Phosphine resistance in India is characterised by a dihydrolipoamide dehydrogenase variant that is otherwise unobserved in eukaryotes

Phosphine (PH3) fumigation is the primary method worldwide for controlling insect pests of stored commodities. Over-reliance on phosphine, however, has led to the emergence of strong resistance. Detailed genetic studies previously identified two loci, rph1 and rph2, that interact synergistically to create a strong resistance phenotype. We compared the genetics of phosphine resistance in strains of Rhyzopertha dominica and Tribolium castaneum from India and Australia, countries having similar pest species but widely differing in pest management practices. Sequencing analysis of the rph2 locus, dihydrolipoamide dehydrogenase (dld), identified two structurally equivalent variants, Proline49>Serine (P49S) in one R. dominica strain and P45S in three strains of T. castaneum from India. These variants of the DLD protein likely affect FAD cofactor interaction with the enzyme. A survey of insects from storage facilities across southern India revealed that the P45/49S variant is distributed throughout the region at very high frequencies, in up to 94% of R. dominica and 97% of T. castaneum in the state of Tamil Nadu. The abundance of the P45/49S variant in insect populations contrasted sharply with the evolutionary record in which the variant was absent from eukaryotic DLD sequences. This suggests that the variant is unlikely to provide a strong selective advantage in the absence of phosphine fumigation.

Genetic conservation of Phosphine Resistance in the Rice Weevil Sitophilus oryzae (L.)

High levels of resistance to phosphine in the rice weevil Sitophilus oryzae have been detected in Asian countries including China and Vietnam, however there is limited knowledge of the genetic mechanism of resistance in these strains. We find that the genetic basis of strong phosphine resistance is conserved between strains of S. oryzae from China, Vietnam and Australia. Each of four strongly resistant strains has an identical amino acid variant in the encoded dihydrolipoamide dehydrogenase (DLD) enzyme that was previously identified as a resistance factor in Rhyzopertha dominica and Tribolium castaneum. The unique amino acid substitution, Asparagine > Threonine (N505T) of all strongly resistant S. oryzae corresponds to the position of an Asparagine > Histidine variant (N506H) that was previously reported in strongly resistant R. dominica. Progeny (F16 and F18) from two independent crosses showed absolute linkage of N505T to the strong resistance phenotype, indicating that if N505T was not itself the resistance variant that it resided within 1 or 2 genes of the resistance factor. Non-complementation between the strains confirmed the shared genetic basis of strong resistance, which was supported by the very similar level of resistance between the strains, with LC50 values ranging from 0.20 to 0.36 mgL-1 for a 48 hour exposure at 25°C. Thus, the mechanism of high level resistance to phosphine is strongly conserved between R. dominica, T. castaneum and S. oryzae. A fitness cost associated with strongly resistant allele was observed in segregating populations in the absence of selection.

Mathematical modelling and numerical simulation of phosphine flow during grain fumigation in leaky cylindrical silos

The phosphine distribution in a cylindrical silo containing grain is predicted. A three-dimensional mathematical model, which accounts for multicomponent gas phase transport and the sorption of phosphine into the grain kernel is developed. In addition, a simple model is presented to describe the death of insects within the grain as a function of their exposure to phosphine gas. The proposed model is solved using the commercially available computational fluid dynamics (CFD) software, FLUENT, together with our own C code to customize the solver in order to incorporate the models for sorption and insect extinction. Two types of fumigation delivery are studied, namely, fan- forced from the base of the silo and tablet from the top of the silo. An analysis of the predicted phosphine distribution shows that during fan forced fumigation, the position of the leaky area is very important to the development of the gas flow field and the phosphine distribution in the silo. If the leak is in the lower section of the silo, insects that exist near the top of the silo may not be eradicated. However, the position of a leak does not affect phosphine distribution during tablet fumigation. For such fumigation in a typical silo configuration, phosphine concentrations remain low near the base of the silo. Furthermore, we find that half-life pressure test readings are not an indicator of phosphine distribution during tablet fumigation.

Spectroscopic studies of the donor properties of triphenyl-amine, -phosphine, -arsine and -stibine interaction with iodine and phenol

The interaction of iodine with triphenylamine ,tripheny lphosphine, triphenylarsine and triphenystibine has been investigated by electronic spectroscopy. Transformation of the outer charge-transfer complexes to the inner complexes (quarternary salts) has been examined. The relations of the ionization potentials of the donors with the hvc.t have been discussed and various c.t. parameters have been estimated. Hydrogen bonding of these donors with phenol have been reported.

Synthesis and spectral studies of polyamide-phosphate esters from phosphine-oxide-containing diols with aryl phosphorodichloridates and their thermal and flammability behaviour

Polyamide-phosphate esters were synthesized by interfacial polycondensation of aryl phosphorodichloridates with the diols of phenoxaphosphine and phosphine oxide in the presence of a phase-transfer catalyst. The polymers were characterized by infra-red and 1H, 13C and 31P nuclear magnetic resonance (n.m.r.) spectroscopy. The molecular weights were determined by end-group analysis using 31P n.m.r. spectral data. The phenoxaphosphine-containing polymers showed superior thermostability and flame retardancy over the phosphine-oxide-containing polymers.

The first bis(phosphine) monoxide (BPMO) complexes of copper(I)

Copper(l) complexes of bis(phosphine) monoxide ligands, bis(diphenylphosphino)ethane monoxide (dppeo) and bis(diphenylphosphino)methane monoxide (dppmo) have been prepared and characterized. One of the complexes with dppeo was characterized by X-ray crystal structure analysis confirming Cu(I) coordination to hard and soft donors. The stability of these complexes in solution was probed via spectroscopic and electrochemical studies. Copper(I) is more readily oxidized in the presence of the hard 0 donor ligands. In solution, they readily exchange the hard donor O, for soft ligands. Although copper(l) prefers soft ligands and is more stable towards oxidation in their presence, it coordinates to hard donors when there is electrostatic or an entropy driven advantage. (C) 2002 Elsevier Science Ltd. All rights reserved.

The first copper(I) complex of tris(hydroxymethyl)phosphine

The first copper(I) complex of tris(hydroxymethyl)phosphine (THP) has been synthesized from a reaction with [Cu(CH3CN)4]ClO4. The crystal structure and spectroscopic properties of this complex showing the tetrahedral coordination around copper and a deprotonated THP coordinated to Cu through P are presented.

Dynamics of H-atom exchange in stable cis-dihydrogen/hydride complexes of ruthenium( II) bearing phosphine and N-N bidentate ligands

Synthesis and characterization of cis, trans-RuH(eta(2)-H-2)(PPh3)(2)(N-N)]OTf] (N-N = 2,2'-bipyridyl (bpy) 1a, 2,2'-bipyrimidine (bpm) 2a; OTf = trifluoromethane sulfonate (CF3SO3)) complexes are reported. The cis-H-2/hydride ligands are involved in H-atom site exchange between the two moieties. This dynamics was investigated by variable temperature NMR spectral studies based on which the mechanism of the exchange process was deduced. The Delta G(#) for the exchange of H-atoms between the eta(2)-H-2 and hydride ligands was determined to be around 8 and 13 kJ mol(-1), respectively, for 1a and 2a. The H-H distances (d(HH), A) in complexes 1a and 2a have been calculated from the T-1(minimum) and (1)J(H, D) and are found to be 1.07 A (slow) and 0.95 A for 1a and 1.04 A (slow) and 0.94 A for 2a, respectively. The molecular structure of 1a was determined by X-ray crystallography.

Stereoselective inverse conjugate addition of nitrogen and carbon nucleophiles to allenyl phosphine oxide. Synthesis of α,β-unsaturated phosphine oxides

Issue in Honor of Prof. Paweł Kafarski

Influence of phosphine flow rate on Si growth rate in gas source molecular beam epitaxy

As reported by other authors, we have also observed that the Si growth rate decreases with increasing phosphine (PH3) flow rate in gas source-Si molecular beam epitaxy using phosphorous (P) as a n-type dopant. Why small quantity PH3 can affect Si growth rate? Up to now, the quantitative characterization of PH3 flow influence on Si growth rate is little known. In this letter, the PH, influence will be analyzed in detail and a model considering strong P surface segregation and its absorption of hydrogen will be proposed to characterize the effect. (C) 2000 Elsevier Science B.V. All rights reserved.

Chiral ferrocene-based phosphine-imine and sulfur-imine ligands for palladium-catalyzed asymmetric allylic alkylation of cycloalkenyl esters

Chiral ferrocene-based phosphine-imine ligands 1-3 and sulfur-imine ligand 4 were applied in the palladium-catalyzed asymmetric allylic alkylation of cycloalkenyl esters. The results revealed that the substitutents in aryl ring, ferrocenylmethyl and benzyliene position strongly affected the enantioselective induction of phosphine-imine ligands, and the most stereoselective ligand was ferrocenylphosphine-imine 1b with a nitro group in the meta-position of phenyl ring. Under the optimized condition, up to 91% (enantiomeric excesses) e.e. of cyclic alkylation product was obtained by the use of 1b. (C) 2004 Elsevier B.V. All rights reserved.

Ethylene Polymerization of the New Titanium Complexes Bearing a Phosphine Oxide-Bridged Bisphenolato Ligand

A series of novel titanium(IV) complexes combining a phosphine oxide-bridged bisphenolato ligand TiCl2{2,2'-O=P-R-3 (4-R-2-6-R-1-C6H2O)(2)}(THF) (6a: R-1 = tBu, R-2 - H, R-3 Ph; 6b: R-1 - Ph, R-2 = H, R-3 = Ph; 6c: R-1 = R-2 = tBu, R-3 = Ph; 6d: R-1 = R-2 cumyl, R-3 = Ph; 6e: R-1 = tBu, R-2 = H, R-3 = PhF5) were prepared by the reaction of corresponding bisphenolato ligands with TiCl4 in THF. X-ray analysis reveals that complex 6a adopts distorted octahedral geometry around the titanium center. These catalysts were performed for ethylene polymerization in the presence of modified methyaluminoxane (MMAO).