyl: A selective herbicide option for the control of the invasive 'Cyperus aromaticus' (Ridley) Mattf. and Kukenth (Navua sedge)

There are currently limited options for the control of the invasive tropical perennial sedge 'Cyperus aromaticus' (Ridley) Mattf. and Kukenth (Navua sedge). The potential for halosulfuron-methyl as a selective herbicide for Navua sedge control in tropical pastures was investigated by undertaking successive field and shade house experiments in North Queensland, Australia. Halosulfuron-methyl and adjuvant rates, and combinations with other herbicides, were examined to identify a herbicide regime that most effectively reduced Navua sedge. Our research indicated that combining halosulfuron- methyl with other herbicides did not improve efficacy for Navua sedge control. We also identified that low rates of halosulfuron-methyl (25 g ha-1 a.i.) were just as effective as higher rates (73 g ha-1 a.i.) at controlling the sedge, and that this control relied on the addition of the adjuvant Bonza at the recommended concentration (1% of the spray volume). Pot trials in the controlled environment of the shade house achieved total mortality under these regimes. Field trials demonstrated more variable results with reductions in Navua sedge ranging between 40-95% at 8-10 weeks after treatment. After this period (16-24 weeks after treatment), regrowth of sedge, either from newly germinated seed, or of small plants protected from initial treatment, indicated sedge populations can rapidly increase to levels similar to pre-application, depending on the location and climatic conditions. Such variable results highlight the need for concerted monitoring of pastures to identify optimal treatment times. Ideally, initial treatment should be done when the sedge is healthy and actively growing, with follow up-treatments applied when new seed heads are produced from regrowth.

Molecular vibrations and conformation of primary dithiocarbamate ester. Infrared and NMR studies on S-methyl dithiocarbamate

The i.r. spectra of a primary dithiocarbamate ester namely, S-methyl dithiocarbamate (SMDTC) and its N-dideuterated compound have been measured between 4000 and 30 cm−1. Spectra in solution and at liquid nitrogen temperature have also been obtained. Assignment of all the fundamentals has been proposed and supported from a full normal coordinate analysis. The band assignments for SMDTC have been compared with those of related molecules and the characteristic bands of primary thioamides are derived. Conformational flexibility of SMDTC has been examined by i.r. and proton NMR spectroscopy. The hindered rotation around the C---N bond has been studied by a complete line shape analysis. The magnitude of ---NH2 and ---CH3 torsional barriers is also estimated from vibrational frequencies and force constants.

Management of mango decline using thiophanate methyl and plant activators through a macro infusion system

Mango decline disease has become a major cause of tree losses of about 7-10% in all mango growing areas of Pakistan. This study evaluated the effectiveness of plant activators used in conjunction with the fungicide thiophanate methyl in managing mango decline disease. The study was conducted in the Multan district using trees rated as 1-2 on a decline severity scale and displaying symptoms of gummosis, bark splitting, canker formation, and leaf drooping. Experimental treatments included three plant activators viz. Bion, Planofix, and Root king in conjunction with or without thiophanate methyl, delivered through a macro infusion system. This was the first time a macro infusion system had been used in Pakistan. The injection system delivered the fungicide/activator mixture into the tree trunk under pressure through a series of holes bored into the xylem tissue. Tree disease symptoms were recorded fortnightly to assess the treatment efficacy. After three months, thiophanate methyl, in combination with Bion, was found to be the most effective treatment with trees displaying no apparent disease symptoms. When thiophanate methyl was used alone, or in combination with Root king and Planofix, the symptoms of bark splitting and gummosis persisted.

Low-dose methyl bromide fumigation as a quarantine disinfestation treatment for nectarines against Queensland fruit fly (Diptera:Tephritidae)

White nectarines (Prunus persica var. nucipersica) were fumigated with methyl bromide (MB) at a nominal treatment dose of 18 g m-3 at 18°C for 5 h and 30 min as a quarantine disinfestation treatment against Bactrocera tryoni, the Queensland fruit fly. Three large scale trials were conducted against each of the four immature lifestages, eggs and first, second and third instars. There were no survivors from the estimated 43,614 eggs, 41,873 first instars, 41,345 second instars and 33,549 third instars treated, thereby resulting in an efficacy of GROTERDAN99.99% mortality at the 95% confidence level for each lifestage. Of the 12 trials reported herein, the highest concentration of MB, sampled from the chamber headspace analysed by gas chromatography, was 18.7 g m-3. The maximum chamber temperature from 5 min readings was 19.7°C and the maximum fruit core temperature was 19.5°C. The treatment time for all trials was exactly 5.5 h. Thus the recommended treatment dose to disinfest nectarines from B. tryoni is 19.0 g m-3 MB at 20.0°C for 5.5 h. Fruit quality trials were conducted on white nectarines at three combinations of treatment parameters: 15 g m-3 MB at 19°C for 5.25 h; 18 g m-3 MB at 19°C for 5.5 h and 21 g m-3 MB at 19°C for 5.5 h. The fruit were stored at 0, 4 and 8 days at 4°C and 8 days at 4°C followed by 4 d at 22°C. They were then were assessed for skin colour, flesh colour, skin defects, flesh defects, fruit weight loss, flesh firmness, total soluble solids, titratable acidity and rots. There was no significant difference between untreated control and MB treated fruits in any of the parameters measured. Thus the treatments did not have adverse effects on fruit quality.

Dilute solution properties of methyl methacrylate�acrylonitrile copolymer (MA1)

This paper deals with studies on the dilute solution properties of methyl methacrylate�acrylonitrile copolymer of 0.289 mole fraction (mf) of acrylonitrile composition. Mark�Houwink parameters for this copolymer have been evaluated in acetonitrile (MeCN), 2-butanone (MEK), dimethylformamide (DMF) and γ-butyrolactone (γ-BL). The solvent power is found to be in the order of MEK < MeCN < DMF < γ-BL at 30°C. Herein, probably for the first time, the steric factor for the copolymer is found to be lower than that for the parent homopolymers and the excess interaction parameter, �AB is found to be negative. This probably suggests that the units are compatible to each other.

Temperature influence on the excess interaction parameter of styrene-methyl methacrylate copolymer

Intrinsic viscosity data for polystyrene, poly(methyl methacrylate) and styrene-methyl methacrylate copolymer of azeotropic composition have been used to evaluate the excess interaction parameters at different temperatures in γ-butyrolactone and dimethylformamide. It is found that these values are positive and show a negligible increase with increase in temperature, indicating therefore that the hetero-contact interactions are not influenced by temperature, contrary to the results obtained by Dondos and Benoit for the same copolymer system in p-xylene and iso-amyl acetate.

New structural insights and molecular-modelling studies of 4-methyl-5-beta-hydroxyethylthiazole kinase from Pyrococcus horikoshii OT3 (PhThiK)

4-Methyl-5-beta-hydroxyethylthiazole kinase (ThiK) catalyses the phosphorylation of the hydroxyl group of 4-methyl-5-beta-hydroxyethylthiazole. This work reports the first crystal structure of an archaeal ThiK: that from Pyrococcus horikoshii OT3 (PhThiK) at 1.85 angstrom resolution with a phosphate ion occupying the position of the beta-phosphate of the nucleotide. The topology of this enzyme shows the typical ribokinase fold of an alpha/beta protein. The overall structure of PhThiK is similar to those of Bacillus subtilis ThiK (BsThiK) and Enterococcus faecalis V583 ThiK (EfThiK). Sequence analysis of ThiK enzymes from various sources indicated that three-quarters of the residues involved in interfacial regions are conserved. It also revealed that the amino-acid residues in the nucleotide-binding, magnesium ion-binding and substrate-binding sites are conserved. Binding of the nucleotide and substrate to the ThiK enzyme do not influence the quaternary association (trimer) as revealed by the crystal structure of PhThiK.

Facile synthesis, ex-vivo and in vitro screening of 3-sulfonamide derivative of 5-(4-chlorophenyl)-1-(2,4-dichlorophenyl)-4-methyl-1H-pyrazole-3-carboxylic acid piperidin-1-ylamide (SR141716) a potent CB1 receptor antagonist

Facile synthesis of biaryl pyrazole sulfonamide derivative of 5-(4-chlorophenyl)-1-(2,4-dichlorophenyl)-4-methyl-1H-pyrazole-3-carboxylic acid piperidin-1-ylamide (SR141716, 1) and an investigation of the effect of replacement of the –CO group in the compound 1 by the –SO2 group in the aminopiperidine region is reported. Primary ex-vivo pharmacological testing and in vitro screening of sulfonamide derivative 2 showed the loss of CB1 receptor antagonism.

Chiral Synthons from Monoterpenes.1 Stereoselective Syntheses of (-)5S, 6S, 9R-6-Isopropyl-9-Methyl-2-Oxaspiro[4.4]Nonan-3-One and (-) 3aR, 6R, 7aR-3a-Methyl-6-Isopropenylhexahydrobenzofuran-2-One

Highly stereoselective syntheses of two C-12 chiral synthons 3 and 9, mentioned in the title, starting from the monoterpenes R-1 imonene and R-carvone, using radical cyc 1 sation as key reaction, are described.