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Sample records for r-3-amino-2-fluoropropyl phosphinic acid

  1. (R)-(3-amino-2-fluoropropyl) phosphinic acid (AZD3355), a novel GABAB receptor agonist, inhibits transient lower esophageal sphincter relaxation through a peripheral mode of action

    DEFF Research Database (Denmark)

    Lehmann, Anders; Antonsson, Madeleine; Holmberg, Ann Aurell

    2009-01-01

    of transient lower esophageal sphincter relaxation (TLESR) with a proposed peripherally acting GABA(B) receptor agonist, (R)-(3-amino-2-fluoropropyl)phosphinic acid (AZD3355). AZD3355 potently stimulated recombinant human GABA(B) receptors and inhibited TLESR in dogs, with a biphasic dose-response curve...... brain; AZD3355, but not baclofen, was concentrated in circumventricular organs as a result of active uptake (shown by avid intracellular sequestration) and related to binding of AZD3355 to native GABA transporters in rat cerebrocortical membranes. AZD3355 was also shown to be transported by all four...

  2. Lewis acidity enhancement of triarylborane by appended phosphine oxide groups.

    Science.gov (United States)

    Kwak, Jaewoo; Nghia, Nguyen Van; Lee, Junseong; Kim, Hyoseok; Park, Myung Hwan; Lee, Min Hyung

    2015-03-14

    A series of mono-, di-, and tri-phosphine oxide substituted triarylboranes, Mes2BAr (1), MesBAr2 (2), and BAr3 (3) (Ar = 4-(Ph2PO)-2,6-Me2-C6H2) were prepared to investigate the effect of a phosphine oxide group (Ph2PO) on Lewis acidity enhancement of triarylboranes. The X-ray crystal structure of 3 revealed peripheral decoration of Ph2PO groups with a C3-axis perpendicular to the trigonal boron center. UV/Vis absorption and PL spectra indicated a significant contribution of π(Mes or phenylene) → pπ(B) charge transfer in the lower-energy electronic transition. The reduction potential measured by cyclic voltammetry showed apparent LUMO stabilization by introduction of phosphine oxide groups, the extent of which gradually increased with the increasing number of phosphine oxide groups. Lewis acidity enhancement was also supported by the gradual increase in fluoride ion affinity in the order 3 > 2 > 1. Theoretical calculations suggest that introduction of a Ph2PO group into a triarylborane significantly enhances the Lewis acidity of the boron center via an inductive electron-withdrawing effect and this effect is additive for multiple phosphine oxide groups.

  3. Toward the formation of alkylphosphonic acids in phosphine ices

    Science.gov (United States)

    Turner, Andrew; Kaiser, Ralf-Ingo

    2016-10-01

    Phosphorus is one of the elemental building blocks of life on Earth and is important for information storage (RNA/DNA), energy transfer (ATP), cell membranes (phospholipids), and structure (bones & teeth). Due to the poor bioavailability of highly oxidized phosphorus (P(V)) found in ubiquitous phosphate (PO43-) minerals, reduced oxidation state (P(III)) compounds have been proposed as a phosphorus source for early life on Earth. Among these, the alkylphosphonic acids, which are the only phosphorus-containing organic compounds discovered in the Murchison meteorite, are a suggested exogenous source of prebiotic phosphorus. Phosphine (PH3) is a known component of the atmospheres of Jupiter and Saturn, and the confirmation of circumstellar phosphine in the carbon-rich envelop of IRC +10216 along with the recent detection of phosphorus in the comet 67P/Churyumov-Gerasimenko provide an additional foundation for studying extraterrestrial phosphorus chemistry and the origins of the alkylphosphonic acids. In the present study, reactions of phosphine ices with water (H2O), carbon dioxide (CO2), and methane (CH4) were investigated using Fourier transform infrared spectroscopy (FTIR), quadrupole mass spectrometry (QMS), and most notably, reflectron time-of-flight mass spectrometry using tunable photoionization (PI-ReTOF-MS). Experiments were conducted at ultra-high vacuum pressures and cryogenic temperatures to better understand reaction pathways and products of phosphorus-containing compounds under icy conditions found in comets or the interstellar medium. The results of this study can provide support to the hypothesis that the alkylphosphonic acids were formed from interstellar phosphine and incorporated into meteorites such as Murchison.

  4. Synthesis of p-aminophenyl aryl H-phosphinic acids and esters via cross-coupling reactions: elaboration to phosphinic acid pseudopeptide analogues of pteroyl glutamic acid and related antifolates.

    Science.gov (United States)

    Yang, Yonghong; Coward, James K

    2007-07-20

    The synthesis of suitably protected p-aminophenyl H-phosphinic acids and esters from the corresponding para-substituted aryl halides has been accomplished via the Pd-catalyzed cross-coupling reaction of anilinium hypophosphite, either in the absence or presence of a tetraalkyl orthosilicate, to provide the free H-phosphinic acid or the corresponding ester, respectively. Subsequent conjugate addition of either a PIII species or phosphorus anion, generated in situ from either the free H-phosphinic acid or ester, to a 2-methylene glutaric acid ester provided the aryl phosphinic acid analogue of p-aminobenzoyl glutamic acid. Alkylation of these suitably protected p-aminophenyl phosphinic acid esters with a 6-(bromomethyl)pteridine or the corresponding (bromomethyl)pyridopyrmidine, followed by hydrolytic removal of protecting groups, provided the target aryl phosphinic acid analogues of folic acid and related antifolates. Alternatively, for the synthesis of the folate or 5-deazafolate analogues on a slightly larger scale, reductive amination with either N2-acetyl or N2-pivaloyl-6-formylpterin or the corresponding formylpyridopyrmidine and the same suitably protected p-aminophenyl phosphinic acid esters, followed by removal of protecting groups, is preferred. In the course of this research, it was observed that the nucleophilicity of both the aniline nitrogen and various PIII species derived from p-aminophenyl phosphinic acid derivatives is significantly reduced compared to that of the unsubstituted counterpart.

  5. Phosphine-free conversion of alcohols into alkyl thiocyanates using trichloroisocyanuric acid/NH4SCN

    Institute of Scientific and Technical Information of China (English)

    Roya Azadi; Babak Mokhtari; Mohamad-Ali Makaremi

    2012-01-01

    A convenient and efficient phosphine-free procedure for the one-pot conversion of primary,secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates is described using trichloroisocyanuric acid/NH4SCN.

  6. Formation And Stabilization Of Silver Nanoparticles In Ethanol By Phosphinic Acid

    Directory of Open Access Journals (Sweden)

    Kim J.-K.

    2015-06-01

    Full Text Available Although phosphinic acid (H3PO2 has a powerful reduction potential, the reduction of silver ions by phosphinic acid salt has not yet been reported. In this work, colloidal silver has successfully synthesized by reducing silver ions in ethanol with phosphinic acid as a reducing agent. The effects of [AgNO3]/[H3PO2] ratios and reaction temperature were considered. Spherical silver nanoparticles with cubic structure were successfully prepared and their diameters were measured to be 8.5±0.9 nm − 11.3±0.2 nm. Half-life analysis showed that the reduction of silver ions proceeded with the reaction order of 1.30 on concentration of phosphinic acid and activation energy of 120.7 kJ/mol.

  7. Silica with immobilized phosphinic acid-derivative for uranium extraction

    Energy Technology Data Exchange (ETDEWEB)

    Budnyak, Tetyana M., E-mail: tetyanabudnyak@yahoo.com [Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine, 17 General Naumov Str., 03164 Kyiv (Ukraine); Strizhak, Alexander V. [Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska Street, 01601 Kyiv (Ukraine); Gładysz-Płaska, Agnieszka; Sternik, Dariusz [Maria Curie Skłodowska University, 2 M. Curie Skłodowska Sq., 20-031 Lublin (Poland); Komarov, Igor V. [Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska Street, 01601 Kyiv (Ukraine); Kołodyńska, Dorota; Majdan, Marek [Maria Curie Skłodowska University, 2 M. Curie Skłodowska Sq., 20-031 Lublin (Poland); Tertykh, Valentin A. [Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine, 17 General Naumov Str., 03164 Kyiv (Ukraine)

    2016-08-15

    Highlights: • A novel benzoimidazol-2-yl-phenylphosphinic acid-silica gel material was prepared. • U(VI) ions are sorbed on the studied adsorbent from the acidic solution. • U(VI) ions form a stable complex with the grafted phosphinic ligand. - Abstract: A novel adsorbent benzoimidazol-2-yl-phenylphosphinic acid/aminosilica adsorbent (BImPhP(O)(OH)/SiO{sub 2}NH{sub 2}) was prepared by carbonyldiimidazole-mediated coupling of aminosilica with 1-carboxymethylbenzoimidazol-2-yl-phenylphosphinic acid. It was obtained through direct phosphorylation of 1-cyanomethylbenzoimidazole by phenylphosphonic dichloride followed by basic hydrolysis of the nitrile. The obtained sorbent was well characterized by physicochemical methods, such as differential scanning calorimetry-mass spectrometry (DSC-MS), surface area and pore distribution analysis (ASAP), scanning electron microscopy (SEM), X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopies. The adsorption behavior of the sorbent and initial silica gel as well as aminosilica gel with respect to uranium(VI) from the aqueous media has been studied under varying operating conditions of pH, concentration of uranium(VI), contact time, and desorption in different media. The synthesized material was found to show an increase in adsorption activity with respect to uranyl ions in comparison with the initial compounds. In particular, the highest adsorption capacity for the obtained modified silica was found at the neutral pH, where one gram of the adsorbent can extract 176 mg of uranium. Under the same conditions the aminosilica extracts 166 mg/g, and the silica – 144 mg/g of uranium. In the acidic medium, which is common for uranium nuclear wastes, the synthesized adsorbent extracts 27 mg/g, the aminosilica – 16 mg/g, and the silica – 14 mg/g of uranium. It was found that 15% of uranium ions leached from the prepared material in acidic solutions, while 4% of uranium can be removed in a phosphate

  8. Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

    Directory of Open Access Journals (Sweden)

    José Luis Viveros-Ceballos

    2016-08-01

    Full Text Available α-Amino-C-phosphinic acids and derivatives are an important group of compounds of synthetic and medicinal interest and particular attention has been dedicated to their stereoselective synthesis in recent years. Among these, phosphinic pseudopeptides have acquired pharmacological importance in influencing physiologic and pathologic processes, primarily acting as inhibitors for proteolytic enzymes where molecular stereochemistry has proven to be critical. This review summarizes the latest developments in the asymmetric synthesis of acyclic and phosphacyclic α-amino-C-phosphinic acids and derivatives, following in the first case an order according to the strategy used, whereas for cyclic compounds the nitrogen embedding in the heterocyclic core is considered. In addition selected examples of pharmacological implications of title compounds are also disclosed.

  9. A novel tridentate bis(phosphinic acid)phosphine oxide based europium(III)-selective Nafion membrane luminescent sensor.

    Science.gov (United States)

    Sainz-Gonzalo, F J; Popovici, C; Casimiro, M; Raya-Barón, A; López-Ortiz, F; Fernández, I; Fernández-Sánchez, J F; Fernández-Gutiérrez, A

    2013-10-21

    A new europium(III) membrane luminescent sensor based on a new tridentate bis(phosphinic acid)phosphine oxide (3) system has been developed. The synthesis of this new ligand is described and its full characterization by NMR, IR and elemental analyses is provided. The luminescent complex formed between europium(III) chloride and ligand 3 was evaluated in solution, observing that its spectroscopic and chemical characteristics are excellent for measuring in polymer inclusion membranes. Included in a Nafion membrane, all the parameters (ligand and ionic additives) that can affect the sensitivity and selectivity of the sensing membrane as well as the instrumental conditions were carefully optimized. The best luminescence signal (λexc = 229.06 nm and λem = 616.02 nm) was exhibited by the sensing film having a Nafion : ligand composition of 262.3 : 0.6 mg mL(-1). The membrane sensor showed a short response time (t95 = 5.0 ± 0.2 min) and an optimum working pH of 5.0 (25 mM acetate buffer solution). The membrane sensor manifested a good selectivity toward europium(III) ions with respect to other trivalent metals (iron, chromium and aluminium) and lanthanide(III) ions (lanthanum, samarium, terbium and ytterbium), although a small positive interference of terbium(III) ions was observed. It provided a linear range from 1.9 × 10(-8) to 5.0 × 10(-6) M with a very low detection limit (5.8 × 10(-9) M) and sensitivity (8.57 × 10(-7) a.u. per M). The applicability of this sensing film has been demonstrated by analyzing different kinds of spiked water samples obtaining recovery percentages of 95-97%.

  10. Palladium-catalyzed air-based oxidative coupling of arylboronic acids with H-phosphine oxides leading to aryl phosphine oxides.

    Science.gov (United States)

    Fu, Tingting; Qiao, Hongwei; Peng, Zhimin; Hu, Gaobo; Wu, Xueji; Gao, Yuxing; Zhao, Yufen

    2014-05-14

    We present a novel and highly efficient methodology that allows for the construction of C-P bonds via the palladium-catalyzed air-based oxidative coupling of various commercially available arylboronic acids with easily oxidized H-phosphine oxides leading to valuable aryl phosphine oxides, particularly triarylphosphine oxides, with the use of air as the green oxidant, broad substrate applicability and good to excellent yields. The described catalytic system should be an efficient complement to the Chan-Lam type reaction and be useful in synthetic programs.

  11. Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties.

    Science.gov (United States)

    David, Tomáš; Procházková, Soňa; Havlíčková, Jana; Kotek, Jan; Kubíček, Vojtěch; Hermann, Petr; Lukeš, Ivan

    2013-02-21

    Three symmetrical methylene-bis[(aminomethyl)phosphinic acids] bearing different substituents on the central carbon atom, (NH(2)CH(2))PO(2)H-C(R(1))(R(2))-PO(2)H(CH(2)NH(2)) where R(1) = OH, R(2) = Me (H(2)L(1)), R(1) = OH, R(2) = Ph (H(2)L(2)) and R(1),R(2) = H (H(2)L(3)), were synthesized. Acid-base and complexing properties of the ligands were studied in solution as well as in the solid state. The ligands show unusually high basicity of the nitrogen atoms (log K(1) = 9.5-10, log K(2) = 8.5-9) if compared with simple (aminomethyl)phosphinic acids and, consequently, high stability constants of the complexes with studied divalent metal ions. The study showed the important role of the hydroxo group attached to the central carbon atom of the geminal bis(phosphinate) moiety. Deprotonation of the hydroxo group yields the alcoholate anion which tends to play the role of a bridging ligand and induces formation of polynuclear complexes. Solid-state structures of complexes [H(2)N=C(NH(2))(2)][Cu(2)(H(-1)L(2))(2)]CO(3)·10H(2)O and Li(2)[Co(4)(H(-1)L(1))(3)(OH)]·17.5H(2)O were determined by X-ray diffraction. The complexes show unexpected geometries forming dinuclear and cubane-like structures, respectively. The dinuclear copper(II) complex contains a bridging μ(2)-alcoholate group with the (-)O-P(=O)-CH(2)-NH(2) fragments of each ligand molecule chelated to the different central ion. In the cubane cobalt(II) complex, one μ(3)-hydroxide and three μ(3)-alcoholate anions are located in the cube vertices and both phosphinate groups of one ligand molecule are chelating the same cobalt(II) ion while each of its amino groups are bound to different neighbouring metal ions. All such three metal ions are bridged by the alcoholate group of a given ligand.

  12. Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: a facile synthesis of β-ketophosphine oxides.

    Science.gov (United States)

    Zhang, Pengbo; Zhang, Liangliang; Gao, Yuzhen; Xu, Jian; Fang, Hua; Tang, Guo; Zhao, Yufen

    2015-05-07

    The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.

  13. Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region.

    Science.gov (United States)

    Guo, Rui; Reiner, Eric J; Bhavsar, Satyendra P; Helm, Paul A; Mabury, Scott A; Braekevelt, Eric; Tittlemier, Sheryl A

    2012-11-01

    A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78 % to 121 %. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145 ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ≈ Erie > Huron > Superior ≈ Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2 ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045 ± 0.023 ng/g. Mean concentrations of PFOA were not significantly different (p > 0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032 ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid.

  14. Determination of phosphine: comparison of rates of desorption by purge-and-trap method and by sulfuric acid treatment.

    Science.gov (United States)

    Saeed, T; Abu-Tabanja, R

    1985-01-01

    Two methods were compared for quantitative determination of phosphine present on fumigated food and materials. The rate of desorption of PH3 by using a purge-and-trap method was shown to be much slower when compared with sulfuric acid treatment and was also simpler. Application of the modified sulfuric acid treatment for real samples is described.

  15. SYNTHESIS OF 1—(N—BENZYLOXYCARBONYLAMINO)ALKANEPHOSPHATES AND—PHOSPHINIC ACIDS CATALYZED BY A CATION EXCHANGE RESIN

    Institute of Scientific and Technical Information of China (English)

    ZHANGYuehua; HUANGWenqiang; 等

    1993-01-01

    An improved method is developed by using strongly acidic cation exchange resin(001×1,H+ form) as a catalyst for the synthesis of diphenyl 1-(N-benzyloxycarbonyl-amino) alkanephosphonates and 1-(N-benzyloxycarbonylamino) alkanephenyl phosphinic acids in high yields.

  16. Gas chromatography of alkylphosphonic and dialkyl phosphinic acids; Cromatografia en fase gaseosa de acidos alquifosfonicos y dialquilfosinicos

    Energy Technology Data Exchange (ETDEWEB)

    Gasco Sanchez, L.; Barrera Peniero, R.; Ramirez Caceres, A.; Marin Munoz, M.

    1978-07-01

    After carrying out an optimization study on the separation conditions for the TMSr- derivatives, of the hexyl-, cyclohexyl-, heptyl-, and octyl-phosphonic acids; dihexyl dicyclohexyl-, heptyl-, and octyl-phosphinic acids, and dioctyl phosphine oxide, their retention indices (I) at two temperatures and on the OV-1 and OV-17 stationary phase were determined. Correlations between I and molecular structure were established. Calibration factors of these compounds in the flame ionization detector were studied, and the results analyzed taking into account the variables affecting the quantitative results, These results were unbiased but they had a lower precision than that usually achievable in gas chromatography. (Author) 24 refs.

  17. Silica with immobilized phosphinic acid-derivative for uranium extraction.

    Science.gov (United States)

    Budnyak, Tetyana M; Strizhak, Alexander V; Gładysz-Płaska, Agnieszka; Sternik, Dariusz; Komarov, Igor V; Kołodyńska, Dorota; Majdan, Marek; Tertykh, Valentin А

    2016-08-15

    A novel adsorbent benzoimidazol-2-yl-phenylphosphinic acid/aminosilica adsorbent (BImPhP(O)(OH)/SiO2NH2) was prepared by carbonyldiimidazole-mediated coupling of aminosilica with 1-carboxymethylbenzoimidazol-2-yl-phenylphosphinic acid. It was obtained through direct phosphorylation of 1-cyanomethylbenzoimidazole by phenylphosphonic dichloride followed by basic hydrolysis of the nitrile. The obtained sorbent was well characterized by physicochemical methods, such as differential scanning calorimetry-mass spectrometry (DSC-MS), surface area and pore distribution analysis (ASAP), scanning electron microscopy (SEM), X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopies. The adsorption behavior of the sorbent and initial silica gel as well as aminosilica gel with respect to uranium(VI) from the aqueous media has been studied under varying operating conditions of pH, concentration of uranium(VI), contact time, and desorption in different media. The synthesized material was found to show an increase in adsorption activity with respect to uranyl ions in comparison with the initial compounds. In particular, the highest adsorption capacity for the obtained modified silica was found at the neutral pH, where one gram of the adsorbent can extract 176mg of uranium. Under the same conditions the aminosilica extracts 166mg/g, and the silica - 144mg/g of uranium. In the acidic medium, which is common for uranium nuclear wastes, the synthesized adsorbent extracts 27mg/g, the aminosilica - 16mg/g, and the silica - 14mg/g of uranium. It was found that 15% of uranium ions leached from the prepared material in acidic solutions, while 4% of uranium can be removed in a phosphate solution.

  18. Phosphinic acid functionalized polyazacycloalkane chelators for radiodiagnostics and radiotherapeutics: unique characteristics and applications.

    Science.gov (United States)

    Notni, Johannes; Šimeček, Jakub; Wester, Hans-Jürgen

    2014-06-01

    Given the wide application of positron emission tomography (PET), positron-emitting metal radionuclides have received much attention recently. Of these, gallium-68 has become particularly popular, as it is the only PET nuclide commercially available from radionuclide generators, therefore allowing local production of PET radiotracers independent of an on-site cyclotron. Hence, interest in optimized bifunctional chelators for the elaboration of (68) Ga-labeled bioconjugates has been rekindled as well, resulting in the development of improved triazacyclononane-triphosphinate (TRAP) ligand structures. The most remarkable features of these ligands are unparalleled selectivity for Ga(III) , rapid Ga(III) complexation kinetics, extraordinarily high thermodynamic stability, and kinetic inertness of the respective Ga(III) chelates. As a result, TRAP chelators exhibit very favorable (68) Ga-labeling properties. Based on the scaffolds NOPO (1,4,7-triazacyclononane-1,4-bis[methylene(hydroxymethyl)phosphinic acid]-7-[methylene(2-carboxyethyl)phosphinic acid]) and TRAP-Pr, tailored for convenient preparation of (68) Ga-labeled monomeric and multimeric bioconjugates, a variety of novel (68) Ga radiopharmaceuticals have been synthesized. These include bisphosphonates, somatostatin receptor ligands, prostate-specific membrane antigen (PSMA)-targeting peptides, and cyclic RGD pentapeptides, for in vivo PET imaging of bone, neuroendocrine tumors, prostate cancer, and integrin expression, respectively. Furthermore, TRAP-based (68) Ga-labeled gadolinium(III) complexes have been proposed as bimodal probes for PET/MRI, and a cyclen-based analogue of TRAP-Pr has been suggested for the elaboration of targeted radiotherapeutics comprising radiolanthanide ions. Thus, polyazacycloalkane-based polyphosphinic acid chelators are a powerful toolbox for pharmaceutical research, particularly for the development of (68) Ga radiopharmaceuticals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Chemical Reaction between Boric Acid and Phosphine Indicates Boric Acid as an Antidote for Aluminium Phosphide Poisoning

    Science.gov (United States)

    Soltani, Motahareh; Shetab-Boushehri, Seyed F.; Shetab-Boushehri, Seyed V.

    2016-01-01

    Objectives: Aluminium phosphide (AlP) is a fumigant pesticide which protects stored grains from insects and rodents. When it comes into contact with moisture, AlP releases phosphine (PH3), a highly toxic gas. No efficient antidote has been found for AlP poisoning so far and most people who are poisoned do not survive. Boric acid is a Lewis acid with an empty p orbital which accepts electrons. This study aimed to investigate the neutralisation of PH3 gas with boric acid. Methods: This study was carried out at the Baharlou Hospital, Tehran University of Medical Sciences, Tehran, Iran, between December 2013 and February 2014. The volume of released gas, rate of gas evolution and changes in pH were measured during reactions of AlP tablets with water, acidified water, saturated boric acid solution, acidified saturated boric acid solution, activated charcoal and acidified activated charcoal. Infrared spectroscopy was used to study the resulting probable adduct between PH3 and boric acid. Results: Activated charcoal significantly reduced the volume of released gas (P <0.01). Although boric acid did not significantly reduce the volume of released gas, it significantly reduced the rate of gas evolution (P <0.01). A gaseous adduct was formed in the reaction between pure AlP and boric acid. Conclusion: These findings indicate that boric acid may be an efficient and non-toxic antidote for PH3 poisoning. PMID:27606109

  20. Chemical Reaction between Boric Acid and Phosphine Indicates Boric Acid as an Antidote for Aluminium Phosphide Poisoning.

    Science.gov (United States)

    Soltani, Motahareh; Shetab-Boushehri, Seyed F; Shetab-Boushehri, Seyed V

    2016-08-01

    Aluminium phosphide (AlP) is a fumigant pesticide which protects stored grains from insects and rodents. When it comes into contact with moisture, AlP releases phosphine (PH3), a highly toxic gas. No efficient antidote has been found for AlP poisoning so far and most people who are poisoned do not survive. Boric acid is a Lewis acid with an empty p orbital which accepts electrons. This study aimed to investigate the neutralisation of PH3 gas with boric acid. This study was carried out at the Baharlou Hospital, Tehran University of Medical Sciences, Tehran, Iran, between December 2013 and February 2014. The volume of released gas, rate of gas evolution and changes in pH were measured during reactions of AlP tablets with water, acidified water, saturated boric acid solution, acidified saturated boric acid solution, activated charcoal and acidified activated charcoal. Infrared spectroscopy was used to study the resulting probable adduct between PH3 and boric acid. Activated charcoal significantly reduced the volume of released gas (P boric acid did not significantly reduce the volume of released gas, it significantly reduced the rate of gas evolution (P boric acid. These findings indicate that boric acid may be an efficient and non-toxic antidote for PH3 poisoning.

  1. Chemical Reaction between Boric Acid and Phosphine Indicates Boric Acid as an Antidote for Aluminium Phosphide Poisoning

    Directory of Open Access Journals (Sweden)

    Motahareh Soltani

    2016-08-01

    Full Text Available Objectives: Aluminium phosphide (AlP is a fumigant pesticide which protects stored grains from insects and rodents. When it comes into contact with moisture, AlP releases phosphine (PH3, a highly toxic gas. No efficient antidote has been found for AlP poisoning so far and most people who are poisoned do not survive. Boric acid is a Lewis acid with an empty p orbital which accepts electrons. This study aimed to investigate the neutralisation of PH3 gas with boric acid. Methods: This study was carried out at the Baharlou Hospital, Tehran University of Medical Sciences, Tehran, Iran, between December 2013 and February 2014. The volume of released gas, rate of gas evolution and changes in pH were measured during reactions of AlP tablets with water, acidified water, saturated boric acid solution, acidified saturated boric acid solution, activated charcoal and acidified activated charcoal. Infrared spectroscopy was used to study the resulting probable adduct between PH3 and boric acid. Results: Activated charcoal significantly reduced the volume of released gas (P <0.01. Although boric acid did not significantly reduce the volume of released gas, it significantly reduced the rate of gas evolution (P <0.01. A gaseous adduct was formed in the reaction between pure AlP and boric acid. Conclusion: These findings indicate that boric acid may be an efficient and non-toxic antidote for PH3 poisoning.

  2. Carbene-metal hydrides can be much less acidic than phosphine-metal hydrides: significance in hydrogenations.

    Science.gov (United States)

    Zhu, Ye; Fan, Yubo; Burgess, Kevin

    2010-05-05

    Acidities of iridium hydride intermediates were shown to be critical in some transformations mediated by the chiral analogues of Crabtree's catalyst, 1-3. To do this, several experiments were undertaken to investigate the acidities of hydrogenation mixtures formed using these iridium-oxazoline complexes. DFT calculations indicated that the acidity difference for Ir-H intermediates in these hydrogenations were astounding; iridium hydride from the N-heterocyclic carbene catalyst 1 was calculated to be around seven pK(a) units less acidic than those from the P-based complexes 2 and 3. Consistent with this, the carbene complex 1 was shown to be more effective for hydrogenations of acid-sensitive substrates. In deuteration experiments, less "abnormal" deuteration was observed, corresponding to fewer complications from acid-mediated alkene isomerization preceding the D(2)-addition step. Finally, simple tests with pH indicators provided visual evidence that phosphine-based catalyst precursors give significantly more acidic reaction mixtures than the corresponding N-heterocyclic carbene ones. These observations indicate carbene-for-phosphine (and similar) ligand substitutions may impact the outcome of catalytic reactions by modifying the acidities of the metal hydrides formed.

  3. Air-stable platinum and palladium complexes featuring bis[2,4-bis(trifluoromethyl)phenyl]phosphinous acid ligands.

    Science.gov (United States)

    Kurscheid, Boris; Neumann, Beate; Stammler, Hans-Georg; Hoge, Berthold

    2011-12-23

    Secondary phosphane oxides, R(2)P(O)H, are commonly used as preligands for transition-metal complexes of phosphinous acids, R(2)P-OH (R=alkyl, aryl), which are relevant as efficient catalysts in cross-coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron-deficient phosphinous acid, (R(f))(2)P-OH, bearing the strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl group towards catalysis-relevant metals, such as palladium and platinum. The preligand bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide, (R(f))(2)P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the trans-configured phosphinous acid platinum complex trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the cis-configured monoanion complex cis-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H](-), featuring the quasi-chelating phosphinous acid phosphinito unit, (R(f))(2)P-O-H···O=P(R(f))(2), which exhibits a strong hydrogen bridge substantiated by an O···O distance of 245.1(4) pm. The second deprotonation step is accompanied by a rearrangement to afford the trans-configured dianion trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)](2-). The reaction of (R(f))(2)P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)]. The equilibrium between the mononuclear [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)] and dinuclear [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F(6)acac)(2)], with a slight excess of (R(f))(2)P

  4. Proposing Boric Acid as an Antidote for Aluminium Phosphide Poisoning by Investigation of the Chemical Reaction Between Boric Acid and Phosphine

    OpenAIRE

    Motahareh Soltani; Seyed Farid Shetab-Boushehri; Hamidreza Mohammadi; Seyed Vahid Shetab-Boushehri

    2013-01-01

    Aluminium phosphide (AlP) is a storage fumigant pesticide, which is used to protect stored grains especially from insects and rodents. It releases phosphine (PH3) gas, a highly toxic mitochondrial poison, in contact with moisture, particularly if acidic. Although the exact mechanism of action is unknown so far, the major mechanism of PH3 toxicity seems to be the inhibition of cytochrome-c oxidase and oxidative phosphorylation which eventually results in adenosine triphosphate (ATP) depletion ...

  5. A General, Simple Catalyst for Enantiospecific Cross Couplings of Benzylic Ammonium Triflates and Boronic Acids: No Phosphine Ligand Required

    Science.gov (United States)

    Basch, Corey H.; Song, Ye-Geun; Watson, Mary P.

    2014-01-01

    Highly improved conditions for the enantiospecific cross coupling of benzylic ammonium triflates with boronic acids are reported. This method relies on the use of Ni(cod)2 without ancillary phosphine or N-heterocyclic carbene ligands as catalyst. These conditions enable the coupling of new classes of boronic acids and benzylic ammonium triflates. In particular, both heteroaromatic and vinyl boronic acids are well tolerated as coupling partners. In addition, these conditions enable the use of ammonium triflates with a variety of substituents at the benzylic stereocenter. Further, naphthyl-substitution is not required on the benzylic ammonium triflate; ammonium triflates with simple aromatic substituents also undergo this coupling. Good to high yields and levels of stereochemical fidelity are observed. This new catalyst system greatly expands the utility of enantiospecific cross couplings of these amine-derived substrates for the preparation of highly enantioenriched products. PMID:25364060

  6. Direct evidence for the availability of reactive, water soluble phosphorus on the early Earth. H-phosphinic acid from the Nantan meteorite.

    Science.gov (United States)

    Bryant, David E; Kee, Terence P

    2006-06-14

    Anoxic irradiation of a type IIICD iron meteorite known to contain the phosphide mineral schreibersite (Fe,Ni)3P in the presence of ethanol/water affords the reactive oxyacid H-phosphinic acid (H3PO2) as the dominant phosphorus product.

  7. Copper-catalyzed decarboxylative C-P cross-coupling of alkynyl acids with H-phosphine oxides: a facile and selective synthesis of (E)-1-alkenylphosphine oxides.

    Science.gov (United States)

    Hu, Gaobo; Gao, Yuxing; Zhao, Yufen

    2014-09-05

    A novel and efficient copper-catalyzed decarboxylative cross-coupling of alkynyl acids for the stereoselective synthesis of E-alkenylphosphine oxides has been developed. In the presence of 10 mol % of CuCl without added ligand, base, and additive, various alkynyl acids reacted with H-phosphine oxides to afford E-alkenylphosphine oxides with operational simplicity, broad substrate scope, and the stereoselectivity for E-isomers.

  8. Solvent extraction of rare earth ions from nitrate media with new extractant di-(2,3-dimethylbutyl)-phosphinic acid

    Institute of Scientific and Technical Information of China (English)

    王俊莲; 陈广; 徐盛明; 尹祉力; 张覃

    2016-01-01

    As a relatively new extractant, di-(2,3-dimethylbutyl)-phosphinic acid (HYY-2) is more efficient to separate heavy rare earths Tm/Yb/Lu than Cyanex 272 and P507. In this paper, HYY-2 was synthesized in our lab, and the extraction equilibrium, ther-modynamics and stripping acidity for La, Gd and Y, which stood for light rare earth elements (REE), middle REE and heavy REE respectively, from nitrate media with this extractant were investigated. Meanwhile, extraction ability, capacity and stripping acidity of HYY-2 were investigated and compared with those of Cyanex 272 and P507. The separation performance for rare earth element cou-ples Gd/Eu and Er/Ywere also studied. Compared to Cyanex 272, it possessed higher extraction capacity; while compared with P507, it has lower stripping acidity. The maximumβGd/Eu 1.46 occurred at pHequilibrium=2.78 and the maximumβEr/Y was 1.47 when pHequilibrium= 2.01.

  9. Bioavailability and bioconcentration potential of perfluoroalkyl-phosphinic and -phosphonic acids in zebrafish (Danio rerio): Comparison to perfluorocarboxylates and perfluorosulfonates.

    Science.gov (United States)

    Chen, Fangfang; Gong, Zhiyuan; Kelly, Barry C

    2016-10-15

    Currently, information regarding bioavailability and bioconcentration potential of perfluoroalkyl phosphinic acids (PFPiAs) in aquatic organisms does not exist. The main objective of the present study was to assess uptake and elimination kinetics of PFPiAs in zebrafish (Danio rerio) following aqueous exposure. The results showed that PFPiA exposure can result in very high steady-state bioconentration factors (BCFss), compared to perfluorocarboxylates and perfluorosulfonates.C6/C10 PFPiA exhibited the highest BCFss, ranging between 10(7) and 10(10), orders of magnitude higher than those for long-chain perfluorocarboxylates. Strong positive relationships were observed between BCFss versus the membrane-water distribution coefficient (Dmw) and the protein-water partition coefficient (Kpw) of the studied perfluoroalkyl substances. However, BCFss exhibited a substantial drop for the very hydrophobic PFPiAs (C8/C10 and C6/C12 PFPiAs). The reduced BCFss of these long-chain PFPiAs (perfluoroalkyl chain length=18; Dmw=10(9)) is likely the result of reduced bioavailability due to interaction with solute molecules/organic matter present in the water phase and/or reduced gill membrane permeability. While PFPiAs can be metabolized to perfluoroalkyl phosphonic acids, the metabolic transformation rate seems insufficient to counteract the high degree of uptake across gill membranes. These findings help to better understand exposure pathways and bioaccumulation behavior of these important perfluorinated acids in aquatic systems.

  10. Synergistic extraction of rare earths with bis(2,4,4-trimethyl pentyl) dithiophosphinic acid and trialkyl phosphine oxide.

    Science.gov (United States)

    Reddy, M L; Bosco Bharathi, J R; Peter, S; Ramamohan, T R

    1999-08-23

    Synergistic extraction of trivalent rare earths from nitrate solutions using mixtures of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301=HX) and trialkyl phosphine oxide (Cyanex 923=TRPO) in xylene has been investigated. The results demonstrate that these trivalent metal ions are extracted into xylene as MX(3).3HX with Cyanex 301 alone. In the presence of Cyanex 923, La(III) and Nd(III) are found to be extracted as MX(2).NO(3).TRPO. On the other hand, Eu(III), Y(III) and heavier rare earths are found to be extracted as MX(3).HX.2TRPO. The addition of a trialkylphosphine oxide to the metal extraction system not only enhances the extraction efficiency of these metal ions but also improves the selectivities significantly, especially between yttrium and heavier lanthanides. The separation factors between these metal ions were calculated and compared with that of commercially important extraction systems like di-2-ethylhexyl phosphoric acid.

  11. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

    Institute of Scientific and Technical Information of China (English)

    Ben Li; Cuiping Wang; Guang Chen; Zhiqiang Zhang

    2013-01-01

    Highly active,air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents.Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture,water/propanol mixture and neat water respectively,the corresponding yields of cross-coupling heteroaryl-aryls were satisfied.The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPdl and POPd2,and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3.The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step.Compared with other solid phase transfer catalysts,TBAB was tested as the ideal one.The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents.Notably,in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products.However in terms of the liquid phase transfer catalyst of PEGs,mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase,which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  12. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents.

    Science.gov (United States)

    Li, Ben; Wang, Cuiping; Chen, Guang; Zhang, Zhiqiang

    2013-06-01

    Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  13. Cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells with dichloromethyl phosphinic acid as a cross-linker

    DEFF Research Database (Denmark)

    Noye, Pernille; Li, Qingfeng; Pan, Chao;

    2008-01-01

    . The produced cross-linked membranes show increased mechanical strength, making it possible to achieve higher phosphoric acid doping levels and therefore higher proton conductivity. Oxidative stability is significantly improved and thermal stability is sufficient in a temperature range of up to 250 degrees C, i......Phosphoric acid doped polybenzimidazole (PBI) membranes have been covalently cross-linked with dichloromethyl phosphinic acid (DCMP). FT-IR measurements showed new bands originating from bonds between the hydrogen bearing nitrogen in the imidazole group of PBI and the CH2 group in DCMP...

  14. Mechanisms of Phosphine Toxicity

    OpenAIRE

    Nisa S. Nath; Ishita Bhattacharya; Andrew G. Tuck; Schlipalius, David I.; Paul R. Ebert

    2011-01-01

    Fumigation with phosphine gas is by far the most widely used treatment for the protection of stored grain against insect pests. The development of high-level resistance in insects now threatens its continued use. As there is no suitable chemical to replace phosphine, it is essential to understand the mechanisms of phosphine toxicity to increase the effectiveness of resistance management. Because phosphine is such a simple molecule (PH3), the chemistry of phosphorus is central to its toxicity...

  15. Proposing Boric Acid as an Antidote for Aluminium Phosphide Poisoning by Investigation of the Chemical Reaction Between Boric Acid and Phosphine

    Directory of Open Access Journals (Sweden)

    Motahareh Soltani

    2013-01-01

    Full Text Available Aluminium phosphide (AlP is a storage fumigant pesticide, which is used to protect stored grains especially from insects and rodents. It releases phosphine (PH3 gas, a highly toxic mitochondrial poison, in contact with moisture, particularly if acidic. Although the exact mechanism of action is unknown so far, the major mechanism of PH3 toxicity seems to be the inhibition of cytochrome-c oxidase and oxidative phosphorylation which eventually results in adenosine triphosphate (ATP depletion and cell death. Death due to AlP poisoning seems to be as a result of myocardial damage. No efficient antidote has been found for AlP poisoning so far, and unfortunately, most of the poisoned human cases die. PH3, like ammonia (NH3, is a Lewis base with a lone-pair electron. However, boric acid (B(OH3 is a Lewis acid with an empty p orbital. It is predicted that lone-pair electron from PH3 is shared with the empty p orbital from B(OH3 and a compound forms in which boron attains its octet. In other words, PH3 is trapped and neutralised by B(OH3. The resulting polar reaction product seems to be excretable by the body due to hydrogen bonding with water molecules. The present article proposes boric acid as a non-toxic and efficient trapping agent and an antidote for PH3 poisoning by investigating the chemical reaction between them.

  16. N-heterocyclic carbene-assisted, bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates.

    Science.gov (United States)

    Ke, Haihua; Chen, Xiaofeng; Zou, Gang

    2014-08-01

    Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N'-dialkylimidazoliums, e.g., N-butyl-N'-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.

  17. Phosphine modified cobalt hydroformylation

    Energy Technology Data Exchange (ETDEWEB)

    Rensburg, H. van; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St. Andrews (United Kingdom); Janse van Rensburg, W. [Sasol Technology, Sasolburg (South Africa)

    2006-07-01

    An ongoing challenge in phosphine modified cobalt hydroformylation is the fundamental understanding of the electronic and steric properties of phosphine ligands that influence the selectivity and activity of the catalytic reaction. A series of acyclic and cyclic phosphines have been prepared and tested in phosphine modified cobalt hydroformylation of 1-octene. Molecular modelling on a series of phospholanes showed some interesting theoretical and experimental correlations. We also evaluated the use of N-heterocyclic carbenes as an alternative for phosphines in modified cobalt hydroformylation. (orig.)

  18. Reaction of the derivatives of trivalent phosphorus acids with 3-azido-. beta. -lactams and the properties of the obtained phosphine imide derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Dimukhametov, M.N.; Nuretdinov, I.A.

    1986-04-20

    3-Azido-..beta..-lactams react with the derivatives of trivalent phosphorus acids under mild conditions with the formation of 3-phosphoranediylamino-1,4-diaryl-2-azetidinones, which are readily hydrolyzed with the elimination of alcohol (thiol) to 3-phosphoranylamino-1,4-diaryl-2-azetidinones. The phosphine imide compounds obtained from the aryl alkyl phosphites are hydrolyzed with the elimination of phenols. 3-Phosphoranediylamino-1,4-diaryl-2-azetidinones react readily with alkyl and acyl halides with the formation of 3-(N-alkylphosphoryl-amino)- and 3-(N-acylphosphorylamino)-1,4-diaryl-2-azetidinones, respectively.

  19. Phosphorescent emissions of phosphine copper(I) complexes bearing 8-hydroxyquinoline carboxylic acid analogue ligands

    Energy Technology Data Exchange (ETDEWEB)

    Małecki, Jan G., E-mail: gmalecki@us.edu.pl [Department of Crystallography, Institute of Chemistry, University of Silesia, Szkolna 9 street, 40-006 Katowice (Poland); Łakomska, Iwona, E-mail: iwolak@chem.umk.pl [Department of Chemistry, Nicolaus Copernicus University, Toruń (Poland); Maroń, Anna [Department of Crystallography, Institute of Chemistry, University of Silesia, Szkolna 9 street, 40-006 Katowice (Poland); Szala, Marcin [Institute of Chemistry, University of Silesia, ul. Szkolna 9, 40-006 Katowice (Poland); Fandzloch, Marzena [Department of Chemistry, Nicolaus Copernicus University, Toruń (Poland); Nycz, Jacek E., E-mail: jacek.nycz@us.edu.pl [Institute of Chemistry, University of Silesia, ul. Szkolna 9, 40-006 Katowice (Poland)

    2015-05-15

    The pseudotetrahedral complexes of [Cu(PPh{sub 3}){sub 2}(L)], where L=8-hydroxy-2-methylquinoline-7-carboxylic acid (1), 8-hydroxy-2,5-dimethylquinoline-7-carboxylic acid (2) or 5-chloro-8-hydroxy-2-methylquinoline-7-carboxylic acid (3) have been synthesized and structurally characterized by X-ray crystallography. Their properties have been examined through combinations of IR, NMR, electronic absorption spectroscopy and cyclic voltammetry. The complexes exhibit extraordinary photophysical properties. Complex (1) in solid state exhibits an emission quantum yield of 4.67% and an excited life time of 1.88 ms (frozen DCM solution up to 6.7 ms). When dissolved in a coordinating solvent (acetonitrile) the charge transfer emission was quenched on a microsecond scale. - Highlights: • Synthesis of copper(I) complexes with 8-hydroxyquinoline carboxylic acid ligands. • Very long lived phosphorescent copper(I) complexes. • [Cu(PPh{sub 3}){sub 2}(L)] where L=8-hydroxy-2-methylquinoline-7-carboxylic acid luminesce in the solid state exhibits extremely long lifetime on millisecond scale (1.9 ms). • In frozen MeOH:EtOH solution lifetime increases to 7 ms. • Quantum efficiency equal to 4.7%.

  20. Phosphine in various matrixes

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Matrix-bound phosphine was determined in the Jiaozhou Bay coastal sediment, in prawn-pond bottom soil, in the eutrophic lake Wulongtan, in the sewage sludge and in paddy soil as well. Results showed that matrix-bound phosphine levels in freshwater and coastal sediment, as well as in sewage sludge, are significantly higher than that in paddy soil. The correlation between matrix bound phosphine concentrations and organic phosphorus contents in sediment samples is discussed.

  1. Catalytic Phosphination and Arsination

    Institute of Scientific and Technical Information of China (English)

    Kwong Fuk Yee; Chan Kin Shing

    2004-01-01

    The catalytic, user-friendly phosphination and arsination of aryl halides and triflates by triphenylphosphine and triphenylarsine using palladium catalysts have provided a facile synthesis of functionalized aryl phosphines and arsines in neutral media. Modification of the cynaoarisne yielded optically active N, As ligands which will be screened in various asymmetric catalysis.

  2. Mechanisms of Phosphine Toxicity

    Directory of Open Access Journals (Sweden)

    Nisa S. Nath

    2011-01-01

    Full Text Available Fumigation with phosphine gas is by far the most widely used treatment for the protection of stored grain against insect pests. The development of high-level resistance in insects now threatens its continued use. As there is no suitable chemical to replace phosphine, it is essential to understand the mechanisms of phosphine toxicity to increase the effectiveness of resistance management. Because phosphine is such a simple molecule (PH3, the chemistry of phosphorus is central to its toxicity. The elements above and below phosphorus in the periodic table are nitrogen (N and arsenic (As, which also produce toxic hydrides, namely, NH3 and AsH3. The three hydrides cause related symptoms and similar changes to cellular and organismal physiology, including disruption of the sympathetic nervous system, suppressed energy metabolism and toxic changes to the redox state of the cell. We propose that these three effects are interdependent contributors to phosphine toxicity.

  3. Mechanisms of phosphine toxicity.

    Science.gov (United States)

    Nath, Nisa S; Bhattacharya, Ishita; Tuck, Andrew G; Schlipalius, David I; Ebert, Paul R

    2011-01-01

    Fumigation with phosphine gas is by far the most widely used treatment for the protection of stored grain against insect pests. The development of high-level resistance in insects now threatens its continued use. As there is no suitable chemical to replace phosphine, it is essential to understand the mechanisms of phosphine toxicity to increase the effectiveness of resistance management. Because phosphine is such a simple molecule (PH(3)), the chemistry of phosphorus is central to its toxicity. The elements above and below phosphorus in the periodic table are nitrogen (N) and arsenic (As), which also produce toxic hydrides, namely, NH(3) and AsH(3). The three hydrides cause related symptoms and similar changes to cellular and organismal physiology, including disruption of the sympathetic nervous system, suppressed energy metabolism and toxic changes to the redox state of the cell. We propose that these three effects are interdependent contributors to phosphine toxicity.

  4. Mechanisms of Phosphine Toxicity

    Science.gov (United States)

    Nath, Nisa S.; Bhattacharya, Ishita; Tuck, Andrew G.; Schlipalius, David I.; Ebert, Paul R.

    2011-01-01

    Fumigation with phosphine gas is by far the most widely used treatment for the protection of stored grain against insect pests. The development of high-level resistance in insects now threatens its continued use. As there is no suitable chemical to replace phosphine, it is essential to understand the mechanisms of phosphine toxicity to increase the effectiveness of resistance management. Because phosphine is such a simple molecule (PH3), the chemistry of phosphorus is central to its toxicity. The elements above and below phosphorus in the periodic table are nitrogen (N) and arsenic (As), which also produce toxic hydrides, namely, NH3 and AsH3. The three hydrides cause related symptoms and similar changes to cellular and organismal physiology, including disruption of the sympathetic nervous system, suppressed energy metabolism and toxic changes to the redox state of the cell. We propose that these three effects are interdependent contributors to phosphine toxicity. PMID:21776261

  5. A structural insight into the P1S1 binding mode of diaminoethylphosphonic and phosphinic acids, selective inhibitors of alanine aminopeptidases

    Energy Technology Data Exchange (ETDEWEB)

    Węglarz-Tomczak, Ewelina; Berlicki, Łukasz; Pawełczak, Małgorzata; Nocek, Bogusław; Joachimiak, Andrzej; Mucha, Artur

    2016-07-01

    N0 -substituted 1,2-diaminoethylphosphonic acids and 1,2-diaminoethylphosphinic dipeptides were explored to unveil the structural context of the unexpected selectivity of these inhibitors of M1 alanine aminopeptidases (APNs) versus M17 leucine aminopeptidase (LAP). The diaminophosphonic acids were obtained via aziridines in an improved synthetic procedure that was further expanded for the phosphinic pseudodipeptide system. The inhibitory activity, measured for three M1 and one M17 metalloaminopeptidases of different sources (bacterial, human and porcine), revealed several potent compounds (e.g., Ki ¼ 65 nM of 1u for HsAPN). Two structures of an M1 representative (APN from Neisseria meningitidis) in complex with N-benzyl-1,2-diaminoethylphosphonic acid and N-cyclohexyl-1,2- diaminoethylphosphonic acid were determined by the X-ray crystallography. The analysis of these structures and the models of the phosphonic acid complexes of the human ortholog provided an insight into the role of the additional amino group and the hydrophobic substituents of the ligands within the S1 active site region.

  6. Emission sources of atmospheric phosphine and simulation of phosphine formation

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Preliminary results on the emission sources of atmospheric phosphine and the types of its precursors in the environment are described. Sunlight plays a more important role than oxygen in its degradation. The vertical profile of phosphine levels in ambient air has been measured. Laboratory simulation of phosphine formation under anaerobic conditions shows that addition of chicken manure, bone powder, or lecithin leads to an increment in phosphine emission. Phosphine can also be adsorbed to soil matrix and thus can survive in soil and sediment. Adsorption and light degradation explain the low ambient levels of phosphine.

  7. Balancing phosphine in manure fermentation.

    Science.gov (United States)

    Eismann, F; Glindemann, D; Bergmann, A; Kuschk, P

    1997-11-01

    The evolution of phosphine gas during the anaerobic batch fermentation of fresh swine manure was detected and correlated to the production of methane and hydrogen sulphide. A close temporal relationship between phosphine liberation and methane formation was found. However, the gaseous phosphine released from manure during fermentation only represents a tiny fraction of the overall phosphine balance. The majority of phosphine is captured in solid manure constituents. This matrix-bound phosphine is eliminated by more than 50% during anaerobic batch-fermentation. Seasonally determined phosphine concentrations in biogas and manure from two large-scale manure treatment plants also revealed net losses of phosphine in fermentation. Consequently, manure has to be considered more as a sink of phosphine rather than a phosphine-generating medium. Furthermore, a close relationship between phosphine in the feed of swine and manure of these swine was observed, implying that phosphine residues in the feed (possibly as a result of grain fumigation) represent an important source of phosphine in manure technologies that is relevant before the faecals of swine enter manure treatment plants.

  8. Synergistic extraction of uranium(VI) by bis(2,4,4-trimethylpentyl) phosphinic acid in the presence of neutral oxo-donors

    Energy Technology Data Exchange (ETDEWEB)

    Meera, R.; Reddy, M.L.P. [Inorganic and Analytical Chemistry Unit, Regional Research Lab. (CSIR), Trivandrum (India)

    2002-07-01

    The extraction behavior of uranium(VI) from nitric acid solutions has been investigated using mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (HBTMPP) and trialkylphosphine oxide (Cyanex 923 = TRPO), triphenylphosphine oxide (TPhPO) or tributylphosphate (TBP). The results demonstrate that uranium(VI) is extracted into xylene as UO{sub 2}(BTMPP){sub 2} with HBTMPP alone and as UO{sub 2}(BTMPP){sub 2}.S (where S = TRPO, TPhPO or TBP) in the presence of neutral oxo-donors. The extraction equilibrium constants of the above extracted complexes have been deduced by non-linear regression analysis with the aid of suitable chemically based model developed taking into account aqueous phase complexation of metal ion with inorganic ligands and all plausible complexes extracted into the organic phase. The addition of a neutral oxo-donor to the metal chelate system significantly enhances the extraction efficiency of uranium(VI). Complexation strength of uranium(VI) with neutral oxo-donors follows the order: TRPO > TPhPO > TBP, which is also the basicity sequence of these ligands. The IR spectral studies of the extracted complexes were used to further clarify the nature of the extracted complexes. (orig.)

  9. Catalytic Asymmetric Synthesis of Phosphine Boronates

    NARCIS (Netherlands)

    Hornillos, Valentin; Vila, Carlos; Otten, Edwin; Feringa, Ben L.

    2015-01-01

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of ,-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good y

  10. Stimulation of gaseous phosphine production from Antarctic seabird guanos and ornithogenic soils

    Institute of Scientific and Technical Information of China (English)

    ZHU Renbin; LIU Yashu; SUN Jianjun; SUN Liguang; GENG Jinju

    2009-01-01

    Matrix-bound phosphine (MBP) is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. Antarctic seabird guanos and ornithogenic soils were used as materials to compare the different digestion methods for transforming matrix-bound phosphine into phosphine gas. The results demonstrated that more phosphine gas in most of Antarctic environmental materials was formed of matrix-bound phosphine by caustic digestion than by acidic digestion. The comparative study on different digestion methods also revealed that the fraction of MBP converted to gaseous phosphine during the digestion depended on the temperature. The optimal digestion temperature was close to 70℃ and the optimal digestion time was about 20 min. Acidic conditions were more favorable for the release of matrix-bound phosphine compared to the central[u1] conditions. The proper additional water dilution can increase the production and emission of phosphine from the Antarctic penguin guanos.

  11. Advances in Homogeneous Catalysis Using Secondary Phosphine Oxides (SPOs): Pre-ligands for Metal Complexes.

    Science.gov (United States)

    Achard, Thierry

    2016-01-01

    The secondary phosphine oxides are known to exist in equilibrium between the pentavalent phosphine oxides (SPO) and the trivalent phosphinous acids (PA). This equilibrium can be displaced in favour of the trivalent tautomeric form upon coordination to late transition metals. This tutorial review provides the state of the art of the use of secondary phosphine oxides as pre-ligands in transition metal-catalysed reactions. Using a combination of SPOs and several metals such as Pd, Pt, Ru, Rh and Au, a series of effective and original transformations have been obtained and will be discussed here.

  12. Phosphine sampling and analysis using silver nitrate impregnated filters.

    Science.gov (United States)

    Demange, M; Elcabache, J M; Grzebyk, M; Peltier, A; Proust, N; Thénot, D; Ducom, P; Fritsch, J

    2000-10-01

    In the field of industrial hygiene, besides the necessity of monitoring phosphine with direct reading apparatus to prevent accidents, there is a need for a method of sampling and analysing phosphine to control workers' exposure. The use of filters impregnated with silver nitrate to collect arsine, phosphine and stibine in workplace air has been described in the literature. Having previously chosen this type of filter to collect arsine, we studied its characteristics for phosphine capture. A filter impregnated with sodium carbonate was used both as a prefilter to collect the particles and to trap arsenic trioxide. After dissolving the silver compounds in nitric acid, ICP emission spectrometry was used to carry out the analysis. This article describes the comparative sampling we performed in a microelectronic laboratory and in a fumigation chamber (130 samples) to determine the concentration of AgNO3 impregnation solution to be used, the detection limit of the method and the retention capacity of the impregnated filters. Interference with other gases reacting with silver nitrate was studied and the storage time for sampled filters and analysis solutions was checked. The detection limit of the adopted method is better than 1 microg per filter, and the retention capacity exceeds 300 microg per filter. The problem of how to sample phosphine when H2S, NH3, or HCl is present has been solved, but the problem of sampling phosphine in atmospheres where acetylene evolves remains. Sampled filters and filter solutions are stable for more than three months at ambient temperature.

  13. Reduction of secondary and tertiary phosphine oxides to phosphines.

    Science.gov (United States)

    Hérault, Damien; Nguyen, Duc Hanh; Nuel, Didier; Buono, Gérard

    2015-04-21

    Achiral or chiral phosphines are widely used in two main domains: ligands in organometallic catalysis and organocatalysis. For this reason, the obtention of optically pure phosphine has always been challenging in the development of asymmetric catalysis. The simplest method to obtain phosphines is the reduction of phosphine oxides. The essential difficulty is the strength of the P=O bond which involves new procedures to maintain a high chemio- and stereoselectivity. The reduction can occur with retention or inversion of the stereogenic phosphorus atom depending on the nature of the reducing agent and the presence of additives. In fact, the reactivity of the phosphine oxides and the mechanism of the reduction are not always well understood. Since the first work in the 1950's, numerous studies have been realised in order to develop methodologies with different reagents or to understand the mechanism of the reaction. In the last decade, efficient stereospecific methodologies have been developed to obtain optically pure tertiary phosphines from P-stereogenic phosphine oxides. In this review, we intend to provide a comprehensive and critical overview of these methodologies.

  14. Simultaneous identification and qualitative determination of hydrocyanic acid and phosphine by gas chromatography with nitrogen-phosphorus detector and Headspace autosampler (hs-gc-npd) in biological fluids

    OpenAIRE

    Monsalve-Salamanca, Luz Adriana; Ortiz-Rangel, María Martha; Mateus-Fontecha, Alexis

    2015-01-01

    Introduction: This article described a simple, rapid, sensitive methodology for the identification and qualitative determination of phosphine and hydrocyanic cyanide in biological (i.e., blood and stomach contents) and non-biological samples by gas chromatography (gc). Methodology: The foregoing was carried out by a selective nitrogen-phosphorus detector (npd) and Headspace (hs) volatile autosampler using acetonitrile (acn) as internal standard (istd). The procedure involves taking and pourin...

  15. CONFIRMATION OF CIRCUMSTELLAR PHOSPHINE

    Energy Technology Data Exchange (ETDEWEB)

    Agúndez, M.; Cernicharo, J. [Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz 3, E-28049 Cantoblanco (Spain); Decin, L. [Sterrenkundig Instituut Anton Pannekoek, University of Amsterdam, Science Park 904, NL-1098 Amsterdam (Netherlands); Encrenaz, P. [LERMA, Observatoire de Paris, 61 Av. de l' Observatoire, F-75014 Paris (France); Teyssier, D. [European Space Astronomy Centre, Urb. Villafranca del Castillo, P.O. Box 50727, E-28080 Madrid (Spain)

    2014-08-01

    Phosphine (PH{sub 3}) was tentatively identified a few years ago in the carbon star envelopes IRC +10216 and CRL 2688 from observations of an emission line at 266.9 GHz attributable to the J = 1-0 rotational transition. We report the detection of the J = 2-1 rotational transition of PH{sub 3} in IRC +10216 using the HIFI instrument on board Herschel, which definitively confirms the identification of PH{sub 3}. Radiative transfer calculations indicate that infrared pumping in excited vibrational states plays an important role in the excitation of PH{sub 3} in the envelope of IRC +10216, and that the observed lines are consistent with phosphine being formed anywhere between the star and 100 R {sub *} from the star, with an abundance of 10{sup –8} relative to H{sub 2}. The detection of PH{sub 3} challenges chemical models, none of which offer a satisfactory formation scenario. Although PH{sub 3} holds just 2% of the total available phosphorus in IRC +10216, it is, together with HCP, one of the major gas phase carriers of phosphorus in the inner circumstellar layers, suggesting that it could also be an important phosphorus species in other astronomical environments. This is the first unambiguous detection of PH{sub 3} outside the solar system, and is a further step toward a better understanding of the chemistry of phosphorus in space.

  16. Confirmation of circumstellar phosphine

    CERN Document Server

    Agundez, M; Decin, L; Encrenaz, P; Teyssier, D

    2014-01-01

    Phosphine (PH3) was tentatively identified a few years ago in the carbon star envelopes IRC+10216 and CRL2688 from observations of an emission line at 266.9 GHz attributable to the J=1-0 rotational transition. We report the detection of the J=2-1 rotational transition of PH3 in IRC+10216 using the HIFI instrument on board Herschel, which definitively confirms the identification of PH3. Radiative transfer calculations indicate that infrared pumping to excited vibrational states plays an important role in the excitation of PH3 in the envelope of IRC+10216, and that the observed lines are consistent with phosphine being formed anywhere between the star and 100 R* from the star, with an abundance of 1e-8 relative to H2. The detection of PH3 challenges chemical models, none of which offers a satisfactory formation scenario. Although PH3 locks just 2 % of the total available phosphorus in IRC+10216, it is together with HCP, one of the major gas phase carriers of phosphorus in the inner circumstellar layers, suggest...

  17. Phosphine in paddy fields and the effects of environmental factors.

    Science.gov (United States)

    Niu, Xiaojun; Wei, Aishu; Li, Yadong; Mi, Lina; Yang, Zhiquan; Song, Xiaofei

    2013-11-01

    Ambient levels of phosphine (PH3) in the air, phosphine emission fluxes from paddy fields and rice plants, and the distribution of matrix-bound phosphine (MBP) in paddy soils were investigated throughout the growing stages of rice. The relationships between MBP and environmental factors were analyzed to identify the principal factors determining the distribution of MBP. The phosphine ambient levels ranged from 2.368±0.6060 ng m(-3) to 24.83±6.529 ng m(-3) and averaged 14.25±4.547 ng m(-3). The highest phosphine emission flux was 22.54±3.897 ng (m(2)h)(-1), the lowest flux was 7.64±4.83 ng (m(2)h)(-1), and the average flux was 14.17±4.977 ng (m(2)h)(-1). Rice plants transport a significant portion of the phosphine emitted from the paddy fields. The highest contribution rate of rice plants to the phosphine emission fluxes reached 73.73% and the average contribution was 43.00%. The average MBP content of 111.6 ng kg(-1)fluctuated significantly in different stages of rice growth and initially increased then decreased with increasing depth. The peak MBP content in each growth stage occurred approximately 10 cm under the surface of paddy soils. Pearson correlation analyses and stepwise multiple regression analysis showed that soil temperature (Ts), acid phosphatase (ACP) and total phosphorus (TP) were the principal environmental factors, with correlative rankings of Ts>ACP>TP.

  18. Phosphine oxide surfactants revisited.

    Science.gov (United States)

    Stubenrauch, Cosima; Preisig, Natalie; Laughlin, Robert G

    2016-04-01

    This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (C(n)DMPO) and alkyl diethyl (C(n)DEPO) phosphine oxide (PO surfactants). The review starts with the synthesis and the general properties (Section 2) of these compounds and continues with their interfacial properties (Section 3) such as surface tension, surface rheology, interfacial tension and adsorption at solid surfaces. We discuss studies on thin liquid films and foams stabilized by PO surfactants (Section 4) as well as studies on their self-assembly into lyotropic liquid crystals and microemulsions, respectively (Section 5). We aim at encouraging colleagues from both academia and industry to take on board PO surfactants whenever possible and feasible because of their broad variety of excellent properties.

  19. Synthesis of a New Type of Amphilic and Water - soluble Tertiary Phosphine Ligands Substituted by an Ethoxylated Phosphonic Acid Chain and Their Palladium Complexes

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N(CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in goodyield; the palladium (Ⅱ) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratiowere also prepared and characterized.

  20. Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride.

    Science.gov (United States)

    Rajendran, Kamalraj V; Gilheany, Declan G

    2012-01-21

    A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.

  1. Catalytic Asymmetric Synthesis of Phosphine Boronates.

    Science.gov (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L

    2015-06-26

    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds.

  2. Comparative effects of gamma irradiation and phosphine fumigation on the quality of white ginseng

    Science.gov (United States)

    Kwon, J.-H. J.-H.; Byun, M.-W. M.-W.; Kim, K.-S. K.-S.; Kang, I.-J. I.-J.

    2000-03-01

    The hygienic, physicochemical, and organoleptic qualities of white ginseng were monitored during 6 months under accelerated conditions (40°C, 90% r.h.) by observing its microbial populations, disinfestation, and some quality attributes following either gamma irradiation at 2.5-10 kGy or commercial phosphine (PH 3) fumigation. In a comparative study, both treatments were found to be effective for disinfecting the stored samples. Phosphine showed no appreciable decontaminating effects on microorganisms contaminated including coliforms, while 5 kGy irradiation was sufficient to control all microorganisms related to the quality of the packed samples. Irradiation at 5 kGy caused negligible changes in physicochemical attributes of the samples, such as ginsenosides, amino acids, fatty acids, and organoleptic properties, whereas phosphine fumigation was found detrimental to sensory flavor ( Pphosphine-, and 2.5-5 kGy-treated samples. Accordingly, irradiation at phosphine fumigation for white ginseng.

  3. Biomimetic peptide-based models of [FeFe]-hydrogenases: utilization of phosphine-containing peptides.

    Science.gov (United States)

    Roy, Souvik; Nguyen, Thuy-Ai D; Gan, Lu; Jones, Anne K

    2015-09-07

    Two synthetic strategies for incorporating diiron analogues of [FeFe]-hydrogenases into short peptides via phosphine functional groups are described. First, utilizing the amine side chain of lysine as an anchor, phosphine carboxylic acids can be coupled via amide formation to resin-bound peptides. Second, artificial, phosphine-containing amino acids can be directly incorporated into peptides via solution phase peptide synthesis. The second approach is demonstrated using three amino acids each with a different phosphine substituent (diphenyl, diisopropyl, and diethyl phosphine). In total, five distinct monophosphine-substituted, diiron model complexes were prepared by reaction of the phosphine-peptides with diiron hexacarbonyl precursors, either (μ-pdt)Fe2(CO)6 or (μ-bdt)Fe2(CO)6 (pdt = propane-1,3-dithiolate, bdt = benzene-1,2-dithiolate). Formation of the complexes was confirmed by UV/Vis, FTIR and (31)P NMR spectroscopy. Electrocatalysis by these complexes is reported in the presence of acetic acid in mixed aqueous-organic solutions. Addition of water results in enhancement of the catalytic rates.

  4. Proposing an Antidote for Poisonous Phosphine in View of Mitochondrial Eectrochemistry Facts

    Directory of Open Access Journals (Sweden)

    Mohammad Abdollahi

    2012-01-01

    Full Text Available Metal phosphides in general are potent pesticides that are a common cause of human poisoning. Various salts of phosphides produce highly toxic phosphine in exposure to gastric acid that results in multi-organ damage and death. There is no antidote for phosphine poisoning and most of human poisoned cases do not survive. All we know so far is that phosphine is a mitochondrial toxin that inhibits cellular respiration and induces oxidative stress. Mechanistically, phosphine as a reducing agent interacts with metal ion cofactors at the active site of enzymes and inhibits key enzymes such as cytochrome C oxidase that lead to inhibition of mitochondrial respiration. Phosphine (E0 = −1.18 V as a reducing agent gives electrons to cytochrome C oxidase (E0 = +0.29 V. Metal phosphides with lower reduction potential are stronger electron donors and thus stronger poisons. Our hypothesis is that if an electron receiver stronger than cytochrome C oxidase is used then it would compete with cytochrome C oxidase in interaction with phosphine. This competition might prevent or reduce the inhibition of cellular respiration. This idea can be tested in an animal model of phosphine toxicity by monitoring cardiovascular state and measuring the cardiac mitochondrial function.

  5. Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

    OpenAIRE

    2012-01-01

    A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.

  6. Nucleoside-O-Methyl-(H)-Phosphinates: Novel Monomers for the Synthesis of Methylphosphonate Oligonucleotides Using H-Phosphonate Chemistry.

    Science.gov (United States)

    Kostov, Ondřej; Páv, Ondřej; Rosenberg, Ivan

    2017-09-18

    This unit comprises the straightforward synthesis of protected 2'-deoxyribonucleoside-O-methyl-(H)-phosphinates in both 3'- and 5'-series. These compounds represent a new class of monomers compatible with the solid-phase synthesis of oligonucleotides using H-phosphonate chemistry and are suitable for the preparation of both 3'- and 5'-O-methylphosphonate oligonucleotides. The synthesis of 4-toluenesulfonyloxymethyl-(H)-phosphinic acid as a new reagent for the preparation of O-methyl-(H)-phosphinic acid derivatives is described. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  7. Phosphine catalysis of allenes with electrophiles.

    Science.gov (United States)

    Wang, Zhiming; Xu, Xingzhu; Kwon, Ohyun

    2014-05-07

    Nucleophilic phosphine catalysis of allenes with electrophiles is one of the most powerful and straightforward synthetic strategies for the generation of highly functionalized carbocycle or heterocycle structural motifs, which are present in a wide range of bioactive natural products and medicinally important substances. The reaction topologies can be controlled through a judicious choice of the phosphine catalyst and the structural variations of starting materials. This Tutorial Review presents selected examples of nucleophilic phosphine catalysis using allenes and electrophiles.

  8. Fixed-charge phosphine ligands to explore gas-phase coinage metal-mediated decarboxylation reactions.

    Science.gov (United States)

    Vikse, Krista; Khairallah, George N; McIndoe, J Scott; O'Hair, Richard A J

    2013-05-14

    A combination of multistage mass spectrometry experiments and density functional theory (DFT) calculations were used to examine the decarboxylation reactions of a series of metal carboxylate complexes bearing a fixed-charge phosphine ligand, [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph). Collision-induced dissociation (CID) of these complexes using an LTQ linear ion mass spectrometer results in three main classes of reactions being observed: (1) decarboxylation; (2) loss of the phosphine ligand; (3) loss of carboxylic acid. The gas-phase unimolecular chemistry of the resultant decarboxylated organometallic ions, [(O3SC6H4)(C6H5)2PM(I)R](-), were also explored using CID experiments, and fragment primarily via loss of the phosphine ligand. Energy-resolved CID experiments on [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph) using a Q-TOF mass spectrometer were performed to gain a more detailed understanding of the factors influencing coinage metal-catalyzed decarboxylation and DFT calculations on the major fragmentation pathways aided in interpretation of the experimental results. Key findings are that: (1) the energy required for loss of the phosphine ligand follows the order Ag phosphine ligand on decarboxylation is also considered in comparison with previous studies on metal carboxylates that do not contain a phosphine ligand.

  9. L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

    KAUST Repository

    Zhong, Fangrui

    2011-03-18

    A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

  10. Comparative effects of gamma irradiation and phosphine fumigation on the quality of white ginseng

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, J.-H.Joong-Ho; Byun, M.-W.Myung-Woo; Kim, K.-S.Kang-Soo; Kang, I.-J.Il-Jun

    2000-03-01

    The hygienic, physicochemical, and organoleptic qualities of white ginseng were monitored during 6 months under accelerated conditions (40 deg. C, 90% r.h.) by observing its microbial populations, disinfestation, and some quality attributes following either gamma irradiation at 2.5-10 kGy or commercial phosphine (PH{sub 3}) fumigation. In a comparative study, both treatments were found to be effective for disinfecting the stored samples. Phosphine showed no appreciable decontaminating effects on microorganisms contaminated including coliforms, while 5 kGy irradiation was sufficient to control all microorganisms related to the quality of the packed samples. Irradiation at 5 kGy caused negligible changes in physicochemical attributes of the samples, such as ginsenosides, amino acids, fatty acids, and organoleptic properties, whereas phosphine fumigation was found detrimental to sensory flavor (P<0.01). Quality deterioration occurred in the commercially-packed samples was in the following order: the control, 10 kGy-, phosphine-, and 2.5-5 kGy-treated samples. Accordingly, irradiation at <5 kGy was found to be an effective alternative to phosphine fumigation for white ginseng. (author)

  11. New class of phosphine oxide donor-based supramolecular coordination complexes from an in situ phosphine oxidation reaction or phosphine oxide ligands.

    Science.gov (United States)

    Shankar, Bhaskaran; Elumalai, Palani; Shanmugam, Ramasamy; Singh, Virender; Masram, Dhanraj T; Sathiyendiran, Malaichamy

    2013-09-16

    A one-pot, multicomponent, coordination-driven self-assembly approach was used to synthesize the first examples of neutral bridging phosphine oxide donor-based supramolecular coordination complexes. The complexes were self-assembled from a fac-Re(CO)3 acceptor, an anionic bridging O donor, and a neutral soft phosphine or hard phosphine oxide donor.

  12. Phosphine photochemistry in Saturn's atmosphere

    Science.gov (United States)

    Kaye, J. A.; Strobel, D. F.

    1983-01-01

    The phosphine photochemistry on Saturn is studied with a 1D photochemical model. The PH3 concentration is rapidly depleted with height (scale height 3.5 km) in the upper troposphere. Formation of P, a probable precursor of P4, (a potential red chromophore in the atmosphere), is highly improbable unless the rate constant for the recombination reaction PH + H2 + M yields PH3 + M is less than 10 to the -41st cm exp 6/molecule-squared sec. Coupling of PH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH, is important. Column production rates of the organophosphorus compounds CH3PH2 and HCP of 3 x 10 to the 8th/sq cm sec are predicted, with potentially observable column densities of greater than 1 x 10 to the 17th/sq cm.

  13. Zwitterion enhanced performance in palladium-​phosphine catalyzed ethylene methoxycarbonylation

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; Garcia-Suarez, Eduardo J.; Xiong, Jianmin;

    2014-01-01

    Zwitterions were used for the first time as promoters in ethylene methoxycarbonylation for the production of methyl propionate. They were found to improve the catalytic performance of the Pd–phosphine system. The presence of zwitterions could contribute to stabilize transition states and active...... catalytic Pd intermediates. The beneficial effect of the zwitterions was found to be most pronounced, when low amount of a strong acid (MeSO3H) was used with respect to palladium (below 2 equiv.). Under these conditions, phosphine ligand alkylation and reaction vessel corrosion are also anticipated...

  14. Copper-catalyzed α-amination of phosphonates and phosphine oxides: a direct approach to α-amino phosphonic acids and derivatives.

    Science.gov (United States)

    McDonald, Stacey L; Wang, Qiu

    2014-02-10

    A direct approach to important α-amino phosphonic acids and its derivatives has been developed by using copper-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the first example of CN bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction is readily promoted at room temperature with as little as 0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope.

  15. Acute Oral Toxicity Potential of 4-Nitrophenyl Methkyl Phenyl Phosphinate.

    Science.gov (United States)

    1982-09-01

    methyl phenyl phosphinate Chemical Abstract Service Registry No.: None Molecular structure: C Ii NO P 13 12 4 .0 0~ NO., CH3 o o...C 56.33 56.17 H 4.36 4.28 N 5.05 5.14 P 11.17 11.25 2. Chemical Name: Polysorbate 80 (Tween 80) Chemical Abstract Service Registry No.: 9005-65-6...administration particularly in chronic toxicity studies in experimental data. 3. Chemical Name: Citric Acid, monohydrate Chemical Abstract Service

  16. Asymmetric α-amination of 3-substituted oxindoles using chiral bifunctional phosphine catalysts

    Directory of Open Access Journals (Sweden)

    Qiao-Wen Jin

    2016-04-01

    Full Text Available A highly enantioselective α-amination of 3-substituted oxindoles with azodicarboxylates catalyzed by amino acids-derived chiral phosphine catalysts is reported. The corresponding products containing a tetrasubstituted carbon center attached to a nitrogen atom at the C-3 position of the oxindole were obtained in high yields and with up to 98% ee.

  17. Palladium phosphine complexes for the telomerization of butadiene

    DEFF Research Database (Denmark)

    2010-01-01

    A phosphine ligand suitable for use in telomerizing butadiene comprises two phenyl groups and a xanthene moiety.......A phosphine ligand suitable for use in telomerizing butadiene comprises two phenyl groups and a xanthene moiety....

  18. Improvement of phosphine fumigation by the use of Speedbox

    OpenAIRE

    Kostyukovsky, M.; Trostanetsky, A.; Yasinov, G.; Menasherov, M; Hazan, T.

    2010-01-01

    Today, phosphine is turning to be a major fumigant for controlling insects in stored products. However, few limitations, such as low temperatures and relatively long exposure time, limit the phosphine use. In order to improve phosphine application, a special devise, containing a heater and a ventilator, called "Speedbox" has been developed by Detia Degesch GmbH Germany. For studying the effectiveness of phosphine fumigation using Speedbox, we have conducted two kinds of experiments: one in a ...

  19. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  20. Worker exposure standard for phosphine gas.

    Science.gov (United States)

    Pepelko, Bill; Seckar, Joel; Harp, Paul R; Kim, James H; Gray, David; Anderson, Elizabeth L

    2004-10-01

    The 1998 U.S. Environmental Protection Agency Office of Pesticide Programs (OPP) re-registration eligibility decision (RED) for phosphine fumigants has generated much interest in defining safe levels of exposure for workers and worker bystanders. This report summarizes the pertinent literature on phosphine toxicity, including animal inhalation studies and human epidemiology studies, and also describes a margin-of-exposure (MOE) analysis based on available worker exposure data. In addition, a safe occupational exposure limit is estimated using typical OPP assumptions, after determination of appropriate uncertainty factors, based on quality of data in the principal study and pharmacokinetic considerations. While a conservative 8-hour time-weighted average (TWA) of 0.1 ppm was calculated, the overall weight of evidence, from a risk-management perspective, supports a conclusion that an occupational TWA of 0.3 ppm provides adequate health protection. In addition, a 15-minute short-term exposure limit (STEL) of 3 ppm was estimated. Finally, in contrast to the MOE analysis described in the OPP's phosphine RED, the MOE analysis described herein does not indicate that fumigation workers are currently being exposed to unacceptable levels of phosphine. Collectively, these findings support the occupational exposure limits of 0.3 ppm (8-hour TWA) and 1 ppm (STEL) established in the updated applicator's manuals for phosphine-generating products, which recently received approval from OPP.

  1. Preliminary investigation on the role of microorganisms in the production of phosphine

    Institute of Scientific and Technical Information of China (English)

    Liu Zhipei; Jia Shengfen; Wang Baojun; Zhang Tao; Liu Shuangjiang

    2008-01-01

    The relationships between the phosphine content and various microbial populations, activities of different enzymes were investigated firstly. The results indicated that the phosphine content of samples from various environments was positively related to total anaerobic microorganisms, organic phosphate compound-dissolving bacteria, denitrifying bacteria, and the activities of alkaline phosphatase and dehydrogenase, with correlation coefficients (R2) up to 0.93, 0.90, 0.69, 0.79, and 0.82, respectively. Results also showed that the phosphine content was not related to total aerobic microorganisms, inorganic phosphate compound-dissolving bacteria, sulfate-reducing bacteria, and the acidic phosphatase activity. Nutrients such as yeast extract and glucose were added, at a time and individually, to normal or autoclaved soil samples. The soil samples were inoculated with sulfate-reducing bacterial enrichments (SRB) and/or denitrifying bacterial enrichment (DNB). After incubation for one month at 30℃, the phosphane content of these samples was analyzed. The results indicated that the addition of glucose or yeast extract could greatly increase the phosphane content. Moreover, it was revealed that inoculation with SRB or DNB could also promote the formation of phosphine. The DNB, however, was more efficient in this regard. The highest phosphine content, about 5 times that of the control, was detected in the sample that was added with both glucose and yeast extract and inoculated with SRB and DNB simultaneously. SRB and DNB were enriched for several generations and the phosphane content of different generations was analyzed. Furthermore, SRB and DNB enrichments were inoculated into different media, in the beginning of enriching, the phosphane content was about the same for different enrichments, and differed more significantly as the enrichment process was carried further. In forth generation, the phosphane content of DNB enrichment was about 3 times of that of SRB

  2. Residue formations of phosphorus hydride polymers and phosphorus oxyacids during phosphine gas fumigations of stored products.

    Science.gov (United States)

    Flora, Jason W; Byers, Loran E; Plunkett, Susan E; Faustini, Daryl L

    2006-01-11

    With the extent of international usage and the critical role phosphine gas (PH3) plays in commercial pest control, identification of the residual components deposited during fumigation is mandatory. It has been postulated that these infrequent residues are primarily composed of phosphoric acid or reduced forms of phosphoric acid [hypophosphorous acid (H3PO2) and phosphorous acid (H3PO3)], due to the oxidative degradation of phosphine. Using environmental scanning electron microscopy, gas phase Fourier transform infrared spectroscopy, and X-ray fluorescence spectroscopy, the structural elucidation and formation mechanism of the yellow amorphous polyhydric phosphorus polymers (P(x)H(y)) that occur in addition to the lower oxyacids of phosphorus in residues deposited during PH3 fumigations of select tobacco commodities are explored. This research determined that nitric oxide gas (or nitrogen dioxide) initiates residue formation of phosphorus hydride polymers and phosphorus oxyacids during PH3 fumigations of stored products.

  3. Phosphine-directed C-H borylation reactions: facile and selective access to ambiphilic phosphine boronate esters.

    Science.gov (United States)

    Crawford, Kristina M; Ramseyer, Timothy R; Daley, Christopher J A; Clark, Timothy B

    2014-07-14

    Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium-catalyzed C-H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine-substituted boronate esters could be deprotected and isolated in pure form.

  4. Reducing injury of lettuce from phosphine fumigation

    Science.gov (United States)

    Low temperature fumigation with pure phosphine free of ammonia has been used in recent years for postharvest pest control on some fresh fruits and vegetables. However, long fumigation treatments cause injuries to lettuce. It is unknown what factors contributed to the injuries. It is important to min...

  5. Consecutive dynamic resolutions of phosphine oxides

    NARCIS (Netherlands)

    Kortmann, Felix A.; Chang, Mu Chieh; Otten, Edwin; Couzijn, Erik P A; Lutz, Martin; Minnaard, Adriaan J.

    2014-01-01

    A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio- and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides. © 2014 The Royal Society o

  6. Mitochondrial modulation of phosphine toxicity and resistance in Caenorhabditis elegans.

    Science.gov (United States)

    Zuryn, Steven; Kuang, Jujiao; Ebert, Paul

    2008-03-01

    Phosphine is a fumigant used to protect stored commodities from infestation by pest insects, though high-level phosphine resistance in many insect species threatens the continued use of the fumigant. The mechanisms of toxicity and resistance are not clearly understood. In this study, the model organism, Caenorhabditis elegans, was employed to investigate the effects of phosphine on its proposed in vivo target, the mitochondrion. We found that phosphine rapidly perturbs mitochondrial morphology, inhibits oxidative respiration by 70%, and causes a severe drop in mitochondrial membrane potential (DeltaPsim) within 5 h of exposure. We then examined the phosphine-resistant strain of nematode, pre-33, to determine whether resistance was associated with any changes to mitochondrial physiology. Oxygen consumption was reduced by 70% in these mutant animals, which also had more mitochondrial genome copies than wild-type animals, a common response to reduced metabolic capacity. The mutant also had an unexpected increase in the basal DeltaPsim, which protected individuals from collapse of the membrane potential following phosphine treatment. We tested whether directly manipulating mitochondrial function could influence sensitivity toward phosphine and found that suppression of mitochondrial respiratory chain genes caused up to 10-fold increase in phosphine resistance. The current study confirms that phosphine targets the mitochondria and also indicates that direct alteration of mitochondrial function may be related to phosphine resistance.

  7. The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

    DEFF Research Database (Denmark)

    Clarke, Celia; Fox, David J; Pedersen, Daniel Sejer;

    2009-01-01

    Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing that...

  8. Palladium-catalyzed α-arylation of benzylic phosphine oxides.

    Science.gov (United States)

    Montel, Sonia; Jia, Tiezheng; Walsh, Patrick J

    2014-01-03

    A novel approach to prepare diarylmethyl phosphine oxides from benzyl phosphine oxides via deprotonative cross-coupling processes (DCCP) is reported. The optimization of the reaction was guided by High-Throughput Experimentation (HTE) techniques. The Pd(OAc)2/Xantphos-based catalyst enabled the reaction between benzyl diphenyl or dicyclohexyl phosphine oxide derivatives and aryl bromides in good to excellent yields (51-91%).

  9. Synthesis of phosphine and antibody-azide probes for in vivo Staudinger ligation in a pretargeted imaging and therapy approach.

    Science.gov (United States)

    Vugts, Danielle J; Vervoort, Annelies; Stigter-van Walsum, Marijke; Visser, Gerard W M; Robillard, Marc S; Versteegen, Ron M; Vulders, Roland C M; Herscheid, J Koos D M; van Dongen, Guus A M S

    2011-10-19

    The application of intact monoclonal antibodies (mAbs) as targeting agents in nuclear imaging and radioimmunotherapy is hampered by the slow pharmacokinetics of these molecules. Pretargeting with mAbs could be beneficial to reduce the radiation burden to the patient, while using the excellent targeting capacity of the mAbs. In this study, we evaluated the applicability of the Staudinger ligation as pretargeting strategy using an antibody-azide conjugate as tumor-targeting molecule in combination with a small phosphine-containing imaging/therapeutic probe. Up to 8 triazide molecules were attached to the antibody without seriously affecting its immunoreactivity, pharmacokinetics, and tumor uptake in tumor bearing nude mice. In addition, two (89)Zr- and (67/68)Ga-labeled desferrioxamine (DFO)-phosphines, a (177)Lu-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-phosphine and a (123)I-cubyl phosphine probe were synthesized and characterized for their pharmacokinetic behavior in nude mice. With respect to the phosphine probes, blood levels at 30 min after injection were phosphine, relative to the azide, in aqueous solution resulted in 20-25% efficiency after 2 h. The presence of 37% human serum resulted in a reduced ligation efficiency (reduction max. 30% at 2 h), while the phosphines were still >80% intact. No in vivo Staudinger ligation was observed in a mouse model after injection of 500 μg antibody-azide, followed by 68 μg DFO-phosphine at t = 2 h, and evaluation in blood at t = 7 h. To explain negative results in mice, Staudinger ligation was performed in vitro in mouse serum. Under these conditions, a side product with the phosphine was formed and ligation efficiency was severely reduced. It is concluded that in vivo application of the Staudinger ligation in a pretargeting approach in mice is not feasible, since this ligation reaction is not bioorthogonal and efficient enough. Slow reaction kinetics will also severely restrict the applicability

  10. Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines

    Science.gov (United States)

    2016-01-01

    Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides with high enantiomeric excess. The new process is demonstrated on a wide range of substrates and leads to products that are well-established P-chiral catalysts and ligands. PMID:27689432

  11. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H

    2016-02-28

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  12. Occupational phosphine exposure in Indian workers.

    Science.gov (United States)

    Misra, U K; Bhargava, S K; Nag, D; Kidwai, M M; Lal, M M

    1988-09-01

    To evaluate the health effects of occupational phosphine exposure, 22 workers engaged in fumigation of stored grains were subjected to a clinical and environmental study. These workers were used to placing aluminum phosphide tablets on the stacks of grains and covering it with a gas-proof plastic cover. The mean age of the workers was 48 years (range 24-60) and mean duration of exposure 11.1 years (range 0.5-29). After fumigation they reported minor symptoms, which included cough (18.2%), dyspnoea (31.8%), tightness around the chest (27.3%), headache (31.8%), giddiness, numbness and lethargy (13.6% each), anorexia and epigastric pain (18.2% each). The abnormal physical signs included bilateral diffuse rhonchi and absent ankle reflex each occurring in one worker. Motor nerve conduction velocity of median and peroneal nerves, and sensory conduction velocity of median and sural nerves were normal. Phosphine concentration in the work environment ranged from 0.17 to 2.11 ppm. Occupational phosphine exposure in the workers was associated with mild to moderate symptoms, which were transient. However, to assess the chronic effects, long-term follow-up is recommended.

  13. Triphenyl Phosphine-Functionalized Chitosan Nanoparticles Enhanced Antitumor Efficiency Through Targeted Delivery of Doxorubicin to Mitochondria

    Science.gov (United States)

    Hou, Jiahui; Yu, Xiwei; Shen, Yaping; Shi, Yijie; Su, Chang; Zhao, Liang

    2017-02-01

    Mitochondria as an important organ in eukaryotic cells produced energy through oxidative phosphorylation and also played an important role in regulating the apoptotic signal transduction process. Importantly, mitochondria like nuclei also contained the functional DNA and were very sensitive to anticancer drugs which could effectively inhibit the synthesis of nucleic acid, especially the production of DNA. In this work, we designed novel triphenyl phosphine (TPP)-conjugated chitosan (CS) nanoparticles (NPs) for efficient drug delivery to cell mitochondria. The results showed that compared with free doxorubicin (Dox), Dox-loaded TPP-NPs were specifically distributed in mitochondria of tumor cells and interfered with the function of mitochondria, thus resulted in the higher cytotoxicity and induced the significant cell apoptosis effect. Taken together, triphenyl phosphine-conjugated chitosan nanoparticles may become a promising mitochondria-targeting nanocarrier candidate for enhancing antitumor effects.

  14. Preparation of phosphines through C–P bond formation

    Directory of Open Access Journals (Sweden)

    Iris Wauters

    2014-05-01

    Full Text Available Phosphines are an important class of ligands in the field of metal-catalysis. This has spurred the development of new routes toward functionalized phosphines. Some of the most important C–P bond formation strategies were reviewed and organized according to the hybridization of carbon in the newly formed C–P bond.

  15. Phosphine-induced physiological and biochemical responses in rice seedlings.

    Science.gov (United States)

    Mi, Lina; Niu, Xiaojun; Lu, Meiqing; Ma, Jinling; Wu, Jiandong; Zhou, Xingqiu

    2014-04-01

    Paddy fields have been demonstrated to be one of the major resources of atmospheric phosphine and may have both positive and negative effects on rice plants. To elucidate the physiological and biochemical responses of rice plants to phosphine, rice seedlings (30 d old) were selected as a model plant and were treated with different concentrations of phosphine (0, 1.4, 4.2, and 7.0 mg m(-3)). Antioxidant enzymes, including superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT), and lipid peroxidation measured via malondialdehyde (MDA) were determined as indicators of the physiological and biochemical responses of the rice seedlings to phosphine exposure. Increasing concentrations of phosphine treatment enhanced the activity of SOD, POD, and CAT. In addition, the MDA content increased with increasing concentrations of phosphine. These results suggested that antioxidant enzymes played important roles in protecting rice seedlings from ROS damage. Moreover, rice seedlings were able to cope with the oxidative stress induced by low concentrations of phosphine via an increase in antioxidant enzymatic activities. However, oxidative stress may not fully be prevented when the plants were exposed to higher concentrations of phosphine.

  16. Intracellular disulfide reduction by phosphine-borane complexes: Mechanism of action for neuroprotection.

    Science.gov (United States)

    Niemuth, Nicholas J; Thompson, Alex F; Crowe, Megan E; Lieven, Christopher J; Levin, Leonard A

    2016-10-01

    Phosphine-borane complexes are novel cell-permeable drugs that protect neurons from axonal injury in vitro and in vivo. These drugs activate the extracellular signal-regulated kinases 1/2 (ERK1/2) cell survival pathway and are therefore neuroprotective, but do not scavenge superoxide. In order to understand the interaction between superoxide signaling of neuronal death and the action of phosphine-borane complexes, their biochemical activity in cell-free and in vitro assays was studied by electron paramagnetic resonance (EPR) spectrometry and using an intracellular dithiol reporter that becomes fluorescent when its disulfide bond is cleaved. These studies demonstrated that bis(3-propionic acid methyl ester) phenylphosphine-borane complex (PB1) and (3-propionic acid methyl ester) diphenylphosphine-borane complex (PB2) are potent intracellular disulfide reducing agents which are cell permeable. EPR and pharmacological studies demonstrated reducing activity but not scavenging of superoxide. Given that phosphine-borane complexes reduce cell injury from mitochondrial superoxide generation but do not scavenge superoxide, this implies a mechanism where an intracellular superoxide burst induces downstream formation of protein disulfides. The redox-dependent cleavage of the disulfides is therefore a novel mechanism of neuroprotection.

  17. Synthesis and Structural Studies of Calcium and Magnesium Phosphinate and Phosphonate Compounds

    Science.gov (United States)

    Bampoh, Victoria Naa Kwale

    The work presented herein describes synthetic methodologies leading to the design of a wide array of magnesium and calcium based phosphinate and phosphonates with possible applications as bone scaffolding materials or additives to bone cements. The challenge to the chemistry of the alkaline earth phosphonate target compounds includes poor solubility of compounds, and poorly understood details on the control of the metal's coordination environment. Hence, less is known on phosphonate based alkaline earth metal organic frameworks as compared to transition metal phosphonates. Factors governing the challenges in obtaining crystalline, well-defined magnesium and calcium solids lie in the large metal diameters, the absence of energetically available d-orbitals to direct metal geometry, as well as the overall weakness of the metal-ligand bonds. A significant part of this project was concerned with the development of suitable reaction conditions to obtain X-ray quality crystals of the reaction products to allow for structural elucidation of the novel compounds. Various methodologies to aid in crystal growth including hydrothermal methods and gel crystallization were employed. We have used phosphinate and phosphonate ligands with different number of phosphorus oxygen atoms as well as diphosphonates with different linker lengths to determine their effects on the overall structural features. An interesting correlation is observed between the dimensionality of products and the increasing number of donor oxygen atoms in the ligands as we progress from phosphinic acid to the phosphorous acids. As an example, monophosphinate ligand only yielded one-dimensional compounds, whereas the phosphonates crystallize as one and two-dimensional compounds, and the di- and triphosphonate based compounds display two or three-dimensional geometries. This thesis provides a selection of calcium and magnesium compounds with one-dimensional geometry, as represented in a calcium phosphinate to novel

  18. Tris(pyrazolyl)phosphine oxide and Tris(triazolyl)phosphine oxide scorpion ligands

    NARCIS (Netherlands)

    Tazelaar, Cornelis G J; Lyaskovskyy, Volodymyr; Van Doorn, Ilana M.; Schaapkens, Xander; Lutz, Martin; Ehlers, Andreas W.; Slootweg, Jack; Lammertsma, Koop

    2014-01-01

    DFT calculations were performed on copper(I) complexes of neutral scorpion ligands based on either pyrazolyl (Pz) or triazolyl (Tz) rings with both methane and phosphine oxide apexes, that is, HC(Pz)3, OP(Pz)3, HC(Tz)3, and OP(Tz)3. The analyses reveal that all four ligands have similar donor proper

  19. Tris(pyrazolyl)phosphine oxide and Tris(triazolyl)phosphine oxide scorpion ligands

    NARCIS (Netherlands)

    Tazelaar, Cornelis G J; Lyaskovskyy, Volodymyr; Van Doorn, Ilana M.; Schaapkens, Xander; Lutz, Martin; Ehlers, Andreas W.; Slootweg, Jack; Lammertsma, Koop

    2014-01-01

    DFT calculations were performed on copper(I) complexes of neutral scorpion ligands based on either pyrazolyl (Pz) or triazolyl (Tz) rings with both methane and phosphine oxide apexes, that is, HC(Pz)3, OP(Pz)3, HC(Tz)3, and OP(Tz)3. The analyses reveal that all four ligands have similar donor proper

  20. Asymmetric synthesis of trans-disubstituted cyclopropanes using phosphine oxides and phosphine boranes

    DEFF Research Database (Denmark)

    Clarke, Celia; Foussat, Stéphanie; Fox, David J;

    2009-01-01

    The stereocontrolled synthesis of trans-disubstituted cyclopropylketones has been achieved from beta-alkyl, gamma-benzoyl phosphine oxides via a three-step cascade reaction incorporating an acyl transfer, phosphinoyl transfer and cyclisation to form the cyclopropane. Using Evans' chiral oxazolidi...

  1. Phosphine and phosphine oxide groups in metal-organic frameworks detected by P K-edge XAS.

    Science.gov (United States)

    Morel, F L; Pin, S; Huthwelker, T; Ranocchiari, M; van Bokhoven, J A

    2015-02-07

    Phosphine metal-organic frameworks (P-MOFs) are crystalline porous coordination polymers that contain phosphorus functional groups within their pores. We present the use of X-ray absorption spectroscopy (XAS) at the P K-edge to determine the phosphine to phosphine oxide ratio in two P-MOFs with MIL-101 topology. The phosphorus oxidation state is of particular interest as it strongly influences the coordination affinity of these materials for transition metals. This method can determine the oxidation state of phosphorus even when the material contains paramagnetic nuclei, differently from NMR spectroscopy. We observed that phosphine in LSK-15 accounts for 72 ± 4% of the total phosphorus groups and that LSK-12 contains only phosphine oxide.

  2. Sublethal exposure to phosphine decreases offspring production in strongly phosphine resistant female red flour beetles, Tribolium castaneum (Herbst.

    Directory of Open Access Journals (Sweden)

    Andrew W Ridley

    Full Text Available The red flour beetle is a cosmopolitan pest of stored grain and stored grain products. The pest has developed resistance to phosphine, the primary chemical used for its control. The reproductive output of survivors from a phosphine treatment is an important element of resistance development but experimental data are lacking. We exposed mated resistant female beetles to 0.135 mg/L of phosphine for 48 h at 25 °C. Following one week of recovery we provided two non-exposed males to half of the phosphine exposed females and to half of the non-exposed control females. Females that had been exposed produced significantly fewer offspring than non-exposed females. Females that remained isolated produced significantly fewer offspring than both exposed females with access to males and non-exposed controls (P<0.05. Some females were permanently damaged from exposure to phosphine and did not reproduce even when given access to males. We also examined the additional effects of starvation prior to phosphine exposure on offspring production. Non-exposed starved females experienced a small reduction in mean offspring production in the week following starvation, followed by a recovery in the second week. Females that were starved and exposed to phosphine demonstrated a very significant reduction in offspring production in the first week following exposure which remained significantly lower than that of starved non-exposed females (P<0.05. These results demonstrate a clear sublethal effect of phosphine acting on the female reproductive system and in some individuals this can lead to permanent reproductive damage. Pest population rebound after a fumigation may be slower than expected which may reduce the rate of phosphine resistance development. The results presented strongly suggest that phosphine resistance models should include sublethal effects.

  3. Communication: Tunnelling splitting in the phosphine molecule

    Science.gov (United States)

    Sousa-Silva, Clara; Tennyson, Jonathan; Yurchenko, Sergey N.

    2016-09-01

    Splitting due to tunnelling via the potential energy barrier has played a significant role in the study of molecular spectra since the early days of spectroscopy. The observation of the ammonia doublet led to attempts to find a phosphine analogous, but these have so far failed due to its considerably higher barrier. Full dimensional, variational nuclear motion calculations are used to predict splittings as a function of excitation energy. Simulated spectra suggest that such splittings should be observable in the near infrared via overtones of the ν2 bending mode starting with 4ν2.

  4. Tunnelling splitting in the phosphine molecule

    CERN Document Server

    Sousa-Silva, Clara; Yurchenko, Sergey N

    2016-01-01

    Splitting due to tunnelling via the potential energy barrier has played a significant role in the study of molecular spectra since the early days of spectroscopy. The observation of the ammonia doublet led to attempts to find a phosphine analogous, but these have so far failed due to its considerably higher barrier. Full dimensional, variational nuclear motion calculations are used to predict splittings as a function of excitation energy. Simulated spectra suggest that such splittings should be observable in the near infrared via overtones of the $\

  5. Emission and distribution of phosphine in paddy fields and its relationship with greenhouse gases.

    Science.gov (United States)

    Chen, Weiyi; Niu, Xiaojun; An, Shaorong; Sheng, Hong; Tang, Zhenghua; Yang, Zhiquan; Gu, Xiaohong

    2017-12-01

    Phosphine (PH3), as a gaseous phosphide, plays an important role in the phosphorus cycle in ecosystems. In this study, the emission and distribution of phosphine, carbon dioxide (CO2) and methane (CH4) in paddy fields were investigated to speculate the future potential impacts of enhanced greenhouse effect on phosphorus cycle involved in phosphine by the method of Pearson correlation analysis and multiple linear regression analysis. During the whole period of rice growth, there was a significant positive correlation between CO2 emission flux and PH3 emission flux (r=0.592, p=0.026, n=14). Similarly, a significant positive correlation of emission flux was also observed between CH4 and PH3 (r=0.563, p=0.036, n=14). The linear regression relationship was determined as [PH3]flux=0.007[CO2]flux+0.063[CH4]flux-4.638. No significant differences were observed for all values of matrix-bound phosphine (MBP), soil carbon dioxide (SCO2), and soil methane (SCH4) in paddy soils. However, there was a significant positive correlation between MBP and SCO2 at heading, flowering and ripening stage. The correlation coefficients were 0.909, 0.890 and 0.827, respectively. In vertical distribution, MBP had the analogical variation trend with SCO2 and SCH4. Through Pearson correlation analysis and multiple stepwise linear regression analysis, pH, redox potential (Eh), total phosphorus (TP) and acid phosphatase (ACP) were identified as the principal factors affecting MBP levels, with correlative rankings of Eh>pH>TP>ACP. The multiple stepwise regression model ([MBP]=0.456∗[ACP]+0.235∗[TP]-1.458∗[Eh]-36.547∗[pH]+352.298) was obtained. The findings in this study hold great reference values to the global biogeochemical cycling of phosphorus in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Production and emission of phosphine gas from wetland ecosystems.

    Science.gov (United States)

    Han, Chao; Gu, Xueyuan; Geng, Jinju; Hong, Yuning; Zhang, Rui; Wang, Xiaorong; Gao, Shixiang

    2010-01-01

    Phosphine is a part of an atmospheric link of phosphorus cycle on earth, which could be an important pathway for phosphorus transport in environment. Wetland ecosystems are important locations for global biogeochemical phosphorus cycle. In this study, production and emission fluxes of free phosphine from four wetlands types in southern China were observed in different seasons. The results showed that the concentration of phosphine liberated from wetlands was at pg/m3-ng/m3 level. The emission concentrations of different wetlands followed the sequence: paddy field (51.83 +/- 3.06) ng/m3 > or = marsh (46.54 +/- 20.55) ng/m3 > lake (37.05 +/- 22.74) ng/m3 > coastal wetland (1.71 +/- 0.73) ng/m3, the positive phosphine emission flux occurred in rice paddy field (6.67 +/- 5.18) ng/(m2 x hr) and marsh (6.23 +/- 26.9) ng/(m2 x hr), while a negative phosphine flux of (-13.11 +/- 35.04) ng/(m2 x hr) was observed on the water-air interface of Lake Taihu, suggesting that paddy field and marsh may be important sources for phosphine gas in atmosphere, while lake may be a sink of atmospheric phosphine gas during the sampling period. Atmospheric phosphine levels and emission flux from Yancheng marsh and rice paddy field varied in different seasons and vegetational zones. Both diffusion resistance in aqueous phase and temperature were dominating factors for the production and transportation of phosphine to atmosphere.

  7. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System.

    Science.gov (United States)

    Buonomo, Joseph A; Aldrich, Courtney C

    2015-10-26

    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

  8. A core metabolic enzyme mediates resistance to phosphine gas.

    Science.gov (United States)

    Schlipalius, David I; Valmas, Nicholas; Tuck, Andrew G; Jagadeesan, Rajeswaran; Ma, Li; Kaur, Ramandeep; Goldinger, Anita; Anderson, Cameron; Kuang, Jujiao; Zuryn, Steven; Mau, Yosep S; Cheng, Qiang; Collins, Patrick J; Nayak, Manoj K; Schirra, Horst Joachim; Hilliard, Massimo A; Ebert, Paul R

    2012-11-09

    Phosphine is a small redox-active gas that is used to protect global grain reserves, which are threatened by the emergence of phosphine resistance in pest insects. We find that polymorphisms responsible for genetic resistance cluster around the redox-active catalytic disulfide or the dimerization interface of dihydrolipoamide dehydrogenase (DLD) in insects (Rhyzopertha dominica and Tribolium castaneum) and nematodes (Caenorhabditis elegans). DLD is a core metabolic enzyme representing a new class of resistance factor for a redox-active metabolic toxin. It participates in four key steps of core metabolism, and metabolite profiles indicate that phosphine exposure in mutant and wild-type animals affects these steps differently. Mutation of DLD in C. elegans increases arsenite sensitivity. This specific vulnerability may be exploited to control phosphine-resistant insects and safeguard food security.

  9. Oxygen enhances phosphine toxicity for postharvest pest control.

    Science.gov (United States)

    Liu, Yong-Biao

    2011-10-01

    Phosphine fumigations under superatmospheric oxygen levels (oxygenated phosphine fumigations) were significantly more effective than the fumigations under the normal 20.9% atmospheric oxygen level against western flower thrips [Frankliniella occidentalis (Pergande)] adults and larvae, leafminer Liriomyza langei Frick pupae, grape mealybug [Pseudococcus maritimus (Ehrhorn)] eggs, and Indianmeal moth [Plodia interpunctella (Hübner)] eggs and pupae. In 5-h fumigations with 1,000 ppm phosphine at 5 degrees C, mortalities of western flower thrips increased significantly from 79.5 to 97.7% when oxygen was increased from 20.9 to 40% and reached 99.3% under 80% O2. Survivorships of leafminer pupae decreased significantly from 71.2% under 20.9% O2 to 16.2% under 40% O2 and reached 1.1% under 80% O2 in 24-h fumigations with 500 ppm phosphine at 5 degrees C. Complete control of leafminer pupae was achieved in 24-h fumigations with 1,000 ppm phosphine at 5 degrees C under 60% O2 or higher. Survivorships of grape mealybug eggs also decreased significantly in 48-h fumigations with 1,000 ppm phosphine at 2 degrees C under 60% O2 compared with the fumigations under 20.9% O2. Indian meal moth egg survivorships decreased significantly from 17.4 to 0.5% in responses to an oxygen level increase from 20.9 to 40% in 48-h fumigations with 1,000 ppm phosphine at 10 degrees C and reached 0.2% in fumigations under 80% O2. When the oxygen level was reduced from 20.9 to 15 and 10% in fumigations, survivorships of Indianmeal moth eggs increased significantly from 17.4 to 32.9 and 39.9%, respectively. Increased O2 levels also resulted in significantly lower survival rates of Indianmeal moth pupae in response to 24-h fumigations with 500 and 1,000 ppm phosphine at 10 degrees C and a complete control was achieved in the 1,000 ppm phosphine fumigations under 60% O2. Oxygenated phosphine fumigations have marked potential to improve insecticidal efficacy. Advantages and limitations of oxygenated

  10. Tris[2-(deuteriomethylsulfanylphenyl]phosphine deuteriochloroform 0.125-solvate

    Directory of Open Access Journals (Sweden)

    Seik Weng Ng

    2008-05-01

    Full Text Available The title deuterated tripodal phosphine, C21H12D9PS3·0.125CDCl3, crystallizes as two independent molecules, one of which lies on a general position and the other about a threefold rotation axis, and as a deuteriochloroform solvate. The solvent molecule is disordered about a site of symmetry 3, so that the ratio of phosphine to solvent is 8:1. The P atom adopts a pyramidal coordination geometry.

  11. Imide/Arylene Ether Copolymers Containing Phosphine Oxide

    Science.gov (United States)

    Jensen, Brian J.; Partos, Richard D.

    1993-01-01

    Phosphine oxide groups react with oxygen to form protective phosphate surface layers. Series of imide/arylene ether block copolymers containing phosphine oxide units in backbone synthesized and characterized. In comparison with commercial polyimide, these copolymers display better resistance to etching by oxygen plasma. Tensile strengths and tensile moduli greater than those of polyarylene ether homopolymer. Combination of properties makes copolymers attractive for films, coatings, adhesives, and composite matrices where resistance to atomic oxygen needed.

  12. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    Science.gov (United States)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31P-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  13. Resistance of stored-product insects to phosphine

    OpenAIRE

    2008-01-01

    The objectives of this work were to assess phosphine resistance in insect populations (Tribolium castaneum, Rhyzopertha dominica, Sitophilus zeamais and Oryzaephilus surinamensis) from different regions of Brazil and to verify if the prevailing mechanism of phosphine resistance in these populations involves reduced respiration rates. Sixteen populations of T. castaneum, 15 of R. dominica, 27 of S. zeamais and eight of O. surinamensis were collected from 36 locations over seven Brazilian state...

  14. Metal-Free Reduction of Phosphine Oxides Using Polymethylhydrosiloxane

    Directory of Open Access Journals (Sweden)

    Emmanuel Nicolas

    2016-11-01

    Full Text Available A simple protocol is presented here for the use of inexpensive polymethylhydrosiloxane (PMHS, a waste product of the silicon industry, as stoichiometric reducing agent for phosphine oxides to phosphines, a highly desirable reaction to recover P-based ligands from their spent form. The reactions were studied by screening parameters, such as substrate to reductant ratio, temperature and reaction time, achieving good conversions and selectivities.

  15. Synthesis, characterization, and activity of yttrium(III) nitrate complexes bearing tripodal phosphine oxide and mixed phosphine-phosphine oxide ligands.

    Science.gov (United States)

    Sues, Peter E; Lough, Alan J; Morris, Robert H

    2012-09-03

    A series of four tripodal phosphine oxide ligands, (OPR(2))(2)CHCH(2)POR(2) (1a-1d), and four mixed phosphine-phosphine oxide ligands, (OPR(2))(2)CHCH(2)PR(2) (3a-3d), were synthesized and coordinated to yttrium to produce Y(NO(3))(3)[(OPR(2))(2)CHCH(2)POR(2)] (2a-2d) and Y(NO(3))(3)[(OPR(2))(2)CHCH(2)PR(2)](OPPh(3)) (4a-4d) complexes. The previously reported ligand 1a and unknown phosphine oxide ligands 1b-1d were generated in an unprecedented trisubstitution reaction of bromoacetaldehyde diethyl acetal, while the novel partially reduced ligands 3a-3d were synthesized from 1a-1d according to a known literature protocol for the selective monoreduction of bisphosphine oxides. The neutral yttrium complexes 2a-2d are nine-coordinate and display a tricapped trigonal-prismatic geometry. Complexes 4a-4d are also neutral, nine-coordinate species and have a pendant phosphine functionality, which provides the potential to form bimetallic early-late transition-metal complexes. Additionally, yttrium complexes 2a-2d were activated with base and tested for the ring-opening polymerization of ε-caprolactone, but the results showed that base by itself was significantly more effective than the yttrium species investigated.

  16. Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore.

    Science.gov (United States)

    Biswas, Sujoy; Pathak, P N; Roy, S B

    2012-06-01

    An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λ(max)) for UO(2)(2+)-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol(-1)cm(-1)). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to > 24h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO(2)(2+)-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ± 2%. This method can be used to determine 2.5-250 μg mL(-1) uranium in ore leach solutions with high accuracy and precision.

  17. Proteomic analysis of peach fruit moth larvae treated with phosphine.

    Science.gov (United States)

    Liu, Tao; Li, Li; Li, Baishu; Zhang, Fanhua; Wang, Yuejin

    2012-01-01

    Phosphine has been used worldwide for the control of stored-product insects for many years. However, the molecular mechanism of its toxicity is not clearly understood. In the current study, larvae of the peach fruit moth were fumigated with phosphine. Proteomic analysis was then performed to identify the regulated proteins. Our results confirmed the phosphine toxicity on the peach fruit moth. The median lethal time LT50 was 38.5 h at 330 ppm at 25 degrees C. During fumigation, the respiration of the peach fruit moth was extremely inhibited. Of the 26 regulated proteins, 16 were identified by MALDI-TOF mass spectrometry after a 24 h treatment. The proteins were classified as related to metabolism (25 %), anti-oxidation (6 %), signal transduction (38 %), or defense (19 %). The rest (13 %) were unclassified. Phosphine regulation of ATP and glutathione contents, as well as of ATP synthase and glutathione S-transferase 2 activities were confirmed by enzyme activity analysis. These results demonstrate that complex transcriptional regulations underlie phosphine fumigation. New theories on the mechanism of phosphine toxicity may also be established based on these results.

  18. Toxicity of phosphine fumigation against Bactrocera tau at low temperature.

    Science.gov (United States)

    Li, Li; Liu, Tao; Li, Baishu; Zhang, Fanhua; Dong, Shujun; Wang, Yuejin

    2014-04-01

    Bactrocera tau (Walker) is one of the most harmful pests to fruits and vegetables. To counteract this pest, the development of phytosanitary treatment is required to comply with the pest regulation requirements of certain countries. This study investigated the toxicity of phosphine fumigation against B. tau under low temperature conditions. Different growth stages (eggs and instars) of B. tau were exposed to 1.07 mg/liter phosphine for 1-10 d at 5 degrees C, and compared with unfumigated flies at 5 degrees C. The results showed that tolerance to cold treatment alone or phosphine fumigation at low temperatures generally increased with the stage of insect development. However, eggs incubated for 12 h at 25 degrees C represented the most tolerant growth stage to phosphine fumigation at 5 degrees C. Furthermore, 8.56- to 2.18-d exposure periods were required to achieve 99% mortality with a range of phosphine concentrations from 0.46 to 3.81 mg/liter. C0.62 t = k expression was obtained from the LT99 values, indicating that the exposure time was more important than the phosphine concentration.

  19. 4-Amino-l,2,4-triazole Resin-supported Palladium Complex as Phosphine-free Catalyst for Suzuki Reaction in Aqueous Phase

    Institute of Scientific and Technical Information of China (English)

    WU Xiang-mei; WANG Yan; GUO Sheng-rong

    2010-01-01

    @@ 1 Introduction The Suzuki cross-coupling reaction is a powerful and versatile method for the generation of unsymme-trical biaryls from arylboronic acids and aryl halides in a single step~([1-3]).However,the reaction is usually performed in the presence of Pd catalyst along with phosphine ligand,which sometimes creates practical problems because organophosphines tend to be expensive,poisonous,and air sensitive.Recently,phosphine-free ligands,such as nitrogen or sulfur-containing ligands~([4-6]) and N-heterocyclic car-benes~([7-12]) have been applied in Suzuki reaction effectively.

  20. Sublethal exposure to phosphine decreases offspring production in strongly phosphine resistant female red flour beetles, Tribolium castaneum (Herbst).

    Science.gov (United States)

    Ridley, Andrew W; Magabe, Seymour; Schlipalius, David I; Rafter, Michelle A; Collins, Patrick J

    2012-01-01

    The red flour beetle is a cosmopolitan pest of stored grain and stored grain products. The pest has developed resistance to phosphine, the primary chemical used for its control. The reproductive output of survivors from a phosphine treatment is an important element of resistance development but experimental data are lacking. We exposed mated resistant female beetles to 0.135 mg/L of phosphine for 48 h at 25 °C. Following one week of recovery we provided two non-exposed males to half of the phosphine exposed females and to half of the non-exposed control females. Females that had been exposed produced significantly fewer offspring than non-exposed females. Females that remained isolated produced significantly fewer offspring than both exposed females with access to males and non-exposed controls (Pphosphine and did not reproduce even when given access to males. We also examined the additional effects of starvation prior to phosphine exposure on offspring production. Non-exposed starved females experienced a small reduction in mean offspring production in the week following starvation, followed by a recovery in the second week. Females that were starved and exposed to phosphine demonstrated a very significant reduction in offspring production in the first week following exposure which remained significantly lower than that of starved non-exposed females (Pphosphine acting on the female reproductive system and in some individuals this can lead to permanent reproductive damage. Pest population rebound after a fumigation may be slower than expected which may reduce the rate of phosphine resistance development. The results presented strongly suggest that phosphine resistance models should include sublethal effects.

  1. Sublethal Exposure to Phosphine Decreases Offspring Production in Strongly Phosphine Resistant Female Red Flour Beetles, Tribolium castaneum (Herbst)

    Science.gov (United States)

    Ridley, Andrew W.; Magabe, Seymour; Schlipalius, David I.; Rafter, Michelle A.; Collins, Patrick J.

    2012-01-01

    The red flour beetle is a cosmopolitan pest of stored grain and stored grain products. The pest has developed resistance to phosphine, the primary chemical used for its control. The reproductive output of survivors from a phosphine treatment is an important element of resistance development but experimental data are lacking. We exposed mated resistant female beetles to 0.135 mg/L of phosphine for 48 h at 25°C. Following one week of recovery we provided two non-exposed males to half of the phosphine exposed females and to half of the non-exposed control females. Females that had been exposed produced significantly fewer offspring than non-exposed females. Females that remained isolated produced significantly fewer offspring than both exposed females with access to males and non-exposed controls (Pphosphine and did not reproduce even when given access to males. We also examined the additional effects of starvation prior to phosphine exposure on offspring production. Non-exposed starved females experienced a small reduction in mean offspring production in the week following starvation, followed by a recovery in the second week. Females that were starved and exposed to phosphine demonstrated a very significant reduction in offspring production in the first week following exposure which remained significantly lower than that of starved non-exposed females (Pphosphine acting on the female reproductive system and in some individuals this can lead to permanent reproductive damage. Pest population rebound after a fumigation may be slower than expected which may reduce the rate of phosphine resistance development. The results presented strongly suggest that phosphine resistance models should include sublethal effects. PMID:23300916

  2. Sorption of Perfluoroalkyl Phosphonates and Perfluoroalkyl Phosphinates in Soils.

    Science.gov (United States)

    Lee, Holly; Mabury, Scott Andrew

    2017-02-22

    Perfluoroalkyl phosphonates (PFPAs) and perfluoroalkyl phosphinates (PFPiAs) are recently discovered perfluoroalkyl acids (PFAAs) that have been widely detected in house dust, aquatic biota, surface water, and wastewater environments. The sorption of C6, C8, and C10 monoalkylated PFPAs and C6/C6, C6/C8, and C8/C8 dialkylated PFPiAs was investigated in seven soils of varying geochemical parameters. Mean distribution coefficients, logKd*, ranged from 0.2 to 2.1 for the PFPAs and PFPiAs and were generally observed to increase with perfluoroalkyl chain length. The logKd* of PFPiAs calculated here (1.6-2.1) were similar to those previously measured for the longer-chain perfluorodecane sulfonate (1.9, PFDS) and perfluoroundecanoate (1.7, PFUnA) in sediments, but overall when compared as a class, were greater than those for the perfluoroalkane sulfonates (-0.8-1.9, PFSAs), perfluoroalkyl carboxylates (-0.4-1.7, PFCAs), and PFPAs (0.2-1.5). No single soil-specific parameter, such as pH and organic carbon content, was observed to control the sorption of PFPAs and PFPiAs, the lack of which may be attributed to competing interferences in the naturally heterogeneous soils. The PFPAs were observed to desorb to a greater extent and likely circulate as aqueous contaminants in the environment, while the more sorptive PFPiAs would be preferentially retained by environmental solid phases.

  3. Fourteen-Day Subchronic Oral Toxicity Study of 4-Nitrophenyl Methyl (Phenyl) Phosphinate in Male and Female Rats.

    Science.gov (United States)

    1982-09-01

    Lewis-- 14 a ~1 A Lewis--15 TEST SUBSTANCE 1. Chemical name: 4-Nitrophenyl Methyl (Phenyl) Phosphinate Chemical Abstract Service Registry No.: None...11.25 2. Chemical name: Polysorbate 80 (Tween 80) Chemical Abstract Service Registry No.: 9005-65-6 Molecular structure: HO(C 2 40) ( C 2 H 4 )XOH...particularly in chronic toxicity studies in experimental data. APPENDIX A (Cant) Lewis--17 3. Chemical name: Citric Acid, monohydrate Chemical Abstract Service

  4. Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity

    Directory of Open Access Journals (Sweden)

    Sergey Tin

    2015-05-01

    Full Text Available In the hydrogenation of sluggish unactivated enamine substrates, Rh complexes of electron-deficient phosphines are demonstrated to be far more reactive catalysts than those derived from triphenylphosphine. These operate at low catalyst loadings (down to 0.01 mol % and are able to reduce tetrasubstituted enamines. The use of the sustainable and environmentally benign solvent (R-limonene for the reaction is also reported with the amine isolated by acid extraction.

  5. Synthesis of hybrid transition-metalloproteins via thiol-selective covalent anchoring of Rh-phosphine and Ru-phenanthroline complexes

    NARCIS (Netherlands)

    den Heeten, R.; Muñoz, B.K.; Popa, G.; Laan, W.; Kamer, P.C.J.

    2010-01-01

    The preparation of hybrid transition metalloproteins by thiol-selective incorporation of organometallic rhodium- and ruthenium complexes is described. Phosphine ligands and two rhodium-diphosphine complexes bearing a carboxylic acid group were coupled to the cysteine of PYP R52G, yielding a metalloe

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

    Science.gov (United States)

    Nguyen, Tam T; Collins, Patrick J; Duong, Tu M; Schlipalius, David I; Ebert, Paul R

    2016-05-01

    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 4 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 2 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 mg L(-1) for a 48-h 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.

  7. Fumigation with phosphine under gas-proof sheets (ODNRI Bulletin No. 26)

    OpenAIRE

    Friendship, R

    1989-01-01

    Although fumigation with phosphine is a simple technique, results, in terms of insect mortality, are often unsatisfactory. This is because complete insect control can only be achieved if an insecticidal concentration of phosphine is maintained for a sufficient length of time. Where multiple fumigations with phosphine have failed to meet these criteria insect resistance to phosphine has become established. This bulletin describes the formulations, equipment, application techniques and safety c...

  8. Responses of phosphate transporter gene and alkaline phosphatase in Thalassiosira pseudonana to phosphine.

    Science.gov (United States)

    Fu, Mei; Song, Xiuxian; Yu, Zhiming; Liu, Yun

    2013-01-01

    Phosphine, which is released continuously from sediment, can affect the eco-physiological strategies and molecular responses of phytoplankton. To examine the effects of phosphine on phosphorus uptake and utilization in Thalassiosira pseudonana, we examined the transcriptional level of the phosphate transporter gene (TpPHO) and the activity of alkaline phosphatase (AKP) in relation to supplement of various concentrations of phosphine. TpPHO expression was markedly promoted by phosphine in both the phosphate-deficient and phosphate-4 µM culture. However, high phosphine concentrations can inhibit TpPHO transcription in the declining growth phase. AKP activity was also higher in the phosphine treatment groups than that of the control. It increased with increasing phosphine concentration in the range of 0 to 0.056 µM but was inhibited by higher levels of phosphine. These responses revealed that phosphine can affect phosphate uptake and utilization in T. pseudonana. This result was consistent with the effect of phosphine on algal growth, while TpPHO expression and AKP were even more sensitive to phosphine than algal growth. This work provides a basic understanding for further research about how phosphine affects phytoplankton.

  9. Comparative Toxicity of Fumigants and a Phosphine Synergist Using a Novel Containment Chamber for the Safe Generation of Concentrated Phosphine Gas

    Science.gov (United States)

    Valmas, Nicholas; Ebert, Paul R.

    2006-01-01

    Background With the phasing out of ozone-depleting substances in accordance with the United Nations Montreal Protocol, phosphine remains as the only economically viable fumigant for widespread use. However the development of high-level resistance in several pest insects threatens the future usage of phosphine; yet research into phosphine resistance mechanisms has been limited due to the potential for human poisoning in enclosed laboratory environments. Principal Findings Here we describe a custom-designed chamber for safely containing phosphine gas generated from aluminium phosphide tablets. In an improvement on previous generation systems, this chamber can be completely sealed to control the escape of phosphine. The device has been utilised in a screening program with C. elegans that has identified a phosphine synergist, and quantified the efficacy of a new fumigant against that of phosphine. The phosphine-induced mortality at 20°C has been determined with an LC50 of 732 ppm. This result was contrasted with the efficacy of a potential new botanical pesticide dimethyl disulphide, which for a 24 hour exposure at 20°C is 600 times more potent than phosphine (LC50 1.24 ppm). We also found that co-administration of the glutathione depletor diethyl maleate (DEM) with a sublethal dose of phosphine (70 ppm, phosphine in a laboratory environment has now been substantially reduced by the implementation of our novel gas generation chamber. We have also identified a novel phosphine synergist, the glutathione depletor DEM, suggesting an effective pathway to be targeted in future synergist research; as well as quantifying the efficacy of a potential alternative to phosphine, dimethyl disulphide. PMID:17205134

  10. Mechanisms and origins of switchable chemoselectivity of Ni-catalyzed C(aryl)-O and C(acyl)-O activation of aryl esters with phosphine ligands.

    Science.gov (United States)

    Hong, Xin; Liang, Yong; Houk, K N

    2014-02-05

    Many experiments have shown that nickel with monodentate phosphine ligands favors the C(aryl)-O activation over the C(acyl)-O activation for aryl esters. However, Itami and co-workers recently discovered that nickel with bidentate phosphine ligands can selectively activate the C(acyl)-O bond of aryl esters of aromatic carboxylic acids. The chemoselectivity with bidentate phosphine ligands can be switched back to C(aryl)-O activation when aryl pivalates are employed. To understand the mechanisms and origins of this switchable chemoselectivity, density functional theory (DFT) calculations have been conducted. For aryl esters, nickel with bidentate phosphine ligands cleaves C(acyl)-O and C(aryl)-O bonds via three-centered transition states. The C(acyl)-O activation is more favorable due to the lower bond dissociation energy (BDE) of C(acyl)-O bond, which translates into a lower transition-state distortion energy. However, when monodentate phosphine ligands are used, a vacant coordination site on nickel creates an extra Ni-O bond in the five-centered C(aryl)-O cleavage transition state. The additional interaction energy between the catalyst and substrate makes C(aryl)-O activation favorable. In the case of aryl pivalates, nickel with bidentate phosphine ligands still favors the C(acyl)-O activation over the C(aryl)-O activation at the cleavage step. However, the subsequent decarbonylation generates a very unstable tBu-Ni(II) intermediate, and this unfavorable step greatly increases the overall barrier for generating the C(acyl)-O activation products. Instead, the subsequent C-H activation of azoles and C-C coupling in the C(aryl)-O activation pathway are much easier, leading to the observed C(aryl)-O activation products.

  11. The phosphine oxides Cyanex 921 and Cyanex 923 as carriers for facilitated transport of chromium (VI)-chloride aqueous solutions.

    Science.gov (United States)

    Alguacil, Francisco José; López-Delgado, Aurora; Alonso, Manuel; Sastre, Ana Maria

    2004-11-01

    The behaviour of the phosphine oxides Cyanex 921 and Cyanex 923 in the facilitated transport of chromium (VI) from chloride solutions is described. Transport is studied as a function of several variables such as stirring speeds of the aqueous phases, membrane phase diluent, hydrochloric acid concentration in the source phase and chromium and carrier concentrations. The separation of chromium (VI) from other metals presented in the source phase as well as the behaviour of phosphine oxides with respect to other neutral organophosphorous derivatives (tri-n-butylphosphate (TBP) and dibutyl butylphosphonate (DBBP)) are also investigated. Moreover, by using hydrazine sulphate in the receiving phase, Cr(VI) is immediately reduced to the less toxic Cr(III).

  12. Tentative detection of phosphine in IRC+10216

    CERN Document Server

    Agúndez, M; Pardo, J R; Guélin, M; Phillips, T G

    2008-01-01

    The J,K = 1,0-0,0 rotational transition of phosphine (PH3) at 267 GHz has been tentatively identified with a T_MB = 40 mK spectral line observed with the IRAM 30-m telescope in the C-star envelope IRC+10216. A radiative transfer model has been used to fit the observed line profile. The derived PH3 abundance relative to H2 is 6 x 10^(-9), although it may have a large uncertainty due to the lack of knowledge about the spatial distribution of this species. If our identification is correct, it implies that PH3 has a similar abundance to that reported for HCP in this source, and that these two molecules (HCP and PH3) together take up about 5 % of phosphorus in IRC+10216. The abundance of PH3, as that of other hydrides in this source, is not well explained by conventional gas phase LTE and non-LTE chemical models, and may imply formation on grain surfaces.

  13. Diagnostic Molecular Markers for Phosphine Resistance in U.S. Populations of Tribolium castaneum and Rhyzopertha dominica

    Science.gov (United States)

    Chen, Zhaorigetu; Schlipalius, David; Opit, George; Subramanyam, Bhadriraju; Phillips, Thomas W.

    2015-01-01

    Stored product beetles that are resistant to the fumigant pesticide phosphine (hydrogen phosphide) gas have been reported for more than 40 years in many places worldwide. Traditionally, determination of phosphine resistance in stored product beetles is based on a discriminating dose bioassay that can take up to two weeks to evaluate. We developed a diagnostic cleaved amplified polymorphic sequence method, CAPS, to detect individuals with alleles for strong resistance to phosphine in populations of the red flour beetle, Tribolium castaneum, and the lesser grain borer, Rhyzopertha dominica, according to a single nucleotide mutation in the dihydrolipoamide dehydrogenase (DLD) gene. We initially isolated and sequenced the DLD genes from susceptible and strongly resistant populations of both species. The corresponding amino acid sequences were then deduced. A single amino acid mutation in DLD in populations of T. castaneum and R. dominica with strong resistance was identified as P45S in T. castaneum and P49S in R. dominica, both collected from northern Oklahoma, USA. PCR products containing these mutations were digested by the restriction enzymes MboI and BstNI, which revealed presence or absence, respectively of the resistant (R) allele and allowed inference of genotypes with that allele. Seven populations of T. castaneum from Kansas were subjected to discriminating dose bioassays for the weak and strong resistance phenotypes. Application of CAPS to these seven populations confirmed the R allele was in high frequency in the strongly resistant populations, and was absent or at a lower frequency in populations with weak resistance, which suggests that these populations with a low frequency of the R allele have the potential for selection of the strong resistance phenotype. CAPS markers for strong phosphine resistance will help to detect and confirm resistant beetles and can facilitate resistance management actions against a given pest population. PMID:25826251

  14. Diagnostic molecular markers for phosphine resistance in U.S. populations of Tribolium castaneum and Rhyzopertha dominica.

    Science.gov (United States)

    Chen, Zhaorigetu; Schlipalius, David; Opit, George; Subramanyam, Bhadriraju; Phillips, Thomas W

    2015-01-01

    Stored product beetles that are resistant to the fumigant pesticide phosphine (hydrogen phosphide) gas have been reported for more than 40 years in many places worldwide. Traditionally, determination of phosphine resistance in stored product beetles is based on a discriminating dose bioassay that can take up to two weeks to evaluate. We developed a diagnostic cleaved amplified polymorphic sequence method, CAPS, to detect individuals with alleles for strong resistance to phosphine in populations of the red flour beetle, Tribolium castaneum, and the lesser grain borer, Rhyzopertha dominica, according to a single nucleotide mutation in the dihydrolipoamide dehydrogenase (DLD) gene. We initially isolated and sequenced the DLD genes from susceptible and strongly resistant populations of both species. The corresponding amino acid sequences were then deduced. A single amino acid mutation in DLD in populations of T. castaneum and R. dominica with strong resistance was identified as P45S in T. castaneum and P49S in R. dominica, both collected from northern Oklahoma, USA. PCR products containing these mutations were digested by the restriction enzymes MboI and BstNI, which revealed presence or absence, respectively of the resistant (R) allele and allowed inference of genotypes with that allele. Seven populations of T. castaneum from Kansas were subjected to discriminating dose bioassays for the weak and strong resistance phenotypes. Application of CAPS to these seven populations confirmed the R allele was in high frequency in the strongly resistant populations, and was absent or at a lower frequency in populations with weak resistance, which suggests that these populations with a low frequency of the R allele have the potential for selection of the strong resistance phenotype. CAPS markers for strong phosphine resistance will help to detect and confirm resistant beetles and can facilitate resistance management actions against a given pest population.

  15. Diagnostic molecular markers for phosphine resistance in U.S. populations of Tribolium castaneum and Rhyzopertha dominica.

    Directory of Open Access Journals (Sweden)

    Zhaorigetu Chen

    Full Text Available Stored product beetles that are resistant to the fumigant pesticide phosphine (hydrogen phosphide gas have been reported for more than 40 years in many places worldwide. Traditionally, determination of phosphine resistance in stored product beetles is based on a discriminating dose bioassay that can take up to two weeks to evaluate. We developed a diagnostic cleaved amplified polymorphic sequence method, CAPS, to detect individuals with alleles for strong resistance to phosphine in populations of the red flour beetle, Tribolium castaneum, and the lesser grain borer, Rhyzopertha dominica, according to a single nucleotide mutation in the dihydrolipoamide dehydrogenase (DLD gene. We initially isolated and sequenced the DLD genes from susceptible and strongly resistant populations of both species. The corresponding amino acid sequences were then deduced. A single amino acid mutation in DLD in populations of T. castaneum and R. dominica with strong resistance was identified as P45S in T. castaneum and P49S in R. dominica, both collected from northern Oklahoma, USA. PCR products containing these mutations were digested by the restriction enzymes MboI and BstNI, which revealed presence or absence, respectively of the resistant (R allele and allowed inference of genotypes with that allele. Seven populations of T. castaneum from Kansas were subjected to discriminating dose bioassays for the weak and strong resistance phenotypes. Application of CAPS to these seven populations confirmed the R allele was in high frequency in the strongly resistant populations, and was absent or at a lower frequency in populations with weak resistance, which suggests that these populations with a low frequency of the R allele have the potential for selection of the strong resistance phenotype. CAPS markers for strong phosphine resistance will help to detect and confirm resistant beetles and can facilitate resistance management actions against a given pest population.

  16. Mechanism of phosphine borane deprotection with amines: the effects of phosphine, solvent and amine on rate and efficiency.

    Science.gov (United States)

    Lloyd-Jones, Guy C; Taylor, Nicholas P

    2015-03-27

    The kinetics of borane transfer from simple tertiary phosphine borane adducts to a wide range of amines have been determined. All data obtained, including second-order kinetics, lack of cross-over, and negative entropies of activation for reaction of triphenylphosphine borane with quinuclidine and triethylamine, are consistent with a direct (SN 2-like) transfer process, rather than a dissociative (SN 1-like) process. The identities of the amine, phosphine, and solvent all impact substantially on the rate (k) and equilibrium (K) of the transfer, which in some cases vary by many orders of magnitude. P-to-N transfer is more efficient with cyclic amines in apolar solvents due to reduced entropic costs and ground-state destabilisation. Taken as a whole, the data allow informed optimisation of the deprotection step from the stand-point of rate, or synthetic convenience. In all cases, both reactants should be present at high initial concentration to gain kinetic benefit from the bimolecularity of the process. Ultimately, the choice of amine is dictated by the identity of the phosphine borane complex. Aryl-rich phosphine boranes are sufficiently reactive to allow use of diethylamine or pyrrolidine as a volatile low polarity solvent and reactant, whereas more alkyl-rich phosphines benefit from the use of more reactive amines, such as 1,4-diaza[2.2.2]bicyclooctane (DABCO), in apolar solvents at higher temperatures.

  17. Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes

    Science.gov (United States)

    Niemeyer, Zachary L.; Milo, Anat; Hickey, David P.; Sigman, Matthew S.

    2016-06-01

    The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentiometric analyses to study a Suzuki reaction, for which the site selectivity of oxidative addition is highly dependent on the nature of the phosphine. These studies shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands on the reaction mechanism(s), and deliver a methodology that should prove useful in future studies of phosphine ligands.

  18. Synthesis of Functionalized Furans via Chemoselective Reduction/Wittig Reaction Using Catalytic Triethylamine and Phosphine.

    Science.gov (United States)

    Lee, Chia-Jui; Chang, Tzu-Hsiu; Yu, Jhen-Kuei; Madhusudhan Reddy, Ganapuram; Hsiao, Ming-Yu; Lin, Wenwei

    2016-08-05

    An efficient protocol for the synthesis of highly functionalized furans via intramolecular Wittig reaction has been developed using catalytic amounts of phosphine and triethylamine. Silyl chloride served as the initial promoter to activate the phosphine oxide. Reduction of the activated phosphine oxide by hydrosilane resulted in generation of phosphine, while decomposition of Et3N·HCl resulted in regeneration of base, which mediated formation of phosphorus ylide. Remarkably, the in situ generated byproduct, Et3N·HCl, also catalyzes reduction of phosphine oxide.

  19. A superior method for the reduction of secondary phosphine oxides.

    Science.gov (United States)

    Busacca, Carl A; Lorenz, Jon C; Grinberg, Nelu; Haddad, Nizar; Hrapchak, Matt; Latli, Bachir; Lee, Heewon; Sabila, Paul; Saha, Anjan; Sarvestani, Max; Shen, Sherry; Varsolona, Richard; Wei, Xudong; Senanayake, Chris H

    2005-09-15

    [reaction: see text] Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70 degrees C. This new reduction has distinct advantages over existing technologies.

  20. Oxygenated phosphine fumigation for control of Nasonovia ribisnigri (Homoptera: Aphididae) on harvested lettuce.

    Science.gov (United States)

    Liu, Yong-Biao

    2012-06-01

    Low temperature regular phosphine fumigations under the normal oxygen level and oxygenated phosphine fumigations under superatmospheric oxygen levels were compared for efficacy against the aphid, Nasonovia ribisnigri (Mosley), and effects on postharvest quality of romaine and head lettuce. Low temperature regular phosphine fumigation was effective against the aphid. However, a 3 d treatment with high phosphine concentrations of > or = 2,000 ppm was needed for complete control of the aphid. Oxygen greatly increased phosphine toxicity and significantly reduced both treatment time and phosphine concentration for control of N. ribisnigri. At 1,000 ppm phosphine, 72 h regular fumigations at 6 degrees C did not achieve 100% mortality of the aphid. The 1,000 ppm phosphine fumigation under 60% O2 killed all aphids in 30 h. Both a 72 h regular fumigation with 2,200 ppm phosphine and a 48 h oxygenated fumigation with 1,000 ppm phosphine under 60% O2 were tested on romaine and head lettuce at 3 degrees C. Both treatments achieved complete control of N. ribisnigri. However, the 72 h regular fumigation resulted in significantly higher percentages of lettuce with injuries and significantly lower lettuce internal quality scores than the 48 h oxygenated phosphine fumigation. Although the oxygenated phosphine fumigation also caused injuries to some treated lettuce, lettuce quality remained very good and the treatment is not expected to have a significant impact on marketability of the lettuce. This study demonstrated that oxygenated phosphine fumigation was more effective and less phytotoxic for controlling N. ribisnigri on harvested lettuce than regular phosphine fumigation and is promising for practical use.

  1. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli

    2015-06-02

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  2. Fabrication and thermal stability studies of polyamide 66 containing triaryl phosphine oxide

    Indian Academy of Sciences (India)

    Xiaofeng Yang; Qiaoling Li; Zhiping Chen; Hongli Han

    2009-08-01

    An intrinsically halogen-free flame retardant polyamide 66 (FR-PA66) was fabricated successfully by two-step polymerization reaction with adipic acid hexamethylene salt (AH salt) and bis(4-carboxyphenyl) phenyl phosphine oxide (BCPPO) as raw materials. The structure, combustion properties and thermal stability were characterized by means of intrinsic viscosity, Fourier transform infrared spectroscopy (FTIR), combustion testing, differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and scanning electron microscope (SEM). Experiments show that BCPPO have excellent copolymerization properties with AH salt. And incorporation of triaryl phosphine oxide (TPO) did not transform the crystal phase structure of PA66. During fabrication of FR-PA66, melt polymerization time exhibits more surprising influence on intrinsic viscosity than aqueous solution polymerization time. The LOI value of FR-PA66 with 9 wt% TPO reaches 27.2, and corresponding UL94 rating reaches V-0. Improved thermo-stability of FR-PA66 can be attributed to both forming of compact char protective layer and further consolidation effect of / synergistic system.

  3. Resistance of Lasioderma serricorne (Coleoptera: Anobiidae) to Fumigation with Phosphine.

    Science.gov (United States)

    Sağlam, Özgür; Edde, Peter A; Phillips, Thomas W

    2015-10-01

    Lasioderma serricorne (F.) is a serious pest of stored products that is known to be resistant to the fumigant pesticide gas phosphine. This study investigated resistance in populations from the southeastern United States, and determined if a recommended treatment schedule could kill resistant insects. A laboratory assay for adult insects was developed that used a discriminating concentration of 50 ppm phosphine applied to insects for 20 h at 25°C followed by 7 d of recovery in air. Survivors were classified as resistant. L. serricorne from six different field populations associated with stored tobacco were surveyed with the assay and all had resistant individuals. Four populations had greater than 90% of their insects resistant. Two industry-recommended treatment schedules were evaluated in laboratory fumigations against mixed life stage cultures of the four most resistant populations: the first at 200 ppm for 4 d at 25°C for controlling phosphine-susceptible L. serricorne and the second at 600 ppm for 6 d at 25°C intended to control phosphine-resistant beetles. The four populations with the highest frequency of resistant individuals from the field sampling study were not controlled by the "normal" treatment intended for susceptible insects. The higher concentration treatment greatly reduced beetle progeny from mixed-stage colony jars, but there were substantial numbers of surviving adults from all four highly resistant populations that represented unacceptable levels of control.

  4. Hydrogen Bonding in Phosphine Oxide/Phosphate-Phenol Complexes

    NARCIS (Netherlands)

    Cuypers, R.; Sudhölter, E.J.R.; Zuilhof, H.

    2010-01-01

    To develop a new solvent-impregnated resin (SIR) system for the removal of phenols and thiophenols from water, complex formation by hydrogen bonding of phosphine oxides and phosphates is studied using isothermal titration calorimetry (ITC) and quantum chemical modeling. Six different computational m

  5. 7 CFR 305.7 - Phosphine treatment schedules.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false Phosphine treatment schedules. 305.7 Section 305.7 Agriculture Regulations of the Department of Agriculture (Continued) ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE PHYTOSANITARY TREATMENTS Chemical Treatments § 305.7...

  6. Phosphine-catalyzed [3+2] annulation of cyanoallenes

    NARCIS (Netherlands)

    Kinderman, S.S.; van Maarseveen, J.H.; Hiemstra, H.

    2011-01-01

    Cyanoallenes were successfully used in organophosphine-catalyzed [3+2]-type annulation to give cyano-substituted dihydropyrroles in good yield. Chiral phosphines were also screened, leading to some initial results in the asymmetric version of cyano­allene-based annulations.

  7. [Effects of free-air CO2 enrichment on phosphine emission from rice field].

    Science.gov (United States)

    Zhang, Rui; Yang, Xiao-Di; Geng, Jin-Ju; Hong, Yu-Ning; Gu, Xue-Yuan; Wang, Xiao-Rong; Wang, Rui; Zhu, Jian-Guo

    2009-09-15

    Phosphine, a trace gas, has been proved to commonly exist in environment. Under free air carbon dioxide enrichment (FACE) condition, the phosphine fluxes were investigated on the function of different nitrogen fertilizer application, NN (normal N, 250 kg/hm2) and LN (low N, 125 kg/hm2). Results showed that phosphine fluxes and concentrations in flourishing stages, both tillering stage and elongation stage, were higher than in slowly growing stages. The highest phosphine flux of (155.2 +/- 22.71) ng/(m2 x h) was observed in tillering stage in NN zone of the FACE area. The highest average phosphine flux of (41.72 +/- 7.006) ng/(m2 x h) was observed in NN zone of FACE area, while the lowest average phosphine flux of (- 1.485 +/- 6.229) ng/(m2 x h) could be detected in LN zone of the ambient area. CO2 enrichment can obviously improve the phospine emission. The nitrogen fertilizing level doesn't play an important role in phosphine emission. Both net fluxes and concentrations of phosphine had obviously positive correlation with temperature. A one-day phosphine flux and concentration experiment was carried out in ripening stage. The result showed that light was the prominent factor influencing phosphine concentration in daytime.

  8. Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides.

    Science.gov (United States)

    Malysheva, Svetlana F; Artem'ev, Alexander V; Gusarova, Nina K; Belogorlova, Nataliya A; Albanov, Alexander I; Liu, C W; Trofimov, Boris A

    2015-01-01

    Secondary phosphine oxides react with vinyl sulfides (both alkyl- and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7-30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides in 70-93% yields.

  9. Experimental and theoretical investigations of the stereoselective synthesis of p-stereogenic phosphine oxides.

    Science.gov (United States)

    Copey, Laurent; Jean-Gérard, Ludivine; Framery, Eric; Pilet, Guillaume; Robert, Vincent; Andrioletti, Bruno

    2015-06-15

    An efficient enantioselective strategy for the synthesis of variously substituted phosphine oxides has been developed, incorporating the use of (1S,2S)-2-aminocyclohexanol as the chiral auxiliary. The method relies on three key steps: 1) Highly diastereoselective formation of P(V) oxazaphospholidine, rationalized by a theoretical study; 2) highly diastereoselective ring-opening of the oxazaphospholidine oxide with organometallic reagents that takes place with inversion of configuration at the P atom; 3) enantioselective synthesis of phosphine oxides by cleavage of the remaining P-O bond. Interestingly, the use of a P(III) phosphine precursor afforded a P-epimer oxazaphospholidine. Hence, the two enantiomeric phosphine oxides can be synthesized starting from either a P(V) or a P(III) phosphine precursor, which constitutes a clear advantage for the stereoselective synthesis of sterically hindered phosphine oxides.

  10. Action of phosphine on production of aflatoxins by various Aspergillus strains isolated from foodstuffs.

    Science.gov (United States)

    Leitao, J; de Saint-Blanquat, G; Bailly, J R

    1987-01-01

    Phosphine is a food fumigant, used until now as an insecticide and rodenticide. The present work researches the action of phosphine treatment on growth and aflatoxin production of 23 Aspergillus strains. Production of aflatoxins B1, B2, G1, and G2 decreased in almost all cases by a ratio of 10 to 100. Phosphine treatment therefore seems favorable to prevent growth of various Aspergillus strains, in the context of keeping food safe. PMID:3426212

  11. Generation of phosphine gas for the control of grain storage pests

    OpenAIRE

    Zhao, B.X.

    2010-01-01

    The phosphine generator is a device for rapid production of phosphine (PH₃) gas to be introduced into grain storage. The aluminum phosphide (ALP) tablets are used as raw material and its effective constituent is 56%. When the aluminum phosphide and water are brought into contact a hydrolyzation reaction takes place to produce the phosphine gas. Controlling the reaction temperature, reaction pressure and the dosage of aluminum phosphide immersed in the water, the hydrolyzation reaction can be ...

  12. Physiological and biochemical responses of rice seeds to phosphine exposure during germination.

    Science.gov (United States)

    Niu, Xiaojun; Mi, Lina; Li, Yadong; Wei, Aishu; Yang, Zhiquan; Wu, Jiandong; Zhang, Di; Song, Xiaofei

    2013-11-01

    Rice seeds (Tianyou, 3618) were used to examine the physiological and biochemical responses to phosphine exposure during germination. A control (0 mg m(-3)) and four concentrations of phosphine (1.4 mg m(-3), 4.2 mg m(-3), 7.0 mg m(-3) and 13.9 mg m(-3)) were used to treat the rice seeds. Each treatment was applied for 90 min once per day for five days. The germination rate (GR); germination potential (GP); germination index (GI); antioxidant enzymes, including superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT); and lipid peroxidation measured through via malondialdehyde (MDA) were determined as indicators of the physiological and biochemical responses of the rice seeds to phosphine exposure. These indicators were determined once per day for five days. The results indicated that the GR, GP and GI of the rice seeds markedly decreased after phosphine exposure. The changes in the activities of the antioxidant enzymes due to the phosphine exposure were also significant. The exposure lowered the CAT and SOD activities and increased POD activity in the treated rice seeds compared with controls. The MDA content exhibited a slow increase trend with the increase of phosphine concentration. These results suggest that phosphine has inhibitory effects on seed germination. In addition, phosphine exposure caused oxidative stress in the seeds. The antioxidant enzymes could play a pivotal role against oxidative injury. Overall, the effect of phosphine on rice seeds is different from what has been reported previously for insects and mammals.

  13. Influences of sediment dessication on phosphorus transformations in an intertidal marsh: formation and release of phosphine.

    Science.gov (United States)

    Hou, Lijun; Liu, Min; Ding, Pingxing; Zhou, Junliang; Yang, Yi; Zhao, Di; Zheng, Yanli

    2011-05-01

    This study investigated the effects of sediment dewatering on the phosphorus transformations concerning about the production and emission of phosphine in the intertidal marsh of the Yangtze Estuary. The concentrations of matrix-bound phosphine ranged from 18.62-72.53 ng kg(-1) and 31.14-61.22 ng kg(-1) within the August and January exposure incubations, respectively. The responses of matrix-bound phosphine concentrations to sediment dessication demonstrate that the production (or accumulation) of matrix-bound phosphine significantly increased with water loss at the start of the emersion incubations. However, further dehydration inhibited the formation of matrix-bound phosphine in sediments. The significant correlations of matrix-bound phosphine with the organic-P bacteria abundance and alkaline phosphatase activities implicate that the production of matrix-bound phosphine within the dessication incubations was linked closely to the microbial decomposition of organic P. The emissions of phosphine generally decreased with sediment dewatering, with the fluxes of 7.51-96.73 ng m(-2)h(-1) and 5.34-77.74 ng m(-2)h(-1) over the exposure incubations of both August and January, respectively. Also, it is observed that the releases of phosphine during the entire exposure periods were affected not only by its production but also by sediment water and redox conditions.

  14. Advances in nucleophilic phosphine catalysis of alkenes, allenes, alkynes, and MBHADs.

    Science.gov (United States)

    Fan, Yi Chiao; Kwon, Ohyun

    2013-12-25

    In nucleophilic phosphine catalysis, tertiary phosphines undergo conjugate additions to activated carbon-carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis.

  15. Effects of phosphine on the neural regulation of gas exchange in Periplaneta americana.

    Science.gov (United States)

    Woodman, James D; Haritos, Victoria S; Cooper, Paul D

    2008-04-01

    Phosphine is used for fumigating stored commodities, however an understanding of the physiological response to phosphine in insects is limited. Here we show how the central pattern generator for ventilation in the central nervous system (CNS) responds to phosphine and influences normal resting gas exchange. Using the American cockroach, Periplaneta americana, that perform discontinuous gas exchange (DGE) at rest, we simultaneously measure ventilatory nervous output from the intact CNS, VCO(2) and water loss from live specimens. Exposure to 800 ppm phosphine at 25 degrees C for 2 h (n=13) during recording did not cause any mortality or obvious sub-lethal effects. Within 60 s of introducing phosphine into the air flow, all animals showed a distinct CNS response accompanied by a burst release of CO(2). The initial ventilatory response to phosphine displaced DGE and was typically followed by low, stable and continuous CO(2) output. CNS output was highest and most orderly under normoxic conditions during DGE. Phosphine caused a series of ventilatory CNS spikes preceding almost complete cessation of CNS output. Minimal CNS output was maintained during the 2 h normoxic recovery period and DGE was not reinstated. VCO(2) was slightly reduced and water loss significantly lower during the recovery period compared with those rates prior to phosphine exposure. A phosphine narcosis effect is rejected based on animals remaining alert at all times during exposure.

  16. SYNTHESIS AND PROPERTIES OF SOLUBLE AROMATIC COPOLYAMIDES CONTAINING PHOSPHINE OXIDE MOIETY

    Institute of Scientific and Technical Information of China (English)

    Xiao-ting Chen; Ming Zhang; Xu-dong Tang

    2008-01-01

    Aromatic copolyamides were synthesized by the Yamazaki phosphorylation method starting from bis(4-carboxyphenyl) phenyl phosphine oxide,terephthalic acid and 4,4'-diaminodiphenyl methane.The copolymers with inherent viscosities of 0.52-0.99 dL/g were obtained.The structures of the copolyamides were characterized by elemental analysis,FTIR and NMR.The glass transition temperatures were measured by DSC and DMA,respectively,and the results showed that the Tgs of the polymers were higher than 287℃.Thermal decomposition temperatures of the copolyamides at 5% weight loss were found in the range of 423-469℃ by TGA.Most of the copolymers were readily soluble in a variety of organic solvents such as NMP,DMAc,m-cresol and so on.The tensile experiments of the thin films showed that the polymers had good mechanical properties.

  17. Suzuki Reaction of Aryl Bromides Using a Phosphine-Free Magnetic Nanoparticle-Supported Palladium Catalyst

    Institute of Scientific and Technical Information of China (English)

    Nghia T. BUI; Trung B. DANG; Ha V. LE; Nam T. S. PHAN

    2011-01-01

    A palladium catalyst immobilized on superparaganetic nanoparticles was prepared with a palladium loading of 0.30 mmol/g.The catalyst was characterized using X-ray diffraction,scanning electron microscopy,transmission electron microscopy,vibrating sample magnetometry,thermogravimetric analysis,Fourier transform infrared,atomic absorption spectrophotometry,and nitrogen adsorption.The immobilized palladium catalyst was an efficient catalyst without added phosphine ligands for the Suzuki cross-coupling reaction of several aryl bromides with phenylboronic acid.The recovery of catalyst was simply by magnetic decantation in the presence of a magnet.The immobilized palladium catalyst can be reused many times without significant degradation in catalytic activity.No leaching of active palladium species into the reaction solution was detected.

  18. Electrochemical chiral recognition by microparticle coatings of Pd complexes with bridging cyclometalated phosphines

    Energy Technology Data Exchange (ETDEWEB)

    Domenech, Antonio [Departament de Quimica Analitica, Facultat de Quimica, Universitat de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia (Spain)], E-mail: antonio.domenech@uv.es; Koshevoy, Igor O.; Penno, Dirk; Ubeda, Maria Angeles [Departament de Quimica Inorganica, Facultat de Quimica, Universitat de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia (Spain)

    2008-03-10

    The palladium(II) dinuclear complex with bridging cyclometalated phosphines, {l_brace}Pd{sub 2}[{mu}-(C{sub 6}H{sub 4})PPh{sub 2}]{sub 2}({mu}-O{sub 2}CCH{sub 3}){sub 2}{r_brace} (Pd{sub 2}L{sub 2}), having a paddlewheel structure, is reversibly oxidized in CH{sub 2}Cl{sub 2} to a dinuclear palladium(III) analogue via two successive one-electron steps. Solid state voltammetry of Pd{sub 2}L{sub 2} in contact with aqueous electrolytes produce as one-electron oxidation with two competing mechanisms involving anion intercalation/anion binding between/to metal centres, chloride ions acting as inhibitors for the first pathway. R- and S-Pd{sub 2}L{sub 2} produces a significant stereoselective electrocatalytic activity with respect to the oxidation of L- and D-glutamic acid in alkaline media.

  19. A New Route to Biaryl Ketones via Carbonylative Suzuki Coupling Catalyzed by MCM-41-supported Bidentate Phosphine Palladium(O) Complex

    Institute of Scientific and Technical Information of China (English)

    ZHENG, Guomin; WANG, Pingping; CAI, Mingzhong

    2009-01-01

    A variety of biaryl ketones can be conveniently synthesized in good to high yields via the first heterogeneous carbonylative Suzuki coupling of arylboronic acids with aryl iodides under atmospheric pressure of carbon monox- ide in the presence of a catalytic amount of MCM-41-supported bidentate phosphine palladium(0) complex [MCM-41-2P-Pd(0)]. This polymeric palladium catalyst can be reused at least 10 times without any decrease in ac- tivity.

  20. Retrievals of Jovian Tropospheric Phosphine from Cassini/CIRS

    Science.gov (United States)

    Irwin, P. G. J.; Parrish, P.; Fouchet, T.; Calcutt, S. B.; Taylor, F. W.; Simon-Miller, A. A.; Nixon, C. A.

    2004-01-01

    On December 30th 2000, the Cassini-Huygens spacecraft reached the perijove milestone on its continuing journey to the Saturnian system. During an extended six-month encounter, the Composite Infrared Spectrometer (CIRS) returned spectra of the Jovian atmosphere, rings and satellites from 10-1400 cm(exp -1) (1000-7 microns) at a programmable spectral resolution of 0.5 to 15 cm(exp -1). The improved spectral resolution of CIRS over previous IR instrument-missions to Jupiter, the extended spectral range, and higher signal-to-noise performance provide significant advantages over previous data sets. CIRS global observations of the mid-infrared spectrum of Jupiter at medium resolution (2.5 cm(exp -1)) have been analysed both with a radiance differencing scheme and an optimal estimation retrieval model to retrieve the spatial variation of phosphine and ammonia fractional scale height in the troposphere between 60 deg S and 60 deg N at a spatial resolution of 6 deg. The ammonia fractional scale height appears to be high over the Equatorial Zone (EZ) but low over the North Equatorial Belt (NEB) and South Equatorial Belt (SEB) indicating rapid uplift or strong vertical mixing in the EZ. The abundance of phosphine shows a similar strong latitudinal variation which generally matches that of the ammonia fractional scale height. However while the ammonia fractional scale height distribution is to a first order symmetric in latitude, the phosphine distribution shows a North/South asymmetry at mid latitudes with higher amounts detected at 40 deg N than 40 deg S. In addition the data show that while the ammonia fractional scale height at this spatial resolution appears to be low over the Great Red Spot (GRS), indicating reduced vertical mixing above the approx. 500 mb level, the abundance of phosphine at deeper levels may be enhanced at the northern edge of the GRS indicating upwelling.

  1. Effects of environmental factors on the production and release of matrix-bound phosphine from lake sediments

    Institute of Scientific and Technical Information of China (English)

    GENG Jinju; WANG Qiang; NIU Xiaojun; WANG Xiaorong

    2007-01-01

    Effects of pH,temperature,and oxygen on the production and release of phosphine in eutrophic lake sediments were investigated under laboratory tests.Results indicated that the elimination of matrix-bound phosphine was accelerated under initial pH 1 or 12.Phosphine levels could reach maximum under initial pH 10.The contents of phosphine increased with the addition of alkali under pH 4-12]The rates of phosphine production and release from lake sediments varied with temperature.20℃ was the most favorable temperature for the production of matrix-bound phosphine.Oxygen showed little effect on matrix-bound phosphine.Matrix-bound phosphine concentrations in lake sediments were concluded to be dependent on a balance of natural generation and depletion processes.

  2. Genes related to mitochondrial functions are differentially expressed in phosphine-resistant and -susceptible Tribolium castaneum.

    Science.gov (United States)

    Oppert, Brenda; Guedes, Raul N C; Aikins, Michael J; Perkin, Lindsey; Chen, Zhaorigetu; Phillips, Thomas W; Zhu, Kun Yan; Opit, George P; Hoon, Kelly; Sun, Yongming; Meredith, Gavin; Bramlett, Kelli; Hernandez, Natalie Supunpong; Sanderson, Brian; Taylor, Madison W; Dhingra, Dalia; Blakey, Brandon; Lorenzen, Marcé; Adedipe, Folukemi; Arthur, Frank

    2015-11-18

    Phosphine is a valuable fumigant to control pest populations in stored grains and grain products. However, recent studies indicate a substantial increase in phosphine resistance in stored product pests worldwide. To understand the molecular bases of phosphine resistance in insects, we used RNA-Seq to compare gene expression in phosphine-resistant and susceptible laboratory populations of the red flour beetle, Tribolium castaneum. Each population was evaluated as either phosphine-exposed or no phosphine (untreated controls) in triplicate biological replicates (12 samples total). Pairwise analysis indicated there were eight genes differentially expressed between susceptible and resistant insects not exposed to phosphine (i.e., basal expression) or those exposed to phopshine (>8-fold expression and 90 % C.I.). However, 214 genes were differentially expressed among all four treatment groups at a statistically significant level (ANOVA, p < 0.05). Increased expression of 44 cytochrome P450 genes was found in resistant vs. susceptible insects, and phosphine exposure resulted in additional increases of 21 of these genes, five of which were significant among all treatment groups (p < 0.05). Expression of two genes encoding anti-diruetic peptide was 2- to 8-fold reduced in phosphine-resistant insects, and when exposed to phosphine, expression was further reduced 36- to 500-fold compared to susceptible. Phosphine-resistant insects also displayed differential expression of cuticle, carbohydrate, protease, transporter, and many mitochondrial genes, among others. Gene ontology terms associated with mitochondrial functions (oxidation biological processes, monooxygenase and catalytic molecular functions, and iron, heme, and tetrapyyrole binding) were enriched in the significantly differentially expressed dataset. Sequence polymorphism was found in transcripts encoding a known phosphine resistance gene, dihydrolipoamide dehydrogenase, in both susceptible and resistant

  3. Platinum-Catalyzed Selective Hydration of Hindered Nitriles and Nitriles with Acid- or Base-Sensitive Groups

    NARCIS (Netherlands)

    Jiang, Xiao-bin; Minnaard, Adriaan J.; Vries, Johannes G. de; Feringa, Bernard

    2004-01-01

    Hindered tertiary nitriles can be hydrolyzed under neutral and mild conditions to the corresponding amides using platinum(II) catalysts with dimethylphosphine oxide or other secondary phosphine oxides (SPOs, phosphinous acids) as ligands. We have found that this procedure also works well for

  4. Chiral magnesium BINOL phosphate-catalyzed phosphination of imines: access to enantioenriched α-amino phosphine oxides.

    Science.gov (United States)

    Ingle, Gajendrasingh K; Liang, Yuxue; Mormino, Michael G; Li, Guilong; Fronczek, Frank R; Antilla, Jon C

    2011-04-15

    A new method to synthesize chiral α-amino phosphine oxides is reported. The reaction combines N-substituted imines and diphenylphosphine oxide and is catalyzed by a chiral magnesium phosphate salt. A wide variety of aliphatic and aromatic aldimines substituted by electron-neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The dibenzocycloheptene protected imines afforded improved enantioselectivity in the resulting products. Substituted diphenylphosphine oxide nucleophiles also showed good reactivity.

  5. Complexation of Diphenyl(phenylacetenyl)phosphine to Rhodium(III) Tetraphenyl Porphyrins : Synthesis and Structural, Spectroscopic, and Thermodynamic Studies

    NARCIS (Netherlands)

    Stulz, Eugen; Scott, Sonya M.; Bond, Andrew D.; Otto, Sijbren; Sanders, Jeremy K.M.

    2003-01-01

    The coordination of diphenyl(phenylacetenyl)phosphine (DPAP) to (X)RhIIITPP (X = I or Me (3); TPP = tetraphenyl porphyrin) was studied in solution and in the solid state. The iodide is readily displaced by the phosphine, leading to the bis-phosphine complex [(DPAP)2Rh(TPP)](I) (4). The methylide on

  6. Complexation of Diphenyl(phenylacetenyl)phosphine to Rhodium(III) Tetraphenyl Porphyrins : Synthesis and Structural, Spectroscopic, and Thermodynamic Studies

    NARCIS (Netherlands)

    Stulz, Eugen; Scott, Sonya M.; Bond, Andrew D.; Otto, Sijbren; Sanders, Jeremy K.M.

    2003-01-01

    The coordination of diphenyl(phenylacetenyl)phosphine (DPAP) to (X)RhIIITPP (X = I or Me (3); TPP = tetraphenyl porphyrin) was studied in solution and in the solid state. The iodide is readily displaced by the phosphine, leading to the bis-phosphine complex [(DPAP)2Rh(TPP)](I) (4). The methylide on

  7. Passivation of nanocrystalline TiO2 junctions by surface adsorbed phosphinate amphiphiles enhances the photovoltaic performance of dye sensitized solar cells

    KAUST Repository

    Wang, Mingkui

    2009-01-01

    We report a new class of molecular insulators that electronically passivate the surface of nanocrystalline titania films for high performance dye sensitized solar cells (DSC). Using electrical impedance measurements we demonstrate that co-adsorption of dineohexyl bis-(3,3-dimethyl-butyl)-phosphinic acid (DINHOP), along with the amphiphilic ruthenium sensitizer Z907Na increased substantially the power output of the cells mainly due to a retardation of interfacial recombination of photo-generated charge carriers. The use of phosphinates as anchoring groups opens up new avenues for modification of the surface by molecular insulators, sensitizers and other electro-active molecules to realize the desired optoelectronic performance of devices based on oxide junctions. © 2009 The Royal Society of Chemistry.

  8. Action of phosphine (PH3) on production of sterigmatocystin by various fungal strains isolated from foodstuffs.

    Science.gov (United States)

    Leitao, J; Bailly, J R; de Saint Blanquat, G

    1990-01-01

    Phosphine is a food fumigant, used until now as an insecticide and rodenticide. The present work researches the action of phosphine treatment on growth and sterigmatocystin production of several fungal strains. Production of sterigmatocystin decreased by a ratio of 100 to 500 or was abolished.

  9. Oxygenated phosphine fumigation for control of Nasonovia ribisnigri (Homoptera: Aphididae) on harvested lettuce

    Science.gov (United States)

    A laboratory study was conducted to compare phosphine fumigations under the normal and superatmospheric oxygen levels on toxicity against Nasonovia ribisnigri (Mosley) and effects on postharvest quality of romaine and head lettuce. Low temperature phosphine fumigation was effective against the aphi...

  10. [Distribution of matrix-bound phosphine in surface sediments of Jinpu Bay].

    Science.gov (United States)

    You, Li-Li; Zong, Hai-Bo; Zhang, Shu-Fang; Yin, Guo-Yu; Li, Tao; Hou, Li-Jun

    2013-10-01

    This work investigated the distribution of matrix-bound phosphine in surface sediments of Jinpu Bay and associated environmental factors in summer, using the gas chromatography combined with a pulsed flame detector (GC-PFPD). It showed that phosphine ubiquitously presented in the sediments of Jinpu Bay. Contents of matrix-bound phosphine varied between 62. 58 and 190. 81 ng.kg-1, with the average value of 114.42 ng.kg-1. In addition, the spatial distribution of matrix-bound phosphine indicated that matrix-bound phosphine in inshore sediments had relatively higher contents than those in offshore sediments. Statistical analysis showed that matrix-bound phosphine significantly related to organic phosphorus and alkaline phosphatase activity ( R = 0. 882, P = 0. 01; R = 0. 819, P =0. 023). However, there were no correlations between matrix-bound phosphine and organic nitrogen, inorganic phosphorus and sediment grain sizes. These results implied that accumulation and distribution of matrix-bound phosphined were mainly affected by the decomposition of organic phosphorus by microorganisms.

  11. Resistance of stored-product insects to phosphine; Resistencia de insetos de produtos armazenados a fosfina

    Energy Technology Data Exchange (ETDEWEB)

    Pimentel, Marco Aurelio Guerra [Universidade Federal de Vicosa (UFV), MG (Brazil). Dept. de Biologia Animal. Setor de Entomologia]. E-mail: marcoagp@gmail.com; Faroni, Leda Rita D' Antonino; Batista, Maurilio Duarte; Silva, Felipe Humberto da [Universidade Federal de Vicosa (UFV), MG (Brazil). Dept. de Engenharia Agricola. Setor de Armazenamento]. E-mail: lfaroni@ufv.br; mauriliodbatista@yahoo.com.br; felipehumberto@gmail.com

    2008-12-15

    The objectives of this work were to assess phosphine resistance in insect populations (Tribolium castaneum, Rhyzopertha dominica, Sitophilus zeamais and Oryzaephilus surinamensis) from different regions of Brazil and to verify if the prevailing mechanism of phosphine resistance in these populations involves reduced respiration rates. Sixteen populations of T. castaneum, 15 of R. dominica, 27 of S. zeamais and eight of O. surinamensis were collected from 36 locations over seven Brazilian states. Each population was tested for resistance to phosphine, based on the response of adults to discriminating concentrations, according to FAO standard method. For each insect species, the production of carbon dioxide of the most resistant and of the most susceptible populations was inversely related to their phosphine resistance. The screening tests identified possible phosphine resistant populations. R. dominica and O. surinamensis were less susceptible to phosphine than the other two species. The populations with lower respiration rate showed a lower mortality at discriminating concentration, possibly related to a phosphine resistance mechanism. Phosphine resistance occurs in stored-product insects, in different regions of Brazil, and the resistance mechanism involves reduced respiration rate. (author)

  12. Tris(pyrazolyl)phosphines with copper(i) : from monomers to polymers

    NARCIS (Netherlands)

    Tazelaar, Cornelis G J; Nicolas, Emmanuel; van Dijk, Tom; Broere, Daniël L J; Cardol, Mitchel; Lutz, Martin; Gudat, Dietrich; Slootweg, J Chris; Lammertsma, Koop

    2016-01-01

    The parent tris(pyrazolyl)phosphine and its 3,5-Me2, 3-Ph, and 3-t-Bu derivatives have been prepared by a simple procedure and show modest Lewis basicity of the phosphorus apex as was established by the magnitude of the (1)JP,Se coupling constant of the phosphine selenides. Because of the chelating

  13. Ion-molecule reactions of tritiated phenyl cations with organic amines and phosphines

    Energy Technology Data Exchange (ETDEWEB)

    Nefedov, V.D.; Toropova, M.A.; Shchepina, N.E. [St. Petersburg State Univ. (Russian Federation)] [and others

    1995-03-01

    Ion-molecule reactions of free multiply tritiated phenyl cations produced by a nuclear chemical method with organic amines and phosphines are studied. The product yields of the ion-molecule reactions of phenyl cations with arylalkylamines and -phosphines are determined by both the nature of the heteroatom and the organic radicals bonded to it.

  14. Effects of phosphine fumigation on survivorship of Epiphyas postvittana (Lepidoptera: Tortricidae) eggs.

    Science.gov (United States)

    Liu, Yong-Biao; Liu, Samuel S; Simmons, Gregory; Walse, Spencer S; Myers, Scott W

    2013-08-01

    Light brown apple moth, Epiphyas postvittana (Walker), eggs were subjected to phosphine fumigations under normal atmospheric and elevated oxygen levels in laboratory-scale chamber experiments to compare their susceptibilities to the two different fumigation methods. In fumigations conducted under atmospheric oxygen at 5 and 10 degrees C, egg survivorship decreased with increase in phosphine concentration but then increased at a concentration of 3,000 ppm; this increase was significant at 10 degrees C. Based on egg survivorship data, phosphine fumigations conducted in a 60% oxygen atmosphere were significantly more effective than those conducted under atmospheric oxygen conditions. Oxygenated phosphine fumigations at 5 and 10 degrees C killed all 1,998 and 2,213 E. postvittana eggs treated, respectively, after 72 h of exposure. These results indicate the great potential of oxygenated phosphine fumigation for the control of E. postvittana eggs.

  15. Complexation of diphenyl(phenylacetenyl)phosphine to rhodium(III) tetraphenyl porphyrins

    DEFF Research Database (Denmark)

    Stulz, Eugen; Scott, Sonya M; Bond, Andrew D

    2003-01-01

    ). The methylide on rhodium in 3 is not displaced, leading selectively to the mono-phosphine complex (DPAP)(Me)Rh(TPP) (5). The first and second association constants, as determined by isothermal titration calorimetry and UV-vis titrations, are in the range 10(4)-10(7) M(-1) (in CH(2)Cl(2)). Using LDI-TOF mass....... The largest values of DeltaG degrees are found for 6. The thermodynamic and UV-vis data reveal that the methylide and the phosphine ligand have an almost identical electronic trans-influence on the sixth ligand....... spectrometry, the mono-phosphine complexes can be detected but not the bis-phosphine complexes. The electronic spectrum of 4 is similar to those previously reported with other tertiary phosphine ligands, whereas (DPAP)(I)Rh(TPP) (6) displays a low energy B-band absorption and a high energy Q-band absorption...

  16. Mono- and bis-phosphine-ligated H93G myoglobin: spectral models for ferrous-phosphine and ferrous-CO cytochrome P450.

    Science.gov (United States)

    Sun, Shengfang; Sono, Masanori; Dawson, John H

    2013-10-01

    To further investigate the properties of phosphines as structural and functional probes of heme proteins, mono- and bis-phosphine [tris(hydroxymethyl)phosphine, THMP] adducts of H93G myoglobin (Mb) have been prepared by stepwise THMP titrations of exogenous ligand-free ferric and ferrous H93G Mb, respectively. Bubbling with CO or stepwise titration with imidazole (Im) of the bis-THMP-ligated ferrous protein generated a mixed ligand (THMP/CO or THMP/Im, respectively) ferrous complexes. Stable oxyferrous H93G(THMP) Mb was formed at -40°C by bubbling the mono-THMP-Fe(II) protein with O2. A THMP-ligated ferryl H93G Mb moiety has been partially formed upon addition of H2O2 to the ferric mono-THMP adduct. All the species prepared above have been characterized with UV-visible (UV-vis) absorption and magnetic circular dichroism (MCD) spectroscopy in this study. The six-coordinate ferrous bis-phosphine and mono-phosphine/CO complexes of H93G Mb exhibit characteristic spectral features (red-shifted Soret/unique-shaped MCD visible bands and hyperporphyrin spectra, respectively) that only have been seen for the analogous phosphine or CO-complexes of thiolate-ligated heme proteins such as cytochrome P450 (P450) and Caldariomyces fumago chloroperoxidase (CPO). However, such resemblance is not seen in phosphine-ligated ferric H93G Mb even though phosphine-bound ferric P450 and CPO display hyperporphyrin spectra. In fact, bis-THMP-bound ferric H93G Mb exhibits MCD and UV-vis absorption spectra that are similar to those of bis-amine- and bis-thioether-ligated H93G Mb complexes. This study also further demonstrates the utility of the H93G cavity mutant for preparing novel heme iron coordination structures. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Isocyanide and Phosphine Oxide Coordination in Binuclear Chromium Pacman Complexes.

    Science.gov (United States)

    Stevens, Charlotte J; Nichol, Gary S; Arnold, Polly L; Love, Jason B

    2013-12-01

    The new binuclear chromium Pacman complex [Cr2(L)] of the Schiff base pyrrole macrocycle H4L has been synthesized and structurally characterized. Addition of isocyanide, C≡NR (R = xylyl, (t)Bu), or triphenylphosphine oxide donors to [Cr2(L)] gives contrasting chemistry with the formation of the new coordination compounds [Cr2(μ-CNR)(L)], in which the isocyanides bridge the two Cr(II) centers, and [Cr2(OPPh3)2(L)], a Cr(II) phosphine oxide adduct with the ligands exogenous to the cleft.

  18. Phosphine on Jupiter and implications for the Great Red Spot

    Science.gov (United States)

    Prinn, R. G.; Lewis, J. S.

    1975-01-01

    A study of the chemistry and photochemistry of the recently discovered phosphine in the atmosphere of Jupiter suggests that the red colorations on this planet result from photochemical production of red phosphorus particles. Chemical-dynamical models of this red phosphorus haze imply that the intensity of the red coloration is a strong function of the strength of vertical turbulent mixing in the atmosphere. If the Jovian Great Red Spot is a region of considerable dynamical activity our model provides a self-consistent explanation for the redness of this region in comparison to the rest of the planet.

  19. Diphenyl[2-(2-pyridylaminomethylphenyl]phosphine oxide

    Directory of Open Access Journals (Sweden)

    Simón Hernández-Ortega

    2010-05-01

    Full Text Available The title compound, C24H21N2OP, was obtained by reacting 2-aminopyridine and 2-(diphenylphosphinylbenzaldehyde in ethanol. It crystallizes with two crystallographically independent molecules in the asymmetric unit. The aminopyridine units and the benzene ring bonded to the phosphine oxide P atom form dihedral angles of 88.58 (7 and 82.47 (9° in the two molecules. The crystal structure displays strong N—H...O and weak C—H...O hydrogen bonds along the b axis and C—H...π aromatic intra- and intermolecular interactions.

  20. Effects of phosphine fumigation on the quality of soybean seeds.

    OpenAIRE

    Krzyzanowski,Francisco Carlos; Lorini,Irineu; França-Neto,José de Barros; Henning,Ademir Assis

    2013-01-01

    Fumigation is a technique employed to eliminate insect pests in stored seeds by using gas. The aim of the experiment was to evaluate the effect of the gas phosphine on germination and on vigor (accelerated aging and seedling length) of soybean seeds. Soybean seeds of two cultivars with two vigor levels were used. Each treatment was replicated four times and each experimental unit consisted of two kilograms of seeds, which were placed in individual 1 m³ gas-tight capacity chambers with phosphi...

  1. Toxicity of phosphine to Carposina niponensis (Lepidoptera: Carposinadae) at low temperature.

    Science.gov (United States)

    Bo, Liu; Fanhua, Zhang; Yuejin, Wang

    2010-12-01

    Carposina niponensis Matsumura (Lepidoptera: Carposinadae), is widely distributed in pome fruit production areas in China and presents a problem in some export markets because it is considered a quarantine pest by some countries. Methyl bromide is the only fumigant used for fumigation of apples (Malus spp.) for export. However, phosphine is a candidate replacement that can be applied directly at low temperature. Here, laboratory tests showed that tolerance of different stages of C. niponensis to phosphine fumigation at 0 degrees C differed greatly; first-second-instar larvae were the least tolerant stage and the mature fifth instars were the most tolerant stage. In the mature larvae, fumigation tests, with a range of phosphine concentrations from 0.42 to 1.95 mg/liters and exposure periods of 24 h to 14 d at 0 degrees C indicated narcosis when phosphine concentration was > or = 1.67 mg/liter and that a 15.52-8.14-d fumigation period was required to achieve 99% mortality with different phosphine concentrations. The expression of C(0.7)T = k was obtained, which indicated that exposure time was much more important than concentration of phosphine in mortality of mature larvae of C. niponensis. All results suggested that phosphine fumigation at low temperature offers promising control of C. niponensis infestation in pome fruit.

  2. Occurrence of matrix-bound phosphine in intertidal sediments of the Yangtze Estuary.

    Science.gov (United States)

    Hou, L J; Chen, H; Yang, Y; Jiang, J M; Lin, X; Liu, M

    2009-08-01

    This study investigated the levels and potential transformation of matrix-bound phosphine in the intertidal sediments (0-5cm) of the Yangtze Estuary. Matrix-bound phosphine concentrations in sediments ranged from 0.65 to 3.25ngkg(-1), with an annual average of 1.53ngkg(-1). In freshwater sediments, the concentrations of matrix-bound phosphine were significantly higher than in the brackish sediments. The maximum concentrations of matrix-bound phosphine appeared in July (1.17-3.25ngkg(-1)), followed by May (0.92-3.01ngkg(-1)), November (0.65-2.41ngkg(-1)) and January (0.51-1.42ngkg(-1)). Matrix-bound phosphine derived probably from the mechanochemical reduction of apatite-bound phosphate and the microbial conversion of organic phosphorus in the intertidal sediments. Its spatial and seasonal distributions, however, were regulated by salinity and sediment temperature. Compared with other aquatic systems (e.g. rivers, lakes and coastal seas), a low level of matrix-bound phosphine was observed in the intertidal sediments, probably implicating a relatively rapid turnover of phosphine in the system.

  3. Effect of the phosphine steric and electronic profile on the Rh-promoted dehydrocoupling of phosphine-boranes.

    Science.gov (United States)

    Hooper, Thomas N; Huertos, Miguel A; Jurca, Titel; Pike, Sebastian D; Weller, Andrew S; Manners, Ian

    2014-04-07

    The electronic and steric effects in the stoichiometric dehydrocoupling of secondary and primary phosphine-boranes H3B·PR2H [R = 3,5-(CF3)2C6H3; p-(CF3)C6H4; p-(OMe)C6H4; adamantyl, Ad] and H3B·PCyH2 to form the metal-bound linear diboraphosphines H3B·PR2BH2·PR2H and H3B·PRHBH2·PRH2, respectively, are reported. Reaction of [Rh(L)(η(6)-FC6H5)][BAr(F)4] [L = Ph2P(CH2)3PPh2, Ar(F) = 3,5-(CF3)2C6H3] with 2 equiv of H3B·PR2H affords [Rh(L)(H)(σ,η-PR2BH3)(η(1)-H3B·PR2H)][BAr(F)4]. These complexes undergo dehydrocoupling to give the diboraphosphine complexes [Rh(L)(H)(σ,η(2)-PR2·BH2PR2·BH3)][BAr(F)4]. With electron-withdrawing groups on the phosphine-borane there is the parallel formation of the products of B-P cleavage, [Rh(L)(PR2H)2][BAr(F)4], while with electron-donating groups no parallel product is formed. For the bulky, electron rich, H3B·P(Ad)2H no dehydrocoupling is observed, but an intermediate Rh(I) σ phosphine-borane complex is formed, [Rh(L){η(2)-H3B·P(Ad)2H}][BAr(F)4], that undergoes B-P bond cleavage to give [Rh(L){η(1)-H3B·P(Ad)2H}{P(Ad)2H}][BAr(F)4]. The relative rates of dehydrocoupling of H3B·PR2H (R = aryl) show that increasingly electron-withdrawing substituents result in faster dehydrocoupling, but also suffer from the formation of the parallel product resulting from P-B bond cleavage. H3B·PCyH2 undergoes a similar dehydrocoupling process, and gives a mixture of stereoisomers of the resulting metal-bound diboraphosphine that arise from activation of the prochiral P-H bonds, with one stereoisomer favored. This diastereomeric mixture may also be biased by use of a chiral phosphine ligand. The selectivity and efficiencies of resulting catalytic dehydrocoupling processes are also briefly discussed.

  4. Oxygenated phosphine fumigation for control of Epiphyas postvittana (Lepidoptera: Tortricidae) eggs on lettuce.

    Science.gov (United States)

    Liu, Samuel S; Liu, Yong-Biao; Simmons, Gregory S

    2014-08-01

    Light brown apple moth, Epiphyas postvittana (Walker), is a quarantined pest in most countries. Its establishment in California and potential spread to other parts of the state and beyond make it urgent to develop effective postharvest treatments to control the pest on fresh commodities. Fumigation with cylindered phosphine at low temperature has emerged to be a practical methyl bromide alternative treatment for postharvest pest control on fresh commodities. However, its use to control E. postvittana eggs on sensitive commodities such as lettuce is problematic. E. postvittana eggs are tolerant of phosphine and long phosphine treatment also injures lettuce. In the current study, E. postvittana eggs were subjected to oxygenated phosphine fumigations to develop an effective treatment at a low storage temperature of 2 degrees C. In addition, soda lime as a CO2 absorbent was tested to determine its effects in reducing and preventing injuries to lettuce associated with phosphine fumigations. Three-day fumigation with 1,000 ppm phosphine under 60% O2 achieved 100% mortality of E. postvittana eggs in small-scale laboratory tests. In the presence of the CO2 absorbent, a 3-d large-scale fumigation of lettuce with 1,700 ppm phosphine under 60% O2 resulted in a relative egg mortality of 99.96% without any negative effect on lettuce quality. The 3-d fumigation treatment without the CO2 absorbent, however, resulted in significant injuries to lettuce and consequential quality reductions. The study demonstrated that oxygenated phosphine fumigation has the potential to control E. postvittana eggs and the CO2 absorbent has the potential to prevent injuries and quality reductions of lettuce associated with long-term oxygenated phosphine fumigation.

  5. Phosphine-free synthesis of CdSe quantum dots in a new co-capping ligand system.

    Science.gov (United States)

    Wang, Chun; Jiang, Yang; Zhang, Zhongping; Li, Guohua; Chen, Lanlan; Jie, Jiansheng

    2009-08-01

    High-quality CdSe quantum dots with zinc blende structure were successfully synthesized via a new cheaper, greener phosphine-free route, using environmentally friendly N,N-dimethyl-oleoyl amide as the solvent of Se. The process eliminates trioctylphoshine from the synthesis, using oleic acid (OA) as a primary capping ligand and benzophenone (BP) as a secondary ligand in the noncoordinating solvent. It has been found that the addition of BP can improve the size distribution (below 10%) of as-synthesized CdSe quantum dots greatly, and the nucleation and growth process can also be well-separated. Moreover, a comprehensive examination on the control of particle size and size distribution was performed by systematically varying the BP/OA molar ratio. The phosphine-free route enables us to obtain high-quality CdSe quantum dots with sharp UV-vis absorption peak, size ranging from 2.8 to 6.8 nm, and narrow full width of half-maximum between 27 and 35 nm with purely band-edge luminescence, and without any post-synthesis processing.

  6. Selective Hydrogenation of Avermectin Catalyzed by Iridium-Phosphine Complexes

    Institute of Scientific and Technical Information of China (English)

    MA, Xiao-Yan; WANG, Kun; ZHANG, Lei; LI, Xian-Jun; LI, Rui-Xiang

    2007-01-01

    A series of new iridium complexes, IrCl(COD)(TMOPP) (1) [COD=1,5-cyclooctadiene, TMOPP=tris(4-methoxyphenyl)phosphine], IrCl(COD)(TFMPP) (2) [TFMPP = tris(4-trifluoromethylphenyl)phosphine], IrCl-(COD)(BDNA) (3) [BDNA=1,8-bis(diphenylphosphinomethyl)naphthalene], IrCl(COD)(BISBI) (4) [BISBI=2,2'-bis(diphenylphosphinomethyl)biphenyl] and IrCl(COD)(BDPB) (5) [BDPB = 1,2-bis(diphenylphosphinomethyl)benzene], were synthesized and characterized by NMR spectra and elemental analyses. In order to obtain the relationships between complex structures and their catalytic properties, IrCl(COD)(DPPM) (6) [DPPM=bis(diphenylphosphino)methane], IrCl(COD)(DPPE) (7) [DPPE= 1,2-bis(diphenylphosphino)ethane], IrCl(COD)-(DPPP) (8) [DPPP=1,3-bis(diphenylphosphino)propane] and IrCl(COD)(TPP) (9) [TPP=triphenylphosphine],were also synthesized according to the reported methods. The hydrogenation results showed that the low electronic density at the central metal was favorable to increase the catalytic activity for the hydrogenation of avermectin, but decrease the selectivity to ivermectin. The complex with a large chelating ring and a bulky chelating backbone would easily cause the cleavage of C-O bond in avermectin to give a byproduct avermectin aglycon.

  7. Do phosphine resistance genes influence movement and dispersal under starvation?

    Science.gov (United States)

    Kaur, Ramandeep; Ebert, Paul R; Walter, Gimme H; Swain, Anthony J; Schlipalius, David I

    2013-10-01

    Phosphine resistance alleles might be expected to negatively affect energy demanding activities such as walking and flying, because of the inverse relationship between phosphine resistance and respiration. We used an activity monitoring system to quantify walking of Rhyzopertha dominica (F.) and a flight chamber to estimate their propensity for flight initiation. No significant difference in the duration of walking was observed between the strongly resistant, weakly resistant, and susceptible strains of R. dominica we tested, and females walked significantly more than males regardless of genotype. The walking activity monitor revealed no pattern of movement across the day and no particular time of peak activity despite reports of peak activity of R. dominica and Tribolium castaneum (Herbst) under field conditions during dawn and dusk. Flight initiation was significantly higher for all strains at 28 degrees C and 55% relative humidity than at 25, 30, 32, and 35 degrees C in the first 24 h of placing beetles in the flight chamber. Food deprivation and genotype had no significant effect on flight initiation. Our results suggest that known resistance alleles in R. dominica do not affect insect mobility and should therefore not inhibit the dispersal of resistant insects in the field.

  8. Preparation of New Chiral Ferroceny Phosphine Ligands and Their Application to Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    S.Fukuzawa

    2007-01-01

    1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 pr...

  9. A novel approach to limit the development of phosphine resistance in Western Australia

    OpenAIRE

    2010-01-01

    Escalating development of resistance to phosphine is of concern to grain storage operators world wide. In Western Australia 85% of grain produced is exported with a guarantee through legislation that it is free of all grain insects. Phosphine plays a vital part in shore-based fumigations to achieve this insectfree status but it is also available for unrestricted use by growers for grain stored on farms. For more than 20 years a campaign has been in place to encourage better use of phosphine. ...

  10. Mitochondrial uncouplers act synergistically with the fumigant phosphine to disrupt mitochondrial membrane potential and cause cell death.

    Science.gov (United States)

    Valmas, Nicholas; Zuryn, Steven; Ebert, Paul R

    2008-10-30

    Phosphine is the most widely used fumigant for the protection of stored commodities against insect pests, especially food products such as grain. However, pest insects are developing resistance to phosphine and thereby threatening its future use. As phosphine inhibits cytochrome c oxidase (complex IV) of the mitochondrial respiratory chain and reduces the strength of the mitochondrial membrane potential (DeltaPsi(m)), we reasoned that mitochondrial uncouplers should act synergistically with phosphine. The mitochondrial uncouplers FCCP and PCP caused complete mortality in populations of both wild-type and phosphine-resistant lines of Caenorhabditis elegans simultaneously exposed to uncoupler and phosphine at concentrations that were individually nonlethal. Strong synergism was also observed with a third uncoupler DNP. We have also tested an alternative complex IV inhibitor, azide, with FCCP and found that this also caused a synergistic enhancement of toxicity in C. elegans. To investigate potential causes of the synergism, we measured DeltaPsi(m), ATP content, and oxidative damage (lipid hydroperoxides) in nematodes subjected to phosphine-FCCP treatment and found that neither an observed 50% depletion in ATP nor oxidative stress accounted for the synergistic effect. Instead, a synergistic reduction in DeltaPsi(m) was observed upon phosphine-FCCP co-treatment suggesting that this is directly responsible for the subsequent mortality. These results support the hypothesis that phosphine-induced mortality results from the in vivo disruption of normal mitochondrial activity. Furthermore, we have identified a novel pathway that can be targeted to overcome genetic resistance to phosphine.

  11. Pd complexes based on phosphine-linked cyclophosphazenes: synthesis, characterization and application in Suzuki coupling reactions

    Energy Technology Data Exchange (ETDEWEB)

    Paula, Vanderlei I. de; Sato, Cintia A.; Buffon, Regina, E-mail: rbuffon@iqm.unicamp.br [Instituto de Quimica, Universidade Estadual de Campinas (IQ/UNICAMP), SP (Brazil)

    2012-07-01

    Palladium complexes were obtained by reaction of phosphine-linked cyclophosphazenes, (P{sub 3}N{sub 3})(O-C{sub 6}H{sub 4}-PR{sub 2}){sub 6}, where R = phenyl, i-propyl or cyclohexyl, with using a Pd/ligand molar ratio of 3/1. The (P{sub 3}N{sub 3})(O-C{sub 6}H{sub 4}-PR{sub 2}){sub 6} Pd{sub 3}(dba)x complexes were characterized by elemental analyses, mass spectrometry, {sup 31}P NMR and FT-IR where a characteristic {nu}{sub C}={sub C} band of dba coordinated to palladium was always observed. All complexes were tested in Suzuki coupling reactions between phenylboronic acid and aryl halides. Turnover numbers as high as ca. 17,500 for the coupling of 2-bromotoluene with chloro phenylboronic acid could be obtained for R = cyclohexyl. The complex based on -PPh{sub 2} was also immobilized in silica matrixes by the sol-gel method. Preliminary experiments showed that the immobilized catalyst could be used in at least three consecutive Suzuki reactions with the same catalytic activity. (author)

  12. Effects of phosphine fumigation on survivorship of Epiphyas postvittana (Lepidoptera: Tortricidae) eggs

    Science.gov (United States)

    Light brown apple moth (LBAM), Epiphyas postvittana (Walker), eggs were subjected to regular and oxygenated phosphine fumigations at different temperatures to compare their susceptibilities to the two different fumigation methods and determine effective treatments in laboratory tests. LBAM eggs wer...

  13. Nucleophilic phosphine organocatalysis: a practical synthetic strategy for the drug-like nitrogen heterocyclic framework construction.

    Science.gov (United States)

    Wang, Yurong; Pan, Jingjing; Chen, Zhidong; Sun, Xiaoqiang; Wang, Zhiming

    2013-05-01

    Nucleophilic phosphine catalysis has proven to be a practical and powerful synthetic strategy in organic chemistry, which can provide easy access to five-, six-, seven-, and eight-membered nitrogen heterocyclic compounds. The reaction topologies can be controlled by a proper choice of the phosphine catalysts, as well as the functionalization of the reaction substrates. In many cases, the reactions take place smoothly at room temperature, with high efficiency and atom economy. This mini-review presents the recent advances in nucleophilic phosphine catalysis for the synthesis of drug-like nitrogen heterocylic compounds. The nitrogen heterocyclic compounds with significant biological activities derived from the library based on nucleophilic phosphine-catalyzed annulation reactions are also highlighted.

  14. Hydroxymethyl phosphine compounds for use as diagnostic and therapeutic pharmaceuticals and method of making same

    Science.gov (United States)

    Katti, Kattesh V.; Karra, Srinivasa Rao; Berning, Douglas E.; Smith, C. Jeffrey; Volkert, Wynn A.; Ketring, Alan R.

    1999-01-01

    A compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical comprises at least one functionalized hydroxyalkyl phosphine donor group and one or more sulfur or nitrogen donor and a metal combined with the ligand.

  15. A New Class of Atomically Precise, Hydride-Rich Silver Nanoclusters Co-Protected by Phosphines

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2016-10-10

    Thiols and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters (NCs). Here, we used simple hydrides (e.g., H–) as ligands along with phosphines, such as triphenylphosphine (TPP), 1,2-bis(diphenylphosphino)ethane [DPPE], and tris(4-fluorophenyl)phosphine [TFPP] to design and synthesize a new class of hydride-rich silver NCs. This class includes [Ag18H16(TPP)10]2+, [Ag25H22(DPPE)8]3+, and [Ag26H22(TFPP)13]2+. Our work reveals a new family of atomically precise NCs protected by H– ligands and labile phosphines, with potentially more accessible active metal sites for functionalization and provides a new set of stable NC sizes with simpler ligand–metal bonding for researchers to explore both experimentally and computationally.

  16. Bis(phosphine)boronium salts. Synthesis, structures and coordination chemistry.

    Science.gov (United States)

    Shuttleworth, Timothy A; Huertos, Miguel A; Pernik, Indrek; Young, Rowan D; Weller, Andrew S

    2013-09-28

    The synthesis of a range of bis(phosphine)boronium salts is reported [(R2HP)2BH2][X] (R = Ph, (t)Bu, Cy) in which the counter anion is also varied (X(-) = Br(-), [OTf](-), [BAr(F)4](-), Ar(F) = 3,5-(CF3)2C6H3). Characterization in the solid-state by X-ray diffraction suggests there are weak hydrogen bonds between the PH units of the boronium cation and the anion (X(-) = Br(-), [OTf](-)), while solution NMR spectroscopy also reveals hydrogen bonding occurs in the order [BAr(F)4](-) < [OTf](-) < Br(-). [(Ph2HP)2BH2][BAr(F)4] reacts with RhH(PPh3)3, by elimination of H2, forming [Rh(κ(1),η-PPh2BH2·PPh2H)(PPh3)2][BAr(F)4] which shows a β-B-agostic interaction from the resulting base stabilised phosphino-borane ligand. Alternatively such ligands can be assembled directly on the metal centre by reaction of in situ generated {Rh(PPh3)3}(+) and Ph2HP·BH3 to afford [Rh(κ(1),η-PPh2BH2·PPh3)(PPh3)2][BAr(F)4], which was characterised by X-ray crystallography. Addition of H3B·PPh2H to the well-defined 16-electron "T-shaped" complex [Rh(P(i)Bu3)2(PPh3)][BAr(F)4] (characterised by X-ray crystallography) formed of a mixture of base-stabilised phosphino borane ligated complexes [Rh(κ(1),η-PR2BH2·PR3)(PR3)2][BAr(F)4] (R = (i)Bu or Ph). These last observations may lend clues to the formation of bis(phosphine)boronium salts in the catalytic dehydrocoupling reaction of phosphine boranes as mediated by Rh(I) compounds.

  17. Sources of matrix-bound phosphine in advanced wastewater treatment system

    Institute of Scientific and Technical Information of China (English)

    DING Lili; LIANG Hanwen; ZHU Yixin; MO Weiheng; WANG Qiang; REN Hongqiang; WANG Xiaorong; M.Edwards; D.Glindemann

    2005-01-01

    @@ Phosphine (PH3), a highly toxic and reductive gas, has been explored in biogases[1,2] and it proves also to be ubiquitous even in remote atmospheric air at a concentration in the order of (pg--ng) /m3 [3]. For more than one hundred years, sources and mechanisms of biological phosphine formation in natural and engineered environments have been investigated and discussed[4].

  18. Phosphine resistance, respiration rate and fitness consequences in stored-product insects.

    Science.gov (United States)

    Pimentel, Marco Aurélio G; Faroni, Lêda Rita D'A; Tótola, Marcos R; Guedes, Raul Narciso C

    2007-09-01

    Resistance to fumigants has been frequently reported in insect pests of stored products and is one of the obstacles in controlling these pests. The authors studied phosphine resistance and its physiological basis in adult insects of 12 populations of Tribolium castaneum (Herbst) (Tenebrionidae), ten populations of Rhyzopertha dominica (F.) (Bostrichidae) and eight populations of Oryzaephilus surinamensis L. (Silvanidae) from Brazil, and the possible existence of fitness costs associated with phosphine resistance in the absence of this fumigant. The bioassays for the detection of phosphine resistance followed the FAO standard method. The production of carbon dioxide and the instantaneous rate of population increase (r(i)) of each population of each species were correlated with their resistance ratios at the LC(50). The resistance ratio at LC(50) in T. castaneum ranged from 1.0- to 186.2-fold, in R. dominica from 2.0- to 71.0-fold and in O. surinamensis from 1.9- to 32.2-fold. Ten populations of T. castaneum, nine populations of R. dominica and seven populations of O. surinamensis were resistant to phosphine. In all three species there was significant association (P phosphine resistance. The populations with lower carbon dioxide production showed a higher resistance ratio, suggesting that the lower respiration rate is the physiological basis of phosphine resistance by reducing the fumigant uptake in the resistant insects. Conversely, populations with higher r(i) showed lower resistance ratios, which could indicate a lower rate of reproduction of the resistant populations compared with susceptible populations. Thus, management strategies based on the interruption of phosphine fumigation may result in reestablishment of susceptibility, and shows good potential for more effective management of phosphine-resistant populations.

  19. Stereoselective Synthesis of Highly Functionalized 2,3-Dihydro-4-pyranones Using Phosphine Oxide as Catalyst.

    Science.gov (United States)

    Kotani, Shunsuke; Miyazaki, Shiki; Kawahara, Kazuya; Shimoda, Yasushi; Sugiura, Masaharu; Nakajima, Makoto

    2016-01-01

    2,3-Dihydro-4-pyranones were synthesized stereoselectively using a chiral phosphine oxide as the catalyst. The phosphine oxide sequentially activated silicon tetrachloride and promoted the double aldol reaction of 4-methoxy-3-buten-2-one with aldehydes. Subsequent stereoselective cyclization afforded the corresponding highly functionalized 2,3-dihydro-4-pyranones bearing three contiguous chiral centers in good yields and with high diastereo- and enantioselectivities.

  20. Rationale behind the resistance of dialkylbiaryl phosphines toward oxidation by molecular oxygen.

    Science.gov (United States)

    Barder, Timothy E; Buchwald, Stephen L

    2007-04-25

    Electron-rich dialkylbiaryl phosphines, which comprise a common class of supporting ligands for Pd-catalyzed cross-coupling reactions, are highly resistant toward oxidation by molecular oxygen. Presented herein are possible reasons why this class of phosphine ligands manifests this property. Experimental and theoretical data suggest that the two alkyl substituents on the phosphorus center and the 2' and 6' positions of the biaryl backbone play an important role in inhibiting oxidation of this class of ligands.

  1. Life stage and resistance effects in modelling phosphine fumigation of Rhyzopertha dominica (F.)

    OpenAIRE

    Thorne, J.; Fulford, G.; Ridley, A.; Schlipalius, D.; P. Collins

    2010-01-01

    Resistance to phosphine in insect pests of stored grain is a serious problem and there is a world-wide need for the development of sustainable resistance management strategies. Here we introduce results from a new mathematical model of resistance development that includes all life stages, rates of oviposition, natural mortality and mortality under fumigation in relation to resistant genotype. The example we discuss is phosphine resistance in the lesser grain borer, Rhyzopertha dominica where ...

  2. Effect of Low-Temperature Phosphine Fumigation on the Survival of Bactrocera correcta (Diptera: Tephritidae).

    Science.gov (United States)

    Liu, Tao; Li, Li; Zhang, Fanhua; Gong, Shaorun; Li, Tianxiu; Zhan, Guoping; Wang, Yuejin

    2015-08-01

    This laboratory-based study examined the effects of low-temperature phosphine fumigation on the survival of the eggs and larvae of the guava fruit fly, Bactrocera correcta (Bezzi). Individual flies at different developmental stages, from 6-h-old eggs to third instars, were exposed to 0.92 mg/liter phosphine for 1-7 d at 5°C. We found that 12-h-old eggs and third instars were the most tolerant to phosphine. Increasing phosphine concentrations from 0.46 to 4.56 mg/liter increased mortality in these two stages. However, increased exposure times were required to achieve equal mortality rates in 12-h-old eggs and third instars when phosphine concentrations were ≥4.56 and ≥3.65 mg/liter, respectively. C(n)t = k expression was obtained at 50, 90, and 99% mortality levels, and the toxicity index (n) ranged from 0.43 to 0.77 for the two stages. The synergistic effects of a controlled atmosphere (CA) with elevated CO(2) levels were also investigated, and we found that a CO(2) concentration between 10% and 15% under CA conditions was optimal for low-temperature phosphine fumigation.

  3. Matrix-bound phosphine in Ny-(A)lesund Area of Arctic

    Institute of Scientific and Technical Information of China (English)

    Feng Ying; Wang Qiang; Yao Ziwei; Geng Jinju

    2009-01-01

    Phosphine, a ubiquitous trace gas in the atmosphere, acts as a carrier of gasous phosphorus in the biogeochemical cycle. The research of phosphine will show new light on the mechanisms of how the phosphorus supplement influence the biogeochemical cycle and global warming. In this paper, we detect the phosphine in Arctic Pole area for the first time. The result shows that matrix-bound phosphine(MBP) exists in all the samplings. Phosphine distributions varied with different environmental origins. Average phosphine concentrations in tundra soil, lake sediments, sea sediments, seabird-droppings and deer guanos were 14.17ng/kg dry, 35.44 kg dry, 67.20 kg dry, 32.9 ng/kg dry, and 25.52 ng/kg dry respectively. Correlation analysis shows that there is an obviously positive correlation between Porg and MBP. It could be concluded that anaerobic decomposition of Porg and the mechano-chemistry action of the rock probably are the possible reasons explaining the mechanism of MBP production in Arctic Pole area.

  4. A Computed Room Temperature Line List for Phosphine

    CERN Document Server

    Sousa-Silva, Clara; Tennyson, Jonathan

    2013-01-01

    An accurate and comprehensive room temperature rotation-vibration transition line list for phosphine (31PH3) is computed using a newly refined potential energy surface and a previously constructed ab initio electric dipole moment surface. Energy levels, Einstein A coefficients and transition intensities are computed using these surfaces and a variational approach to the nuclear motion problem as implemented in the program TROVE. A ro-vibrational spectrum is computed, covering the wavenumber range 0 to 8000 cm-1. The resulting line list, which is appropriate for temperatures up to 300 K, consists of a total of 137 million transitions between 5.6 million energy levels. Several of the band centres are shifted to better match experimental transition frequencies. The line list is compared to the most recent HITRAN database and other laboratorial sources. Transition wavelengths and intensities are generally found to be in good agreement with the existing experimental data, with particularly close agreement for the ...

  5. Reaction paths of phosphine dissociation on silicon (001)

    Science.gov (United States)

    Warschkow, O.; Curson, N. J.; Schofield, S. R.; Marks, N. A.; Wilson, H. F.; Radny, M. W.; Smith, P. V.; Reusch, T. C. G.; McKenzie, D. R.; Simmons, M. Y.

    2016-01-01

    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  6. Reaction paths of phosphine dissociation on silicon (001)

    Energy Technology Data Exchange (ETDEWEB)

    Warschkow, O.; McKenzie, D. R. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Curson, N. J. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia); London Centre for Nanotechnology and Department of Electronic and Electrical Engineering, University College London, 17-19 Gordon Street, London WC1H 0AH (United Kingdom); Schofield, S. R. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia); London Centre for Nanotechnology and Department of Physics and Astronomy, University College, 17-19 Gordon Street, London WC1H 0AH (United Kingdom); Marks, N. A. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Discipline of Physics & Astronomy, Curtin University, GPO Box U1987, Perth, WA (Australia); Wilson, H. F. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); CSIRO Virtual Nanoscience Laboratory, Parkville, VIC 3052 (Australia); School of Applied Sciences, RMIT University, Melbourne, VIC 3000 (Australia); Radny, M. W.; Smith, P. V. [School of Mathematical and Physical Sciences, The University of Newcastle, Callaghan, NSW 2308 (Australia); Reusch, T. C. G.; Simmons, M. Y. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia)

    2016-01-07

    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH{sub 3}) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH{sub 2}+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH{sub 2} fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH{sub 3} stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  7. Cu-catalyzed arylation of phosphinic amide facilitated by (±)-trans-cyclohexane-1,2-diamine

    Institute of Scientific and Technical Information of China (English)

    Juan Li; Song Lin Zhang; Chuan Zhou Tao; Yao Fu; Qing Xiang Guo

    2007-01-01

    Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-transcyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10times in Cu-catalyzed cross coupling.

  8. Synthesis and Thermal Rearrangement of Tetramethyldisilane-bridged Bis(cyclopentadienyl) Diiron Complexes with Bis(phosphine)Substitution

    Institute of Scientific and Technical Information of China (English)

    孙秀丽; 王佰全; 等

    2003-01-01

    Photolysis of [Me2SiSiMe2)[C5H4Fe(CO2)]2with a series of bis(phosphine)ligands Ph2P(CH2)n PPh2(n=1-4) leads to the formation of the corresponding diiron complexes with intramolecular and intermolecular bis(phosphine) substitution.When these complexes were heated in refluxing xylene.only in the complexes with intermolecular bis(phosphine )substitution the thermal rearrangement reaction occurred.

  9. Distinction between coordination and phosphine ligand oxidation: interactions of di- and triphosphines with Pn(3+) (Pn = P, As, Sb, Bi).

    Science.gov (United States)

    Chitnis, Saurabh S; Vos, Kevin A; Burford, Neil; McDonald, Robert; Ferguson, Michael J

    2016-01-14

    Reactions of polydentate phosphines with sources of Pn(3+) (Pn = P, As, Sb, Bi) yield complexes of Pn(1+) (Pn = P, As) or Pn(3+) (Pn = Sb, Bi) acceptors. The distinction between coordination of a phosphine center to Pn and oxidation of a phosphine ligand is dependent on Pn. The first structurally verified triphosphine complexes of Sb(III) and Bi(III) acceptors are reported.

  10. Phosphine-initiated cation exchange for precisely tailoring composition and properties of semiconductor nanostructures: old concept, new applications.

    Science.gov (United States)

    Gui, Jing; Ji, Muwei; Liu, Jiajia; Xu, Meng; Zhang, Jiatao; Zhu, Hesun

    2015-03-16

    Phosphine-initiated cation exchange is a well-known inorganic chemistry reaction. In this work, different phosphines have been used to modulate the thermodynamic and kinetic parameters of the cation exchange reaction to synthesize complex semiconductor nanostructures. Besides preserving the original shape and size, phosphine-initiated cation exchange reactions show potential to precisely tune the crystallinity and composition of metal/semiconductor core-shell and doped nanocrystals. Furthermore, systematic studies on different phosphines and on the elementary reaction mechanisms have been performed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Characterization of secondary phosphine oxide ligands on the surface of iridium nanoparticles.

    Science.gov (United States)

    Cano, Israel; Martínez-Prieto, Luis M; Fazzini, Pier F; Coppel, Yannick; Chaudret, Bruno; van Leeuwen, Piet W N M

    2017-08-16

    The synthesis of iridium nanoparticles (IrNPs) ligated by various secondary phosphine oxides (SPOs) is described. This highly reproducible and simple method via H2 reduction produces well dispersed, small nanoparticles (NPs), which were characterized by the state-of-the-art techniques, such as TEM, HRTEM, WAXS and ATR FT-IR spectroscopy. In particular, multinuclear solid state MAS-NMR spectroscopy with and without cross polarization (CP) enabled us to investigate the different binding modes adopted by the ligand at the nanoparticle surface, suggesting the presence of three possible types of coordination: as a purely anionic ligand Ir-P(O)R2, as a neutral acid R2P-O-H and as a monoanionic bidentate H-bonded dimer R2P-O-HO[double bond, length as m-dash]PR2. Specifically, the higher basicity of the dicyclohexyl system leads to the formation of IrNPs in which the bidentate binding mode is most abundant. Such cyclohexyl groups are bent towards the edges, as is suggested by the study of (13)CO coordination on the NP surface. This study also showed that the number of surface sites on faces available for bridging CO molecules is higher than the number of sites for terminal CO species on edges and apices, which is unexpected taking into account the small size of the nanoparticles. In addition, the IrNPs present a high chemoselectivity in the hydrogenation of cinnamaldehyde to the unsaturated alcohol.

  12. Synthesis of hybrid transition-metalloproteins via thiol-selective covalent anchoring of Rh-phosphine and Ru-phenanthroline complexes.

    Science.gov (United States)

    den Heeten, René; Muñoz, Bianca K; Popa, Gina; Laan, Wouter; Kamer, Paul C J

    2010-09-28

    The preparation of hybrid transition metalloproteins by thiol-selective incorporation of organometallic rhodium- and ruthenium complexes is described. Phosphine ligands and two rhodium-diphosphine complexes bearing a carboxylic acid group were coupled to the cysteine of PYP R52G, yielding a metalloenzyme active in the rhodium catalyzed hydrogenation of dimethyl itaconate. The successful coupling was shown by (31)P NMR spectroscopy and ESI mass spectroscopy. In addition wild-type PYP (PYP WT), PYP R52G and ALBP were successfully modified with a (eta(6)-arene) ruthenium(II) phenanthroline complex via a maleimide linker.

  13. Detection and characterisation of strong resistance to phosphine in Brazilian Rhyzopertha dominica (F.) (Coleoptera: Bostrychidae).

    Science.gov (United States)

    Lorini, Irineu; Collins, Patrick J; Daglish, Gregory J; Nayak, Manoj K; Pavic, Hervoika

    2007-04-01

    As failure to control Rhyzopertha dominica (F.) with phosphine is a common problem in the grain-growing regions of Brazil, a study was undertaken to investigate the frequency, distribution and strength of phosphine resistance in R. dominica in Brazil. Nineteen samples of R. dominica were collected between 1991 and 2003 from central storages where phosphine fumigation had failed to control this species. Insects were cultured without selection until testing in 2005. Each sample was tested for resistance to phosphine on the basis of the response of adults to discriminating concentrations of phosphine (20 and 48 h exposures) and full dose-response assays (48 h exposure). Responses of the Brazilian R. dominica samples were compared with reference susceptible, weak-resistance and strong-resistance strains from Australia in parallel assays. All Brazilian population samples showed resistance to phosphine: five were diagnosed with weak resistance and 14 with strong resistance. Five samples showed levels of resistance similar to the reference strong-resistance strain. A representative highly resistant sample was characterised by exposing mixed-age cultures to a range of constant concentrations of phosphine for various exposure periods. Time to population extinction (TPE) and time to 99.9% suppression of population (LT(99.9)) values of this sample were generally similar to those of the reference strong-resistance strain. For example, at 0.1, 0.5 and 1.0 mg L(-1), LT(99.9) values for BR33 and the reference strong-resistance strain were respectively 21, 6.4 and 3.7 days and 17, 6.2 and 3.8 days. With both strains, doubling phosphine concentrations to 2 mg L(-1) resulted in increased LT(99.9) and TPE. High level and frequency of resistance in all population samples, some of which had been cultured without selection for up to 12 years, suggest little or no fitness deficit associated with phosphine resistance. The present research indicates that widespread phosphine resistance may

  14. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.;

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...

  15. Performance of phosphine in fumigation of bagged paddy rice in indoor and outdoor stores.

    Science.gov (United States)

    Rajendran, S; Muralidharan, N

    2001-10-01

    Phosphine fumigation trials were carried out on bag-stacks of paddy rice to study the differences in gas loss rates and concentration-time (Ct) products achieved during the treatment of indoor and outdoor stacks. Stacks (89-132t) were fumigated singly under 250&mgr;m thick polyethylene sheeting, which was sealed with a double layer of sand-snakes to the concrete floor. Phosphine was applied as an aluminium phosphide formulation and the fumigations continued for 7 days. In the first experiment, stacks of paddy rice with moisture contents ranging from 12.2 to 13.7% were held in either indoor or in outdoor storage and subjected to fumigation at the rate of 2, 3 or 4g of phosphine/tonne. The outdoor stacks held relatively low levels of phosphine with Ct products for the indoor stacks of 135, 171 and 294gh/m(3), respectively, whilst the corresponding values for the outdoor stacks were 70, 85 and 166gh/m(3) only. The average gas loss rate was 14.5% per day for the indoor stacks and 29.5% for the outdoor stacks. In the second experiment, old stacks of paddy rice inside a godown, one each with grains at 8.8 and 9.8% moisture content, were fumigated at 3g phosphine/tonne. Release of phosphine was delayed and fumigant sorption was less and therefore higher Ct products of 204 and 216gh/m(3) were achieved. In the stacks built outdoors, the resident infestations of Rhyzopertha dominica, Cryptolestes sp. and Oryzaephilus surinamensis were completely controlled despite lower Ct products. On the other hand, in the stacks of old paddy, R. dominica survived the treatment. Subsequent testing showed that the population had a degree of resistance to phosphine.

  16. Synthèse de mono et diphosphines dérivées d'amino acides ou de peptides, appliquées en chimie de coordination et pour le greffage de fullerène C60

    OpenAIRE

    Minois, Pauline,

    2013-01-01

    The synthesis of secondary phosphine borane amino acids or dipeptides and their applications for the preparation of chiral ligands or for the grafting of fullerene, is described. These compounds were synthesized in good yield (up to 98%) without racemization. The principle of the synthesis is based on the alkylation of primary phosphine borane with a γ-iodo amino acid using phase transfer conditions. Tertiary diphosphine amino acids are obtained with 70% yield after a second alkylation. These...

  17. Phosphine fumigation and residues in dry-cured ham in commercial applications.

    Science.gov (United States)

    Zhao, Y; Abbar, S; Phillips, T W; Schilling, M W

    2015-09-01

    Dry-cured hams often become infested with ham mites (Tyrophagus putrescentiae) during the aging process. Methyl bromide has been used to fumigate dry cured ham plants and is the only available fumigant that is effective at controlling ham mite infestations. However, methyl bromide will eventually be phased out of all industries. This research was designed to determine the efficacy of phosphine fumigation at controlling ham mites and red-legged beetles and any impact of phosphine fumigation on the sensory quality and safety of dry cured hams. Fumigation trials were conducted in simulated ham aging houses and commercial ham aging houses. Mite postembryonic mortality was 99.8% in the simulated aging houses and >99.9% in commercial aging houses three weeks post fumigation. Sensory tests with trained panelists indicated that there were no detectable differences (P > 0.05) between phosphine fumigated and control hams. In addition, residual phosphine concentration was below the legal limit of 0.01 ppm in ham slices that were taken from phosphine fumigated hams.

  18. [PH3 residues in hazelnuts, soybeans and wheat following phosphine fumigation with non-constant concentrations].

    Science.gov (United States)

    Noack, S; Wohlgemuth, R

    1985-02-01

    In model tests hazelnuts, soy beans and wheat were fumigated with phosphine (PH3) at non constant concentrations. The influence of different concentration characteristics on the fumigation and the decomposition of phosphine residues was investigated in accordance with the fumigation technique. At the beginning the concentration increases, and after attaining the maximum gradually decreases to zero. The level of residues during the fumigation as well as the behaviour of residues during the storage of the fumigated products was monitored with a gas chromatographic method. The residues correlate with the concentration of phosphine, they also pass through a peak. The rate of decomposition of residues which had been formed in the phase of increasing concentration is greater than the rate of residues of equal magnitude which had been formed during the decreasing phase. When the concentration is even the maximum residue occurs later than the maximum concentration; when there is a steep trend both maximums coincide. This behaviour can be explained by the sorption and diffusion of phosphine. A comparison is made with the phosphine concentration which occurs during fumigation in practice. The parameters which produce a constant concentration trend with only one maximum and a non constant trend with an often increasing and decreasing concentration are discussed. The different behaviour of residues in these cases is described. Conclusions are drawn for the practice of fumigation.

  19. Henry's Law constant for phosphine in seawater: determination and assessment of influencing factors

    Institute of Scientific and Technical Information of China (English)

    FU Mei; YU Zhiming; LU Guangyuan; SONG Xiuxian

    2013-01-01

    The Henry's Law constant (k) for phosphine in seawater was determined by multiple phase equilibration combined with headspace gas chromatography.The effects of pH,temperature,and salinity on k were studied.The k value for phosphine in natural seawater was 6.415 at room temperature (approximately 23℃).This value increases with increases in temperature and salinity,but no obvious change was observed at different pH levels.At the same temperature,there was no significant difference between the k for phosphine in natural seawater and that in artificial seawater.This implies that temperature and salinity are major determining factors for k in marine environment.Double linear regression with Henry's Law constants for phosphine as a function of temperature and salinity confirmed our observations.These results provide a basis for the measurement of trace phosphine concentrations in seawater,and will be helpful for future research on the status ofphosphine in the oceanic biogeochemical cycle of phosphorus.

  20. Phosphine-gold(I) compounds as anticancer agents: general description and mechanisms of action.

    Science.gov (United States)

    Lima, João Carlos; Rodriguez, Laura

    2011-12-01

    Gold complexes have been explored as metallodrugs with great potential applications as antitumoral agents. In particular, gold-phosphine derivatives seemed quite promising since the use of the antiarthritic auranofin drug (thiolate-Au-PEt3 complex) presented also biological activity against different cancer cells. So, different auranofin analogues have been explored within this context and for this reason, the main number of phosphine-gold complexes developed with this goal contain thiolate ligands. Other complexes have been also studied such as tetrahedral bis(phosphine)gold(I) and phosphine-gold-halides. Very recently, phosphine-gold-alkynyl complexes have also shown very interesting biological activities although few reports are published related to them. Their mechanism of action seems to be clearly different that the used by platinum drugs (DNA intercalating processes) and recent studies point to be related to the inhibition of Trx reductase. Cellular uptake and biodistribution studies are well reported in the original works but the use of luminescence techniques is relatively less explored. For this, the use of these techniques is also specifically reported in this review.

  1. Spread of phosphine resistance among brazilian populations of three species of stored product insects.

    Science.gov (United States)

    Pimentel, Marco A G; Faroni, Lêda R D'A; Silva, Felipe H da; Batista, Maurílio D; Guedes, Raul N C

    2010-01-01

    The resistance to fumigant insecticides in stored-products insects is often recorded. Several factors influence the evolution of insecticide resistance. Among these, the frequency of applications and the migration of resistant populations are of primary importance for the stored-product insects. The aim of this study was to characterize the spectrum and investigate the status of phosphine resistance in Brazil, in 13 populations of the Coleoptera Tribolium castaneum Herbst (Tenebrionidae), ten populations of Rhyzopertha dominica (Fabr.) (Bostrichidae), and eight populations of Oryzaephilus surinamensis (L.) (Silvanidae). The pattern of resistance dispersion in the populations of these species was also verified. The bioassays for the detection of phosphine resistance followed the FAO standard method. To test the influence of migration in the evolution of the phosphine resistance, the difference of mortality in the discriminating concentration and the geographical distance among each pair wise combination of collection sites were correlated. None of the populations exhibited mortality above 90% in the discriminating concentration, for the three species. Mortality in the discriminating concentration increased with the geographical distance for R.dominica and O.surinamensis. However, no significant linear response was observed among the variables for T.castaneum populations. These results suggest that the dispersion of insects and the local selection are relevant in the evolution of the phosphine resistance in populations of R.dominica and O.surinamensis. In contrast, grain trade and local selection are probably the factors that determine the evolution of the phosphine resistance in populations of T. castaneum.

  2. Biomolecule conjugation strategy using novel water-soluble phosphine-based chelating agents

    Science.gov (United States)

    Katti, Kattesh V.; Gali, Hariprasad; Volkert, Wynn A.

    2004-08-24

    This invention describes a novel strategy to produce phosphine-functionalized biomolecules (e.g. peptides or proteins) for potential use in the design and development of site-specific radiopharmaceuticals for diagnosis or therapy of specific cancers. Hydrophilic alkyl phosphines, in general, tend to be oxidatively unstable. Therefore, incorporation of such phosphine functionalities on peptide (and other biomolecule) backbones, without oxidizing the P.sup.III centers, is difficult. In this context this discovery reports on a new technology by which phosphines, in the form of bifunctional chelating agents, can be directly incorporated on biomolecular backbones using manual synthetic or solid phase peptide synthesis methodologies. The superior ligating abilities of phosphine ligands, with various diagnostically (e.g. TC-99m) or therapeutically (e.g. Re186/188, Rh-105, Au-199) useful radiometals, coupled with the findings that the resulting complexes demonstrate high in vivo stability makes this approach useful in the development of radiolabeled biomolecules for applications in the design of tumor-specific radiopharmaceuticals.

  3. Hydroformylation of propene and 1-hexene catalysed by a alpha-zirconium phosphate supported rhodium-phosphine complex

    DEFF Research Database (Denmark)

    Karlsson, Magnus; Andersson, C; Hjortkjær, Jes

    2001-01-01

    The reaction of the amphiphilic ligand {4-[bis(diethylaminoethyl)aminomethyl]diphenyl}phosphine with alpha -zirconium phosphate, of intermediate surface area (24m(2) g(-1)), provided a phosphine functionalised support in which electrostatic interaction between ammonium groups on the ligand and de...

  4. Iridium-catalysed dehydrocoupling of aryl phosphine-borane adducts: synthesis and characterisation of high molecular weight poly(phosphinoboranes).

    Science.gov (United States)

    Paul, Ursula S D; Braunschweig, Holger; Radius, Udo

    2016-06-30

    The thermal dehydrogenative coupling of aryl phosphine-borane adducts with iridium complexes bearing a bis(phosphinite) pincer ligand is reported. This catalysis produces high molecular weight poly(phosphinoboranes) [ArPH-BH2]n (Ar = Ph, (p)Tol, Mes). Furthermore, we investigated the reactivity of these pincer complexes towards primary phosphines and their respective borane adducts on a stoichiometric scale.

  5. Phosphine absorption in the 5-micron window of Jupiter

    Science.gov (United States)

    Beer, R.; Taylor, F. W.

    1979-01-01

    Since the original suggestion by Gillett et al. (1969) it has generally been assumed that the region of partial transparency near 5 micron in Jupiter's atmosphere (the 5-micron window) is bounded by the nu sub 4 NH3 at 6.1 micron and the nu sub 3 CH4 band at 3.3 micron. New measurements of Jupiter and of laboratory phosphine (PH3) samples show that PH3 is a significant contributor to the continuum opacity in the window and in fact defines its short-wavelength limit. This has important implications for the use of 5-micron observations as a means to probe the deep atmospheric structure of Jupiter. The abundance of PH3 which results from a comparison of Jovian and laboratory spectra is about 3 to 5 cm-am. This is five to eight times less than that found by Larson et al. (1977) in the same spectral region, but is in good agreement with the result of Tokunaga et al. (1979) from 10-micron observations.

  6. Carbonylation of Ethene Catalysed by Pd(II-Phosphine Complexes

    Directory of Open Access Journals (Sweden)

    Gianni Cavinato

    2014-09-01

    Full Text Available This review deals with olefin carbonylation catalysed by Pd(II-phosphine complexes in protic solvents. In particular, the results obtained in the carbonylation with ethene are reviewed. After a short description of the basic concepts relevant to this catalysis, the review treats in greater details the influence of the bite angle, skeletal rigidity, electronic and steric bulk properties of the ligand on the formation of the products, which range from high molecular weight perfectly alternating polyketones to methyl propanoate. It is shown that the steric bulk plays a major role in directing the selectivity. Particular emphasis is given to the factors governing the very active and selective catalysis to methyl propanoate, including the mechanism of the catalytic cycles with diphosphine- and monophosphine-catalysts. A brief note on the synthesis of methyl propanoate using a “Lucite” type catalyst in ionic liquids is also illustrated. A chapter is dedicated to the carbonylation of olefins in aqueous reaction media. The nonalternating CO-ethene copolymerization is also treated.

  7. Phosphine-induced oxidative damage in rats: attenuation by melatonin.

    Science.gov (United States)

    Hsu, C; Han, B; Liu, M; Yeh, C; Casida, J E

    2000-02-15

    Phosphine (PH(3)), from hydrolysis of aluminum, magnesium and zinc phosphide, is an insecticide and rodenticide. Earlier observations on PH(3)-poisoned insects, mammals and a mammalian cell line led to the proposed involvement of oxidative damage in the toxic mechanism. This investigation focused on PH(3)-induced oxidative damage in rats and antioxidants as candidate protective agents. Male Wistar rats were treated ip with PH(3) at 2 mg/kg. Thirty min later the brain, liver, and lung were analyzed for glutathione (GSH) levels and lipid peroxidation (as malondialdehyde and 4-hydroxyalkenals) and brain and lung for 8-hydroxydeoxyguanosine (8-OH-dGuo) in DNA. PH(3) caused a significant decrease in GSH concentration and elevation in lipid peroxidation in brain (36-42%), lung (32-38%) and liver (19-25%) and significant increase of 8-OH-dGuo in DNA of brain (70%) and liver (39%). Antioxidants administered ip 30 min before PH(3) were melatonin, vitamin C, and beta-carotene at 10, 30, and 6 mg/kg, respectively. The PH(3)-induced changes were significantly or completely blocked by melatonin while vitamin C and beta-carotene were less effective or inactive. These findings establish that PH(3) induces and melatonin protects against oxidative damage in the brain, lung and liver of rats and suggest the involvement of reactive oxygen species in the genotoxicity of PH(3).

  8. A computed room temperature line list for phosphine

    Science.gov (United States)

    Sousa-Silva, Clara; Yurchenko, Sergei N.; Tennyson, Jonathan

    2013-06-01

    An accurate and comprehensive room temperature rotation-vibration transition line list for phosphine (31PH3) is computed using a newly refined potential energy surface and a previously constructed ab initio electric dipole moment surface. Energy levels, Einstein A coefficients and transition intensities are computed using these surfaces and a variational approach to the nuclear motion problem as implemented in the program TROVE. A ro-vibrational spectrum is computed, covering the wavenumber range 0-8000 cm-1. The resulting line list, which is appropriate for temperatures up to 300 K, consists of a total of 137 million transitions between 5.6 million energy levels. Several of the band centres are shifted to better match experimental transition frequencies. The line list is compared to the most recent HITRAN database and other laboratorial sources. Transition wavelengths and intensities are generally found to be in good agreement with the existing experimental data, with particularly close agreement for the rotational spectrum. An analysis of the comparison between the theoretical data created and the existing experimental data is performed, and suggestions for future improvements and assignments to the HITRAN database are made.

  9. P-Stereogenic Phosphines for the Stabilisation of Metal Nanoparticles. A Surface State Study

    Directory of Open Access Journals (Sweden)

    Eva Raluy

    2016-12-01

    Full Text Available Palladium and ruthenium nanoparticles have been prepared following the organometallic precursor decomposition methodology, under dihydrogen pressure and in the presence of borane protected P-stereogenic phosphines. NMR (Nuclear Magnetic Resonance monitoring of the corresponding syntheses has permitted to determine the optimal metal/ligand ratio for leading to small and well-dispersed nanoparticles. Exchange ligand reactions of the as-prepared materials have proven the strong interaction of the phosphines with the metal surface; only oxidative treatment using hydrogen peroxide could release the phosphine-based stabiliser from the metal surface. Pd and Ru nanoparticles have been evaluated in hydrogenation reactions, confirming the robustness of the stabilisers, which selectively permitted the hydrogenation of exocyclic C=C bonds, preventing the coordination of the aromatic rings and as a result, their hydrogenation.

  10. Phosphine resistance in Tribolium castaneum and Rhyzopertha dominica from stored wheat in Oklahoma.

    Science.gov (United States)

    Opit, G P; Phillips, T W; Aikins, M J; Hasan, M M

    2012-08-01

    Phosphine gas, or hydrogen phosphide (PH3), is the most common insecticide applied to durable stored products worldwide and is routinely used in the United States for treatment of bulk-stored cereal grains and other durable stored products. Research from the late 1980s revealed low frequencies of resistance to various residual grain protectant insecticides and to phosphine in grain insect species collected in Oklahoma. The present work, which used the same previously established discriminating dose bioassays for phosphine toxicity as in the earlier study, evaluated adults of nine different populations of red flour beetle, Tribolium castaneum (Herbst), and five populations of lesser grain borer, Rhyzopertha dominica (F.) collected from different geographic locations in Oklahoma. One additional population for each species was a laboratory susceptible strain. Discriminating dose assays determined eight out of the nine T. castaneum populations, and all five populations of R. dominica, contained phosphine-resistant individuals, and highest resistance frequencies were 94 and 98%, respectively. Dose-response bioassays and logit analyses determined that LC99 values were approximately 3 ppm for susceptible and 377 ppm for resistant T. castaneum, and approximately 2 ppm for susceptible and 3,430 ppm for resistant R. dominica. The most resistant T. castaneum population was 119-fold more resistant than the susceptible strain and the most resistant R. dominica population was over 1,500-fold more resistant. Results suggest a substantial increase in phosphine resistance in these major stored-wheat pests in the past 21 yr, and these levels of resistance to phosphine approach those reported for other stored-grain pest species in other countries.

  11. The first determination of atmospheric phosphine in Antarctica

    Institute of Scientific and Technical Information of China (English)

    ZHU RenBin; KONG DeMing; SUN LiGuang; GENG JinJu; WANG XiaoRong

    2007-01-01

    It is generally thought that phosphine (PH3) concentrations exist at the low ng/m3 level during the night and at the pg/m3 level during daylight in the remote atmosphere of the lower troposphere. The first determination of gaseous PH3 on the Antarctic Millor Peninsula is reported in this paper. No PH3 was detected in the air samples around 10:00 when it was sunny. However, PH3 was found in all the 10:00 air samples when it was cloudy or light snow with the average of 75.3±28.8 ng/m3 (n=5). It was also found in nearly all the samples around 22:00 with the average of 87.2±70.9 ng/m3 (n=11). Atmospheric PH3 concentrations around 22:00 were generally higher than those around 10:00 in January and they were almost the same in February. In addition, PH3 concentrations around 22:00 showed a downtrend with the decreasing air temperature, suggesting that light intensity and air temperature had an important effect on atmospheric PH3 concentration. It is very surprising to have found that high concentrations of PH3 exist in the Antarctic atmosphere under the influence of strong UV-radiation and light intensity. The tentative analyses show that dry, cold and very clean atmosphere may be very suitable for the PH3 survival and cause the concentration to increase and accumulate in the local atmosphere. New approaches for the PH3 formation and the process of atmospheric chemistry may exist under such an extreme environment. Atmospheric PH3 may also be from the emissions of local sources.

  12. Phosphine-induced oxidative damage in rats: role of glutathione.

    Science.gov (United States)

    Hsu, Ching-Hung; Chi, Bei-Ching; Liu, Ming-Yie; Li, Jih-Heng; Chen, Chiou-Jong; Chen, Ruey-Yu

    2002-09-30

    Phosphine (PH(3)), generated from aluminium, magnesium and zinc phosphide, is a widely used pesticide. PH(3) induces oxidative stress in insects, mammalian cells, animals, and humans. The involvement of glutathione (GSH) in PH(3)-induced oxidative toxicity is controversial. GSH levels in various tested tissues were reduced in aluminium phosphide-poisoned rats and humans, while the levels remained unchanged in insects and mammalian cells. This study examines the effectiveness of endogenous GSH as a protective agent against PH(3)-induced oxidative damage in rats. The association of PH(3)-induced nephrotoxicity and cardiotoxicity with free radical production was also tested. Male Wistar rats, administered intraperitoneally (I.P.) with PH(3) at 4 mg/kg, were evaluated 30 min after treatment for PH(3) toxicity to organs. PH(3) significantly decreased GSH, GSH peroxidase and catalase, while significantly increased lipid peroxidation (as malondialdehyde and 4-hydroxyalkenals), DNA oxidation (as 8-hydroxydeoxyguaonsoine) and superoxide dismutase (SOD) levels in kidney and heart. These changes were significantly alleviated by melatonin (10 mg/kg I.P., 30 min before PH(3)), with the exception of SOD activity in heart tissue. The study also found that buthionine sulfoximine (1 g/kg I.P., 24 h before PH(3)) significantly enhanced the effect of PH(3) on GSH loss and lipid peroxidation elevation in lung. These findings indicate that (1) endogenous GSH plays a crucial role as a protective factor in modulating PH(3)-induced oxidative damage, and (2) PH(3) could injure kidney and heart (as noted earlier with brain, liver and lung) via oxidative stress and the antioxidant melatonin effectively prevents the damage.

  13. Insights into amine binding to biaryl phosphine palladium oxidative addition complexes and reductive elimination from biaryl phosphine arylpalladium amido complexes via density functional theory.

    Science.gov (United States)

    Barder, Timothy E; Buchwald, Stephen L

    2007-10-03

    We present results on the binding of a variety amines to monoligated oxidative addition complexes of the type L1Pd(Ar)Cl, where L is 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos, 1) or 2-dicyclohexylphosphino-2',4',6'-tri-ispropylbiphenyl (XPhos, 2). The binding of an amine to oxidative addition complexes composed of 1 and 2 is more complex than with smaller ligands as intermediate Pd(II) complexes with bulky biaryl phosphine ligands disfavor amine binding to favorable conformations of oxidative addition complexes. Additionally, thermodynamic and kinetic parameters for reductive elimination from complexes of the type L1Pd(amido)Ph (where amido = EtNH, Me2N, PhNH) are discussed. From this data, we suggest a possible mechanism for (biaryl phosphine) Pd-catalyzed amination reactions that is more intricate than previously thought.

  14. Phosphinate stabilised ZnO and Cu colloidal nanocatalysts for CO2 hydrogenation to methanol.

    Science.gov (United States)

    Brown, N J; Weiner, J; Hellgardt, K; Shaffer, M S P; Williams, C K

    2013-12-07

    Colloidal solutions of ZnO-Cu nanoparticles can be used as catalysts for the reduction of carbon dioxide with hydrogen. The use of phosphinate ligands for the synthesis of the nanoparticles from organometallic precursors improves the reductive stability and catalytic activity of the system.

  15. Fumigation with Phosphine for Postharvest Insect Control on Lettuce, Broccoli, and Strawberries

    Science.gov (United States)

    U.S. exported lettuce, broccoli, and strawberries often harbor western flower thrips (Frankliniella occidentalis), a quarantined pest in Taiwan, and therefore require quarantine treatment. Pure phosphine fumigation at a low temperature of 2°C was studied as an alternative to methyl bromide to contro...

  16. Inheritance and Characterization of Strong Resistance to Phosphine in Sitophilus oryzae (L.)

    Science.gov (United States)

    Nguyen, Tam T.; Collins, Patrick J.; Ebert, Paul R.

    2015-01-01

    Sitophilus oryzae (Linnaeus) is a major pest of stored grain across Southeast Asia and is of increasing concern in other regions due to the advent of strong resistance to phosphine, the fumigant used to protect stored grain from pest insects. We investigated the inheritance of genes controlling resistance to phosphine in a strongly resistant S. oryzae strain (NNSO7525) collected in Australia and find that the trait is autosomally inherited and incompletely recessive with a degree of dominance of -0.66. The strongly resistant strain has an LC50 52 times greater than a susceptible reference strain (LS2) and 9 times greater than a weakly resistant strain (QSO335). Analysis of F2 and backcross progeny indicates that two or more genes are responsible for strong resistance, and that one of these genes, designated So_rph1, not only contributes to strong resistance, but is also responsible for the weak resistance phenotype of strain QSO335. These results demonstrate that the genetic mechanism of phosphine resistance in S. oryzae is similar to that of other stored product insect pests. A unique observation is that a subset of the progeny of an F1 backcross generation are more strongly resistant to phosphine than the parental strongly resistant strain, which may be caused by multiple alleles of one of the resistance genes. PMID:25886629

  17. LOW TEMPERATURE PHOSPHINE FUMIGATION FOR POSTHARVEST PEST CONTROL ON FRESH VEGETABLES

    Science.gov (United States)

    U.S. exported lettuce, broccoli, asparagus, and strawberries often harbor western flower thrips (Frankliniella occidentalis), a quarantined pest in Taiwan, and therefore require quarantine treatment. Fumigation with pure phosphine at a low temperature of 2°C was studied to control western flower t...

  18. Oxygenated phosphine fumigation for postharvest control of light brown apple moth on lettuce

    Science.gov (United States)

    Postharvest treatment for light brown apple moth (LBAM), Epiphyas postvittana (Walker), is needed to safe guard domestic distribution and export of U.S. fresh fruits and vegetables including lettuce as the pest becomes established in California with risk of potential spread. Oxygenated phosphine fu...

  19. Inheritance and characterization of strong resistance to phosphine in Sitophilus oryzae (L..

    Directory of Open Access Journals (Sweden)

    Tam T Nguyen

    Full Text Available Sitophilus oryzae (Linnaeus is a major pest of stored grain across Southeast Asia and is of increasing concern in other regions due to the advent of strong resistance to phosphine, the fumigant used to protect stored grain from pest insects. We investigated the inheritance of genes controlling resistance to phosphine in a strongly resistant S. oryzae strain (NNSO7525 collected in Australia and find that the trait is autosomally inherited and incompletely recessive with a degree of dominance of -0.66. The strongly resistant strain has an LC50 52 times greater than a susceptible reference strain (LS2 and 9 times greater than a weakly resistant strain (QSO335. Analysis of F2 and backcross progeny indicates that two or more genes are responsible for strong resistance, and that one of these genes, designated So_rph1, not only contributes to strong resistance, but is also responsible for the weak resistance phenotype of strain QSO335. These results demonstrate that the genetic mechanism of phosphine resistance in S. oryzae is similar to that of other stored product insect pests. A unique observation is that a subset of the progeny of an F1 backcross generation are more strongly resistant to phosphine than the parental strongly resistant strain, which may be caused by multiple alleles of one of the resistance genes.

  20. Inheritance and characterization of strong resistance to phosphine in Sitophilus oryzae (L.).

    Science.gov (United States)

    Nguyen, Tam T; Collins, Patrick J; Ebert, Paul R

    2015-01-01

    Sitophilus oryzae (Linnaeus) is a major pest of stored grain across Southeast Asia and is of increasing concern in other regions due to the advent of strong resistance to phosphine, the fumigant used to protect stored grain from pest insects. We investigated the inheritance of genes controlling resistance to phosphine in a strongly resistant S. oryzae strain (NNSO7525) collected in Australia and find that the trait is autosomally inherited and incompletely recessive with a degree of dominance of -0.66. The strongly resistant strain has an LC50 52 times greater than a susceptible reference strain (LS2) and 9 times greater than a weakly resistant strain (QSO335). Analysis of F2 and backcross progeny indicates that two or more genes are responsible for strong resistance, and that one of these genes, designated So_rph1, not only contributes to strong resistance, but is also responsible for the weak resistance phenotype of strain QSO335. These results demonstrate that the genetic mechanism of phosphine resistance in S. oryzae is similar to that of other stored product insect pests. A unique observation is that a subset of the progeny of an F1 backcross generation are more strongly resistant to phosphine than the parental strongly resistant strain, which may be caused by multiple alleles of one of the resistance genes.

  1. Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

    DEFF Research Database (Denmark)

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie;

    2014-01-01

    Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

  2. The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fabrizi, G.; Cacchi, S.;

    2006-01-01

    The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected...

  3. Hydroxyalkyl phosphine gold complexes for use as diagnostic and therapeutic pharmaceuticals and method of making same

    Science.gov (United States)

    Katti, Kattesh V.; Berning, Douglas E.; Volkert, Wynn A.; Ketring, Alan R.

    1998-01-01

    A complex and method for making same for use as a diagnostic or therapeutic pharmaceutical includes a ligand comprising at least one hydroxyalkyl phosphine donor group bound to a gold atom to form a gold-ligand complex that is stable in aqueous solutions containing oxygen, serum and other body fluids.

  4. Penguins significantly increased phosphine formation and phosphorus contribution in maritime Antarctic soils.

    Science.gov (United States)

    Zhu, Renbin; Wang, Qing; Ding, Wei; Wang, Can; Hou, Lijun; Ma, Dawei

    2014-11-14

    Most studies on phosphorus cycle in the natural environment focused on phosphates, with limited data available for the reduced phosphine (PH3). In this paper, matrix-bound phosphine (MBP), gaseous phosphine fluxes and phosphorus fractions in the soils were investigated from a penguin colony, a seal colony and the adjacent animal-lacking tundra and background sites. The MBP levels (mean 200.3 ng kg(-1)) in penguin colony soils were much higher than those in seal colony soils, animal-lacking tundra soils and the background soils. Field PH3 flux observation and laboratory incubation experiments confirmed that penguin colony soils produced much higher PH3 emissions than seal colony soils and animal-lacking tundra soils. Overall high MBP levels and PH3 emissions were modulated by soil biogeochemical processes associated with penguin activities: sufficient supply of the nutrients phosphorus, nitrogen, and organic carbon from penguin guano, high soil bacterial abundance and phosphatase activity. It was proposed that organic or inorganic phosphorus compounds from penguin guano or seal excreta could be reduced to PH3 in the Antarctic soils through the bacterial activity. Our results indicated that penguin activity significantly increased soil phosphine formation and phosphorus contribution, thus played an important role in phosphorus cycle in terrestrial ecosystems of maritime Antarctica.

  5. Effects of Outside Air Temperature on Movement of Phosphine Gas in Concrete Elevator Bins

    Science.gov (United States)

    Studies that measured the movement and concentration of phosphine gas in upright concrete bins over time indicated that fumigant movement was dictated by air currents, which in turn, were a function of the difference between the average grain temperature and the average outside air temperature durin...

  6. Hessian fly mortality by phosphine-carbon dioxide fumigation and postharvest drying

    Science.gov (United States)

    Hessian fly, Mayetiola destructor (Say), puparia, the stage of regulatory concern that may be found in weeds contaminating exported hay, may be controlled with a phosphine and carbon dioxide gas mixture dispensed from cylinders at a minimum dose of 750 ppm, temperature of 20°C (68°F) or higher, and ...

  7. Factors Affecting Energy Barriers for Pyramidal Inversion in Amines and Phosphines: A Computational Chemistry Lab Exercise

    Science.gov (United States)

    Montgomery, Craig D.

    2013-01-01

    An undergraduate exercise in computational chemistry that investigates the energy barrier for pyramidal inversion of amines and phosphines is presented. Semiempirical calculations (PM3) of the ground-state and transition-state energies for NR[superscript 1]R[superscript 2]R[superscript 3] and PR[superscript 1]R[superscript 2]R[superscript 3] allow…

  8. Structure and spectroscopy of uranyl and thorium complexes with substituted phosphine oxide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Breshears, Andrew T.; Barnes, Charles L.; Wagle, Durgesh V.; Baker, Gary A.; Walensky, Justin R. [Missouri Univ., Columbia, MO (United States). Dept. of Chemistry; Takase, Michael K. [California Institute of Technology, Pasadena, CA (United States). Beckman Institute

    2015-05-01

    Phosphine oxide ligands are important in the chemistry of the nuclear fuel cycle. We have synthesized and characterized a series of phosphine oxide ligands with polycyclic aromatic hydrocarbon (PAH) groups to enhance the spectroscopic features of uranyl, UO{sub 2}{sup 2+}, and to make detection more efficient. Complexation of OPPh{sub 2}R, R = C{sub 10}H{sub 7} (naphthyl); C{sub 14}H{sub 9} (phenanthrenyl); C{sub 14}H{sub 9} (anthracenyl); and C{sub 16}H{sub 9} (pyrenyl), to UO{sub 2}(NO{sub 3}){sub 2} afforded the eight-coordinate complexes, UO{sub 2}(NO{sub 3}){sub 2}(OPPh{sub 2}R){sub 2}. An eleven-coordinate complex, Th(NO{sub 3}){sub 4}[OPPh{sub 2}(C{sub 14}H{sub 9})]{sub 3}, C{sub 14}H{sub 9} = phenanthrenyl, was structurally characterized, and was found to be the first thorium compound isolated with three phosphine oxide ligands bound. The phosphine oxide ligands were not fluorescent but the anthracenyl-substituted ligand showed broad, red-shifted emission at approximately 50 nm relative to typical anthracene, making this ligand set a possibility for use in detection. The synthesis and spectroscopy of the uranyl and thorium complexes are presented.

  9. Tris(pyrazolyl)phosphine Oxides. Synthesis and Coordination Chemistry with Copper(I)

    NARCIS (Netherlands)

    Tazelaar, C.G.J.; Lyaskovskyy, V.; van Dijk, T.; Broere, D.L.J.; Kolfschoten, L.A.; Khiar, R.O.H.; Lutz, M.; Slootweg, J.C.; Lammertsma, K.

    2012-01-01

    A set of substituted tris(pyrazolyl)phosphine oxides (OP(pzx)3) has been prepared in high yield and applied as neutral scorpion-type ligands. The P apex provides a convenient spectroscopic handle. Substitution at the 3-position of the pyrazolyl ring influences the steric demands of the ligand, while

  10. Tri(t-butyl)phosphine-assisted selective hydrosilylation of terminal alkynes

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A highly efficient and regio-/stereoselective method of hydrosilylating terminal alkynes was developed using Pt(DVDS)-tri(t-butyl) phosphine catalyst system at room temperature.Trans-products or alpha-products were obtained almost exclusively depending on the alkynes and silanes employed.

  11. Intermediates in the Rh-catalysed dehydrocoupling of phosphine-borane.

    Science.gov (United States)

    Huertos, Miguel A; Weller, Andrew S

    2012-07-21

    Active species, product distributions and a suggested catalytic cycle are reported for the dehydrocoupling of the phosphine-borane H(3)B·P(t)Bu(2)H to give HP(t)Bu(2)BH(2)P(t)Bu(2)BH(3) using the [Rh(COD)(2)][BAr(F)(4)] pre-catalyst.

  12. Penguins significantly increased phosphine formation and phosphorus contribution in maritime Antarctic soils

    Science.gov (United States)

    Zhu, Renbin; Wang, Qing; Ding, Wei; Wang, Can; Hou, Lijun; Ma, Dawei

    2014-01-01

    Most studies on phosphorus cycle in the natural environment focused on phosphates, with limited data available for the reduced phosphine (PH3). In this paper, matrix-bound phosphine (MBP), gaseous phosphine fluxes and phosphorus fractions in the soils were investigated from a penguin colony, a seal colony and the adjacent animal-lacking tundra and background sites. The MBP levels (mean 200.3 ng kg−1) in penguin colony soils were much higher than those in seal colony soils, animal-lacking tundra soils and the background soils. Field PH3 flux observation and laboratory incubation experiments confirmed that penguin colony soils produced much higher PH3 emissions than seal colony soils and animal-lacking tundra soils. Overall high MBP levels and PH3 emissions were modulated by soil biogeochemical processes associated with penguin activities: sufficient supply of the nutrients phosphorus, nitrogen, and organic carbon from penguin guano, high soil bacterial abundance and phosphatase activity. It was proposed that organic or inorganic phosphorus compounds from penguin guano or seal excreta could be reduced to PH3 in the Antarctic soils through the bacterial activity. Our results indicated that penguin activity significantly increased soil phosphine formation and phosphorus contribution, thus played an important role in phosphorus cycle in terrestrial ecosystems of maritime Antarctica. PMID:25394572

  13. Coinage metal coordination chemistry of stable primary, secondary and tertiary ferrocenylethyl-based phosphines.

    Science.gov (United States)

    Azizpoor Fard, M; Rabiee Kenaree, A; Boyle, P D; Ragogna, P J; Gilroy, J B; Corrigan, J F

    2016-02-21

    Ferrocene-based phosphines constitute an important auxiliary ligand in inorganic chemistry. Utilizing the (ferrocenylethyl)phosphines (FcCH2CH2)3-nHnP (Fc = ferrocenyl; n = 2, 1; n = 1, 2; n = 0, 3) the synthesis of a series of coordination complexes [(FcCH2CH2)3-nHnPCuCl]4 (n = 2, 1-CuCl; n = 0, 3-CuCl), [(FcCH2CH2)2HPCuCl] (2-CuCl), {[(FcCH2CH2)H2P]2AgCl}2 (1-AgCl), [(FcCH2CH2)2HPAgCl] (2-AgCl), [(FcCH2CH2)3PAgCl]4 (3-AgCl), [(FcCH2CH2)3PM(OAc)]4 (M = Cu, 3-CuOAc M = Ag, 3-AgOAc), [(FcCH2CH2)3-nHnPAuCl] (n = 1, 2-AuCl; n = 0, 3-AuCl), via the reaction between the free phosphine and MX (M = Cu, Ag and Au; X = Cl, OAc), is described. The reaction between the respective phosphine with a suspension of metal-chloride or -acetate in a 1 : 1 ratio in THF at ambient temperature affords coordinated phosphine-coinage metal complexes. Varying structural motifs are observed in the solid state, as determined via single crystal X-ray analysis of 1-CuCl, 3-CuCl, 1-AgCl, 3-AgCl, 3-CuOAc, 3-AgOAc, 2-AuCl and 3-AuCl. Complexes 1-CuCl and 3-CuCl are tetrameric Cu(i) cubane-like structures with a Cu4Cl4 core, whereas silver complexes with primary and tertiary phosphine reveal two different structural types. The structure of 1-AgCl, unlike the rest, displays the coordination of two phosphines to each silver atom and shows a quadrangle defined by two Ag and two Cl atoms. In contrast, 3-AgCl is distorted from a cubane structure via elongation of one of the ClAg distances. 3-CuOAc and 3-AgOAc are isostructural with step-like cores, while complexes 2-AuCl and 3-AuCl reveal a linear geometry of a phosphine gold(i) chloride devoid of any aurophilic interactions. All of the complexes were characterized in solution by multinuclear (1)H, (13)C{(1)H} and (31)P NMR spectroscopic techniques; the redox chemistry of the series of complexes was examined using cyclic voltammetry. This class of complexes has been found to exhibit one reversible Fe(ii)/Fe(iii) oxidation couple, suggesting the

  14. Synthesis and coordination chemistry of tridentate (PNN) amine enamido phosphine ligands with ruthenium.

    Science.gov (United States)

    Wambach, T C; Lenczyk, C; Patrick, B O; Fryzuk, M D

    2016-04-07

    Tridentate amine-imine-phosphine ligands, R2PC5H7NC2H4NEt2 [(R)PNN(H)], where R = Pr(i) or Bu(t) are synthesized using a straightforward protocol of condensation, deprotonation, and addition of a chlorodialkylphosphine. Multinuclear NMR spectroscopy shows the ligands exist exclusively in the enamine tautomeric form in solution. Treating these ligands with RuHCl(PPr(i)3)2(CO) forms the desired coordination compounds, RuHCl[(R)PNN(H)](CO), where the imine tautomeric form of the ligands coordinates to ruthenium. Deuterium labelling experiments show Ru-H/N-D scrambling occurs during ligand coordination. Treating the RuHCl[(R)PNN(H)](CO) precursors with potassium tert-butoxide allows for the synthesis of two new ruthenium enamido-phosphine complexes, RuH[(R)PNN](CO), which were fully characterized. The structure of one of the derivatives was confirmed by X-ray crystallography (R = Pr(i)). The reactivity of the enamido-phosphine complexes with H2 and benzyl alcohol is also reported. For the enamido phosphine complex where R = Pr(i), the reaction with H2 is reversible and forms (RuH(CO)[(Pri)PNN(H)])2(μ-H)2, a hydride-bridged dimer that results from cooperative activation of H2. The reactivity of both amine-enamido-phosphine ruthenium compounds with benzyl alcohol establishes that the complexes are catalyst precursors for acceptorless dehydrogenation (AD), although the turnover frequencies measured using both catalyst precursors are modest.

  15. Laboratory Studies of Phosphine Chemistry Relevant to the Jovian and Saturnian Atmospheres

    Science.gov (United States)

    Liu, Yingdi; Matsiev, Daniel; Robertson, Robert; White, Jason

    2016-10-01

    The photochemistry of phosphine (PH3) in the tropospheres of Saturn and Jupiter is initiated by ultraviolet (UV) radiation and then follows a cascade of chemical reactions that result in P-H hydrides as well as the condensed chromophore red phosphorus (P4). A key intermediate in this pathway is diphosphine (P2H4). The rate constants for the photodissociation of phosphine into initial phosphino radicals and consequently into formation of diphosphine are currently unavailable, limiting their applicability to observational measurements. The condensation of diphosphine to ice in the cold tropospheres is also poorly understood due to the difficulties in synthesizing, handling, and analyzing the compound.Our presentation will describe two experiments at SRI International to produce rate constants for the photochemistry initiated by UV light interacting with phosphine and diphosphine and properties related to the condensed phases of these species. One study seeks to produce property values for application in photochemical and cloud/haze models. Specifically, we extend the measured vapor pressure curve for diphosphine to temperatures relevant to temperatures of Saturn and Jupiter. A sophisticated vapor pressure cell has been constructed and tested and is coupled to a Fourier transform infrared (FTIR) and mass spectrometer for high-fidelity species diagnostics. A companion study investigates phosphine photochemistry to measure the rate constants of key intermediate species related to the loss of PH3 and the formation of P2H4. The experiments employ laser photolysis at 193 nm followed by time-resolved mid-IR laser-based species detection of reactants, and the products provide basic chemical kinetic data useful for interpreting phosphine photochemistry in planetary atmospheres.These two studies are intended to supply basic physical measurements to aid in the interpretation of outer planet atmospheric observations. For both studies, we will present our latest laboratory

  16. Five-coordinate [Pt(II)(bipyridine)2(phosphine)](n+) complexes: long-lived intermediates in ligand substitution reactions of [Pt(bipyridine)2](2+) with phosphine ligands.

    Science.gov (United States)

    Lo, Warrick K C; Cavigliasso, Germán; Stranger, Robert; Crowley, James D; Blackman, Allan G

    2014-04-07

    The reaction of [Pt(N-N)2](2+) [N-N = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy)] with phosphine ligands [PPh3 or PPh(PhSO3)2(2-)] in aqueous or methanolic solutions was studied by multinuclear ((1)H, (13)C, (31)P, and (195)Pt) NMR spectroscopy, X-ray crystallography, UV-visible spectroscopy, and high-resolution mass spectrometry. NMR spectra of solutions containing equimolar amounts of [Pt(N-N)2](2+) and phosphine ligand give evidence for rapid formation of long-lived, 5-coordinate [Pt(II)(N-N)2(phosphine)](n+) complexes. In the presence of excess phosphine ligand, these intermediates undergo much slower entry of a second phosphine ligand and loss of a bpy ligand to give [Pt(II)(N-N)(phosphine)2](n+) as the final product. The coordination of a phosphine ligand to the Pt(II) ion in the intermediate [Pt(N-N)2(phosphine)](n+) complexes is supported by the observation of (31)P-(195)Pt coupling in the (31)P NMR spectra. The 5-coordinate nature of [Pt(bpy)2{PPh(PhSO3)2}] is confirmed by X-ray crystallography. X-ray crystal structural analysis shows that the Pt(II) ion in [Pt(bpy)2{PPh(PhSO3)2}]·5.5H2O displays a distorted square pyramidal geometry, with one bpy ligand bound asymmetrically. These results provide strong support for the widely accepted associative ligand substitution mechanism for square planar Pt(II) complexes. X-ray structural characterization of the distorted square planar complex [Pt(bpy)(PPh3)2](ClO4)2 confirms this as the final product of the reaction of [Pt(bpy)2](2+) with PPh3 in CD3OD. The results of density functional calculations on [Pt(bpy)2](2+), [Pt(bpy)2(phosphine)](n+), and [Pt(bpy)(phosphine)2](n+) indicate that the bonding energy follows the trend of [Pt(bpy)(phosphine)2](n+) > [Pt(bpy)2(phosphine)](n+) > [Pt(bpy)2](2+) for stability and that the formation reactions of [Pt(bpy)2(phosphine)](n+) from [Pt(bpy)2](2+) and [Pt(bpy)(phosphine)2](n+) from [Pt(bpy)2(phosphine)](n+) are energetically favorable. These

  17. On the Resolution of Secondary Phosphine Oxides via Diastereomeric Complex Formation : The Case of tert-Butylphenylphosphine Oxide

    NARCIS (Netherlands)

    Holt, Jarle; Maj, Anna M.; Schudde, Ebe P.; Pietrusiewicz, K. Michal; Sieron, Lelsaw; Wieczorek, Wanda; Jerphagnon, Thomas; Arends, Isabel W. C. E.; Hanefeld, Ulf; Minnaard, Adriaan J.

    2009-01-01

    The secondary phosphine oxide, t-BuPhHP=O most prominent chiral member of this compound class, has been re solved in high yield and with excellent ee. This resolution discloses ail efficient route to enantiopure phosphorus compounds.

  18. Synthesis of 3-Allyl-4-phosphachromones by Cyclized Coupling of Ethyl o-Hydroxyphenyl(ethynyl)phosphinate with Allyl Bromide

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    3-Allyl-4-phosphachromones as the phosphorus analogues of chromone were firstly prepared in good yields and high regioselectivity by the palladium(Ⅱ)-catalyzed cyclized coupling reaction of ethyl o-hydroxyphenyl(ethynyl)-phosphinate with allyl bromide.

  19. Resistance of stored-product insects to phosphine Resistência de insetos de produtos armazenados à fosfina

    OpenAIRE

    2008-01-01

    The objectives of this work were to assess phosphine resistance in insect populations (Tribolium castaneum, Rhyzopertha dominica, Sitophilus zeamais and Oryzaephilus surinamensis) from different regions of Brazil and to verify if the prevailing mechanism of phosphine resistance in these populations involves reduced respiration rates. Sixteen populations of T. castaneum, 15 of R. dominica, 27 of S. zeamais and eight of O. surinamensis were collected from 36 locations over seven Brazilian state...

  20. Influence of bidentate structure of an aryl phosphine oxide ligand on photophysical properties of its Eu~Ⅲ complex

    Institute of Scientific and Technical Information of China (English)

    许辉; 魏莹; 赵保敏; 黄维

    2010-01-01

    The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...

  1. Low temperature phosphine fumigation for control of oriental fruit fly on loquat%枇杷携带桔小实蝇磷化氢低温熏蒸技术研究

    Institute of Scientific and Technical Information of China (English)

    王迪; 徐文雅; 刘涛; 李丽; 张凡华; 叶秀娟; 陈艳; 王跃进

    2014-01-01

    To investigate the toxicity of phosphine against the oriental fruit fly(Bactrocera dorsalis Hendel) in loquat, 2, 4 and 6 days fumigation were conducted with 2.28 mg/L phosphine at 8℃. Phosphine tolerance tests show that the tolerances of different developmental stages of B. dorsalis in order were: 3rd instars>2nd instars>1st instars>eggs. And all stages of oriental fruit fl y was completely killed after 4 days fumigation. Phytotoxicity test show that phosphine fumigation had no significant effects on internal quality parameters of the loquat, including fruit firmness, soluble sugar content and total acids. Our results indicated that low temperature phosphine fumigation was effective against the oriental fruit fly and did not have any adverse effects on the quality of loquat, thus had great potential for phytosanitary treatment of B. dorsalis in loquats.%为了明确磷化氢在检疫处理枇杷(Eriobotrya japonica Lindl.)携带桔小实蝇(Bactrocera dorsalis Hendel)中应用的可能,本文在8℃下,使用2.28 mg/L 磷化氢,分别熏蒸处理2、4、6 d,并测定了磷化氢熏蒸对各虫态桔小实蝇的毒性及枇杷品质的影响。对各虫态桔小实蝇的毒力结果表明,枇杷中桔小实蝇各虫态对磷化氢的耐受性为3龄幼虫>2龄幼虫>1龄幼虫>卵,3龄幼虫是最耐受虫态,2.28 mg/L 磷化氢熏蒸4 d 可完全杀灭各虫态的桔小实蝇。品质测定结果表明,磷化氢熏蒸对枇杷的硬度、可溶性糖和总酸度等品质无明显影响,且对枇杷呼吸速率有一定抑制作用,降低了贮藏期间营养物质的消耗和损失,因而在枇杷的检疫处理中极具应用前景。

  2. Oxygenated Phosphine Fumigation for Control of Light Brown Apple Moth (Lepidoptera: Tortricidae) Eggs on Cut-Flowers.

    Science.gov (United States)

    Liu, Samuel S; Liu, Yong-Biao; Simmons, Gregory S

    2015-08-01

    Light brown apple moth, Epiphyas postvittana (Walker), eggs were subjected to oxygenated phosphine fumigation treatments under 70% oxygen on cut flowers to determine efficacy and safety. Five cut flower species: roses, lilies, tulips, gerbera daisy, and pompon chrysanthemums, were fumigated in separate groups with 2,500 ppm phosphine for 72 h at 5°C. Egg mortality and postharvest quality of cut flowers were determined after fumigation. Egg mortalities of 99.7-100% were achieved among the cut flower species. The treatment was safe to all cut flowers except gerbera daisy. A 96-h fumigation treatment with 2,200 ppm phosphine of eggs on chrysanthemums cut flowers also did not achieve complete control of light brown apple moth eggs. A simulation of fumigation in hermetically sealed fumigation chambers with gerbera daisy showed significant accumulations of carbon dioxide and ethylene by the end of 72-h sealing. However, oxygenated phosphine fumigations with carbon dioxide and ethylene absorbents did not reduce the injury to gerbera daisy, indicating that it is likely that phosphine may directly cause the injury to gerbera daisy cut flowers. The study demonstrated that oxygenated phosphine fumigation is effective against light brown apple moth eggs. However, it may not be able to achieve the probit9 quarantine level of control and the treatment was safe to most of the cut flower species.

  3. Continuous real-time monitoring of phosphine concentrations in air using electrochemical detectors interfaced by radio telemetry.

    Science.gov (United States)

    Thorn, Tommy G; Chodyniecki, Edward M; Ingold, Kenneth W; Long, Gerald A; Miller, Charles D; Robinson, Edward A; Cowan, F Scott; Thomas, Robert L

    2002-05-01

    This work involves the novel use of a radio telemetry-based system that continuously monitors phosphine using two different types of electrochemical detectors (ECD/RT). The ECD/RT units were used to monitor phosphine inside and at varying distances from large tobacco storage warehouses. A master controller unit transferred the data to a personal computer that received and displayed the data. Supervisory control and data acquisition software assimilated the data from each ECD/RT unit, displayed and updated it as new transmissions were received, and stored the data in secure databases. Phosphine concentrations outside five warehouses simultaneously under fumigation and at the facility boundaries were Phosphine levels ranged from 0 to 580 ppm inside sealed warehouses. A comparison was made between the data collected at an ECD/RT unit approximately 4 m downwind of a sealed warehouse and a colorimetric tube at the same location. The final phosphine concentration from the colorimetric method was 0.05 ppm and the average over the 20-minute collection period for the ECD/RT was 0.13 ppm. This system allows for continuous, remote monitoring around warehouses under fumigation and superior time resolution allowing timely response to fugitive emissions of phosphine.

  4. Study on the Extraction of L-Phenylalanine with Organo-phosphoric Acid in Two and Three-phase System

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Li(张莉); FU,Xun(傅洵); HU,Zheng-Shui(胡正水); LI,Qiu-Hong(李秋红); XU,Ting(徐婷)

    2002-01-01

    The extraction behaviors of L-phenylalanine by di-( 2,4,4trimethylpentyl) phosphinic acid, di-(2,4,4-trimethylpentyl)monothiophosphinic acid and di-(2-ethylhwxyl) phosphoric acid were studied in both two-phase and three-phase systems respectively. The equilibrium constants for these extraction reactions were calculated .

  5. Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand.

    Science.gov (United States)

    Shang, Rui; Ilies, Laurean; Nakamura, Eiichi

    2016-08-17

    Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.

  6. Acute phosphine poisoning aboard a grain freighter. Epidemiologic, clinical, and pathological findings.

    Science.gov (United States)

    Wilson, R; Lovejoy, F H; Jaeger, R J; Landrigan, P L

    1980-07-11

    Two children and 29 of 31 crew members aboard a grain freighter became acutely ill after inhaling the toxic fumigant phosphine; one child died. Predominant symptoms were headache, fatigue, nausea, vomiting, cough, and shortness of breath. Abnormal physical findings included jaundice, paresthesias, ataxia, intention tremor, and diplopia. Focal myocardial infiltration with necrosis, pulmonary edema, and widespread small-vessel injury were found at postmortem examination of the dead child. The surviving child showed ECG and echocardiographic evidence of myocardial injury and transient elevation of the MB fraction of serum creatinine phosphokinase. Illness was significantly associated with living or working amidships or on the forward deck areas of the vessel. Phosphine gas was found to have escaped from the holds through a cable housing located near the midships ventilation intake and around hatch covers on the forward deck. The outbreak illustrates the hazards associated with shipboard fumigation.

  7. Rate constant for the reaction of atomic oxygen with phosphine at 298 K

    Science.gov (United States)

    Stief, L. J.; Payne, W. A.; Nava, D. F.

    1987-01-01

    The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.

  8. Recent Advances in the Application of Chiral Phosphine Ligands in Pd-Catalysed Asymmetric Allylic Alkylation

    Directory of Open Access Journals (Sweden)

    Erika Martin

    2011-01-01

    Full Text Available One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used. Particularly interesting are chiral phosphines which have proved to be effective asymmetric inductors in several such reactions. The present review covers the application of phosphine-donor ligands in Pd-catalysed asymmetric allylic alkylation in the last decade.

  9. Effect of zinc and cerium addition on property of copper-based adsorbents for phosphine adsorption

    Institute of Scientific and Technical Information of China (English)

    宁平; 易红宏; 余琼粉; 唐晓龙; 杨丽萍; 叶智青

    2010-01-01

    A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tail gas. N2 adsorption isotherm and X-ray diffrac-tion (XRD) results suggested that the addition of Zn could increase the adsorbent ultramicropores, decrease the adsorbent supermicropores and the adsorbent average pore diameter. Therefore it enhanced the PH3 adsorption capacity. Appropriate amoun...

  10. Redox reactions of [FeFe]-hydrogenase models containing an internal amine and a pendant phosphine.

    Science.gov (United States)

    Zheng, Dehua; Wang, Mei; Chen, Lin; Wang, Ning; Sun, Licheng

    2014-02-03

    A diiron dithiolate complex with a pendant phosphine coordinated to one of the iron centers, [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe2(CO)5}] (1), was prepared and structurally characterized. The pendant phosphine is dissociated together with a CO ligand in the presence of excess PMe3, to afford [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe(CO)2(PMe3)}2] (2). Redox reactions of 2 and related complexes were studied in detail by in situ IR spectroscopy. A series of new Fe(II)Fe(I) ([3](+) and [6](+)), Fe(II)Fe(II) ([4](2+)), and Fe(I)Fe(I) (5) complexes relevant to Hox, Hox(CO), and Hred states of the [FeFe]-hydrogenase active site were detected. Among these complexes, the molecular structures of the diferrous complex [4](2+) with the internal amine and the pendant phosphine co-coordinated to the same iron center and the triphosphine diiron complex 5 were determined by X-ray crystallography. To make a comparison, the redox reactions of an analogous complex, [(μ-SCH2)2N(CH2C6H5){Fe(CO)2(PMe3)}2] (7), were also investigated by in situ IR spectroscopy in the absence or presence of extrinsic PPh3, which has no influence on the oxidation reaction of 7. The pendant phosphine in the second coordination sphere makes the redox reaction of 2 different from that of its analogue 7.

  11. Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst.

    Science.gov (United States)

    Adam, Rosa; Bheeter, Charles Beromeo; Cabrero-Antonino, Jose R; Junge, Kathrin; Jackstell, Ralf; Beller, Matthias

    2017-03-09

    A general procedure for the catalytic hydrogenation of nitriles to primary amines by using a non-noble metal-based system is presented. Co(acac)3 in combination with tris[2-(dicyclohexylphosphino)ethyl]phosphine efficiently catalyzes the selective hydrogenation of a wide range of (hetero)aromatic and aliphatic nitriles to give the corresponding amines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Electron-rich linear triplatinum complexes stabilized by a spinning tetraphosphine, tris(diphenylphosphinomethyl)phosphine.

    Science.gov (United States)

    Tanase, Tomoaki; Koike, Kanako; Uegaki, Miho; Hatada, Satoko; Nakamae, Kanako; Kure, Bunsho; Ura, Yasuyuki; Nakajima, Takayuki

    2016-05-01

    Linear triplatinum complexes with 48e(-), [Pt3(μ-tdpmp)2(RNC)2](PF6)2 (R = 2,6-xylyl (3), (t)Bu (4)), were synthesized by using a branched tetraphosphine, tris(diphenylphosphinomethyl)phosphine (tdpmp), and characterized by crystallographic and spectroscopic analyses to show their novel dynamic behaviour in the solution state, in which the linear Pt3 unit was stabilized by two spinning tetraphosphine ligands.

  13. P-chiral phosphine-sulfonate/palladium-catalyzed asymmetric copolymerization of vinyl acetate with carbon monoxide.

    Science.gov (United States)

    Nakamura, Akifumi; Kageyama, Takeharu; Goto, Hiroki; Carrow, Brad P; Ito, Shingo; Nozaki, Kyoko

    2012-08-01

    Utilization of palladium catalysts bearing a P-chiral phosphine-sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained γ-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination-insertion (co)polymerization of vinyl acetate.

  14. Evaluation of phosphine genotoxicity at occupational levels of exposure in New South Wales, Australia.

    Science.gov (United States)

    Barbosa, A; Bonin, A M

    1994-10-01

    Phosphine has been claimed to cause chromosomal damage at exposures close to the current time weighted average exposure standard of 0.3 ppm (0.4 mg/m3). The current study involved 31 phosphine fumigators and 21 controls during the high fumigation season. All were volunteers and were evaluated for genotoxicity variables, including micronuclei in peripheral blood lymphocytes and urine mutagenicity. In parallel, all fumigators and 17 controls were evaluated for full haematology, multiple biochemical analysis, whole blood organochlorines, and whole blood and serum cholinesterase activity. The results for micronuclei showed no significant differences between fumigators and controls, but detected a strong association between age and increased frequency of micronuclei. Measurement of urine mutagenicity did not show any significant difference between fumigators and controls, but did show increased excretion of mutagens in smokers. All haematological and biochemical variables were within normal ranges, except for some non-specific changes in biochemistry. At monitored occupational exposures of phosphine exposure and genotoxic or toxicological effects in fumigators.

  15. Evaluation of phosphine genotoxicity at occupational levels of exposure in New South Wales, Australia.

    Science.gov (United States)

    Barbosa, A; Bonin, A M

    1994-01-01

    Phosphine has been claimed to cause chromosomal damage at exposures close to the current time weighted average exposure standard of 0.3 ppm (0.4 mg/m3). The current study involved 31 phosphine fumigators and 21 controls during the high fumigation season. All were volunteers and were evaluated for genotoxicity variables, including micronuclei in peripheral blood lymphocytes and urine mutagenicity. In parallel, all fumigators and 17 controls were evaluated for full haematology, multiple biochemical analysis, whole blood organochlorines, and whole blood and serum cholinesterase activity. The results for micronuclei showed no significant differences between fumigators and controls, but detected a strong association between age and increased frequency of micronuclei. Measurement of urine mutagenicity did not show any significant difference between fumigators and controls, but did show increased excretion of mutagens in smokers. All haematological and biochemical variables were within normal ranges, except for some non-specific changes in biochemistry. At monitored occupational exposures of phosphine exposure and genotoxic or toxicological effects in fumigators. PMID:8000496

  16. Decomposition Products of Phosphine Under Pressure: PH2 Stable and Superconducting?

    Science.gov (United States)

    Shamp, Andrew; Terpstra, Tyson; Bi, Tiange; Falls, Zackary; Avery, Patrick; Zurek, Eva

    2016-02-17

    Evolutionary algorithms (EAs) coupled with density functional theory (DFT) calculations have been used to predict the most stable hydrides of phosphorus (PHn, n = 1-6) at 100, 150, and 200 GPa. At these pressures phosphine is unstable with respect to decomposition into the elemental phases, as well as PH2 and H2. Three metallic PH2 phases were found to be dynamically stable and superconducting between 100 and 200 GPa. One of these contains five formula units in the primitive cell and has C2/m symmetry (5FU-C2/m). It comprises 1D periodic PH3-PH-PH2-PH-PH3 oligomers. Two structurally related phases consisting of phosphorus atoms that are octahedrally coordinated by four phosphorus atoms in the equatorial positions and two hydrogen atoms in the axial positions (I4/mmm and 2FU-C2/m) were the most stable phases between ∼160-200 GPa. Their superconducting critical temperatures (Tc) were computed as 70 and 76 K, respectively, via the Allen-Dynes modified McMillan formula and using a value of 0.1 for the Coulomb pseudopotential, μ*. Our results suggest that the superconductivity recently observed by Drozdov, Eremets, and Troyan when phosphine was subject to pressures of 207 GPa in a diamond anvil cell may result from these, and other, decomposition products of phosphine.

  17. Synthesis and Optical Properties of a Dithiolate/Phosphine-Protected Au28 Nanocluster

    KAUST Repository

    Aljuhani, Maha A.

    2016-12-17

    While monothiols and simple phosphines are commonly exploited for size-controlled synthesis of atomically precise gold nanoclusters (NCs), dithiols or dithiol-phosphine combinations are seldom applied. Herein, we used a dithiol (benzene-1,3-dithiol, BDT) and a phosphine (triphenylphosphine, TPP) together as ligands and synthesized an atomically precise gold NC with the formula [Au28(BDT)4(TPP)9]2+. This NC exhibited multiple absorption features and a charge of +2, which are distinctly different from the reported all-thiolated [Au28(SR)20]0 NC (SR: monothiolate). The composition of [Au28(BDT)4(TPP)9]2+ NC was deduced from high-resolution electrospray ionization mass spectrometry (ESI MS) and it was further corroborated by thermogravimetric analysis (TGA). Differential pulse voltammetry (DPV) revealed a HOMO–LUMO gap of 1.27 eV, which is in good agreement with the energy gap of 1.3 eV obtained from its UV–vis spectrum. The successful synthesis of atomically precise, dithiol-protected Au28 NC would stimulate theoretical and experimental research into bidentate ligands as a new path for expanding the library of different metal NCs, which have so far been dominated by monodentate thiols.

  18. Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants.

    Science.gov (United States)

    McCann, Billy W; Silva, Nuwan De; Windus, Theresa L; Gordon, Mark S; Moyer, Bruce A; Bryantsev, Vyacheslav S; Hay, Benjamin P

    2016-06-20

    Computer-aided molecular design and high-throughput screening of viable host architectures can significantly reduce the efforts in the design of novel ligands for efficient extraction of rare earth elements. This paper presents a computational approach to the deliberate design of bis-phosphine oxide host architectures that are structurally organized for complexation of trivalent lanthanides. Molecule building software, HostDesigner, was interfaced with molecular mechanics software, PCModel, providing a tool for generating and screening millions of potential R2(O)P-link-P(O)R2 ligand geometries. The molecular mechanics ranking of ligand structures is consistent with both the solution-phase free energies of complexation obtained with density functional theory and the performance of known bis-phosphine oxide extractants. For the case where the link is -CH2-, evaluation of the ligand geometry provides the first characterization of a steric origin for the "anomalous aryl strengthening" effect. The design approach has identified a number of novel bis-phosphine oxide ligands that are better organized for lanthanide complexation than previously studied examples.

  19. Pd-catalyzed ethylene methoxycarbonylation with Brønsted acid ionic liquids as promoter and phase-separable reaction media

    DEFF Research Database (Denmark)

    Garcia-Suarez, Eduardo J.; Khokarale, Santosh Govind; Nguyen van Buu, Olivier;

    2014-01-01

    Brønsted acid ionic liquids (BAILs) were prepared and applied as combined acid promoters and reaction media in Pd–phosphine catalyzed methoxycarbonylation of ethylene to produce methyl propionate. The BAILs served as alternatives to common mineral acids required for the reaction, e.g. methanesulf...

  20. Two stage leaching of activated spent HDS catalyst and solvent extraction of aluminium using organo-phosphinic extractant, Cyanex 272.

    Science.gov (United States)

    Park, Kyung Ho; Mohapatra, Debasish; Nam, Chul-Woo

    2007-09-05

    Spent catalyst generally contains valuable metals like Mo, Co, Ni on a supporting material, such as gamma-A1(2)O(3). In the present study, a two stage alkali/acid leaching process is proposed to selectively target molybdenum and cobalt/nickel separately to facilitate the downstream processing. Prior to the leaching, the spent catalyst was calcined at 500 degrees C to remove C and S; and to convert metal sulphides to metal oxides. 98% Mo, 93% Co and 90% Ni was effectively recovered by this process. The sulphuric acid leaching of spent catalyst, previously treated by alkali solutions to remove Mo, yielded a solution rich in Ni, Co and Al. In order to recover Co and Ni, the Al impurity must be eliminated. The extraction and stripping of Al has been carried out using the organo-phosphinic extractant, Cyanex 272 diluted in carbon tetrachloride. Quantitative Al extraction efficiency was achieved with 1.0M Cyanex 272 in two stages at an aqueous:organic (A:O) phase ratio of 1:1 and equilibrium pH of 3.2. Complete stripping of Al from the loaded organic was carried out using 2M H(2)SO(4) at an A:O phase ratio of 1:1. The extraction reaction proceeded via the cation exchange mechanism and the extracted species was assumed to be AlA(3).3HA. The extraction of Al was carried out in the presence of various ions to ascertain the tolerance limit of individual ions. The regenerated solvent was successfully used for 8 cycles without any significant loss of extraction efficiency, suggesting that Cyanex 272 is extremely stable under present experimental conditions.

  1. Low temperature phosphine fumigation for postharvest control of western flower thrips (Thysanoptera: Thripidae) on lettuce, broccoli, asparagus, and strawberry.

    Science.gov (United States)

    Liu, Yong-Biao

    2008-12-01

    U.S. exported lettuce, broccoli, asparagus, and strawberries often harbor western flower thrips, Frankliniella occidentalis (Pergande) (Thysanoptera: Thripidae), a quarantined pest in Taiwan, and therefore require quarantine treatment. Fumigation with diluted pure phosphine at a low temperature of 2 degrees C was studied to control western flower thrips and to determine effects on the quality of the treated products. Total thrips control was achieved in > or = 18-h fumigation treatments with > or = 250 ppm phosphine. One day fumigation treatment with 1,000 ppm phosphine was tested on lettuce and broccoli. One-day fumigation treatments with 500 ppm and 1,000 ppm phosphine were tested on asparagus and strawberry. Visual quality of lettuce, broccoli, and asparagus was evaluated after 2-wk posttreatment storage. Strawberry quality was evaluated immediately after fumigation and after 1-wk posttreatment storage. For all the products, there were no significant differences between the treatments and the controls in postharvest quality, and there were no injuries caused by the fumigation treatments. Therefore, phosphine fumigation at low temperature was promising for postharvest control of western flower thrips on lettuce, broccoli, asparagus, and strawberry.

  2. Synthesis and Coordination Chemistry of a Phosphine-Decorated Fluorescein: "Double Turn-On" Sensing of Gold(III) Ions in Water.

    Science.gov (United States)

    Christianson, Anna M; Gabbaï, François P

    2016-06-20

    Although phosphine ligands are ubiquitous in transition metal chemistry, few reports of fluorescent phosphines exist that explore the effect of metal coordination on the photophysical properties of a phosphine-bound fluorescent group. The coordination chemistry of a derivative of fluorescein decorated with an o-phenylene-linked phosphine group has been studied with late transition metals. An Au(I) complex of the phosphine-decorated fluorescein has been structurally characterized, showing that the metal center is held closely over the plane of the fluorophore. Despite the presence of the heavy metal center, however, the phosphine-gold complex displays greatly increased fluorescence compared to the free ligand, in which photoelectron transfer from the lone-pair-bearing phosphine causes low emission. The phosphine-decorated fluorescein ligand was tested in a simple sensing system for metal ions in aqueous solution and shows a "turn-on" response to Au, Ag, and Hg, with an especially dramatic response to Au(III) species. The selectivity for Au(III) was determined to be the result of a "double turn-on" response that is both reaction- and coordination-based.

  3. Rapid synthesis of an electron-deficient t-BuPHOX ligand: cross-coupling of aryl bromides with secondary phosphine oxides

    KAUST Repository

    McDougal, Nolan T.

    2010-10-01

    Herein an efficient and direct copper-catalyzed coupling of oxazoline-containing aryl bromides with electron-deficient secondary phosphine oxides is reported. The resulting tertiary phosphine oxides can be reduced to prepare a range of PHOX ligands. The presented strategy is a useful alternative to known methods for constructing PHOX derivatives.

  4. Nutritional and toxicological effects of long-term ingestion of phosphine-fumigated diet by the rat.

    Science.gov (United States)

    Cabrol Telle, A M; de Saint Blanquat, G; Derache, R; Hollande, E; Periquet, B; Thouvenot, J P

    1985-11-01

    The fumigation of stored foodstuffs with phosphine (PH3) is likely to become widely used in the future because of its technological efficiency and the rapid desorption of the fumigant. In a long-term feeding study of a phosphine-fumigated diet, rats were monitored for weight gain, food intake, plasma chemistry, haematology and urinary changes. Histopathological studies, including organ-weight determinations, were carried out after treatment of the rats for 1 and 2 yr. The results show that ingestion of a phosphine-fumigated diet by the rat for 2 yr does not cause any marked modification of growth, food intake, nitrogen balance, body composition, functional behaviour or the incidence or type of tumours.

  5. Influence of phosphine on hatching of Cryptolestes ferrugineus (Coleoptera: Cucujidae), Lasioderma serricorne (Coleoptera: Anobiidae) and Oryzaephilus surinamensis (Coleoptera: Silvanidae).

    Science.gov (United States)

    Rajendran, Somiahnadar; Parveen, Hajira; Begum, Khamrunissa; Chethana, Ramesh

    2004-11-01

    The hatching and mortality response of 0- to 48-h-old eggs of field strains of the stored-product insects Cryptolestes ferrugineus (Stephens), Lasioderma serricorne (F) and Oryzaephilus surinamensis (L) following phosphine fumigation for 24, 48 or 120 h at 27 (+/- 2) degrees C was investigated. Hatching was delayed and reduced in the first few days in a phosphine-resistant strain of C ferrugineus that was treated with 2.0-7.0 mg litre(-1) doses for 48 h (5-80% mortality) and with 1.0-2.0 mg litre(-1) for 120 h (44-84% mortality). In both the exposures there were significant increases in hatching on later days when compared with the corresponding controls. Developmental delay was, however, not evident in susceptible strains of C ferrugineus, L serricorne and O surinamensis that were exposed to phosphine for 24 h.

  6. Photophysical properties of endohedral amine-functionalized bis(phosphine) Pt(II) complexes as models for emissive metallacycles.

    Science.gov (United States)

    Pollock, J Bryant; Cook, Timothy R; Schneider, Gregory L; Lutterman, Daniel A; Davies, Andrew S; Stang, Peter J

    2013-08-19

    The photophysical properties of bis(phosphine) Pt(II) complexes constructed from 2,6-bis(pyrid-3-ylethynyl) aniline and 2,6-bis(pyrid-4-ylethynyl) aniline vary significantly, even though the complexes differ only in the position of the coordinating nitrogen. By capping the ligands with an aryl bis(phosphine) Pt(II) metal acceptor, the photophysical properties of the two isomeric systems were directly compared, revealing that the low-energy absorption and emission bands of the two systems were separated by 30 nm (1804 cm(-1)) and 39 nm (1692 cm(-1)), respectively. From the analysis of time-dependent density functional (TD-DFT) calculations and excited-state lifetime measurements, it was determined that the nature of the Pt-N bond in the HOMO and the sums of the radiative (k(rad)) and nonradiative (k(nr)) rate constants were significantly different in the two systems. As the dominant nonradiative decay pathway in aniline systems is relaxation from the triplet state through intersystem crossing (ISC), the difference in k(nr) can be ascribed to changes in ISC between isomers of the bis(phosphine) Pt(II)-capped 2,6-bis(pyrid-3-ylethynyl) aniline system. It was also determined that the photophysical properties of these capped systems can be altered by functionalizing the aryl capping ligand on the bis(phosphine) Pt(II) metal center, which perturbs the molecular orbitals involved in the observed optical transitions. In addition, an isoelectronic bis(phosphine) Pd(II)-capped system was prepared for comparison with the bis(phosphine) Pt(II) suite of complexes. The Pd(II) system showed significant changes in its low-energy absorption band, but preserved the characteristic emissive properties of its Pt(II) analogue with an even higher quantum yield.

  7. Transition metal chemistry of cyclodiphosphanes containing phosphine and amide-phosphine functionalities: formation of a stable dipalladium(II) complex containing a Pd-P σ-bond.

    Science.gov (United States)

    Balakrishna, Maravanji S; Venkateswaran, Ramalingam; Mague, Joel T

    2010-12-14

    Cyclodiphosphazanes containing phosphine or phosphine plus amide functionalities {((t)BuNP(OC(6)H(4)PPh(2)-o)}(2) (3), {(t)BuNP(OCH(2)CH(2)PPh(2))}(2) (4), {(t)BuHN((t)BuNP)(2)OC(6)H(4)PPh(2)-o} (5), and {(t)BuHN((t)BuNP)(2)OCH(2)CH(2)PPh(2)} (6) were synthesized by reacting cis-{(t)BuNPCl}(2) (1) and cis-[(t)BuHN((t)BuNP)(2)Cl] (2) with corresponding phosphine substituted nucleophiles. The reactions of 3 and 5 with excess of elemental sulfur or selenium produce the corresponding tetra and trichalcogenides, {((t)BuNP(E)(OC(6)H(4)P(E)Ph(2)-o)}(2) (7, E = S; 8, E = Se) and {(t)BuHN((t)BuNP)(2)OC(6)H(4)P(E)Ph(2)-o} (9, E = S; 10, E = Se), respectively, in quantitative yields. The reactions between 3 and [Rh(COD)Cl](2) or [M(COD)Cl](2) (M = Pd or Pt) afford bischelated complexes [Rh(CO)Cl{(t)BuNP(OC(6)H(4)PPh(2)-o)}](2) (11), and [MCl(2){(t)BuNP(OC(6)H(4)PPh(2)-o)}](2) (12, M = Pd; 13, M = Pt) in good yield. The 1 : 2 reaction between 3 and [PdCl(η(3)-C(3)H(5))](2) in dichloromethane resulted initially in the formation of a tripalladium complex of the type [Pd(3)Cl(4)(η(3)-C(3)H(5))(2){(t)BuNPOC(6)H(4)PPh(2)}(2)] (14a) which readily reacts with moisture to form an interesting binuclear complex, [Cl(2)Pd{μ-(PPh(2)C(6)H(4)OP(μ-(t)BuN)(2)P(O)}(μ-Cl)Pd(OC(6)H(4)PPh(2))] (14b). One of the palladium(II) atoms forms a simple six-membered chelate ring, whereas the other palladium(II) atom facilitates the moisture assisted cleavage of one of the endocyclic P-O bonds followed by the oxidation of P(III) to P(V) thus forming a Pd-P σ-bond. The broken ortho-phosphine substituted phenoxide ion forms a five-membered palladacycle with the same palladium(II) atom. Similar reaction of 5 with [PdCl(η(3)-C(3)H(5))](2) also affords a binuclear complex [{PdCl(η(3)-C(3)H(5))}(t)BuNH{(t)BuNP}(2)OC(6)H(4)PPh(2){PdCl(2)}] (15) containing a PdCl(2) moiety which forms a six-membered chelate ring via ring-phosphorus and PPh(2) moieties on one side and a PdCl(η(3)-C(3)H(5)) fragment

  8. Loss of phosphine from unsealed bins of wheat at six combinations of grain temperature and grain moisture content.

    Science.gov (United States)

    Reed; Pan

    2000-07-01

    Hard red winter wheat (1.4 t) at 11.1 or 13.5% moisture content (wet basis) and 20, 25, or 30 degrees C was fumigated with tablets of an aluminum phosphide formulation in unsealed, cylindrical grain bins of corrugated metal. The fumigant leakage rate was manipulated to approximate that commonly encountered in farm and commercial-scale bins of this type. Phosphine concentration profiles were recorded and phosphine loss and sorption were characterized to determine which conditions provided the greatest probability of successful fumigation in these bins. Phosphine leakage and sorption were both positively related to grain temperature and moisture content. The fumigant concentration profiles were compared with previously-published data relating temperature to the developmental rate and fumigant susceptibility of lesser grain borer eggs, which are phosphine-resistant but become less resistant as they age. The mean phosphine concentration observed at the time corresponding to one-half of the calculated egg development time was compared to the lethal concentration (LC(99)) for a 2-day exposure at each temperature-moisture combination. In the low-moisture grain at 20 degrees C, the observed fumigant concentration was below the lethal concentration, due to the long development time under these conditions. At 25 and 30 degrees C in the low-moisture wheat, the likelihood of complete kill appeared more favorable because the fumigant concentration remained above the published LC(99) for more than half of the egg development time. In the wheat with 13.5% moisture content, rapid fumigant sorption and loss resulted in phosphine concentrations below the LC(99) at one-half of the development time at 20 or 25 degrees C. At 30 degrees C, due to the very rapid development rate, the observed phosphine concentration exceeded the LC(99) half-way through the egg development period despite the rapid rate of fumigant sorption and loss. Repeated fumigation of the same grain reduced the rate

  9. Improved fumigation process for stored foodstuffs by using phosphine in sealed chambers.

    Science.gov (United States)

    Formato, Andrea; Naviglio, Daniele; Pucillo, Gian Pio; Nota, Giorgio

    2012-01-11

    In this paper we present an innovative device designed and constructed to improve the fumigation process for stored foodstuffs with the use of phosphine gas in sealed chambers. The device allowed a considerable reduction in phosphine production time (from about 5 to 7 days for traditional systems to 2 days for the equipment considered), maintaining the system below the inflammability threshold, and at the same time achieving the total exhaustion of aluminum (or magnesium) phosphide so as to avoid toxic residues at the end of the process. With the standard device currently available on the market, after the normal 5-7 day fumigating period, the powder residue contains as much as 1-2% (w/w) of phosphide. Thus the residues, according to current legislation, have to be considered toxic and harmful. To overcome this disadvantage, appropriate modifications were made to the cylindrical tray used for the fumigation process: a nebulizer was installed, which has the function of increasing the moisture of the air spreading around the phosphide pellets and allowing a more rapid reaction with phosphide. Moreover, the cylindrical tray was also heated by means of an electrical resistance, and temperature was checked by a thermostat, so as to always obtain the same efficiency, independently of outside temperature, for both hot and cold periods, since reaction speed depends on the system temperature considered. In addition, a control device for air saturation allows condensation processes to be avoided. Using the modified cylindrical tray we performed tests to determine the best values of humidity and temperature for the process concerned, avoiding phosphine concentrations that might result in a fire hazard, and the remixing of phosphide pellets inside the cylindrical tray. Our experimental data allowed us to obtain a mathematical model used to gain an insight into the process in question.

  10. The relation between phosphine sorption and terminal gas concentrations in successful fumigation of food commodities.

    Science.gov (United States)

    Reddy, Palvai Vanitha; Rajashekar, Yellappa; Begum, Khamrunissa; Leelaja, Bhadravathi Chandrappa; Rajendran, Somiahnadar

    2007-01-01

    Owing to increased tolerance and the development of resistance in stored product insects to the fumigant phosphine, in recent years there has been a shift in the target terminal concentration from 100 ppm (100 mL m(-3)) to a higher level of 1000 ppm to achieve 100% insect mortality in 7 day commodity treatments. Therefore, there is a need to investigate whether the revised target concentration could be achieved for food commodities fumigated with phosphine at the standard dose of 2 g m(-3) for 7 days under airtight conditions at > or = 25 degrees C. When different types of food commodity (total 74) were fumigated (300 g per replicate) with phosphine at 2 g m(-3) for 7 days, the terminal gas concentrations in the free space of the commodities varied from 0 to > 2000 ppm. In chambers containing no substrate, a 1417 ppm concentration was recorded. Paddy rice, most of the oilseeds, shelled tree nuts, butter beans, cardamom, green gram splits, coriander powder, rice bran and cocoa powder were more sorptive (> or =60%), such that the target concentration of 1000 ppm was not achieved at the end of 7 days. For these commodities, increased doses of 3-6 g m(-3) were required to attain 1000 ppm. In-shell almonds, green cardamom, in-shell peanuts, leaf tea, tamarind pulp and sunflower seeds were exceptionally sorptive (>90%), so that 0, 41, 112, 168, 203 and 217 ppm respectively were noted at the end of 7 days; the dose must exceed 6 g m(-3) for effective fumigation of these commodities.

  11. Cyclam Derivatives with a Bis(phosphinate) or a Phosphinato-Phosphonate Pendant Arm: Ligands for Fast and Efficient Copper(II) Complexation for Nuclear Medical Applications.

    Science.gov (United States)

    David, Tomáš; Kubíček, Vojtěch; Gutten, Ondrej; Lubal, Přemysl; Kotek, Jan; Pietzsch, Hans-Jürgen; Rulíšek, Lubomír; Hermann, Petr

    2015-12-21

    Cyclam derivatives bearing one geminal bis(phosphinic acid), -CH2PO2HCH2PO2H2 (H2L(1)), or phosphinic-phosphonic acid, -CH2PO2HCH2PO3H2 (H3L(2)), pendant arm were synthesized and studied as potential copper(II) chelators for nuclear medical applications. The ligands showed good selectivity for copper(II) over zinc(II) and nickel(II) ions (log KCuL = 25.8 and 27.7 for H2L(1) and H3L(2), respectively). Kinetic study revealed an unusual three-step complex formation mechanism. The initial equilibrium step leads to out-of-cage complexes with Cu(2+) bound by the phosphorus-containing pendant arm. These species quickly rearrange to an in-cage complex with cyclam conformation II, which isomerizes to another in-cage complex with cyclam conformation I. The first in-cage complex is quantitatively formed in seconds (pH ≈5, 25 °C, Cu:L = 1:1, cM ≈ 1 mM). At pH >12, I isomers undergo nitrogen atom inversion, leading to III isomers; the structure of the III-[Cu(HL(2))] complex in the solid state was confirmed by X-ray diffraction analysis. In an alkaline solution, interconversion of the I and III isomers is mutual, leading to the same equilibrium isomeric mixture; such behavior has been observed here for the first time for copper(II) complexes of cyclam derivatives. Quantum-chemical calculations showed small energetic differences between the isomeric complexes of H3L(2) compared with analogous data for isomeric complexes of cyclam derivatives with one or two methylphosphonic acid pendant arm(s). Acid-assisted dissociation proved the kinetic inertness of the complexes. Preliminary radiolabeling of H2L(1) and H3L(2) with (64)Cu was fast and efficient, even at room temperature, giving specific activities of around 70 GBq of (64)Cu per 1 μmol of the ligand (pH 6.2, 10 min, ca. 90 equiv of the ligand). These specific activities were much higher than those of H3nota and H4dota complexes prepared under identical conditions. The rare combination of simple ligand synthesis, very

  12. Inhalation of phosphine gas following a fire associated with fumigation of processed pistachio nuts.

    Science.gov (United States)

    O'Malley, Michael; Fong, Harvard; Sánchez, Martha E; Roisman, Rachel; Nonato, Yvette; Mehler, Louise

    2013-01-01

    On December 10, 2009, a fumigation stack containing aluminum phosphide became soaked with rain water and caught fire at a pistachio processing plant in Kern County, California. Untrained plant personnel responding to the fire had exposure to pyrolysis by-products, particulates, and extinguisher ingredients. Ten workers taken for medical evaluation had respiratory and nonspecific systemic symptoms consistent with exposure to phosphine gas. Six of the 10 workers had respiratory distress, indicated by chest pain, shortness of breath, elevated respiratory rate, or decreased oxygen saturation. Recommendations are made for the management of similar illnesses and prevention of similar exposures.

  13. Accidental phosphine gas poisoning with fatal myocardial dysfunction in two families.

    Science.gov (United States)

    Akhtar, Saleem; Rehman, Arshalooz; Bano, Surraya; Haque, Anwarul

    2015-05-01

    Aluminum phosphide is commonly used as a rodenticide and insecticide and is one of the most fatal poisons. The active ingredient is Phosphine gas which inhibits cytochrome oxidase and cellular oxygen utilization. The clinical symptoms are due to multiorgan involvement including cardiac toxicity which is the most common cause of mortality. Severity of clinical manifestations depends upon the amount of the gas to which a person is exposed. There is no specific antidote available. High index of suspicion and early aggressive treatment is the key to success. We report 2 cases of aluminum phosphide toxicity in 2 families due to incidental exposure after fumigation.

  14. Synthesis, Characterisation and Reactions of Phosphine-Substituted Alkynylboronates and Alkynyltrifluoroborate Salts

    Directory of Open Access Journals (Sweden)

    Jérôme F. Vivat

    2014-12-01

    Full Text Available The synthesis and structural characterisation of phosphine-substituted alkynylboronates is reported. A P(III-centred alkynylboronate (2 was prepared that showed little evidence for the conjugation of the P-lone pair to the boron via the alkyne π-system, as judged by X-ray crystallography studies of 2 and a related P(V compound, 3. In addition, corresponding alkynyltrifluoroborate salts were prepared that showed improved stability by comparison to their boronic ester counterparts. These salts undergo Pd-catalysed cross-coupling reactions with aryl halides.

  15. D301 resin as a solid base for phosphine-free Heck reactions with heteroaryl halides

    Institute of Scientific and Technical Information of China (English)

    Wen Pei; Xiang Mei Wu

    2008-01-01

    A new and practical method of the D301 resin,a weak basic anion exchange resin with secondary amine functionality (Grade Matrix Structure:Styrene-DVB D301R),used as base to Heck reactions catalyzed by palladium reagent without phosphine compound as ligand is described.It was found that the D301 resin used as base is an efficient and reusable base and can be regenerated and recycled in the reaction.The olefination of heteroaryl halides prepared the corresponding products in good yields using D301 resin as base.

  16. Reduction of 4-azidonaphthalimide with different phosphine ligands and exploration of their spectroscopic properties

    Science.gov (United States)

    Xu, Shou De; Fang, Cheng Hui; Tian, Guang Xuan; Chen, Yi; Dou, Ye Hong; Kou, Jun Feng; Wu, Xiang Hua

    2015-12-01

    A convenient, high efficient method for the reduction of 4-azidonaphthalimide to 4-aminonaphthalimide (1) by using PMe3 has been developed. Several 4-substituted 1,8-naphthalimide iminophosphoranes were also successfully synthesized. Their structures were characterized by NMR and MS analyses. The structures of compounds 2 and 3 were also confirmed by single crystal X-ray diffraction analysis. Their optoelectronic properties of these naphthalimides were investigated. The results indicated that their optical properties could be tuned by different phosphine ligands, which make them novel potential organic luminescent materials.

  17. Permanent magnetism in phosphine- and chlorine-capped gold: from clusters to nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Marquez, Miguel A., E-mail: miguel.angel@icmse.csic.es; Guerrero, Estefania; Fernandez, Asuncion [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) (Spain); Crespo, Patricia; Hernando, Antonio [Instituto de Magnetismo Aplicado (UCM-ADIF-CSIC) (Spain); Lucena, Raquel; Conesa, Jose C. [Instituto de Catalisis y Petroleoquimica (CSIC) (Spain)

    2010-05-15

    Magnetometry results have shown that gold NPs ({approx}2 nm in size) protected with phosphine and chlorine ligands exhibit permanent magnetism. When the NPs size decreases down to the subnanometric size range, e.g. undecagold atom clusters, the permanent magnetism disappears. The near edge structure of the X-ray absorption spectroscopy data points out that charge transfer between gold and the capping system occurs in both cases. These results strongly suggest that nearly metallic Au bonds are also required for the induction of a magnetic response. Electron paramagnetic resonance observations indicate that the contribution to magnetism from eventual iron impurities can be disregarded.

  18. Efficacies of spinosad and a combination of chlorpyrifos-methyl and deltamethrin against phosphine-resistant Rhyzopertha dominica (Coleoptera: Bostrichidae) and Tribolium castaneum (Coleoptera: Tenebrionidae) on wheat.

    Science.gov (United States)

    Bajracharya, N S; Opit, George P; Talley, J; Jones, C L

    2013-10-01

    Highly phosphine-resistant populations of Rhyzopertha dominica (F.) (Coleoptera: Bostrichidae) and Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae) have recently been found in Oklahoma grain storage facilities. These findings necessitate development of a phosphine resistance management strategy to ensure continued effective use of phosphine. Therefore, we investigated the efficacies of two grain insecticides, namely, spinosad applied at label rate of 1 ppm and a mixture of chlorpyrifos-methyl and deltamethrin applied at label rates of 3 and 0.5 ppm, respectively, against highly phosphine-resistant R. dominica and T. castaneum. Adult mortality and progeny production suppression of spinosad- or chlorpyrifos-methyl + deltamethrin mixture-treated wheat that had been stored for 2, 84, 168, 252, and 336 d posttreatment were assessed. We found that both spinosad and chlorpyrifos-methyl + deltamethrin were effective against phosphine-resistant R. dominica and caused 83-100% mortality and also caused total progeny production suppression for all storage periods. Spinosad was not effective against phosphine-resistant T. castaneum; the highest mortality observed was only 3% for all the storage periods. Chlorpyrifos-methyl + deltamethrin was effective against phosphine-resistant T. castaneum only in treated wheat stored for 2 and 84 d, where it caused 93-99% mortality. However, chlorpyrifos-methyl + deltamethrin was effective and achieved total suppression of progeny production in T. castaneum for all the storage periods. Spinosad was not as effective as chlorpyrifos-methyl + deltamethrin mixture at suppressing progeny production of phosphine-resistant T. castaneum. These two insecticides can be used in a phosphine resistance management strategy for R. dominica and T. castaneum in the United States.

  19. Palladium catalyst system comprising zwitterion and/or acid-​functionalized ionic liquid

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3...

  20. Palladium catalyst system comprising zwitterion and/or acid-functionalized ionic liquid

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3...

  1. Magnetometry and electron paramagnetic resonance studies of phosphine- and thiol-capped gold nanoparticles

    Science.gov (United States)

    Guerrero, E.; Muñoz-Márquez, M. A.; Fernández, A.; Crespo, P.; Hernando, A.; Lucena, R.; Conesa, J. C.

    2010-03-01

    In the last years, the number of studies performed by wholly independent research groups that confirm the permanent magnetism, first observed in our research lab, for thiol-capped Au nanoparticles (NPs) has rapidly increased. Throughout the years, the initial magnetometry studies have been completed with element-specific magnetization measurements based on, for example, the x-ray magnetic circular dichroism technique that have allowed the identification of gold as the magnetic moment carrier. In the research work here presented, we have focused our efforts in the evaluation of the magnetic behavior and iron impurities content in the synthesized samples by means of superconducting quantum interference device magnetometry and electron paramagnetic resonance spectrometry, respectively. As a result, hysteresis cycles typical of a ferromagnetic material have been measured from nominally iron-free gold NPs protected with thiol, phosphine, and chlorine ligands. It is also observed that for samples containing both, capped gold NPs and highly diluted iron concentrations, the magnetic behavior of the NPs is not affected by the presence of paramagnetic iron impurities. The hysteresis cycles reported for phosphine-chlorine-capped gold NPs confirm that the magnetic behavior is not exclusively for the metal-thiol system.

  2. Copper(i) complexes with phosphine derived from sparfloxacin. Part I - structures, spectroscopic properties and cytotoxicity.

    Science.gov (United States)

    Komarnicka, Urszula K; Starosta, Radosław; Kyzioł, Agnieszka; Jeżowska-Bojczuk, Małgorzata

    2015-07-28

    In this paper we present new copper(i) iodide or copper(i) thiocyanate complexes with hydroxymethyldiphenylphosphine (PPh2(CH2OH)) or phosphine derivatives of sparfloxacin, a 3(rd) generation fluoroquinolone antibiotic agent (PPh2(CH2-Sf)) and 2,9-dimethyl-1,10-phenanthroline (dmp) or 2,2'-biquinoline (bq) auxiliary ligands. The synthesised complexes were fully characterised by NMR and UV-Vis spectroscopy as well as by mass spectrometry. Selected structures were additionally analysed using X-ray and DFT methods. All complexes proved to be stable in solution in the presence of water and atmospheric oxygen for several days. The cytotoxic activity of the complexes was tested against two cancer cell lines (CT26 - mouse colon carcinoma and A549 - human lung adenocarcinoma). Applying two different incubation times, the studies enabled a preliminary estimation of the dependence of the selectivity and the mechanism of action on the type of diimine and phosphine ligands. The results obtained showed that complexes with PPh2(CH2-Sf) are significantly more active than those with PPh2(CH2OH). On the other hand, the relative impact of diimine on cytotoxicity is less pronounced. However, the dmp complexes are characterised by strong inhibitory properties, while the bq ones are rather not. This confirms the interesting and promising biological properties of the investigated group of copper(i) complexes, which undoubtedly are worthy of further biological studies.

  3. Effects of Phosphine-Carbene Substitutions on the Electrochemical and Thermodynamic Properties of Nickel Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Galan, Brandon R.; Wiedner, Eric S.; Helm, Monte L.; Linehan, John C.; Appel, Aaron M.

    2014-05-12

    Nickel(II) complexes containing chelating N-heterocyclic carbene-phosphine ligands ([NiL2](BPh4)2, for which L = [MeIm(CH2)2PR2]) have been synthesized for the purpose of studying how this class of ligand effects the electrochemical properties compared to the nickel bis- diphosphine analogues. The nickel complexes were synthesized and characterized by x-ray crystallography and electrochemical methods. Based on the half wave potentials (E1/2), substitution of an NHC for one of the phosphines in a diphoshine ligand results in shifts in potential to 0.6 V to 1.2 V more negative than the corresponding nickel bis-diphosphine complexes. These quantitative results highlight the substantial effect that NHC ligands can have upon the electronic properties of the metal complexes. BRG, JCL, and AMA acknowledge the support by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MLH acknoledges the support of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  4. Substituted tertiary phosphine Ru(II) organometallics: catalytic utility on the hydrolysis of etofibrate in pharmaceuticals.

    Science.gov (United States)

    Reddy, P Muralidhar; Shanker, Kanne; Rohini, Rondla; Sarangapani, M; Ravinder, Vadde

    2008-10-01

    Some new organometallics of ruthenium(II) of the type [RuCl2(COD)(CO)L] (1a-f) and [RuCl2(COD)L2] (2a-f) (where L is substituted tertiary phosphines), have been synthesized by using precursors [RuCl2(COD)(CO)(CH3CN)] (1) and [RuCl2(COD)(CH3CN)2] (2) with the substituted tertiary phosphine ligands in 1:1 and 1:2 molar ratio. The organometallics (2a-f) have been further reacted with carbonmonoxide to produce compounds of the type [RuCl2(CO)L2] (3a-f). These compounds were characterized by elemental analysis, IR, NMR (1H, 13C and 31P), mass and electronic spectral data. The catalytic activity of all these organometallics were studied and found that they are efficient catalysts for hydrolysis of etofibrate. The hydrolyzed product was separated by column chromatography and the percent yields are found in the range of 98.6-99.1%.

  5. Matrix-bound phosphine:A new form of phosphorus found in sediment of Jiaozhou Bay

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Matrix-bound phosphine (PH3), a new form of phosphorus, was found in sediment of Jiaozhou Bay in December 2001. Concentration and distribution of PH3 in different layers of sediment with different stations were analyzed. The results show that PH3 concentrations are various with different layers and different stations. PH3 concentrations in the bottom layer of sediment (20-30 cm) are usually higher than those in the surface layer (0-4 cm). The highest PH3 concentration in our investigation reaches 685 ng/kg (dry), which is much higher than those in terrestrial paddy soil, marsh and landfill that have been reported up to now. The correlation analysis indicates that there is no apparent correlation between the concentrations of PH3 and inorganic phosphorus in sediment. However, the correlation between the concentrations of phosphine and organic phosphorus in the bottom layer of sediment is remarkable (R2=0.83). It is considered that PH3 in sediment of Jiaozhou Bay is mainly produced from the decomposition of organic phosphorus in the anaerobic condition, and so PH3 concentrations are related to organic phosphorus concentration and anaerobic environment in sediment. The discovery of PH3 in sediment will give people some new ideas on the mechanisms of phosphorus supplement and biogeochemical cycle in Jiaozhou Bay.

  6. Synthesis of tetrakis (hydroxymethyl) phosphonium chloride by high-concentration phosphine in industrial off-gas.

    Science.gov (United States)

    Huang, Xiaofeng; Wei, Yanfu; Zhou, Tao; Qin, Yangsong; Gao, Kunyang; Ding, Xinyue

    2013-01-01

    With increasing consumption of phosphate rock and acceleration of global phosphate production, the shortage of phosphate resources is increasing with the development and utilization of phosphate. China's Ministry of Land and Resources has classified phosphate as a mineral that cannot meet China's growing demand for phosphate rock in 2010. The phosphorus chemical industry is one of the important economic pillars for Yunnan province. Yellow phosphorus production in enterprises has led to a significant increase in the amount of phosphorus sludge. This paper focuses on phosphine generation in the process of phosphoric sludge utilization, where the flame retardant tetrakis (hydroxymethyl) phosphonium chloride (THPC) is synthesized by high concentrations of phosphine. The optimum conditions are determined at a space velocity of 150 h(-1), a reaction temperature of 60 °C, 0.75 g of catalyst, and a ratio of raw materials of 4:1. Because of the catalytic oxidation of copper chloride (CuCl2), the synthesis of THPC was accelerated significantly. In conclusion, THPC can be efficiently synthesized under optimal conditions and with CuCl2 as a catalyst.

  7. Inhibition of egg development by phosphine in the cosmopolitan pest of stored products Liposcelis bostrychophila (Psocoptera: Liposcelididae).

    Science.gov (United States)

    Nayak, Manoj K; Collins, Patrick J; Pavic, Hervoika; Kopittke, Rosemary A

    2003-11-01

    Phosphine-induced delay in development of eggs was investigated as a mechanism of resistance to this fumigant in Liposcelis bostrychophila Badonnel. One-day-old eggs of a susceptible and a strongly resistant strain of L bostrychophila were exposed to a range of phosphine concentrations for 6days at 30 (+/- 1) degrees C and 70 (+/- 2)% RH. Delay in mean hatching period occurred in both susceptible and resistant eggs, although it was more pronounced in the latter. A maximum delay of 2.65 days was recorded for eggs of the susceptible strain at 0.01 mg litre(-1) (the highest concentration at which eggs survived) and 13.39 days for the resistant strain at 1 mg litre(-1) (the highest concentration tested). Delay in egg development time was positively correlated with increasing phosphine concentration. Our results reveal that the most successful strategy to control resistant L bostrychophila is to apply relatively low concentrations of phosphine for extended exposure times (eg 0.05 mg litre(-1) for 16 days) that allow all eggs to hatch to the much less tolerant nymph stage.

  8. Oxygenated phosphine fumigation for control of light brown apple moth, Epiphyas postvittana (Lepidoptera: Tortricidae), eggs on cut-flowers

    Science.gov (United States)

    Light brown apple moth, Epiphyas postvittana, eggs were subjected to oxygenated phosphine fumigation treatments on cut flowers to determine efficacy and safety. Five cut flower species: roses, lilies, tulips, gerbera daisy, and pompon chrysanthemums, were fumigated in separate groups with 2500 ppm ...

  9. Pure phosphine fumigation treatment at low temperature for postharvest control of western flower thrips on lettuce, broccoli, asparagus, and strawberries

    Science.gov (United States)

    U.S. exported lettuce, broccoli, asparagus, and strawberries often harbor western flower thrips (Frankliniella occidentalis), a quarantined pest in Taiwan, and therefore require quarantine treatment. Pure phosphine fumigation at a low temperature of 2°C was studied as an alternative fumigant to meth...

  10. Advances in postharvest pest control on perishable commodities using ultralow oxygen treatment and low temperature phosphine funigation

    Science.gov (United States)

    Recent research in postharvest pest control on fresh fruits and vegetables for export to markets have resulted in promising ultralow oxygen (ULO) treatments and low temperature phosphine fumigation treatments for a variety of pests on different commodities. Lettuce aphid (Nasonovia ribisnigri), wes...

  11. Effects of phosphine and methyl bromide fumigation on the volatile flavor profile and sensory quality of dry cured ham.

    Science.gov (United States)

    Sekhon, R K; Schilling, M W; Phillips, T W; Aikins, M J; Hasan, M M; Corzo, A; Mikel, W B

    2010-10-01

    In separate experiments, randomized complete block designs with three replications were utilized to evaluate the effects of phosphine (PH(3)) (0, 200 and 1000ppm for 48h) and methyl bromide (MB) (0, 4, 8, 16, and 32mg/L for 48h) fumigation concentration on the volatile flavor compound concentrations in dry cured ham. Minimal differences existed (P>0.05) in the presence and concentration of aroma active compounds in both PH(3) and MB fumigated hams but sulfur and oxidation compounds were more prevalent (Pfumigated treatments when compared to the control. As phosphine fumigation concentration increased, the residual concentration of phosphine also increased in the hams (Pphosphine allowed in stored food products (0.01ppm) in the United States. A triangle test (n=56) indicated that consumers could not discriminate (P>0.75) between the control hams and those that were fumigated with PH(3). Minimal aroma/flavor differences existed among MB, PH3 and control hams, and dry cured ham that was fumigated with PH(3) was safe for consumption based on residual phosphine concentrations in the meat tissue.

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

    Science.gov (United States)

    Kaur, R; Subbarayalu, M; Jagadeesan, R; Daglish, G J; Nayak, M K; Naik, H R; Ramasamy, S; Subramanian, C; Ebert, P R; Schlipalius, D I

    2015-09-01

    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.

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

    Science.gov (United States)

    Kaur, R; Subbarayalu, M; Jagadeesan, R; Daglish, G J; Nayak, M K; Naik, H R; Ramasamy, S; Subramanian, C; Ebert, P R; Schlipalius, D I

    2015-01-01

    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. PMID:25853517

  14. 1,3-Dicarbonyl compounds as phosphine-free ligands for Pd-catalyzed Heck and Suzuki reactions

    Institute of Scientific and Technical Information of China (English)

    Xin Cui; Juan Li; Lei Liu; Qing Xiang Guo

    2007-01-01

    Some 1,3-dicarbonyl compounds (such as pentane-2,4-dione and 3-oxo-N-phenylbutanamide) were found to constitute highly efficient, yet low-priced and phosphine-free ligands for the Pd-catalyzed Heck and Suzuki reactions of aryl bromides and iodides with very high turnover numbers (ca.103-104).

  15. Synthesis of novel chiral phosphine-triazine ligand derived from α-phenylethylamine for Pd-catalyzed asymmetric allylic alkylation

    Institute of Scientific and Technical Information of China (English)

    Jia Di Huang; Xiang Ping Hu; Zhuo Zheng

    2008-01-01

    A novel chiral phosphine-triazine ligand was synthesized from chiral model reaction of Pd-catalyzed allylic alkylation of rac-l,3-diphenylprop-2-en-l-yl pivalate with dimethyl malonate, good enantioselectivity (90% e.e.) was obtained by using this ligand.

  16. Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanylethyl(diorganylphosphine oxides

    Directory of Open Access Journals (Sweden)

    Svetlana F. Malysheva

    2015-10-01

    Full Text Available Secondary phosphine oxides react with vinyl sulfides (both alkyl- and aryl-substituted sulfides under aerobic and solvent-free conditions (80 °C, air, 7–30 h to afford 1-hydroxy-2-(organosulfanylethyl(diorganylphosphine oxides in 70–93% yields.

  17. Treatment of California stone fruit with methyl bromide or phosphine to eliminate peach twig borer, Anarsia lineatella

    Science.gov (United States)

    The goal of this project is to develop postharvest chamber fumigations that ensure complete mortality of peach twig borer (PTB) in California stone fruit exports; results from preliminary toxicological and phytotoxicological research are presented. Fumigations with 1500 ppm phosphine over a 24 h ex...

  18. Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a "Smart" Probe Answer!

    Science.gov (United States)

    Ali, Moussa; Dondaine, Lucile; Adolle, Anais; Sampaio, Carla; Chotard, Florian; Richard, Philippe; Denat, Franck; Bettaieb, Ali; Le Gendre, Pierre; Laurens, Véronique; Goze, Christine; Paul, Catherine; Bodio, Ewen

    2015-06-11

    Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. The in vitro biological action of the gold complexes and the phosphonium derivative were investigated, and a preliminary in vivo study in healthy zebrafish larvae allowed us to evaluate gold complex biodistribution and toxicity. The different analyses carried out showed that these gold complexes were stable and behaved differently from phosphonium and auranofin, both in vitro and in vivo. Two-photon microscopy experiments demonstrated that the cellular targets of these gold complexes are not the same as those of the phosphonium analogue. Moreover, despite similar IC50 values in some cancer cell lines, gold complexes displayed a low toxicity in vivo, in contrast to the phosphonium salt. They are therefore suitable for future in vivo investigations.

  19. Total Synthesis of (±)-Hirsutine: Application of Phosphine-Catalyzed Imine–Allene [4 + 2] Annulation

    Science.gov (United States)

    Villa, Reymundo A.; Xu, Qihai; Kwon, Ohyun

    2012-01-01

    The total synthesis of the indole alkaloid hirsutine has been achieved, with a key step being the application of our phosphine-catalyzed [4 + 2] annulation of an imine with ethyl α-methylallenoate. From commercially available indole-2-carboxaldehyde, the target was synthesized in 14 steps and 6.7% overall yield. PMID:22920858

  20. Total synthesis of (±)-hirsutine: application of phosphine-catalyzed imine-allene [4 + 2] annulation.

    Science.gov (United States)

    Villa, Reymundo A; Xu, Qihai; Kwon, Ohyun

    2012-09-07

    The total synthesis of the indole alkaloid hirsutine has been achieved, with a key step being the application of our phosphine-catalyzed [4 + 2] annulation of an imine with ethyl α-methylallenoate. From commercially available indole-2-carboxaldehyde, the target was synthesized in 14 steps and 6.7% overall yield.

  1. Application of monodentate secondary phosphine oxides, a new class of chiral ligands, in Ir(I)-catalyzed asymmetric imine hydrogenation

    NARCIS (Netherlands)

    Jiang, X.B.; Minnaard, A.J.; Hessen, B.; Feringa, B.L.; Duchateau, A.L.L.; Andrien, J.G.O.; Boogers, J.A.F.; de Vries, J.G.; L. L. Duschateau, A.

    2003-01-01

    Secondary phosphine oxides were prepared from R1PCl2 and R2MgBr, followed by hydrolysis. They were obtained in an enantiopure form by preparative chiral HPLC. These new monodentate ligands were tested in the iridium-catalyzed hydrogenation of imines at 25 bar. Enantioselectivities up to 76% were obt

  2. Phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates: synthesis of 2-pyrrolines.

    Science.gov (United States)

    Tian, Junjun; Zhou, Rong; Sun, Haiyun; Song, Haibin; He, Zhengjie

    2011-04-01

    In this report, a phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates is described. This reaction represents the first realization of catalytic [4 + 1] cyclization of 1,3-azadienes with in situ formed phosphorus ylides, which provides highly efficient and diastereoselective synthesis of 2-pyrrolines.

  3. Phosphine resistance in the rust red flour beetle, Tribolium castaneum (Coleoptera: Tenebrionidae): inheritance, gene interactions and fitness costs.

    Science.gov (United States)

    Jagadeesan, Rajeswaran; Collins, Patrick J; Daglish, Gregory J; Ebert, Paul R; Schlipalius, David I

    2012-01-01

    The recent emergence of heritable high level resistance to phosphine in stored grain pests is a serious concern among major grain growing countries around the world. Here we describe the genetics of phosphine resistance in the rust red flour beetle Tribolium castaneum (Herbst), a pest of stored grain as well as a genetic model organism. We investigated three field collected strains of T. castaneum viz., susceptible (QTC4), weakly resistant (QTC1012) and strongly resistant (QTC931) to phosphine. The dose-mortality responses of their test- and inter-cross progeny revealed that most resistance was conferred by a single major resistance gene in the weakly (3.2×) resistant strain. This gene was also found in the strongly resistant (431×) strain, together with a second major resistance gene and additional minor factors. The second major gene by itself confers only 12-20× resistance, suggesting that a strong synergistic epistatic interaction between the genes is responsible for the high level of resistance (431×) observed in the strongly resistant strain. Phosphine resistance is not sex linked and is inherited as an incompletely recessive, autosomal trait. The analysis of the phenotypic fitness response of a population derived from a single pair inter-strain cross between the susceptible and strongly resistant strains indicated the changes in the level of response in the strong resistance phenotype; however this effect was not consistent and apparently masked by the genetic background of the weakly resistant strain. The results from this work will inform phosphine resistance management strategies and provide a basis for the identification of the resistance genes.

  4. Studies on the effects of phosphine on Salmonella enterica serotype Enteritidis in culture medium and in black pepper (Piper nigrum).

    Science.gov (United States)

    Castro, M F P M; Rezende, A C B; Benato, E A; Valentini, S R T; Furlani, R P Z; Tfouni, S A V

    2011-04-01

    The effect of phosphine on Salmonella enterica serotype Enteritidis inoculated in culture medium and in black pepper grains (Piper nigrum), as well as on the reduction of the microbial load of the dried and moisturized product, was verified. The postfumigation effect was verified in inoculated samples with 0.92 and 0.97 water activity (a(w)) exposed to 6 g/m(3) phosphine for 72 h, dried to 0.67 a(w), and stored for 24, 48, and 72 h. No decreases were observed in Salmonella Enteritidis populations in culture medium when fumigant concentrations up to 6 g/m(3) were applied for 48 h at 35°C. However, the colonies showed reductions in size and atypical coloration as the phosphine concentration increased. No reduction in Salmonella counts occurred on the inoculated dried samples after fumigation. On the other hand, when phosphine at concentrations of 6 g/m(3) was applied on moisturized black pepper for 72 h, decreases in Salmonella counts of around 80% were observed. The counts of total aerobic mesophilic bacterium populations of the dried and moisturized black pepper were not affected by the fumigant treatment. The results of the postfumigation studies indicated that Salmonella Enteritidis was absent in the fumigated grains after drying and storage for 72 h, indicating a promising application for this technique. It was concluded that for Salmonella Enteritidis control, phosphine fumigation could be applied to black pepper grains before drying and the producers should rigidly follow good agricultural practices, mainly during the drying process, in order to avoid product recontamination. Additional work is needed to confirm the findings with more Salmonella serotypes and strains.

  5. Aluminum dialkyl phosphinate flame retardants and their hydrolysates: analytical method and occurrence in soil and sediment samples from a manufacturing site.

    Science.gov (United States)

    Niu, Yumin; Liu, Jingfu; Liang, Yong; Hao, Zhineng; Liu, Jiyan; Liu, Yuchen; Sun, Xue

    2014-03-18

    Aluminum dialkyl phosphinates (ADPs) are emerging phosphorus flame retardants due to their superior characteristics, but their analytical method, and occurrence and fate in environments have never been reported. For the first time, we developed a method for the analysis of trace ADPs and their hydrolysates (dialkyl phosphinic acids, DPAs), and studied their occurrences and fates in soils and sediments. We found that ADPs are hardly dissolved in water and organic solvents, but are dissolved and hydrolyzed to DPAs in 30 mM NH3·H2O, thus both ADPs and DPAs can be determined by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) in the form of DPAs. ADPs and DPAs in soil and sediment samples were determined by (i) extracting both ADPs and DPAs with 75 mM NH3 · H2O, and selectively extract DPAs only with formic acid-water-methanol (5:5:90, v/v/v); (ii) quantifying the total content of ADPs and DPAs, and DPAs by LC-MS/MS analysis of the DPA contents in the former and the latter extract, respectively; and (iii) calculating ADPs from the content difference between the former and the latter extracts. The limit of quantifications (LOQs) of the proposed method were 0.9-1.0 μg/kg, and the mean recoveries ranged from 69.0% to 112.4% with relative standard deviations ≤ 21% (n = 6). In soil and sediment samples around a manufacturing plant, ADPs and DPAs were detected in surface soils in the ranges of 3.9-1279.3 and 1.0-448.6 μg/kg, respectively. While ADPs were found in all the samples of the soil and sediment cores from the drain outlet and the waste residue treatment site at levels ranging from 30.8 to 4628.0 μg/kg, DPAs were found in more than 90% of these samples with concentrations in the range of 1.1-374.6 μg/kg. The occurrences of ADPs and DPAs are not in correlation with the total organic carbon, whereas the occurrences of DPAs are highly correlated with the sample pH. Our study also suggests that the DPAs in the samples sourced

  6. Low temperature phosphine fumigation of pre-chilled iceberg lettuce under insulation cover for postharvest control of western flower thrips, Frankliniella occidentalis (Thysanoptera: Thripidae).

    Science.gov (United States)

    Fumigation of chilled iceberg lettuce under an insulation cover was studied to develop economical alternatives to conduct low temperature phosphine fumigation for control of western flower thrips, Frankliniella occidentalis (Pergande), on exported lettuce. Vacuum cooled commercial iceberg lettuce o...

  7. Effect of Electronic Factor in Ru-phosphine-diamine Complexes on Selective Hydrogenation of C=C and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu; Yu,Xiaojun; YU,Changbin; XIA,Yuqing; LI,Ruixiang; CHEN,Hua; LI,Xianjun

    2009-01-01

    A series of ruthenium complexes bearing different phosphines and diamines were synthesized and their compo-nents and structures were characterized by NMR spectra and elemental analyses. The catalytic properties of these complexes for the hydrogenation of benzylideneacetone and the mixture of acetophenone and styrene were investi-gated. The results showed that the basicity increase of phosphine or diamine dramatically facilitates the hydrogena-tion activity and selectivity to C=O double bond. On the contrary, the basicity decrease of phosphine or diamine not only slows down the catalytic activity, but also significantly suppresses the hydrogenation selectivity to C=O double bond. Based on the effect of electron factors of these complexes on the hydrogenation activity and selectiv-ity of benzylideneacetone and the mixture of styrene and acetophenone, the activation mechanism of dihydrogen in ruthenium-phosphine-diamine system was proposed.

  8. Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1'-binaphthyl framework and their application in asymmetric hydrogenation.

    Science.gov (United States)

    Gu, Peng; Zhang, Jun; Xu, Qin; Shi, Min

    2013-10-07

    The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with LiO(t)Bu, and subsequent complexation with [Ir(COD)Cl]2 and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).

  9. Alkynyl functionalized iminopyridine copper(I) phosphine complexes: Synthesis, spectroscopic characterization and photophysical properties

    Energy Technology Data Exchange (ETDEWEB)

    Jadhav, A.N.; Chavan, S.S., E-mail: sanjaycha2@rediffmail.com

    2014-04-15

    Some copper(I) complexes of type [Cu(L{sub 1})(PPh{sub 3}){sub 2}/(dppe)]X (1a–6a) and [Cu(L{sub 2})(PPh{sub 3}){sub 2}/(dppe)]X (1b–6b) [where L{sub 1}=N-(2-pyridylmethylene)-4-(trimethylsilylethynyl)aniline, L{sub 2}=N-(2-pyridylmethylene)-4-(phenylethynyl)aniline, PPh{sub 3}=triphenylphosphine, dppe=1,2-bis(diphenylphosphino)ethane, and X=ClO{sub 4}{sup −}, BF{sub 4}{sup −} and PF{sub 6}{sup −}] have been prepared and characterized on the basis of their elemental analyses and spectroscopic studies (IR, UV–visible, {sup 1}H NMR and {sup 31}P NMR). The representative complex of the series [Cu(L{sub 2})(PPh{sub 3}){sub 2}]ClO{sub 4}{sup −} (1b) has been characterized by single crystal X-ray diffraction which reveals that in the complex the central copper(I) ion assumes highly distorted-tetrahedral geometry. The UV–visible spectra indicate that the ancillary phosphine ligands significantly perturb the MLCT state of copper(I) complexes. Room temperature luminescence is observed for all copper(I) complexes in dichloromethane solution, indicating that alkynyl functionality on iminopyridine ligands enhances the emission property of copper(I) complexes and varies considerably with ancillary phosphine ligands. The thermal behavior of complexes revealed that copper(I) complexes with dppe ligand are thermally more stable than PPh{sub 3} complexes. All the complexes exhibit a quasireversible redox behavior corresponding to Cu(I)/Cu(II) couple and are sensitive to phosphine ligand. -- Highlights: • Synthesis of copper(I) complexes of alkynyl functionalized Schiff base. • Characterization by elemental analyses, IR, {sup 1}H NMR and {sup 31}P NMR spectral studies. • Electrochemical properties indicate a quasireversible redox behavior for all copper(I) complexes • All the copper(I) complexes exhibit intraligand (π→π{sup ⁎}) luminescence in dichloromethane.

  10. Simple tertiary phosphines to hexaphosphane ligands: Syntheses, transition metal chemistry and their catalytic applications

    Indian Academy of Sciences (India)

    Maravanji S Balakrishna; Sowmya Rao; Bimba Choubey

    2012-11-01

    Designing efficient phosphorus-based ligands to make catalysts for homogeneous catalysis has been a great challenge for chemists. Despite a plethora of phosphorus ligands ranging from simple tertiary phosphines to polyphosphines are known, the enthusiasm to generate new ones is mainly due to the demand from industry for economical and robust catalytic system operational under normal atmospheric conditions. In this context, we have developed new synthetic methodologies for making unusual inorganic ring systems containing trivalent phosphorus centres, novel phosphorus-based multidentate and hybrid ligands and explored their rich transition metal chemistry and catalytic applications. We have also fine tuned a few existing ligand systems with donor functionalities to employ them in homogeneous catalysis. The details are summarized in this account.

  11. Nickel Phosphine Catalysts with Pendant Amines for Electrocatalytic Oxidation of Alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, Charles J.; Wiedner, Eric S.; Roberts, John A.; Appel, Aaron M.

    2015-01-01

    Nickel phosphine complexes with pendant amines have been found to be electrocatalysts for the oxidation of primary and secondary alcohols, with turnover frequencies as high as 3.3 s-1. These complexes are the first electrocatalysts for alcohol oxidation based on non-precious metals, which will be critical for use in fuel cells. The research by CJW, ESW, and AMA was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The research by JASR was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  12. Observations of the J = 10 manifold of the pure rotational band of phosphine on Saturn

    Science.gov (United States)

    Haas, M. R.; Erickson, E. F.; Goorvitch, D.; Mckibbin, D. D.; Rank, D. M.

    1986-01-01

    Saturn was observed in the vicinity of the J = 10 manifold of the pure rotational band of phosphine on 1984 July 10 and 12 from NASA's Kuiper Airborne Observatory with the facility far-infrared cooled grating spectrometer. On each night observations of the full disk plus rings were made at 4 to 6 discrete wavelengths which selectively sampled the manifold and the adjacent continuum. The previously reported detection of this manifold is confirmed. After subtraction of the flux due to the rings, the data are compared with disk-averaged models of Saturn. It is found that PH3 must be strongly depleted above the thermal inversion (approx. 70 mbar). The best fitting models consistent with other observational constaints indicate that PH3 is significantly depleted at even deeper atmospheric levels ( or = 500 mbar), implying an eddy diffusion coefficient for Saturn of 10 to the 4 cm sq/sec.

  13. Hydroformylation of olefins with cobalt/phosphonate- and cobalt/sufonate-phosphines

    Energy Technology Data Exchange (ETDEWEB)

    Martin, A.; Kant, M. [Leibniz-Institut fuer Katalyse e.V., Berlin (Germany); Giuffrida, G.; Rosano, S. [Sasol Italy S.p.A., Paderno Dugnano (Italy)

    2006-07-01

    The hydroformylation of an industrial decene mixture with cobalt/phosphonate- and cobalt/sulfonate-phosphines used as catalysts was carried out. Highest aldehyde yield of ca. 60-65 mol% beside 2-5 mol% decane, 1-5 mol% decenes and 2-5 mol% of other oxoproducts was obtained at 170 C, 160-200 bar syngas pressure and a reaction time of 12-16 h. The reminder is a fraction of non-GC-detectable heavy oligomers (15-20 %). Best olefin conversion was reached with Ph{sub 2}P(p-C{sub 6}H{sub 4}-SO{sub 3}Li) and TPPTS as ligands, best stability of biphasic system with TPPTS and Ph{sub 2}P-(CH{sub 2}){sub 3}-SO{sub 3}Li. The terminal aldehyde selectivity amounted to 36-42 mol% of the aldehyde pool. (orig.)

  14. Cooperative titanocene and phosphine catalysis: accelerated C-X activation for the generation of reactive organometallics.

    Science.gov (United States)

    Fleury, Lauren M; Kosal, Andrew D; Masters, James T; Ashfeld, Brandon L

    2013-01-18

    The study presented herein describes a reductive transmetalation approach toward the generation of Grignard and organozinc reagents mediated by a titanocene catalyst. This method enables the metalation of functionalized substrates without loss of functional group compatibility. Allyl zinc reagents and allyl, vinyl, and alkyl Grignard reagents were generated in situ and used in the addition to carbonyl substrates to provide the corresponding carbinols in yields up to 99%. It was discovered that phosphine ligands effectively accelerate the reductive transmetalation event to enable the metalation of C-X bonds at temperatures as low as -40 °C. Performing the reactions in the presence of chiral diamines and amino alcohols led to the enantioselective allylation of aldehydes.

  15. Palladium(II) complexes supported by a bidentate bis(secondary)phosphine linked by pyridine

    KAUST Repository

    Winston, Matthew S.

    2014-10-01

    A series of complexes of the type (PNP-H2)PdX2 (X=Cl, Br, I) have been synthesized, where PNP-H2 is a bis(secondary)phosphine ligand linked by a pyridine, 2,6-(2\\'-(Ph(H)P)(C6H4))2(C5H3N). Due to chirality at phosphorus, the parent ligand exists as a mixture of nearly equivalent rac and meso diastereomers non-interconverting at room temperature. When ligated to Pd(II) halides, however, the diastereomeric ratio is dependent upon the halide. The chloro, bromo, and iodo complexes have been characterized crystallographically. Conformationally similar meso diastereomers of each dihalide are roughly C s symmetric in the solid state, while the rac diastereomers (identified only for X=Br, I) show substantially different solid-state conformations. © 2014 Elsevier B.V.

  16. Scalable noninjection phosphine-free synthesis and optical properties of tetragonal-phase CuInSe2 quantum dots

    Science.gov (United States)

    Liu, Feng; Zhu, Jun; Xu, Yafeng; Zhou, Li; Dai, Songyuan

    2016-05-01

    Phosphine-free synthesis of CISe quantum dots (QDs) is highly desirable, yet it has been challenging. The main difficulty lies in achieving phosphine-free Se precursors. Most reported protocols for the synthesis of size-confined CISe QDs highly depend on the use of air-sensitive, toxic, and expensive alkylphosphines to prepare reactive Se precursors and to confine particle growth. Herein, we present a new amine/thiol combination-based route to Se precursors that may enable a general synthesis of phosphine-free selenide QDs. What's more, instead of the traditional ``hot-injection'' method, we also report the first one-pot noninjection synthesis of high quality CISe QDs enabled by our strategy. A very high chemical yield of ~95% is demonstrated, as well as the facile gram-scale production of monodisperse CISe QDs. By simply adjusting the amount of 1-dodecanethiol used in the synthesis, we are able to produce CISe QDs with continuous tunability of the particle size from ~2 nm to ~10 nm, and hence their intrinsic optical properties.Phosphine-free synthesis of CISe quantum dots (QDs) is highly desirable, yet it has been challenging. The main difficulty lies in achieving phosphine-free Se precursors. Most reported protocols for the synthesis of size-confined CISe QDs highly depend on the use of air-sensitive, toxic, and expensive alkylphosphines to prepare reactive Se precursors and to confine particle growth. Herein, we present a new amine/thiol combination-based route to Se precursors that may enable a general synthesis of phosphine-free selenide QDs. What's more, instead of the traditional ``hot-injection'' method, we also report the first one-pot noninjection synthesis of high quality CISe QDs enabled by our strategy. A very high chemical yield of ~95% is demonstrated, as well as the facile gram-scale production of monodisperse CISe QDs. By simply adjusting the amount of 1-dodecanethiol used in the synthesis, we are able to produce CISe QDs with continuous tunability

  17. Synthesis, characterization, and crystal structure of mercury(II) complex containing new phosphine oxide salt

    Science.gov (United States)

    Samiee, Sepideh; Kooti, Nadieh; Gable, Robert W.

    2017-02-01

    The reaction of new phosphonium-phosphine oxide salt [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]Br (1) with mercury(II) iodide in a methanolic solution yielded [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2[Hg2I5Br](2). These two compounds were fully characterized by elemental analysis, IR, 1H, 31P, and 13C NMR spectra. Crystal and molecular structure of 2 has been determined by means of X-ray diffraction. In mercury compound, the phosphine oxide salt is found as a counter ion letting the mercury(II) ion to bound halides to all four coordination sites and to give dimermercurate(II) ions as the structure-constructing species. The neighboring [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2+cations are joined together by intramolecular Csbnd H⋯O hydrogen bonds to give a 1-D chain structure along the crystallographic b-axis. The [Hg2I5Br]2-anions act as cross-linkers between neighbouring strands extending the supramolecular structure into 2D layers in (110) planes as well as balances the charge of the complex. The significant effects of Csbnd H⋯X (Xdbnd O, Br and I) and π⋯π aromatic interactions play a major role in the crystal packing of compound 2.

  18. Remote plasma enhanced chemical vapor deposition of GaP with in situ generation of phosphine precursors

    Science.gov (United States)

    Choi, S. W.; Lucovsky, G.; Bachmann, K. J.

    1992-01-01

    Thin homoepitaxial films of gallium phosphide (GaP) have been grown by remote plasma enhanced chemical vapor deposition utilizing in situ-generated phosphine precursors. The GaP forming reaction is kinetically controlled with an activation energy of 0.65 eV. The increase of the growth rate with increasing radio frequency (RF) power between 20 and 100 W is due to the combined effects of increasingly complete excitation and the spatial extension of the glow discharge toward the substrate; however, the saturation of the growth rate at even higher RF power indicates the saturation of the generation rate of phosphine precursors at this condition. Slight interdiffusion of P into Si and Si into GaP is indicated from GaP/Si heterostructures grown under similar conditions as the GaP homojunctions.

  19. Remote plasma enhanced chemical vapor deposition of GaP with in situ generation of phosphine precursors

    Science.gov (United States)

    Choi, S. W.; Lucovsky, G.; Bachmann, Klaus J.

    1993-01-01

    Thin homoepitaxial films of gallium phosphide (GaP) were grown by remote plasma enhanced chemical vapor deposition utilizing in situ generated phosphine precursors. The GaP forming reaction is kinetically controlled with an activation energy of 0.65 eV. The increase of the growth rate with increasing radio frequency (rf) power between 20 and 100 W is due to the combined effects of increasingly complete excitation and the spatial extension of the glow discharge toward the substrate, however, the saturation of the growth rate at even higher rf power indicates the saturation of the generation rate of phosphine precursors at this condition. Slight interdiffusion of P into Si and Si into GaP is indicated from GaP/Si heterostructures grown under similar conditions as the GaP homojunctions.

  20. Resistance of stored-product insects to phosphine Resistência de insetos de produtos armazenados à fosfina

    Directory of Open Access Journals (Sweden)

    Marco Aurélio Guerra Pimentel

    2008-12-01

    Full Text Available The objectives of this work were to assess phosphine resistance in insect populations (Tribolium castaneum, Rhyzopertha dominica, Sitophilus zeamais and Oryzaephilus surinamensis from different regions of Brazil and to verify if the prevailing mechanism of phosphine resistance in these populations involves reduced respiration rates. Sixteen populations of T. castaneum, 15 of R. dominica, 27 of S. zeamais and eight of O. surinamensis were collected from 36 locations over seven Brazilian states. Each population was tested for resistance to phosphine, based on the response of adults to discriminating concentrations, according to FAO standard method. For each insect species, the production of carbon dioxide of the most resistant and of the most susceptible populations was inversely related to their phosphine resistance. The screening tests identified possible phosphine resistant populations. R. dominica and O. surinamensis were less susceptible to phosphine than the other two species. The populations with lower respiration rate showed a lower mortality at discriminating concentration, possibly related to a phosphine resistance mechanism. Phosphine resistance occurs in stored-product insects, in different regions of Brazil, and the resistance mechanism involves reduced respiration rate.Os objetivos deste trabalho foram avaliar a resistência à fosfina, em populações de insetos (Tribolium castaneum, Rhyzopertha dominica, Sitophilus zeamais e Oryzaephilus surinamensis, de diferentes regiões do Brasil, e verificar se o mecanismo predominante de resistência à fosfina, nessas populações, envolve a redução das taxas respiratórias. Dezesseis populações de T. castaneum, 15 de R. dominica, 27 de S. zeamais e oito de O. surinamensis foram coletadas em 36 locais de sete estados brasileiros. Cada população foi testada quanto à resistência à fosfina, com base na resposta dos adultos à concentração discriminante, de acordo com o método padr

  1. Pd-catalyzed amidation of aryl chlorides using monodentate biaryl phosphine ligands: a kinetic, computational, and synthetic investigation.

    Science.gov (United States)

    Ikawa, Takashi; Barder, Timothy E; Biscoe, Mark R; Buchwald, Stephen L

    2007-10-31

    We present results on the amidation of aryl halides and sulfonates utilizing a monodentate biaryl phosphine-Pd catalyst. Our results are in accord with a previous report that suggests that the formation of kappa(2)-amidate complexes is deleterious to the effectiveness of a catalyst for this transformation and that their formation can be prevented by the use of appropriate bidentate ligands. We now provide data that suggest that the use of certain monodentate ligands can also prevent the formation of the kappa(2)-amidate complexes and thereby generate more stable catalysts for the amination of aryl chlorides. Furthermore, computational studies shed light on the importance of the key feature(s) of the biaryl phosphines (a methyl group ortho to the phosphorus center) that enable the coupling to occur. The use of ligands that possess a methyl group ortho to the phosphorus center allows a variety of aryl and heteroaryl chlorides with various amides to be coupled in high yield.

  2. The reductive P-P coupling of primary and secondary phosphines mediated by N-heterocyclic carbenes.

    Science.gov (United States)

    Schneider, Heidi; Schmidt, David; Radius, Udo

    2015-06-25

    The dehydrogenative coupling of primary and secondary phosphines with the N-heterocyclic carbene iPr2Im (1,3-di-isopropyl-imidazolin-2-ylidene) has been reported. The dehydrogenation of R2PH affords diphosphines R2P-PR2. The reaction of iPr2Im with ArPH2 leads to the formation of NHC phosphinidene adducts iPr2Im[double bond, length as m-dash]PAr and cyclic oligophosphines P4Ar4, P5Ar5 and P6Ar6, depending on the stoichiometry used. The NHC acts in these reactions as a phosphine activator and hydrogen acceptor.

  3. Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin (UC); (Xiamen)

    2016-08-10

    Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.

  4. Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine- Phosphoramidite Ligands

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    HU Juan, WANG Dao-yong, ZHENG Zhuo, HU Xiang-ping J. Mol. Catal. (China) 2012, 26(6), 487 ~492 Chiral phosphine-phosphoramidite ligand, ( So, S,, )-2b, was found to be highly efficient in the Rh-catalyzed asymmetric hydrogenation of various α-enol ester phosphonates, in which excellent enantioselectivities (up to 〉99% ee) and high catalyticactivity ( S/C up to 5000) were achieved.

  5. Gene interactions constrain the course of evolution of phosphine resistance in the lesser grain borer, Rhyzopertha dominica.

    Science.gov (United States)

    Schlipalius, D I; Chen, W; Collins, P J; Nguyen, T; Reilly, P E B; Ebert, P R

    2008-05-01

    Phosphine, a widely used fumigant for the protection of stored grain from insect pests, kills organisms indirectly by inducing oxidative stress. High levels of heritable resistance to phosphine in the insect pest of stored grain, Rhyzopertha dominica have been detected in Asia, Australia and South America. In order to understand the evolution of phosphine resistance and to isolate the responsible genes, we have undertaken genetic linkage analysis of fully sensitive (QRD14), moderately resistant (QRD369) and highly resistant (QRD569) strains of R. dominica collected in Australia. We previously determined that two loci, rph1 and rph2, confer high-level resistance on strain QRD569, which was collected in 1997. We have now confirmed that rph1 is responsible for the moderate resistance of strain QRD369, which was collected in 1990, and is shared with a highly resistant strain from the same geographical region, QRD569. In contrast, rph2 by itself confers only very weak resistance, either as a heterozygote or as a homozygote and was not discovered in the field until weak resistance (probably due to rph1) had become ubiquitous. Thus, high-level resistance against phosphine has evolved via stepwise acquisition of resistance alleles, first at rph1 and thereafter at rph2. The semi-dominance of rph2 together with the synergistic interaction between rph1 and rph2 would have led to rapid selection for homozygosity. A lack of visible fitness cost associated with alleles at either locus suggests that the resistance phenotype will persist in the field.

  6. The rph2 gene is responsible for high level resistance to phosphine in independent field strains of Rhyzopertha dominica.

    Science.gov (United States)

    Mau, Yosep S; Collins, Patrick J; Daglish, Gregory J; Nayak, Manoj K; Ebert, Paul R

    2012-01-01

    The lesser grain borer Rhyzopertha dominica (F.) is one of the most destructive insect pests of stored grain. This pest has been controlled successfully by fumigation with phosphine for the last several decades, though strong resistance to phosphine in many countries has raised concern about the long term usefulness of this control method. Previous genetic analysis of strongly resistant (SR) R. dominica from three widely geographically dispersed regions of Australia, Queensland (SR(QLD)), New South Wales (SR(NSW)) and South Australia (SR(SA)), revealed a resistance allele in the rph1 gene in all three strains. The present study confirms that the rph1 gene contributes to resistance in a fourth strongly resistant strain, SR2(QLD), also from Queensland. The previously described rph2 gene, which interacts synergistically with rph1 gene, confers strong resistance on SR(QLD) and SR(NSW). We now provide strong circumstantial evidence that weak alleles of rph2, together with rph1, contribute to the strong resistance phenotypes of SR(SA) and SR2(QLD). To test the notion that rph1 and rph2 are solely responsible for the strong resistance phenotype of all resistant R. dominica, we created a strain derived by hybridising the four strongly resistant lines. Following repeated selection for survival at extreme rates of phosphine exposure, we found only slightly enhanced resistance. This suggests that a single sequence of genetic changes was responsible for the development of resistance in these insects.

  7. The rph2 gene is responsible for high level resistance to phosphine in independent field strains of Rhyzopertha dominica.

    Directory of Open Access Journals (Sweden)

    Yosep S Mau

    Full Text Available The lesser grain borer Rhyzopertha dominica (F. is one of the most destructive insect pests of stored grain. This pest has been controlled successfully by fumigation with phosphine for the last several decades, though strong resistance to phosphine in many countries has raised concern about the long term usefulness of this control method. Previous genetic analysis of strongly resistant (SR R. dominica from three widely geographically dispersed regions of Australia, Queensland (SR(QLD, New South Wales (SR(NSW and South Australia (SR(SA, revealed a resistance allele in the rph1 gene in all three strains. The present study confirms that the rph1 gene contributes to resistance in a fourth strongly resistant strain, SR2(QLD, also from Queensland. The previously described rph2 gene, which interacts synergistically with rph1 gene, confers strong resistance on SR(QLD and SR(NSW. We now provide strong circumstantial evidence that weak alleles of rph2, together with rph1, contribute to the strong resistance phenotypes of SR(SA and SR2(QLD. To test the notion that rph1 and rph2 are solely responsible for the strong resistance phenotype of all resistant R. dominica, we created a strain derived by hybridising the four strongly resistant lines. Following repeated selection for survival at extreme rates of phosphine exposure, we found only slightly enhanced resistance. This suggests that a single sequence of genetic changes was responsible for the development of resistance in these insects.

  8. The rph2 Gene Is Responsible for High Level Resistance to Phosphine in Independent Field Strains of Rhyzopertha dominica

    Science.gov (United States)

    Mau, Yosep S.; Collins, Patrick J.; Daglish, Gregory J.; Nayak, Manoj K.; Ebert, Paul R.

    2012-01-01

    The lesser grain borer Rhyzopertha dominica (F.) is one of the most destructive insect pests of stored grain. This pest has been controlled successfully by fumigation with phosphine for the last several decades, though strong resistance to phosphine in many countries has raised concern about the long term usefulness of this control method. Previous genetic analysis of strongly resistant (SR) R. dominica from three widely geographically dispersed regions of Australia, Queensland (SRQLD), New South Wales (SRNSW) and South Australia (SRSA), revealed a resistance allele in the rph1 gene in all three strains. The present study confirms that the rph1 gene contributes to resistance in a fourth strongly resistant strain, SR2QLD, also from Queensland. The previously described rph2 gene, which interacts synergistically with rph1 gene, confers strong resistance on SRQLD and SRNSW. We now provide strong circumstantial evidence that weak alleles of rph2, together with rph1, contribute to the strong resistance phenotypes of SRSA and SR2QLD. To test the notion that rph1 and rph2 are solely responsible for the strong resistance phenotype of all resistant R. dominica, we created a strain derived by hybridising the four strongly resistant lines. Following repeated selection for survival at extreme rates of phosphine exposure, we found only slightly enhanced resistance. This suggests that a single sequence of genetic changes was responsible for the development of resistance in these insects. PMID:22461899

  9. Insights into functional-group-tolerant polymerization catalysis with phosphine-sulfonamide palladium (II) complexes

    KAUST Repository

    Jian, Zhongbao

    2014-12-08

    Two series of cationic palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NHC6H3(2,6-R1,R2)]PdMe}2[A]2 (X1+-A: R1=R2=H: H1+-A; R1=R2=CH(CH3)2: DIPP1+-A; R1=H, R2=CF3: CF31+-A; A=BF4 or SbF6) and neutral palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NC6H3(2,6-R1,R2)]PdMe(L)} (X1-acetone: L=acetone; X1-dmso: L=dimethyl sulfoxide; X1-pyr: L=pyridine) chelated by a phosphine-sulfonamide were synthesized and fully characterized. Stoichiometric insertion of methyl acrylate (MA) into all complexes revealed that a 2,1 regiochemistry dominates in the first insertion of MA. Subsequently, for the cationic complexes X1+-A, β-H elimination from the 2,1-insertion product X2+-AMA-2,1 is overwhelmingly favored over a second MA insertion to yield two major products X4+-AMA-1,2 and X5+-AMA. By contrast, for the weakly coordinated neutral complexes X1-acetone and X1-dmso, a second MA insertion of the 2,1-insertion product X2MA-2,1 is faster than β-H elimination and gives X3MA as major products. For the strongly coordinated neutral complexes X1-pyr, no second MA insertion and no β-H elimination (except for DIPP2-pyrMA-2,1) were observed for the 2,1-insertion product X2-pyrMA-2,1. The cationic complexes X1+-A exhibited high catalytic activities for ethylene dimerization, affording butenes (C4) with a high selectivity of up to 97.7% (1-butene: 99.3%). Differences in activities and selectivities suggest that the phosphine-sulfonamide ligands remain coordinated to the metal center in a bidentate fashion in the catalytically active species. By comparison, the neutral complexes X1-acetone, X1-dmso, and X1-pyr showed very low activity towards ethylene to give traces of oligomers. DFT analyses taking into account the two possible coordination modes (O or N) of the sulfonamide ligand for the cationic system CF31+ suggested that the experimentally observed high activity in ethylene dimerization is the result of a facile first ethylene insertion into the O-coordinated PdMe isomer and

  10. Genetic characterization of field-evolved resistance to phosphine in the rusty grain beetle, Cryptolestes ferrugineus (Laemophloeidae: Coleoptera).

    Science.gov (United States)

    Jagadeesan, Rajeswaran; Collins, Patrick J; Nayak, Manoj K; Schlipalius, David I; Ebert, Paul R

    2016-02-01

    Inheritance of resistance to phosphine fumigant was investigated in three field-collected strains of rusty grain beetle, Cryptolestes ferrugineus, Susceptible (S-strain), Weakly Resistant (Weak-R) and Strongly Resistant (Strong-R). The strains were purified for susceptibility, weak resistance and strong resistance to phosphine, respectively, to ensure homozygosity of resistance genotype. Crosses were established between S-strain×Weak-R, S-strain×Strong-R and Weak-R×Strong-R, and the dose mortality responses to phosphine of these strains and their F1, F2 and F1-backcross progeny were obtained. The fumigations were undertaken at 25°C and 55% RH for 72h. Weak-R and Strong-R showed resistance factors of 6.3× and 505× compared with S-strain at the LC50. Both weak and strong resistances were expressed as incompletely recessive with degrees of dominance of -0.48 and -0.43 at the LC50, respectively. Responses of F2 and F1-backcross progeny indicated the existence of one major gene in Weak-R, and at least two major genes in Strong-R, one of which was allelic with the major factor in Weak-R. Phenotypic variance analyses also estimated that the number of independently segregating genes conferring weak resistance was 1 (nE=0.89) whereas there were two genes controlling strong resistance (nE=1.2). The second gene, unique to Strong-R, interacted synergistically with the first gene to confer a very high level of resistance (~80×). Neither of the two major resistance genes was sex linked. Despite the similarity of the genetics of resistance to that previously observed in other pest species, a significant proportion (~15 to 30%) of F1 individuals survived at phosphine concentrations higher than predicted. Thus it is likely that additional dominant heritable factors, present in some individuals in the population, also influenced the resistance phenotype. Our results will help in understanding the process of selection for phosphine resistance in the field which will inform

  11. Synthesis and Mossbauer spectroscopic studies of chemically oxidized ferrocenyl(phenyl)phosphines.

    Science.gov (United States)

    Durfey, D A; Kirss, R U; Frommen, C; Feighery, W

    The electrochemical potentials of Fc3-xPPhx, (1-3, x = 0-2) and (FcPPh)n (4) indicate that iodine should oxidize ferrocenyl(phenyl)phosphines. The molar conductivity of solutions of 1-3 increases sharply when the solutions are titrated with iodine, leveling off after the addition of > 2 equiv of oxidant, consistent with formation of 1:1 electrolytes. Diamagnetic salts 6-9 are observed upon addition of a benzene solution of iodine to a benzene solution of 1-4 at ambient temperature in ratios of I2/metallocene ranging from 1:1 to 2:1. Well-resolved 1H and 31P NMR spectra are obtained for 6-8. Absorptions assigned to the I3- anion dominate the UV-vis spectrum of 6-8, whereas characteristic absorptions for [Fc][I3] are absent. Mossbauer spectra of 7-9 reveal isomer shifts consistent with low-spin iron(II) in ferrocene derivatives rather than those in ferricenium ions. Small amounts of low-spin FeIII appear to be present in 6. Taken together, the results suggest that 6-9 are iodophosphonium salts and not ferricenium salts. Diferrocenyl(phenyl)phosphine oxide (5) reacts with iodine to produce a diamagnetic, dark solid 10. Low-spin FeII is observed at 77 and 293 K in the Mossbauer spectra of 10 with no evidence for oxidation of FeII to FeIII. Compound 10 is proposed to be a neutral complex between 5 and I2. Reactions between 5 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) yield [Fc2P(=O)][DDQ]2 (11). Mossbauer spectroscopy of 11 indicates the presence of a mixture of low-spin FeII and low-spin FeIII at 77 K, suggesting that some electron transfer occurs from 5 to DDQ. The fraction of low-spin FeIII increases at room temperature.

  12. Palladium(II) complexes with tris(2-carboxyethyl)phosphine, structure, reactions and cytostatic activity.

    Science.gov (United States)

    Pruchnik, Hanna; Lis, Tadeusz; Latocha, Małgorzata; Zielińska, Aleksandra; Pruchnik, Florian P

    2016-03-01

    Water soluble and air stable P(RCOOH)3 (R=C2H4) (TCEP) is an efficient reducing agent used in biochemistry to break S-S bond in peptides, proteins and other compounds containing S-S bonds. The similarity between the coordination chemistry of Pd(II) and Pt(II) led to the investigations of antitumor activity of palladium(II) compounds however the Pd(II) complexes with TCEP were not investigated. New palladium(II) complexes with (TCEP): trans-[PdCl2(TCEP)2] (1) and trans-[Pd2(μ-Cl)2Cl2(TCEP)2] (2) were fully characterized by (1)H, (13)C, (31)P NMR, IR and ESI-MS spectroscopic techniques. Complexes are stable in non-aqueous DMSO and DMF. In aqueous solutions Cl ligands are substituted by COO groups of phosphines. Complex 2, after crystallization from water gives polymeric compound with bridging phosphine ligand [PdCl{P(RCOO-κO-μ-O')(RCOOH)2-κP}] (3). Structures of trans-[PdCl2{P(RCOOD)3}2] (1a), trans-[Pd2(μ-Cl)2PdCl2{P(RCOOD)3}2] (2a), and [PdCl{P(RCOO-κO-μ-O')(RCOOD)2-κP}]n (3a) have been determined by X-ray crystallography. NMR and ESI-MS spectra reveal that [PdP2(RCOO-κO)2(RCOO)n(RCOOH)4-n](n)(-) complexes are formed in aqueous solution of 1. Geometry optimization in the gas phase at the B3LYP/3-21G** level indicated that complex 2 with butterfly structure is more stable than that with coplanar coordination. In aqueous solution of 2, the main products [Pd2{P(RCOO-κO-μ-O')(RCOO-κO)(RCOOH)}2] and [Pd{P(RCOO-κO)2(RCOOH)}(H2O)] exist in equilibrium which depends on temperature: content of mononuclear compound increases as the temperature is raised. Complexes 1 and 2 are active agents against melanoma and breast cancer cells.

  13. Cationic Gold Clusters Ligated with Differently Substituted Phosphines: Effect of Substitution on Ligand Reactivity and Binding

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Olivares, Astrid M.; Hill, David E.; Laskin, Julia

    2015-01-01

    We present a systematic study of the effect of the number of methyl (Me) and cyclohexyl (Cy) functional groups in monodentate phosphine ligands on the solution-phase synthesis of ligated sub-nanometer gold clusters and their gas-phase fragmentation pathways. Small mixed ligand cationic gold clusters were synthesized using ligand exchange reactions between pre-formed triphenylphosphine ligated (PPh3) gold clusters and monodentate Me- and Cy-substituted ligands in solution and characterized using electrospray ionization mass spectrometry (ESI-MS) and collision-induced dissociation (CID) experiments. Under the same experimental conditions, larger gold-PPh3 clusters undergo efficient exchange of unsubstituted PPh3 ligands for singly Me- and Cy-substituted PPh2Me and PPh2Cy ligands. The efficiency of ligand exchange decreases with an increasing number of Me or Cy groups in the substituted phosphine ligands. CID experiments performed for a series of ligand-exchanged gold clusters indicate that loss of a neutral Me-substituted ligand is preferred over loss of a neutral PPh¬3 ligand while the opposite trend is observed for Cy-substituted ligands. The branching ratio of the competing ligand loss channels is strongly correlated with the electron donating ability of the phosphorous lone pair as determined by the relative proton affinity of the ligand. The results indicate that the relative ligand binding energies increase in the order PMe3 < PPhMe2 < PPh2Me < PPh3< PPh2Cy < PPhCy2< PCy3. Furthermore, the difference in relative ligand binding energies increases with the number of substituted PPh3-mMem or PPh3-mCym ligands (L) exchanged onto each cluster. This study provides the first experimental determination of the relative binding energies of ligated gold clusters containing differently substituted monophosphine ligands, which are important to controlling their synthesis and reactivity in solution. The results also indicate that ligand substitution is an important

  14. On the origin of reversible hydrogen activation by phosphine-boranes.

    Science.gov (United States)

    Rajeev, Ramanan; Sunoj, Raghavan B

    2009-11-23

    Mechanistic insights into the factors responsible for the reversible hydrogen-activation ability exhibited by an aryl phosphine-borane system ((CH(3))(2)P-C(6)F(4)-B(CF(3))(2)) are presented. A detailed evaluation of the energies of various intermediates, generated by the addition of molecular hydrogen, and their interconverting barriers have been carried out using ab initio and DFT methods. Several rearrangement possibilities of the H(2)-phosphino-borane adduct have been investigated so as to unravel the lower energy pathways that convert the initial adduct to a series of other intermediates. The initial adduct formed by the heterolytic addition of a molecular hydrogen across the C-B bond is identified to undergo a series of rearrangement reactions until it terminates at the C-P end of the molecule. Among the possible 1,n-migrations (for which n=1-5), 1,2-proton migrations are found to possess lower energy transition states, whereas 1,2-hydride (in a zwitterionic intermediate) and 1,4-proton-coupled electron transfers exhibited much higher energy transition states. The minimum energy pathway for the transfer of a proton and hydride from the C-B bond to the C-P bond is found to involve a cascade of 1,2-proton transfers followed by a 1,2-hydride migration and finally a 1,4-proton-coupled electron transfer. The higher energy pathways identified for the hydride transfer suggest the possibility of a cascade of reversible proton migrations from a thermodynamically stable intermediate (M(a)). Possible uptake of two hydrogen molecules by the phosphine-borane system is additionally considered in the present study, in which relatively higher barriers than those with one molecule of hydrogen are observed. The computed thermodynamic parameters are found to be in accordance with the experimental observations, in which the uptake and storage of molecular hydrogen are carried out at lower temperatures whereas the liberation demands elevated temperatures.

  15. Toxicity of phosphine on the developmental stages of rust-red flour beetle, Tribolium castaneum Herbst over a range of concentrations and exposures.

    Science.gov (United States)

    Manivannan, S

    2015-10-01

    The susceptibility of the developmental stages of rust-red flour beetle, Tribolium castaneum to a range of concentrations of phosphine over varying durations from 24 to 168 h was reconnoitered in the laboratory at 25 ± 2 °C. Responses of the life stages exposed to phosphine were compared with those of un-treated controls over 24, 48, 72, 96, 120, 144 and 168 h exposures and mortality was assessed after 14 days. Among the life stages tested, pupae were more tolerant to phosphine followed by the egg and the larval instars. At 24 h, the maximum LC50 value was observed in case of egg; 1.571 mgL(-1); followed by the pupae, 6(th) instar, 4(th) instar and 2(nd) instar larvae with LC50 values of 1.184, 0.336, 0.212 and 0.081 mgL(-1) respectively. However, continued exposure of the developmental stages to phosphine, recorded maximum LC values in the pupae followed by egg and the larval instars. A linear increase in the mortality response was witnessed in all the insect stages when the exposure periods were extended from 24 to 168 h with increasing concentrations of phosphine, conversely significant increase in mortality was greatly apparent during the initial treatment periods.

  16. Kinetics and Mechanism of the Aminolyses of Bis(2-oxo-3-oxazolidinyl) Phosphinic Chloride in Acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Barai, Hasi Rani; Lee, Hai Whang [Inha Univ., Incheon (Korea, Republic of)

    2013-11-15

    The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and 35.0 .deg. C, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted S{sub N}2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects (k{sub H}/k{sub D}) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

  17. Free atmospheric phosphine concentrations and fluxes in different wetland ecosystems, China

    Energy Technology Data Exchange (ETDEWEB)

    Han Chao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Geng Jinju, E-mail: jjgeng@nju.edu.c [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Hong Yuning [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Zhang Rui [School of Chemistry and Environmental Science, Nanjing Normal University, Nanjing 210097 (China); Gu Xueyuan; Wang Xiaorong; Gao Shixiang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210046 (China); Glindemann, Dietmar [Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA 24061 (United States)

    2011-02-15

    Atmospheric phosphine (PH{sub 3}) fluxes from typical types of wetlands and PH{sub 3} concentrations in adjacent atmospheric air were measured. The seasonal distribution of PH{sub 3} in marsh and paddy fields were observed. Positive PH{sub 3} fluxes are significantly related to high air temperature (summer season) and increased vegetation. It is concluded that vegetation speeds up the liberation of PH{sub 3} from soils, while water coverage might function as a diffusion barrier from soils or sediments to the atmosphere. The concentrations of atmospheric PH{sub 3} (ng m{sup -3}) above different wetlands decrease in the order of paddy fields (51.8 {+-} 3.1) > marsh (46.5 {+-} 20.5) > lake (37.0 {+-} 22.7) > coastal wetland (1.71 {+-} 0.73). Highest atmospheric PH{sub 3} levels in marsh are found in summer. In paddy fields, atmospheric PH{sub 3} concentrations in flourishing stages are higher than those in slowly growing stages. - Research highlights: P could migrate as PH{sub 3} gas in different wetland ecosystems. Wetlands act as a source and sink of atmospheric PH{sub 3}. Positive PH{sub 3} fluxes are significantly related to high temperature and increased vegetation. Environmental PH{sub 3} concentrations in China are generally higher. - Environmental PH{sub 3} concentrations in China are generally higher compared to other parts of the world.

  18. Tuning luminescent properties of CdSe nanoclusters by phosphine surface passivation

    Science.gov (United States)

    Lysova, Iryna; Anton, Halina; Dmitruk, Igor; Mely, Yves

    2016-12-01

    Appropriate surface ligands are required for tuning the physicochemical and photophysical properties of nanoclusters (NCs). These surface ligands are especially critical for passivating the small (CdSe)33,34 NCs where the majority of atoms are at the NC surface. In this study, triphenylphosphine (TPP), trioctylphosphine (TOP) and tris(pentafluorophenyl)phosphine (TPFP) have been tested as capping agents for alkylamine-coated CdSe NCs. TPP and TOP compounds are found to increase the quantum yield of photoluminescence (PL) from 0.15% to 0.6% and 0.53%, respectively, and to preserve this increased PL with time, probably by preventing charge leakage as a result of their binding to Se atoms. Since no dramatic change in the shape of NCs’ PL spectrum occurs after surface treatment, both the exciton band and the low-energy broad band in magic NCs are thought to describe the intrinsic luminescence properties of the NCs. As a result, the PL increase due to Se passivation is thought to be mainly caused by a decrease in the efficiency of the NC nonradiative pathways.

  19. Effects of applied potential on phosphine formation in synthetic wastewater treatment by Microbial Electrolysis Cell (MEC).

    Science.gov (United States)

    Liu, Wei; Niu, Xiaojun; Chen, Weiyi; An, Shaorong; Sheng, Hong

    2017-04-01

    Phosphine (PH3) emission from conventional biological wastewater treatment is very inefficient (ng-μg m(-3)). In this work, we investigated the feasibility of promoting PH3 formation from inorganic phosphorus (IP) or organic phosphorus (OP) containing synthetic wastewater treatment by Microbial Electrolysis Cell (MEC) for the first time. Positive effect of applied potential on PH3 production was observed after methanogens was inhibited. The highest production of PH3 (1103.10 ± 72.02 ng m(-3)) was obtained in IP-fed MEC operated at -0.6 V, which was about 5-fold and 2-fold compared to that in open circuit experiment and OP-fed MEC, respectively. Meanwhile, PH3 formation corresponded positively with current density and alkaline phosphatase activity. This result showed that suitable potential could enhance the activity of relevant enzymes and boost the biosynthesis of PH3. Bacterial communities analysis based on high-throughput sequencing revealed that applied potential was conductive to the enrichment of phosphate-reducing organisms in contrast to the control test. These results provide a new idea for resource utilization of phosphorus in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Study on crystallization behaviour of co-polyamide 66 containing triaryl phosphine oxide

    Indian Academy of Sciences (India)

    Yang Xiao Feng; Li Qiao Ling; Chen Zhi Ping; Yang Yong Feng; Zhang Lei

    2012-04-01

    In this paper, the isothermal crystallization and non-isothermal crystallization behaviour of flame retardant co-polyamide 66 (FR-PA66) containing triaryl phosphine oxide (TPO) were researched by employing differential scanning calorimetry (DSC), polarized optical microscopy (POM), respectively. The effects of TPO groups on nucleation mechanism, nucleation pattern and crystallization rate of FR-PA66 were discussed in detail. Experimental results show that TPO unit does not nucleate first during crystallization process of FR-PA66. The nucleationmechanism and nucleation pattern of FR-PA66 do not virtually change with incorporation of TPO groups when compared with polyamide 66 (PA66). The mainly crystallization process of FR-PA66 is still free nucleation and growing during the prime crystallization stage, and is unimensional nucleation and growing during the second crystallization stage. But at the second crystallization stage, we think there is a para-crystal forming with the maincrystal unimensional nucleation and growing. In addition, incorporation of TPO groups result in the decrement of both nucleation rate and crystallization rate of FR-PA66, and the increment of crystallization activation energy. Hence the TPO groups were unfavourable for FR-PA66 crystallization. In addition, incorporation of TPO groups also result in the decrement of crystallization region of FR-PA66, and increment of spherulite defect.

  1. Synthesis of novel and diverse naphtho[1,2-b]furans by phosphine-catalyzed [3+2] annulation of activated 1,4-naphthoquinones and acetylenecarboxylates.

    Science.gov (United States)

    Xia, Likai; Magar, Krishna Bahadur Somai; Lee, Yong Rok

    2015-02-01

    A new phosphine-catalyzed [3+2] annulation reaction between activated 1,4-naphthoquinones and acetylenecarboxylates is described. This reaction provides a facile and efficient route to a variety of biologically promising and novel naphtho[1,2-b]furans. This devised method provides a first example for the synthesis of diverse naphtho[1,2-b]furan derivatives from 1,4-naphthoquinones via phosphine-catalyzed [3+2] annulation. A variety of novel naphtho[1,2-b]furans were synthesized via the phosphine-catalyzed [3+2] annulation of activated 1,4-naphthoquinones and electron-deficient acetylenecarboxylates. In some reactions, both furannulation adducts and reductive/nucleophilic conjugate addition products were produced.

  2. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

    Directory of Open Access Journals (Sweden)

    Fuentes José A

    2012-12-01

    Full Text Available Abstract Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S-1-amino-2-indanol, (S,S-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L(DMSO] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.

  3. Susceptibility of Two Strains of the Confused Flour Beetle (Coleoptera: Tenebrionidae) Following Phosphine Structural Mill Fumigation: Effects of Concentration, Temperature, and Flour Deposits.

    Science.gov (United States)

    Aulicky, R; Stejskal, V; Frydova, B; Athanassiou, C G

    2015-12-01

    In this study, we evaluated phosphine efficacy against two strains of the confused flour beetle, Tribolium confusum Jacquelin du Val (Coleoptera: Tenebrionidae), one laboratory strain, with no previous exposure to phosphine, and one field strain, originated from the flour mill on which we performed the fumigation. The standard Detia Degesh Phosphine Resistance Kit showed that the adults of the field strain of T. confusum required 4.4 × longer time to be knocked down than the laboratory strain. In order to assess the efficacy of phosphine in the field against these strains, aluminium phosphide (AlP) was applied in a flour mill in Czech Republic, in 2014. In this application, temperature among the six floors of the flour mill varied between 20 and 30°C, relative humidity (RH) between 44 and 78%, and phosphine concentration-time-products (CtP) between 24 and 38 g.m(-3).h(-1). Moreover, the insects were bioassayed in dishes that contained either no commodity or 1, 3, and 5 cm of flour. Nevertheless, despite these variations, all adults and larvae from both strains were dead, regardless of the floor, the quantity of the commodity, and the conditions prevailing. However, larval emergence from eggs that were used in the bioassays for both strains was recorded in some of the locations tested. In addition, larval emergence was negatively correlated with both temperature and RH. At the same time, emergence was generally similar between strains. The results of the present study illustrate that highly visible dead adults and larvae after the application of phosphine falsely imply good fumigation efficacy, given that a considerable number of eggs are very likely to survive in a wider range of conditions, and the concomitant larval emergence may result in rapid population grown right after the fumigation.

  4. New surfactant phosphine ligands and platinum(II) metallosurfactants. Influence of metal coordination on the critical micelle concentration and aggregation properties.

    Science.gov (United States)

    Parera, Elisabet; Comelles, Francesc; Barnadas, Ramon; Suades, Joan

    2010-01-19

    We have prepared the first platinum(II) metallosurfactants from a new family of linear surfactant phosphines Ph(2)P(CH(2))(n)SO(3)Na {1 (n = 2), 2 (n = 6), and 3 (n = 10)}, which were synthesized by reaction between the halosulfonates X(CH(2))(n)SO(3)Na and sodium diphenylphosphide. The metallosurfactants cis-[PtCl(2)L(2)] (L = 1-3) were obtained after reaction between the phosphines and PtCl(2) in dimethylsulfoxide. All compounds were fully characterized by the usual methods {NMR ((1)H, (13)C, (31)P, (195)Pt), IR, MS-ESI and HRMS}. By exploring the surfactant properties of phosphines 1-3 and their respective platinum metallosurfactants cis-[PtCl(2)L(2)] (L = 1-3) through surface tension measurements, dynamic light scattering spectroscopy, and cryo-TEM microscopy, we were able to analyze the influence of the metal coordination on the critical micelle concentration (cmc) and the aggregation properties. The cmc values of platinum metallosurfactants were considerably lower than those obtained for the free phosphines 1-3. This behavior could be understood by an analogy between the structure of cis-[PtCl(2)L(2)] complexes and bolaform surfactants. The calculated values of area per molecule also showed different tendencies between 1-3 and cis-[PtCl(2)L(2)] complexes, which could be explained on the basis of the possible conformations of these compounds in the air-water interface. The study of aggregates by dynamic light scattering spectroscopy and cryo-TEM microscopy showed the formation of spherical disperse medium size vesicles in all cases. However, substantial differences were observed between the three free phosphines (the population of micellar aggregates increased with long chain length) and also between phosphines and their respective metallosurfactants.

  5. MCM-41-Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins%MCM-41-Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins

    Institute of Scientific and Technical Information of China (English)

    胡荣华; 郝文燕; 蔡明中

    2011-01-01

    MCM-41-supported bidentate phosphine rhodium complex (MCM-41-2P-RhC13) was conveniently synthesized from commercially available and cheap γ-aminopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that the title complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.

  6. Effectiveness of Sulfuryl Fluoride Fumigation for the Control of Phosphine-Resistant Grain Insects Infesting Stored Wheat.

    Science.gov (United States)

    Opit, George P; Thoms, Ellen; Phillips, Thomas W; Payton, Mark E

    2016-04-01

    A field experiment was conducted in eight 13.6-MT steel bins containing 6.8 MT each of wheat to assess efficacy of sulfuryl fluoride or SF fumigant to control phosphine-resistant and susceptible Rhyzopertha dominica (F.) and Tribolium castaneum (Herbst). Approximately 400 adults of each type of beetle were added to each bin. Additionally, muslin bags containing immature stages and adults, with their respective diets, were also placed in bins. Four bins were fumigated with SF and others were untreated control bins. The SF dosages in treated bins ranged from 1,196–1,467 mg-h/liter. Mortality of adults in each bag was assessed 5 d postfumigation; diet minus adults was incubated in a jar, and number of adults counted after 8 wk. No significant change occurred in number of insect-damaged kernels in SF-treated bins. In trier samples from SF-treated bins, R. dominica numbers declined from 24 prefumigation to 0 at 3- and 6-wk postfumigation; T. castaneum numbers were unchanged. In WBII traps from SF-treated bins, numbers R. dominica and T. castaneum declined from 25 and 33, respectively, prefumigation to 0 or near 0 at 3- and 6-wk postfumigation. Mortalities of resistant and susceptible adult R. dominica, and adult and large larvae of T. castaneum in SF-treated bags was 100%. For all four types of beetles, adult numbers in jars associated with SF-treated bins were 0 or near 0. Results show SF is effective against all life stages of phosphine-resistant R. dominica and T. castaneum, and can be used for phosphine resistance management.

  7. Evaluation of sorbent materials for the sampling and analysis of phosphine, sulfuryl fluoride and methyl bromide in air.

    Science.gov (United States)

    Magnusson, R; Rittfeldt, L; Åstot, C

    2015-01-02

    Phosphine (PH3), sulfuryl fluoride (SO2F2) and methyl bromide (CH3Br) are highly toxic chemical substances commonly used for fumigation, i.e., pest control with gaseous pesticides. Residues of fumigation agents constitute a health risk for workers affected, and therefore accurate methods for air sampling and analysis are needed. In this study, three commercial adsorbent tubes; Carbosieve SIII™, Air Toxics™ and Tenax TA™, were evaluated for sampling these highly volatile chemicals in air and their subsequent analysis by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The breakthrough volume (BTV) of each fumigant was experimentally determined on the different adsorbents at concentrations at or above their permissible exposure limits, using a method based on frontal chromatography of generated fumigant atmospheres. Carbosieve SIII™, a molecular sieve possessing a very high specific area, proved to be a better adsorbent than both Air Toxics™ and Tenax TA™, resulting in at least a 4-fold increase of the BTV50%. BTV50% for Carbosieve SIII™ at 20°C was measured as 4.7L/g, 5.5L/g and 126L/g for phosphine, sulfuryl fluoride and methyl bromide, respectively, implying safe sampling volumes of 1.9L, 2.2L and 50L, respectively, for a commercial tube packed with 800mg Carbosieve SIII™. The temperature dependence of BTV was strong for Carbosieve SIII™, showing a reduction of 3-5%/°C in breakthrough volume within the range -20 to 40°C. Furthermore, although Carbosieve SIII™ reportedly has a higher affinity for water than most other adsorbents, relative humidity had only a moderate influence on the retention capacity of phosphine. Overall, the applicability of Carbosieve SIII™ adsorbent sampling in combination with TD-GC-MS analysis was demonstrated for highly volatile fumigants.

  8. Evidence for a SN2-type pathway in the exchange of phosphines at a [PhSe]+ centre.

    Science.gov (United States)

    Forfar, Laura C; Green, Michael; Haddow, Mairi F; Hussein, Sharifa; Lynam, Jason M; Slattery, John M; Russell, Christopher A

    2015-01-07

    A range of thio- and seleno-phosphonium cationic complexes [RE(PR'3)](+)[X](-) (R = Me, Ph; E = S, Se; X = GaCl4, SbF6) have been synthesised and structurally characterised. Reaction of [PhSPPh3][GaCl4] and [PhSePPh3][GaCl4] with P(t)Bu3 results in the ready transfer of the "RS(+)" and "RSe(+)" fragments from PPh3 to the stronger electron donor P(t)Bu3. NMR experiments combined with an Eyring analysis on the corresponding degenerate phosphine exchange reaction allowed the thermodynamic values for the phosphine exchange reaction of the sulfur cation (ΔH(‡) 18.7 ± 12.0 kJ mol(-1); ΔS(‡) -99.3 ± 36.3 J mol(-1) K(-1)) to be compared with the corresponding values (ΔH(‡) 2.4 ± 1.1 kJ mol(-1) and ΔS(‡) -58.1 ± 5.0 J mol(-1) K(-1)) for the [PhSePPh3](+) system. Importantly, the large negative entropy of activation and linear dependence on the rate of exchange are compatible with an SN2-type exchange process. This conclusion is supported by DFT calculations which confirm that the phosphine exchange process occurs via an associative mechanism. The rate of exchange was found to increase from sulfur to selenium and those with aryl substituents underwent exchange faster than those with alkyl substituents.

  9. Bridging Binding Modes of Phosphine-Stabilized Nitrous Oxide to Zn(C6F5)2

    NARCIS (Netherlands)

    Neu, Rebecca C.; Otten, Edwin; Stephan, Douglas W.

    2009-01-01

    Reaction of [tBu3PN2O(B(C6H4F)3)] with 1, 1.5, or 2 equivalents of Zn(C6F5)2 affords the species [{tBu3PN2OZn(C6F5)2}2], [{tBu3PN2OZn(C6F5)2}2Zn(C6F5)2], and [tBu3PN2O{Zn(C6F5)2}2] displaying unique binding modes of Zn to the phosphine-stabilized N2O fragment.

  10. Triphenyl phosphine adducts of platinum(IV) and palladium(II) dithiocarbamates complexes: a spectral and in vitro study

    Science.gov (United States)

    Manav, N.; Mishra, A. K.; Kaushik, N. K.

    2004-11-01

    Triphenyl phosphine adducts of dithiocarbamate complexes of platinum(IV) and palladium(II) of the type [Pt(L) 2PPh 3Cl 2] and [Pd(L) 2PPh 3] [L: morpholine dithiocarbamate (L 1), aniline dithiocarbamate (L 2) and N-(methyl, cyclohexyl) dithiocarbamate (L 3)] were prepared and characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. Thermal studies of the complexes were carried out. In vitro antitumor activity has been screened towards human adenocarcinoma cell lines and showed significant inhibition even at very low concentration.

  11. Addition of Zn during the phosphine-based synthesis of indium phospide quantum dots: doping and surface passivation

    OpenAIRE

    2015-01-01

    Zinc-doped InP(Zn) colloidal quantum dots (QDs) with narrow size distribution and low defect concentration were grown for the first time via a novel phosphine synthetic route and over a wide range of Zn doping. We report the influence of Zn on the optical properties of the obtained quantum dots. We propose a mechanism for the introduction of Zn in the QDs and show that the incorporation of Zn atoms into the InP lattice leads to the formation of Zn acceptor levels and a luminescence tail in th...

  12. Synthesis of polymeric phosphine-carborane complexes Rh(I) and their catalytic properties in hydrogenation of olefins and dienes

    Energy Technology Data Exchange (ETDEWEB)

    Kalinin, V.N.; Melnik, O.A.; Sakharova, A.A.; Frunze, T.M.; Zakharkin, L.I.; Borunova, N.V.; Sharf, V.Z.

    1985-11-01

    Methylmethacrylate copolymers with 1-isopropenyl-(3)-1,2-dicarbamdecaborate salts were synthesized which, after reaction with Rh(PPh/sub 3/)/sub 3/Cl were converted to polymeric phosphine-carborane complexes. Their catalytic properties in hydrogenation and isomerization of olefins and dienes were investigated. These catalysts were found to be highly active. Hydrogenation of dienes was not as rapid as that of olefins. The rates depended significantly on the solvent used. The unique aspect of this catalytic system is the fact that, even at the early synthetic stage, the labile hydrogen atom of dicarbamdecaborate anion shifts toward Rh forming a monohydride complex. 6 references, 3 figures.

  13. Induced Circular Dichroism in Phosphine Gold(I) Aryl Acetylide Urea Complexes through Hydrogen-Bonded Chiral Co-Assemblies.

    Science.gov (United States)

    Dubarle-Offner, Julien; Moussa, Jamal; Amouri, Hani; Jouvelet, Benjamin; Bouteiller, Laurent; Raynal, Matthieu

    2016-03-14

    Phosphine gold(I) aryl acetylide complexes equipped with a central bis(urea) moiety form 1D hydrogen-bonded polymeric assemblies in solution that do not display any optical activity. Chiral co-assemblies are formed by simple addition of an enantiopure (metal-free) complementary monomer. Although exhibiting an intrinsically achiral linear geometry, the gold(I) aryl acetylide fragment is located in the chiral environment displayed by the hydrogen-bonded co-assemblies, as demonstrated by induced circular dichroism (ICD). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Transcriptional inhibition of the Catalase gene in phosphine-induced oxidative stress in Drosophila melanogaster.

    Science.gov (United States)

    Liu, Tao; Li, Li; Zhang, Fanhua; Wang, Yuejin

    2015-10-01

    Phosphine (PH3) is a toxic substance to pest insects and is therefore commonly used in pest control. The oxidative damage induced by PH3 is considered to be one of the primary mechanisms of its toxicity in pest insects; however, the precise mode of PH3 action in this process is still unclear. In this study, we evaluated the responses of several oxidative biomarkers and two of the main antioxidant enzymes, catalase (CAT) and superoxide dismutase (SOD), after fumigation treatment with PH3 in Drosophila melanogaster as a model system. The results showed that larvae exposed to sub-lethal levels of PH3 (0.028 mg/L) exhibited lower aerobic respiration rates and higher levels of hydrogen peroxide (H2O2) and lipid peroxidation (LPO). Furthermore, unlike SOD, the activity and expression of CAT and its encoding gene were downregulated by PH3 in a time- and dose-dependent manner. Finally, the responses of six potential transcription factors of PH3 were determined by real-time polymerase chain reaction to explore the regulation mechanism of DmCAT by PH3. There were no significant effects of PH3 on three nuclear factor-kappa B homologs (DORSAL, DIF, and RELISH) or two activator protein-1 genes (JUN and FOS), while dramatic inhibition of DNA replication-related element factor (DREF) expression was observed after fumigation with PH3, suggesting that PH3 could inhibit the expression of DmCAT via the DRE/DREF system. These results confirmed that PH3 induces oxidative stress and targets CAT by downregulating its encoding gene in Drosophila. Our results provide new insight into the signal transduction mechanism between PH3 and its target genes.

  15. Synthesis and Reactivity of Iron-Iridium Heterobimetallic Complexes Using Tridentate Phosphine Ligands

    OpenAIRE

    Nawar, N. [نجوى نوار

    1994-01-01

    Treatment of {Fe (CO)3 {(PPh2) 2 C=CH2}] with PPh2H gives the addition product [Fe (CO)3 {(PPh2) 2 CHCH2 PPh2}] (1). The uncoordinated phosphine group of complex 1 reacts with Ir4 (CO)12 to give mono-, di- and tri-substituted heterobimetallic cluster complexes. درس تفاعل المتراكب [} C0)3 Fe {(PPh2)2 C=CH2)] مع ثنائي فينيل الفوسفين وفق تفاعل مايكل للإضافة . ‏وقد استخدمت المتراكبات الناتجة في تحضير متراكبات ثنائية الفلز غير المتجانس . وقد أظهرت الدراسة أن مجموعة الفوسفين غير المرتبطة في ...

  16. Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

    Directory of Open Access Journals (Sweden)

    Adam N. Swinburne

    2016-09-01

    Full Text Available The construction of lanthanide(III chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac3{(ArF3PO}(H2O] and [Ln(F7-acac3{(ArF3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+. Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac3{(ArF3PO}(H2O] (1, [Yb(hfac3{(ArF3PO}(H2O] (5, [Sm(F7-acac3{(ArF3PO}2] (6 and [Yb(F7-acac3{(ArF3PO}2] (10 exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1; 1.4% (10 and in the solid state (ΦLn = 8.5% (1; 2.0% (5; 26% (6; 11% (10, which are amongst the largest values for this class of compounds to date.

  17. P-Fluorous Phosphines as Electron-Poor/Fluorous Hybrid Functional Ligands for Precious Metal Catalysts: Synthesis of Rh(I, Ir(I, Pt(II, and Au(I Complexes Bearing P-Fluorous Phosphine Ligands

    Directory of Open Access Journals (Sweden)

    Shin-ichi Kawaguchi

    2017-01-01

    Full Text Available P-Fluorous phosphine (R2PRf, in which the perfluoroalkyl group is directly bonded to the phosphorus atom, is a promising ligand because it has a hybrid functionality, i.e., electron-poor and fluorous ligands. However, examples of P-fluorous phosphine–metal complexes are still rare, most probably because the P-fluorous group is believed to decrease the coordination ability of the phosphines dramatically. In contrast, however, we have succeeded in synthesizing a series of P-fluorous phosphine–coordinated metal complexes such as rhodium, iridium, platinum, and gold. Furthermore, the electronic properties of R2PnC10F21 are investigated by X-ray analysis of PtCl2(Ph2PnC10F212 and the infrared CO stretching frequency of RhCl(CO(R2PnC10F212. IrCl(CO(Ph2PnC10F212- and AuCl(R2PnC10F21-catalyzed reactions are also demonstrated.

  18. Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic imines.

    Science.gov (United States)

    Quan, Mao; Tang, Liang; Shen, Jiaqi; Yang, Guoqiang; Zhang, Wanbin

    2017-01-03

    A Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic aldimines and ketimines is reported. Our tropos phosphine-oxazoline biphenyl ligand is crucial for the high catalytic activity, which coordinates to Ni(ii) to form a complex with a single axial configuration. The desired chiral amine products could be prepared with excellent yields (up to 99%) and enantioselectivities (up to 99.8%) under mild reaction conditions.

  19. Discovery of Brigatinib (AP26113), a Phosphine Oxide-Containing, Potent, Orally Active Inhibitor of Anaplastic Lymphoma Kinase.

    Science.gov (United States)

    Huang, Wei-Sheng; Liu, Shuangying; Zou, Dong; Thomas, Mathew; Wang, Yihan; Zhou, Tianjun; Romero, Jan; Kohlmann, Anna; Li, Feng; Qi, Jiwei; Cai, Lisi; Dwight, Timothy A; Xu, Yongjin; Xu, Rongsong; Dodd, Rory; Toms, Angela; Parillon, Lois; Lu, Xiaohui; Anjum, Rana; Zhang, Sen; Wang, Frank; Keats, Jeffrey; Wardwell, Scott D; Ning, Yaoyu; Xu, Qihong; Moran, Lauren E; Mohemmad, Qurish K; Jang, Hyun Gyung; Clackson, Tim; Narasimhan, Narayana I; Rivera, Victor M; Zhu, Xiaotian; Dalgarno, David; Shakespeare, William C

    2016-05-26

    In the treatment of echinoderm microtubule-associated protein-like 4 (EML4)-anaplastic lymphoma kinase positive (ALK+) non-small-cell lung cancer (NSCLC), secondary mutations within the ALK kinase domain have emerged as a major resistance mechanism to both first- and second-generation ALK inhibitors. This report describes the design and synthesis of a series of 2,4-diarylaminopyrimidine-based potent and selective ALK inhibitors culminating in identification of the investigational clinical candidate brigatinib. A unique structural feature of brigatinib is a phosphine oxide, an overlooked but novel hydrogen-bond acceptor that drives potency and selectivity in addition to favorable ADME properties. Brigatinib displayed low nanomolar IC50s against native ALK and all tested clinically relevant ALK mutants in both enzyme-based biochemical and cell-based viability assays and demonstrated efficacy in multiple ALK+ xenografts in mice, including Karpas-299 (anaplastic large-cell lymphomas [ALCL]) and H3122 (NSCLC). Brigatinib represents the most clinically advanced phosphine oxide-containing drug candidate to date and is currently being evaluated in a global phase 2 registration trial.

  20. The rph1 gene is a common contributor to the evolution of phosphine resistance in independent field isolates of Rhyzopertha dominica.

    Science.gov (United States)

    Mau, Yosep S; Collins, Patrick J; Daglish, Gregory J; Nayak, Manoj K; Pavic, Hervoika; Ebert, Paul R

    2012-01-01

    Phosphine is the only economically viable fumigant for routine control of insect pests of stored food products, but its continued use is now threatened by the world-wide emergence of high-level resistance in key pest species. Phosphine has a unique mode of action relative to well-characterised contact pesticides. Similarly, the selective pressures that lead to resistance against field sprays differ dramatically from those encountered during fumigation. The consequences of these differences have not been investigated adequately. We determine the genetic basis of phosphine resistance in Rhyzopertha dominica strains collected from New South Wales and South Australia and compare this with resistance in a previously characterised strain from Queensland. The resistance levels range from 225 and 100 times the baseline response of a sensitive reference strain. Moreover, molecular and phenotypic data indicate that high-level resistance was derived independently in each of the three widely separated geographical regions. Despite the independent origins, resistance was due to two interacting genes in each instance. Furthermore, complementation analysis reveals that all three strains contain an incompletely recessive resistance allele of the autosomal rph1 resistance gene. This is particularly noteworthy as a resistance allele at rph1 was previously proposed to be a necessary first step in the evolution of high-level resistance. Despite the capacity of phosphine to disrupt a wide range of enzymes and biological processes, it is remarkable that the initial step in the selection of resistance is so similar in isolated outbreaks.

  1. The rph1 gene is a common contributor to the evolution of phosphine resistance in independent field isolates of Rhyzopertha dominica.

    Directory of Open Access Journals (Sweden)

    Yosep S Mau

    Full Text Available Phosphine is the only economically viable fumigant for routine control of insect pests of stored food products, but its continued use is now threatened by the world-wide emergence of high-level resistance in key pest species. Phosphine has a unique mode of action relative to well-characterised contact pesticides. Similarly, the selective pressures that lead to resistance against field sprays differ dramatically from those encountered during fumigation. The consequences of these differences have not been investigated adequately. We determine the genetic basis of phosphine resistance in Rhyzopertha dominica strains collected from New South Wales and South Australia and compare this with resistance in a previously characterised strain from Queensland. The resistance levels range from 225 and 100 times the baseline response of a sensitive reference strain. Moreover, molecular and phenotypic data indicate that high-level resistance was derived independently in each of the three widely separated geographical regions. Despite the independent origins, resistance was due to two interacting genes in each instance. Furthermore, complementation analysis reveals that all three strains contain an incompletely recessive resistance allele of the autosomal rph1 resistance gene. This is particularly noteworthy as a resistance allele at rph1 was previously proposed to be a necessary first step in the evolution of high-level resistance. Despite the capacity of phosphine to disrupt a wide range of enzymes and biological processes, it is remarkable that the initial step in the selection of resistance is so similar in isolated outbreaks.

  2. The rph1 Gene Is a Common Contributor to the Evolution of Phosphine Resistance in Independent Field Isolates of Rhyzopertha Dominica

    Science.gov (United States)

    Mau, Yosep S.; Collins, Patrick J.; Daglish, Gregory J.; Nayak, Manoj K.; Pavic, Hervoika; Ebert, Paul R.

    2012-01-01

    Phosphine is the only economically viable fumigant for routine control of insect pests of stored food products, but its continued use is now threatened by the world-wide emergence of high-level resistance in key pest species. Phosphine has a unique mode of action relative to well-characterised contact pesticides. Similarly, the selective pressures that lead to resistance against field sprays differ dramatically from those encountered during fumigation. The consequences of these differences have not been investigated adequately. We determine the genetic basis of phosphine resistance in Rhyzopertha dominica strains collected from New South Wales and South Australia and compare this with resistance in a previously characterised strain from Queensland. The resistance levels range from 225 and 100 times the baseline response of a sensitive reference strain. Moreover, molecular and phenotypic data indicate that high-level resistance was derived independently in each of the three widely separated geographical regions. Despite the independent origins, resistance was due to two interacting genes in each instance. Furthermore, complementation analysis reveals that all three strains contain an incompletely recessive resistance allele of the autosomal rph1 resistance gene. This is particularly noteworthy as a resistance allele at rph1 was previously proposed to be a necessary first step in the evolution of high-level resistance. Despite the capacity of phosphine to disrupt a wide range of enzymes and biological processes, it is remarkable that the initial step in the selection of resistance is so similar in isolated outbreaks. PMID:22363668

  3. Development of a 4,4’-biphenyl/phosphine-based COF for the heterogeneous Pd-catalysed telomerisation of 1,3-butadiene

    NARCIS (Netherlands)

    Hausoul, P.J.C.|info:eu-repo/dai/nl/313957630; Eggenhuisen, T.M.|info:eu-repo/dai/nl/313959498; Nand, D.|info:eu-repo/dai/nl/337731403; Baldus, M.|info:eu-repo/dai/nl/314410864; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Klein Gebbink, R.J.M.|info:eu-repo/dai/nl/166032646; Bruijnincx, P.C.A.|info:eu-repo/dai/nl/33799529X

    2013-01-01

    The improved synthesis, characterisation and application of a microporous 4,40-biphenyl/phosphine-based covalent organic framework (COF) for the heterogeneous Pd-catalysed telomerisation of 1,3-butadiene with phenol and glycerol are presented. The solid polyphosphine is amorphous, microporous and an

  4. A direct, modular, and efficient construction of the P-C-P structural motif through coupling of manganese carbyne complexes with phosphines.

    Science.gov (United States)

    Valyaev, Dmitry A; Bastin, Stéphanie; Utegenov, Kamil I; Lugan, Noël; Lavigne, Guy; Ustynyuk, Nikolai A

    2014-02-17

    Easily available carbyne complexes of manganese were used as a source of carbyne fragments in an unconventional synthesis of backbone-substituted diphosphinomethanes and cyclic P-ylides upon coupling with secondary or tertiary phosphines, respectively, followed by demetalation under mild conditions.

  5. Steric, electronic, and secondary effects on the coordination chemistry of ionic phosphine ligands and the catalytic behavior of their metal complexes

    NARCIS (Netherlands)

    Snelders, D.J.M.; van Koten, G.; Klein Gebbink, R.J.M.

    2011-01-01

    The effects of introducing ionic functionalities in phosphine ligands on the coordination chemistry of these ligands and the catalytic behavior of the corresponding metal complexes are reviewed. The steric and electronic consequences of such functionalizations are discussed. Apart from these steric

  6. Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways

    Science.gov (United States)

    Na, Risong; Jing, Chengfeng; Xu, Qihai; Jiang, Hui; Wu, Xi; Shi, Jiayan; Zhong, Jiangchun; Wang, Min; Benitez, Diego; Tkatchouk, Ekaterina; Goddard, William A.; Guo, Hongchao; Kwon, Ohyun

    2011-01-01

    In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways—the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen–containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolodiazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol—the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates—suggest that it might find extensive applications in heterocycle synthesis. PMID:21812448

  7. Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways.

    Science.gov (United States)

    Na, Risong; Jing, Chengfeng; Xu, Qihai; Jiang, Hui; Wu, Xi; Shi, Jiayan; Zhong, Jiangchun; Wang, Min; Benitez, Diego; Tkatchouk, Ekaterina; Goddard, William A; Guo, Hongchao; Kwon, Ohyun

    2011-08-31

    In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways-the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol--the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates--suggest that it might find extensive applications in heterocycle synthesis.

  8. Alkynylation of aryl halides with perfluoro-tagged palladium nanoparticles immobilized on silica gel under aerobic, copper- and phosphine-free conditions in water.

    Science.gov (United States)

    Bernini, Roberta; Cacchi, Sandro; Fabrizi, Giancarlo; Forte, Giovanni; Petrucci, Francesco; Prastaro, Alessandro; Niembro, Sandra; Shafir, Alexandr; Vallribera, Adelina

    2009-06-07

    The utilization of perfluoro-tagged palladium nanoparticles immobilized on fluorous silica gel through fluorous-fluorous interactions (Pd(np)-/FSG) or linked to silica gel by covalent bonds (Pd(np)-) in the alkynylation of terminal alkynes with aryl halides under aerobic, copper- and phosphine-free conditions in water, and their recovery and re-utilization, is described.

  9. Steric, electronic, and secondary effects on the coordination chemistry of ionic phosphine ligands and the catalytic behavior of their metal complexes

    NARCIS (Netherlands)

    Snelders, D.J.M.; van Koten, G.; Klein Gebbink, R.J.M.

    2011-01-01

    The effects of introducing ionic functionalities in phosphine ligands on the coordination chemistry of these ligands and the catalytic behavior of the corresponding metal complexes are reviewed. The steric and electronic consequences of such functionalizations are discussed. Apart from these steric

  10. Synthesis of A Novel Photosensitive Prepolymer with Trimethylolpropane Triglycidylether and Acrylic Acid as Starting Materials

    Institute of Scientific and Technical Information of China (English)

    HUANG Biwu; HUANG Shuhuai; SHI Yusheng; MO Jianhua

    2005-01-01

    A novel photosensitive prepolymer of trimethylolpropane triglycidylether triacrylate was synthesized by utilizing trimethylolpropane triglycidylether and acrylic acid as two starting materials, triphenyl phosphine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthesis conditions were that the concentration of triphenyl phosphine was 0.85wt% of reactants, the concentration of p-hydroxyanisole was 0.3wt% of reactants, and the reaction temperature was at 90-110 ℃. Benzil dimethyl ketal of a UV-cured initiator was added to the synthesized trimethylolpropane triglycidylether triacrylate to prepare a kind of UV-cured coating. The mechanical properties of the UV-cured films were determined, giving 28.43 MPa of tensile strength, 965.59MPa of Young's modulus and 4.10% of elongation at tear.

  11. Polymer versus phosphine stabilized Rh nanoparticles as components of supported catalysts: implication in the hydrogenation of cyclohexene model molecule.

    Science.gov (United States)

    Ibrahim, M; Garcia, M A S; Vono, L L R; Guerrero, M; Lecante, P; Rossi, L M; Philippot, K

    2016-11-28

    The solution synthesis of rhodium nanoparticles (Rh NPs) was achieved from the organometallic complex [Rh(η(3)-C3H5)3] under mild reaction conditions in the presence of a polymer (PVP), a monophosphine (PPh3) and a diphosphine (dppb) as a stabilizer, leading to very small Rh NPs of 2.2, 1.3 and 1.7 nm mean size, with PVP, PPh3 and dppb, respectively. The surface properties of these nanoparticles were compared using a model catalysis reaction namely, hydrogenation of cyclohexene, first under colloidal conditions and then under supported conditions after their immobilization onto an amino functionalized silica-coated magnetite support. PVP-stabilized Rh NPs were the most active catalyst whatever the catalytic conditions as a result of a strong coordination of the phosphine ligands at the metal surface that blocks some surface atoms even after several recycles of the supported nanocatalysts and limit the reactivity of the metallic surface.

  12. Emission Properties, Solubility, Thermodynamic Analysis and NMR Studies of Rare-Earth Complexes with Two Different Phosphine Oxides

    Directory of Open Access Journals (Sweden)

    Hiroki Iwanaga

    2010-07-01

    Full Text Available The paper proposes novel molecular designs for rare-earth complexes involving the introduction of two different phosphine oxide structures into one rare-earth ion. These designs are effective for improving solubility and emission intensity. Additionally, the complexes are indispensable for realizing high performances in LEDs and security media. The thermodynamic properties of Eu(III complexes are correlated with the solubility. Correlations between coordination structures and emission intensity were explained by NMR analysis. The luminous flux of red LED devices with Eu(III complexes is very high (20 mA, 870 m lumen. A new white LED has its largest spectra intensity in the red region and a human look much more vividly under this light.

  13. Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

    Science.gov (United States)

    Siochi, Emilie

    1995-01-01

    Gel Permeation Chromatography (GPC) was used to analyze poly(arylene ether phosphine oxide)s whose backbones were identical except for the ketone content and placement. These samples were exposed to low Earth orbit environment (predominantly atomic oxygen) on space shuttle flights. The materials and their unexposed controls were then characterized by GPC to investigate the effect of atomic oxygen on the molecular weight distributions. Analysis of the soluble portion of the samples revealed that there was significant loss of high molecular weight species. The presence of insoluble material also suggested that crosslinking was induced by the atomic oxygen exposure and that this very likely occurred at the high molecular weight portion of the molecular weight distribution.

  14. Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

    Science.gov (United States)

    Yamamoto, Kosuke; Shimizu, Takashi; Igawa, Kazunobu; Tomooka, Katsuhiko; Hirai, Go; Suemune, Hiroshi; Usui, Kazuteru

    2016-11-01

    A series of novel optically active [5]helicene-derived phosphine ligands (L1, with a 7,8-dihydro[5]helicene core structure- and L2, with a fully aromatic [5]helicene core structure) were synthesized. Despite their structural similarities, L1 and L2 exhibit particularly different characteristics in their use as chiral ligands. L1 was highly effective in the asymmetric allylation of indoles with 1,3-diphenylallyl acetate (up to 99% ee), and in the etherification of alcohols (up to 96% ee). In contrast, L2 was highly effective in the stereocontrol of helical chirality in Suzuki-Miyaura coupling (SMC) reaction (up to 99% ee). Density functional theory analysis was employed to propose a model that accounts for the origin of the enantioselectivity in these reactions.

  15. The preparation of sol-gel materials doped with ionic liquids and trialkyl phosphine oxides for yttrium(III) uptake.

    Science.gov (United States)

    Liu, Yinghui; Sun, Xiaoqi; Luo, Fang; Chen, Ji

    2007-12-01

    A new material (IL923SGs) composed of ionic liquids and trialkyl phosphine oxides (Cyanex 923) for Y(III) uptake was prepared via a sol-gel method. The hydrophobic ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate (C8mim+ PF6(-)) was used as solvent medium and pore templating material. The extraction of Y(III) by IL923SGs was mainly due to the complexation of metal ions with Cyanex 923 doped in the solid silica. Ionic liquid was stably doped into the silica gel matrix providing a diffusion medium for Cyanex 923, and this will result in higher removal efficiencies and excellent stability for metal ions separation. IL923SGs were also easily regenerated and reused in the subsequent removal of Y(III) in four cycles.

  16. The preparation of sol-gel materials doped with ionic liquids and trialkyl phosphine oxides for Yttrium(III) uptake

    Energy Technology Data Exchange (ETDEWEB)

    Liu Yinghui [Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Sun Xiaoqi [Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Luo Fang [Key Laboratory of Polyoxometalates Science of Ministry of Education, College of Chemistry, Northeast Normal University, Changchun 130024 (China); Chen Ji [Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)], E-mail: jchen@ciac.jl.cn

    2007-12-05

    A new material (IL923SGs) composed of ionic liquids and trialkyl phosphine oxides (Cyanex 923) for Y(III) uptake was prepared via a sol-gel method. The hydrophobic ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate (C{sub 8}mim{sup +}PF{sub 6}{sup -}) was used as solvent medium and pore templating material. The extraction of Y(III) by IL923SGs was mainly due to the complexation of metal ions with Cyanex 923 doped in the solid silica. Ionic liquid was stably doped into the silica gel matrix providing a diffusion medium for Cyanex 923, and this will result in higher removal efficiencies and excellent stability for metal ions separation. IL923SGs were also easily regenerated and reused in the subsequent removal of Y(III) in four cycles.

  17. Polymerization behaviour of butyl bis(hydroxymethyl)phosphine oxide: Phosphorus containing polyethers for Li-ion conductivity

    Indian Academy of Sciences (India)

    Heeralal Vignesh Babu; Billakanti Srinivas; Khevath Praveen Kumar Naik; Krishnamurthi Muralidharan

    2015-04-01

    Synthesis of phosphorus containing polyethers and their lithium-ion conductivities for the potential use as solid polymer electrolyte (SPE) in high-energy density lithium-ion batteries have been described. Co-polymerization of butyl bis(hydroxymethyl)phosphine oxide with three different dibromo monomers were carried out to produce three novel phosphorous containing polyethers (P1–P3). These polymers were obtained via nucleophilic substitution reactions and were characterized by 1H, 31P NMR spectral data and gel permeation chromatography. SPEs were prepared using polyethers (P1 and P2) with various amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The lithium-ion conductivity of SPE2 containing 40 wt% of LiTFSI was 2.1 × 10−5 S cm−1 at room temperature and 3.7 × 10−4 S cm−1 at 80°C.

  18. Research on the phosphine fumigation technology against codling moth%苹果蠹蛾磷化氢熏蒸技术研究

    Institute of Scientific and Technical Information of China (English)

    刘涛; 李丽; 李柏树; 张凡华; 王跃进

    2011-01-01

    In order to determine whether phosphine could be used to control codling moth ( Lepidoptera Tortrici-dae) in apples, phosphine fumigation at several concentrations, exposure times and temperatures were performed, and the quality of fumigated apples were further measured in this study. Our results show that the test pest could be completely killed after 0. 76mg/l phosphine fumigation for 96h at 251 , but the surface injury occurred during the storage; 100% mortality could be achieved after 3.04mg/l phosphine fumigation for 264h at 5°C, while no surface injury occurred. Further quality analysis show that there weren' t significant change on the inner quality of all the apples fumigated at 5°C after 14 days storage. These results indicated that phosphine was effective to kill the codling moth while its adverse effect on the quality of apples could be greatly reduced at low temperature, so control of codling moth using phosphine was achievable.%为了明确磷化氢熏蒸技术在苹果蠹蛾检疫处理中的应用可能,本文在常温和低温条件下分别使用不同剂量磷化氢对苹果中的苹果蠹蛾幼虫进行了熏蒸,并测定了不同条件磷化氢熏蒸对苹果品质的影响.结果表明,25℃下0.76mg/L磷化氢熏蒸96h虽然能完全杀灭苹果中的苹果蠹蛾幼虫,但是会产生药害;5℃下3.04mg/L磷化氢熏蒸264h可完全杀灭苹果中的苹果蠹蛾幼虫,且无药害;进一步的品质测定结果表明,5℃不同剂量磷化氢熏蒸264h的苹果在室温贮藏14d后,其失重率、糖度、酸度等品质指标均无明显变化.本文的结果表明,磷化氢低温熏蒸能在保持苹果品质的同时有效杀灭其中的苹果蠹蛾幼虫,因而在苹果的检疫处理中极具应用前景.

  19. Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

    Science.gov (United States)

    Zhang, Pan; Ni, Shao-Fei; Dang, Li

    2016-09-20

    The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation.

  20. Occurrence of matrix-bound phosphine in polar ornithogenic tundra ecosystems: effects of alkaline phosphatase activity and environmental variables.

    Science.gov (United States)

    Zhu, Renbin; Ma, Dawei; Ding, Wei; Bai, Bo; Liu, Yashu; Sun, Jianjun

    2011-09-01

    Phosphine (PH(3)), a reduced phosphorus compound, is a highly toxic and reactive atmospheric trace gas. In this study, a total of ten ornithogenic soil/sediment profiles were collected from tundra ecosystems of east Antarctica and Arctic, and matrix-bound phosphine (MBP), the phosphorus fractions and alkaline phosphatase activity (APA) were analyzed. High MBP concentrations were found in these profiles with the range from 39.59 ng kg(-1) dw to 11.77 μg kg(-1) dw. MBP showed a consistent vertical distribution pattern in almost all the soil profiles, and its concentrations increased at soil surface layers and then decreased with depths. MBP levels in the ornithogenic soils were two to three orders of magnitude lower than those in ornithogenic sediments. The yield of PH(3) as a fraction of total P in all the profiles ranged from 10(-5) to 10(-9) mgPH(3) mg(-1)P with higher mean PH(3) yield in the ornithogenic sediments. The ornithogenic soils showed high concentrations of total phosphorus (TP), organic phosphorus (OP), inorganic phosphorus (IP) and metal elements (Cu, Zn, Mn, Fe, Al and Ca) but low MBP levels, vice versa for the ornithogenic sediments. No correlation had been obtained between MBP concentrations and IP, OP and TP. There existed an exponential correlation (r=0.67, psoil/sediment moisture. MBP concentrations showed a significant positive correlation with APA (r=0.668, psoils/sediments. Our results indicated that MBP is an important gaseous link in the phosphorus biogeochemical cycles of ornithogenic tundra ecosystems in Antarctica and Arctic.

  1. Extraction and stripping of rare earths using mixtures of acidic phosphorusbased reagents

    Institute of Scientific and Technical Information of China (English)

    WANG Xianglan; LI Wei; LI Deqian

    2011-01-01

    Studies were carried out on the extraction characters of trivalent rare earths from chloride solutions using organophosphorus acids 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP) combined with [di-(2-ethylhexyl)-phosphoric acid (HDEHP), isopropylphosphonic acid l-hexyl-4-ethyloctyl ester (HHEOIPP), bis(2,4,4-trimethylpentyl)-phosphinic acid (Cyanex 272), bis(2,4,4-trimethypen-tyl)-monothiophosphinic acid (Cyanex 302) or bis(2,4,4-trimethypentyl)-dithiophosphinic acid (Cyanex 301)] as extractants. The effect of the equilibrium aqueous acidity on the extraction was studied. According to the corresponding separation factors for adjacent pairs of rare earths,it could be concluded that HEHEHP and Cyanex 272 could be employed for the separation of Tm(Ⅲ), Yb(Ⅲ), Lu(Ⅲ) from the other rare earths. Taking Yb(Ⅲ) as an example, based on the different stripping acid, the potential of the stripping was estimated.

  2. 浅谈磷化氢环流熏蒸技术的应用%DISCUSSION ON APPLICATION OF PHOSPHINE RECIRCULATION FUMIGATION TECHNOLOGY

    Institute of Scientific and Technical Information of China (English)

    张来林; 赵英杰; 李昭; 卢凤桐; 谭永清

    2001-01-01

    本文简要介绍了磷化氢环流熏蒸技术的发展概况和系统组成,对环流熏蒸系统配套的产气形式、设备分类、设计、安全性、操作管理以及仓房的气密性等问题进行了阐述.%The development of phosphine recirculation fumigation technology and its system constitution were briefly introduced in this paper.Some problems of necessary accessories to fumigation technology such as phosphine generation method,classification and design of recirculation fumigation equipment,safety,operation management and gas tightness of warehouse were discussed as well.

  3. Crystal structure of poly[(μ3-thio-cyanato-κ(3) N:S:S)(tri-methyl-phosphine sulfide-κS)copper(I)].

    Science.gov (United States)

    Corfield, Peter W R

    2014-11-01

    In the title compound, [Cu(NCS)(C3H9PS)] n , the thio-cyanate ions bind the Cu(I) atoms covalently, forming infinite -Cu-SCN-Cu- chains parallel to the a axis. Each Cu(I) atom is also coordinated to a tri-methyl-phosphine sulfide group via a Cu-S bond. Two crystallographically independent chains propagate in opposite directions, and are held together in a ribbon arrangement by long bonds between Cu(I) atoms in the first chain and thio-cyanate S atoms in the second, with Cu-S = 2.621 (1) Å. The geometry around the Cu(I) atoms in the first chain is distorted tetra-hedral, with angles involving the long Cu-S bond much less than ideal, and the S-Cu-N angle between the phosphine sulfide S atom and the thio-cyanate N atom opening out to 133.19 (9)°. Each Cu(I) atom in the second chain appears to be disordered between two positions 0.524 (4) Å apart, with occupancy factors of 0.647 (6) and 0.353 (6). The Cu(I) atom in the major site is in a distorted trigonal-planar configuration, with the S-Cu-N angle between the phosphine sulfide and the thio-cyanate N atom again opened out, to 137.01 (15)°. The Cu(I) atom in the minor site, however, forms in addition a long bond [Cu-S = 2.702 (5) Å] to the phosphine sulfide of the first chain, not the thio-cyanate S atom, to provide a further link between the chains.

  4. Phosphine-free synthesis of high quality ZnSe, ZnSe/ZnS, and Cu-, Mn-doped ZnSe nanocrystals.

    Science.gov (United States)

    Shen, Huaibin; Wang, Hongzhe; Li, Xiaomin; Niu, Jin Zhong; Wang, Hua; Chen, Xia; Li, Lin Song

    2009-12-21

    High quality zinc blende ZnSe and ZnSe/ZnS core/shell nanocrystals have been synthesized by two converse injection methods (i.e. zinc precursor injection or selenium precursor injection) when Se-ODE complex was chosen as the phosphine-free selenium precursor. Absorption spectroscopy, fluorescence spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM) were used to characterize the as-synthesized ZnSe and ZnSe/ZnS nanocrystals. The quality of the as-prepared ZnSe nanocrystals reached the same high level compared with the method using phosphine selenium precursors since the quantum yields were between 40 and 60% and photoluminescence (PL) full width at half-maximum (FWHM) was well controlled between 14 and 17 nm. The parameter window for the growth of high quality ZnSe nanocrystals was found to be much broader and monodisperse ZnSe nanocrystals were synthesized successfully even when the reaction temperature was set as low as 240 degrees C. As cores, such zinc blende ZnSe nanocrystals were also used to synthesize ZnSe/ZnS core/shell nanocrystals with high fluorescence quantum yields of 70%. Cu(2+) or Mn(2+) doped ZnSe nanocrystals were also synthesized by simply modifying this phosphine-free method. The emission range has been extended to 500 and 600 nm with the use of Cu(2+) and Mn(2+) dopants compared with the emission coverage of ZnSe at around 400 nm. This is the first totally "green approach" (i.e. phosphine-free synthesis) for the synthesis of high quality ZnSe, ZnSe/ZnS, and Cu(2+) or Mn(2+) doped ZnSe nanocrystals.

  5. Luminescent copper(ı) (pseudo)halide complexes with neocuproine and a novel bulky tris (aminomethyl) phosphine derived from 2-piperazinopyridine

    Energy Technology Data Exchange (ETDEWEB)

    Starosta, Radosław, E-mail: radoslaw.starosta@chem.uni.wroc.pl; Komarnicka, Urszula K.; Puchalska, Małgorzata

    2013-11-15

    A novel bulky phosphine derived from 2-piperazinopyridine P(CH{sub 2}N(CH{sub 2}CH{sub 2}){sub 2}N-2-py){sub 3} (1) and its chalcogenide derivatives (oxide, sulfide and selenide) have been synthesized and characterized by elemental analysis, NMR spectroscopy and mass spectrometry. Next, two new copper(I) iodide or isothiocyanate complexes with 1 and 2,9-dimethyl-1,10-phenanthroline (dmp): [CuI(dmp)(1)] (1I) and [CuNCS(dmp)(1)] (1T), have been also synthesized and characterized by elemental analysis and studied by NMR, UV–vis, IR and luminescence spectroscopies. The X-ray structure of the complex 1T·1.81(CH{sub 3}COCH{sub 3}) was determined. The coordination geometry around the Cu(I) center is pseudo-tetrahedral with distortions resulting mostly from the molecular packing in the crystal cell. Both complexes exhibit orange photoluminescence in the solid state, which is much stronger for 1I than for 1T. The luminescence spectra of both complexes at room and 77 K temperatures show relatively large bands with a typical batochromic shift accompanying the lowering of the temperature. On the basis of TDDFT calculations we interpreted these bands as of (MX,MPR{sub 3})LCT type resulting mainly from the transitions from the copper–iodine (or isothiocyanate) bonds and a small admixture of copper–phosphine bonds to antibonding orbitals of dmp diimine. Highlights: • A novel tris(aminomethyl)phosphine is obtained from 2-piperazinopyridine • Two new CuI and CuNCS complexes with dmp and a novel phosphine are presented. • An X-ray structure of one of the complexes is characterized. • Solid-state UV–vis and luminescence spectra of the complexes are discussed. • Main absorbance and luminescence bands are of (MX,MPR{sub 3})LCT type.

  6. Rh nanoparticles stabilized by PEG-substituted triphenyl-phosphine: A highly active and recyclable catalyst for aqueous biphasic hydrogenation of benzene

    Institute of Scientific and Technical Information of China (English)

    Ya Dong Lu; Yan Hua Wang; Zi Lin Jin

    2010-01-01

    Rh nanoparticles stabilized by PEG-substituted triphenyl-phosphine(PETPP,P[C6H4-p-(OCH2CH2)nOH]3)combining double stabilization effects demonstrated high activity and good recyclability in aqueous biphasic hydrogenation of benzene.The value of turnover frequency(TOF)was 3333 h-1.Furthermore,the rhodium nanoparticle catalyst could be easily recycled for five times without loss in activity.

  7. Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

    OpenAIRE

    Fujita, Shin-ichiro; Akihara, Shuji; Arai, Masahiko

    2006-01-01

    The recyclability of water-soluble ruthenium–phosphine complex catalysts was investigated in water–toluene and in water–pressurized carbon dioxide systems for selective hydrogenation of trans-cinnamaldehyde (CAL). For the first hydrogenation run, the selectivity for cinnamyl alcohol (COL) is high for both toluene and dense CO2, because of interfacial catalysis in which the reaction mainly occurs at the interface between the aqueous phase and the other toluene or dense CO2 phase. The total CAL...

  8. An Electronic Rationale for Observed Initiation Rates in Ruthenium-Mediated Olefin Metathesis: Charge Donation in Phosphine And N-Heterocyclic Carbene Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Getty, K.; Delgado-Jaime, M.U.; Kennepohl, P.

    2009-06-01

    Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.

  9. Phosphine-catalyzed [3+2] cycloaddition reactions of azomethine imines with electron-deficient alkenes: a facile access to dinitrogen-fused heterocycles.

    Science.gov (United States)

    Li, Zhen; Yu, Hao; Liu, Honglei; Zhang, Lei; Jiang, Hui; Wang, Bo; Guo, Hongchao

    2014-02-03

    An efficient method for the phosphine-catalyzed [3+2] cycloaddition reaction of azomethine imines with diphenylsulfonyl alkenes to give dinitrogen-fused bi- or tricyclic heterocyclic compounds in high yields has been described. Moreover, two phenylsulfonyl groups installed on the heterocyclic products could be conveniently removed or transformed to other functional groups, making the reaction more useful. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Phosphine-Free Palladium-Catalyzed Direct C-3 Arylation of 2-Phenylimidazo[1,2-a]pyridine Using Silver(I Carboxylate

    Directory of Open Access Journals (Sweden)

    Sridevi Kona

    2013-01-01

    Full Text Available Phosphine-free palladium-catalyzed direct arylation of 2-phenyl-imidazo[1,2-a]pyridine has been developed with the concept of using silver(I carboxylate. This protocol efficiently catalyzes the C-H arylation of 2-phenyl-imidazo[1,2-a]pyridine with aryl iodides to afford the corresponding 2-phenyl-3-aryl-imidazo[1,2-a]pyridines in moderate to-good yields.

  11. Homogeneous catalysts supported on soluble polymers: biphasic Suzuki-Miyaura coupling of aryl chlorides using phase-tagged palladium-phosphine catalysts.

    Science.gov (United States)

    an der Heiden, Markus; Plenio, Herbert

    2004-04-02

    The Suzuki-Miyaura coupling of aryl chlorides and PhB(OH)(2) under biphasic conditions (DMSO/heptane) can be performed in almost quantitative yields over several cycles by means of polymeric Pd catalysts with soluble polyethylene glycol phase tags. Three sterically demanding and electron-rich phosphines 1-CH(2)Br,4-CH(2)P(1-Ad)(2)-C(6)H(4), and 2-PCy(2),2'-OH-biphenyl, and 2-PtBu(2),2'-OH-biphenyl were covalently bonded to 2000 Dalton MeOPEG-OH. The catalysts, which were formed in situ from Na(2)[PdCl(4)], the respective polymeric phosphine, KF/K(3)PO(4), and PhB(OH)(2), efficiently couple aryl chlorides at 80 degrees C at 0.5 mol % loading, resulting in a >90 % yield of the respective biphenyl derivatives. The use of polar phase tags allows the efficient recovery of palladium-phosphine catalysts by simple phase separation of the catalyst-containing DMSO solution and the product-containing n-heptane phase. The high activity (TOF) of the catalyst remains almost constant over more than five reaction cycles, which involve the catalytic reaction, separation of the product phase from the catalyst phase, and addition of new reactants to initiate the next cycle. The Buchwald type biphenyl phosphines form the most active Pd catalysts, which are 1.3-2.8 times more active than catalysts derived from diadamantyl-benzylphosphine, but appear to be less robust in the recycling experiments. There is no apparent leaching of the catalyst into the heptane solution (<0.05 %), as evidenced by spectrophotometric measurements, and contamination of the product with Pd is avoided.

  12. Synthesis and crystal structures of (phosphine)technetium(V) complexes with phenylimido and phenyldiazenido ligands using the precursor PhNHNHCOCH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Rochon, F.D.; Melanson, R.; Kong, Pi-Chang [Universite du Quebec a Montreal, Quebec (Canada)

    1995-04-26

    Reaction of NH{sub 4}[TcO{sub 4}] to yield Tc(NPh)(PMePh{sub 2}){sub 2}X{sub 3} (X = Cl (I); Br (II)) is discussed. Crystal structures of I and II were obtained by X-ray diffraction. When dimethyl diphenyl phosphine was used as ligand, an organodiazenido ligand resulted from an unprecedented rearrangement. The resulting compound was studied by X-ray diffraction.

  13. Complexation of amidocarbamoyl phosphine oxides with Ln{sup +3} (Ln = La, Nd, Pm, Sm and Eu) cation series: structural and thermodynamical features

    Energy Technology Data Exchange (ETDEWEB)

    Hosseinnejad, Tayebeh; Kazemi, Tayebeh [Alzahra Univ., Tehran (Iran, Islamic Republic of). Dept. of Chemistry

    2016-05-01

    In the present study, we have mainly investigated the nature of interactions in Ln{sup 3+} (Ln = La, Nd, Pm, Sm, Eu) complexes with amidocarbamoyl methyl phosphine oxide (CMPO) and amidocarbamoyl propyl phosphine oxide (CPPO) ligands based on density functional theory (DFT) approaches. In the first step, thermodynamical properties for complexation of CMPO and CPPO ligands with Ln{sup 3+} cation series have been determined in the gas phase and with the presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) computations. The trend of metal-ligand interaction strength has been analyzed and compared with the trend of ionic hardness within the series of lanthanide cations and different size of alkyl chain of amidocarbamoyl phosphine oxide ligand. The calculated thermochemical results in the gas and solution phases reveals that there is a consistency between increasing trend in the hardness of Ln{sup 3+} cation series and also electron-donating property of alkyl chain with increasing in thermodynamical stability of [Ln-CMPO]{sup 3+} and [Ln-CPPO]{sup 3+} complex series. We have also demonstrated that in the complexation reaction of all complex series, using n-hexane as solvent is more favorable thermodynamically than chloroform and toluene. It should be stated that this issue has been observed in many experiments. Finally, analysis of calculated deformation energies and also the variation in bond order of some selected key bonds in CMPO and CPPO ligands and their corresponded Ln{sup 3+} complexes series show a similar trend with increasing in the hardness of Ln{sup 3+} cation series and electron-donating of alkyl chain of amidocarbamoyl phosphine oxide ligand.

  14. Structural and Anti-Fungal Evaluation of Palladium(II Complexes Ligated by Triphenyl Phosphine and Isomeric 1-substituted phenyl tetrazoline-5-thione

    Directory of Open Access Journals (Sweden)

    R.N. PANDEY

    2013-06-01

    Full Text Available A series of phosphine complexes of palladium (II ligated with 1-substituted phenyl tetrazoline-5-thione have been prepared and identification of complexes are established on the basis of elemental analysis, magnetic susceptibility, conductivity, IR, UV-vis and 1H NMR spectral data. The phenyl ring was substituted to correlate the electronic effect of such substituents on the magnitude of the anti-fungal activity against Aspergillus favus species.

  15. Phosphine-catalyzed [4+1] annulation of 1,3-(aza)dienes with maleimides: highly efficient construction of azaspiro[4.4]nonenes.

    Science.gov (United States)

    Yang, Mei; Wang, Tianyi; Cao, Shixuan; He, Zhengjie

    2014-11-14

    Phosphine-catalyzed [4+1] annulation of electron-deficient 1,3-dienes or 1,3-azadienes with maleimides has been successfully developed under very mild conditions, providing a convenient and highly efficient method for constructing 2-azaspiro[4.4]nonenes and 1,7-diazaspiro[4.4]nonenes. This reaction represents the first example of [4+1] cyclization between electron-deficient 4π-conjugated systems and non-allylic phosphorus ylides.

  16. Hydrogen storage and delivery: the carbon dioxide - formic acid couple.

    Science.gov (United States)

    Laurenczy, Gábor

    2011-01-01

    Carbon dioxide and the carbonates, the available natural C1 sources, can be easily hydrogenated into formic acid and formates in water; the rate of this reduction strongly depends on the pH of the solution. This reaction is catalysed by ruthenium(II) pre-catalyst complexes with a large variety of water-soluble phosphine ligands; high conversions and turnover numbers have been realised. Although ruthenium(II) is predominant in these reactions, the iron(II) - tris[(2-diphenylphosphino)-ethyl]phosphine (PP3) complex is also active, showing a new perspective to use abundant and inexpensive iron-based compounds in the CO2 reduction. In the catalytic hydrogenation cycles the in situ formed metal hydride complexes play a key role, their structures with several other intermediates have been proven by multinuclear NMR spectroscopy. In the other hand safe and convenient hydrogen storage and supply is the fundamental question for the further development of the hydrogen economy; and carbon dioxide has been recognised to be a viable H2 vector. Formic acid--containing 4.4 weight % of H2, that is 53 g hydrogen per litre--is suitable for H2 storage; we have shown that in aqueous solutions it can be selectively decomposed into CO-free (CO < 10 ppm) CO2 and H2. The reaction takes place under mild experimental conditions and it is able to generate high pressure H2 (up to 600 bar). The cleavage of HCOOH is catalysed by several hydrophilic Ru(II) phosphine complexes (meta-trisulfonated triphenylphosphine, mTPPTS, being the most efficient one), either in homogeneous systems or as immobilised catalysts. We have also shown that the iron(II)--hydrido tris[(2-diphenylphosphino)ethyl]phosphine complex catalyses with an exceptionally high rate and efficiency (turnover frequency, TOF = 9425 h(-1)mol(-1); turnover number, TON = 92400) the formic acid cleavage, in environmentally friendly propylene carbonate solution, opening the way to use cheap, non-noble metal based catalysts for this

  17. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

    Institute of Scientific and Technical Information of China (English)

    XUXin; ZHUTun

    2002-01-01

    Solvent extraction equiliria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester, di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent of the e/r value and hydration energy of the metal ions. The minor shift of the P→O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P→O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compunds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effects is explained by using IR spectra of the loaded organic phase.

  18. Bisphosphonic acids as effective inhibitors of Mycobacterium tuberculosis glutamine synthetase.

    Science.gov (United States)

    Kosikowska, Paulina; Bochno, Marta; Macegoniuk, Katarzyna; Forlani, Giuseppe; Kafarski, Paweł; Berlicki, Łukasz

    2016-12-01

    Inhibition of glutamine synthetase (GS) is one of the most promising strategies for the discovery of novel drugs against tuberculosis. Forty-three bisphosphonic and bis-H-phosphinic acids of various scaffolds, bearing aromatic substituents, were screened against recombinant GS from Mycobacterium tuberculosis. Most of the studied compounds exhibited activities in micromolar range, with N-(3,5-dichlorophenyl)-2-aminoethylidenebisphoshonic acid, N-(3,5-difluorophenyl)-2-aminoethylidene-bisphoshonic acid and N-(3,4-dichlorophenyl)-1-hydroxy-1,1-ethanebisphosphonic acid showing the highest potency with kinetic parameters similar to the reference compound - L-methionine-S-sulfoximine. Moreover, these inhibitors were found to be much more effective against pathogen enzyme than against the human ortholog. Thus, with the bone-targeting properties of the bisphosphonate compounds in mind, this activity/selectivity profile makes these compounds attractive agents for the treatment of bone tuberculosis.

  19. Effects of Different Phosphorus Sources on Phosphine Production from Anaerobic Sludge%不同磷源对厌氧活性污泥产生磷化氢的影响

    Institute of Scientific and Technical Information of China (English)

    孙亮; 张朝升; 张可方; 荣宏伟; 刘涛

    2012-01-01

    The effects of five kinds of phosphorus sources (potassium dihydrogen phosphate, dipo-tassium hydrogen phosphate, sodium hexametaphosphate, potassium hypophosphite and sodium hypo-phosphite) on phosphine production from anaerobic activated sludge were studied in dynamic experiments. The results showed that when potassium hypophosphite was used as the phosphorus source, there was a strong negative linear relationship between TP concentration and phosphine production. The correlation coefficient was - 0. 93 , and the maximum production of phosphine was 495. 36 ng/L. When sodium hexametaphosphate was used as phosphorus source, a weak linear relationship was observed between TP concentration and phosphine production. The correlation coefficient was - 0. 62, and the minimum production of phosphine was 289. 65 ng/L. Hypophosphite was more likely to be used by microorganisms for production of phosphine. The effect of different concentrations of potassium hypophosphite on phosphine production was further investigated, and the result displayed that higher concentration of potassium hypophosphite would inhibit phosphine production. The maximum production of phosphine was achieved at potassium hypophosphite concentration of about 50 mg/L.%通过动态试验,研究了5种不同磷源(磷酸二氢钾、磷酸氢二钾、六偏磷酸钠、次磷酸钾、亚磷酸钠)对厌氧活性污泥产生磷化氢的影响.结果表明,以次磷酸钾为磷源时,TP浓度与磷化氢产量呈较好的负线性关系,相关系数为-0.93,且磷化氢的产量最大,达到495.36 ng/L;而当以六偏磷酸钠为磷源时,TP浓度与磷化氢产量的线性相关性最差,相关系数为-0.62,且磷化氢的产量最低,为289.65 ng/L.可见,次磷酸盐更容易被微生物利用产生磷化氢.考察了次磷酸钾浓度对磷化氢产量的影响,结果表明,次磷酸钾浓度太高会抑制磷化氢的产生,次磷酸钾浓度为50mg/L左右时,磷化氢的产量最大.

  20. 膦化物在燃油体系中自由基氧化反应的研究%Study of the radical chain oxidation of potential antioxidant phosphine

    Institute of Scientific and Technical Information of China (English)

    高莉

    2012-01-01

    With low oxidation potential, phosphine can react with oxygen to form stable compound, and work as potential anti oxygen agent. The oxidation of fuel is a radical chain reaction. The experiment results indicated that phosphine also occurs the radical chain oxidation. The metal chelating agent and radical inhibitor can effectively inhibit the radical chain oxidation of phosphine. The reaction rate increases as the temperature increase,and radical chain oxidation product of phosphine is phosphine oxide.%三价膦化物具有低的氧化势,易与氧气反应生成稳定的化合物,为潜在的燃油抗氧剂.燃油的氧化反应为过氧自由基链反应,实验结果表明,膦化物在此体系中也发生了自由基氧化反应,金属离子螯合剂和自由基抑制剂能有效地抑制膦化物自由基氧化反应的进行,其反应速率随反应温度的升高而加快,反应产物为氧化膦.

  1. Synergistic Effects of Oxygen on Phosphine and Ethyl Formate for the Control of Phthorimaea operculella (Lepidoptera: Gelechiidae).

    Science.gov (United States)

    Kim, Hyun Kyung; Lee, Seon-Woo; Kim, Ju-Il; Yang, Jeong-Oh; Koo, Hyun-Na; Kim, Gil-Hah

    2015-12-01

    Phosphine (PH3) and ethyl formate (EF) are two potentially powerful postharvest fumigant insecticides. We investigated the effectiveness of both PH3 and EF as fumigants at all developmental stages of the potato tuber moth Phthorimaea operculella Zeller, and we also studied the synergistic effects of these fumigants under controlled atmospheres of 50 and 80% oxygen (O2). The larval stage of P. operculella was the most susceptible to fumigation with PH3 at both 5°C and 20°C. All of the developmental stages showed greater susceptibility to PH3 at 20°C than at 5°C, whereas the susceptibility of adult P. operculella to this fumigant was not affected by temperature. The toxicity of EF did not differ with temperature for any of the P. operculella developmental stages. The atmospheric oxidation of PH3 increased the toxicity of this fumigant toward all developmental stages at both temperatures. In contrast, no differences in toxicity were observed for oxidized EF compared with EF alone at any developmental stage. In conclusion, using fumigation tests, we showed that atmospherically oxidized PH3 was much more effective against P. operculella than PH3 alone, demonstrating a synergistic effect for this fumigant and O2. Therefore, treatment with PH3 and high concentrations of O2, as described in this study, could be useful for managing the postharvest pest P. operculella.

  2. Syntheses, characterization and antifungal activity of heteroleptic nickel(II) complexes with N-alkylsulfonyldithiocarbimates and phosphines

    Science.gov (United States)

    Vidigal, Antonio E. C.; Rubinger, Mayura M. M.; Oliveira, Marcelo R. L.; Guilardi, Silvana; Souza, Rafael A. C.; Ellena, Javier; Zambolim, Laércio

    2016-06-01

    Four nickel(II) complexes of general formula [Ni(RSO2Ndbnd CS2) (PPh3)2] where R = CH3 (2a), CH3CH2 (2b), CH3(CH2)3 (2c) and CH3(CH2)7 (2d) and PPh3 = triphenylphosphine; and two nickel(II) complexes of general formula [Ni(RSO2Ndbnd CS2)dppe] where R = CH3(CH2)3 (3c) and CH3(CH2)7 (3d) and dppe = 1,2-bis(diphenylphosphine)ethane) were prepared. These new complexes were obtained by the reaction of nickel(II) chloride hexahydrate with potassium N-alkylsulfonyldithiocarbimates and the appropriate phosphine using ethanol/water as solvent. The IR, UV-Vis and 1H, 13C and 31P NMR spectra, elemental analysis of Ni and the HR-ESI-MS were consistent with the formation of square planar nickel(II) complexes with mixed ligands. The structures of the compounds 2b and 2c were determined by single crystal X-ray diffraction. The compounds are isostructural and crystallize in the space group P 1 bar of the triclinic system. The activities of the complexes were investigated in vitro against Botrytis cinerea, Colletotrichum acutatum and Alternaria solani, fungi species that affect various commercially important plants. All the complexes were active.

  3. Water-soluble phosphine-protected Au9 clusters: Electronic structures and nuclearity conversion via phase transfer

    Science.gov (United States)

    Yao, Hiroshi; Tsubota, Shuhei

    2017-08-01

    In this article, isolation, exploration of electronic structures, and nuclearity conversion of water-soluble triphenylphosphine monosulfonate (TPPS)-protected nonagold (Au9) clusters are outlined. The Au9 clusters are obtained by the reduction of solutions containing TPPS and HAuCl4 and subsequent electrophoretic fractionation. Mass spectrometry and elemental analysis reveal the formation of [Au9(TPPS)8]5- nonagold cluster. UV-vis absorption and magnetic circular dichroism (MCD) spectra of aqueous [Au9(TPPS)8]5- are quite similar to those of [Au9(PPh3)8]3+ in organic solvent, so the solution-phase structures are likely similar for both systems. Simultaneous deconvolution analysis of absorption and MCD spectra demonstrates the presence of some weak electronic transitions that are essentially unresolved in the UV-vis absorption. Quantum chemical calculations for a model compound [Au9(pH3)8]3+ show that the possible (solution-phase) skeletal structure of the nonagold cluster has D2h core symmetry rather than C4-symmetrical centered crown conformation, which is known as the crystal form of the Au9 compound. Moreover, we find a new nuclearity conversion route from Au9 to Au8; that is, phase transfer of aqueous [Au9(TPPS)8]5- into chloroform using tetraoctylammonium bromide yields [Au8(TPPS)8]6- clusters in the absence of excess phosphine.

  4. Ruthenium(III)/phosphine/pyridine complexes applied in the hydrogenation reactions of polar and apolar double bonds

    Science.gov (United States)

    Rodrigues, Claudia; Delolo, Fábio G.; Ferreira, Lucas M.; da S. Maia, Pedro I.; Deflon, Victor M.; Rabeah, Jabor; Brückner, Angelika; Norinder, Jakob; Börner, Armin; Bogado, André L.; Batista, Alzir A.

    2016-05-01

    In this work, five ruthenium(III) complexes containing phosphine and pyridine based ligands with general formula mer-[RuCl3(dppb)(N)] [where dppb = 1,4-bis(diphenylphosphino)butane and N = pyridine (py), 4-methylpyridine (4-Mepy), 4-vinylpyridine (4-Vpy), 4-tert-butylpyridine (4-tBupy) and 4-phenylpyridine (4-Phpy)] were synthesized and characterized using spectroscopic and electrochemical techniques, as well as magnetic susceptibility to check the paramagnetism of these compounds. These complexes were tested as catalytic precursors in hydrogenation reactions with cyclohexene, undecanal and cyclohexanecarboxaldehyde, as compounds bearing Cdbnd C and Cdbnd O groups. Broad screening was carried out in order to find the optimal reaction conditions with the highest conversion. It was found that by using a ratio of Ru-catalyst/substrate = 1:530 at 80 °C and 15 bar of H2 for 24 h, cyclohexene can be reduced. Hydrogenation of undecanal was possible using a Ru-catalyst/substrate ratio of 1:100 at 160 °C and 100 bar for 24 h, and for the reduction of cyclohexanecarboxaldehyde the reaction conditions were Ru-catalyst/substrate ratio of 1:100 at 160 °C and 50 bar for 24 h.

  5. ExoMol line lists VII: The rotation-vibration spectrum of phosphine up to 1500 K

    CERN Document Server

    Sousa-Silva, Clara; Tennyson, Jonathan; Yurchenko, Sergei N

    2014-01-01

    A comprehensive hot line list is calculated for $^{31}$PH$_3$ in its ground electronic state. This line list, called SAlTY, contains almost 16.8 billion transitions between 7.5 million energy levels and it is suitable for simulating spectra up to temperatures of 1500~K. It covers wavelengths longer than 1~$\\mu$m and includes all transitions to upper states with energies below $hc \\cdot 18\\,000$~cm$^{-1}$ and rotational excitation up to $J=46$. The line list is computed by variational solution of the Schr\\"odinger equation for the rotation-vibration motion employing the nuclear-motion program TROVE. A previously reported {\\it ab initio} dipole moment surface is used as well as an updated `spectroscopic' potential energy surface (PES), obtained by refining an existing \\textit{ab initio} surface through least-squares fitting to the experimentally derived energies. Detailed comparisons with other available sources of phosphine transitions confirms SAlTY's accuracy and illustrates the incompleteness of previous ex...

  6. Addition of Zn during the phosphine-based synthesis of indium phospide quantum dots: doping and surface passivation

    Directory of Open Access Journals (Sweden)

    Natalia E. Mordvinova

    2015-06-01

    Full Text Available Zinc-doped InP(Zn colloidal quantum dots (QDs with narrow size distribution and low defect concentration were grown for the first time via a novel phosphine synthetic route and over a wide range of Zn doping. We report the influence of Zn on the optical properties of the obtained quantum dots. We propose a mechanism for the introduction of Zn in the QDs and show that the incorporation of Zn atoms into the InP lattice leads to the formation of Zn acceptor levels and a luminescence tail in the red region of the spectra. Using photochemical etching with HF, we confirmed that the Zn dopant atoms are situated inside the InP nanoparticles. Moreover, doping with Zn is accompanied with the coverage of the QDs by a zinc shell. During the synthesis Zn myristate covers the QD nucleus and inhibits the particle growth. At the same time the zinc shell leads to an increase of the luminescence quantum yield through the reduction of phosphorous dangling bonds. A scenario for the growth of the colloidal InP(Zn QDs was proposed and discussed.

  7. Suppression of spore germination and aflatoxin biosynthesis in Aspergillus parasiticus during and after exposure to high levels of phosphine.

    Science.gov (United States)

    Antonacci, L; Salvat, A E; Faifer, G C; Godoy, H M

    1999-01-01

    Agar cultures of toxigenic Aspergillus parasiticus NRRL 2999 were exposed to phosphine (PH3), in levels ranging from 0 to 2000 ppm (vol/vol). It was found that with PH3 concentrations of 400 ppm or higher the growth of the fungus was totally arrested. When PH3 was vented and the agar plates were exposed to open air, 100% of the initial CFU developed into fully grown colonies after PH3 levels below 300 ppm, but at higher PH3 concentrations only 50% of the colonies developed. The same strain of A. parasiticus was inoculated into high moisture corn under conditions highly favorable for aflatoxin production, and it was exposed to a range of PH3 levels. After exposure to 500 ppm PH3, both fungal growth and aflatoxin synthesis resumed shortly after elimination of the toxic gas, but after exposure to PH3 levels of 1000 ppm and higher, the physical appearance of the contaminated corn was remarkably changed, showing reduced mycelial growth and almost complete absence of green pigmentation. In addition, aflatoxin synthesis was totally absent for the remainder of the experiment (20 days). These results strongly suggest that exposure to PH3 levels of 1000 ppm or higher could bring about persistent metabolic changes in surviving Aspergillus organisms.

  8. Full Protection of Intensely Luminescent Gold(I)-Silver(I) Cluster by Phosphine Ligands and Inorganic Anions.

    Science.gov (United States)

    Lei, Zhen; Pei, Xiao-Li; Guan, Zong-Jie; Wang, Quan-Ming

    2017-06-12

    An intensely luminescent gold(I)-silver(I) cluster [(C)(AuPPhpy2 )6 Ag6 (CF3 CO2 )3 ](BF4 )5 (PPhpy2 =bis(2-pyridyl)phenylphosphine) (3) is synthesized by the reaction of [(C)(AuPPhpy2 )6 Ag4 ](BF4 )6 with AgCF3 CO2 . All eight faces of the octahedral C@Au6 core in 3 are capped, that is, six faces are capped by silver ions and two by tetrafluoroborates. Cluster 3 is intensely luminescent in solution with a quantum yield of 92 %. Ligation of CF3 CO2(-) ions is vital for the construction and emission properties of 3, as confirmed by DFT calculations. BF4(-) ions are involved in the protecting sphere of the metal core, as evidenced by (19) F NMR data. The participation of phosphines, CF3 CO2(-) , and BF4(-) ions in the protection of the emissive core and the enhancement of the rigidity of the cluster result in the high emission efficiency. This is the first example of organic ligands and inorganic anions forming a rigid protecting sphere for luminescent coinage-metal clusters. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Biphasic and SAPC Hydroformylation Catalyzed by Rh-phosphines Bound to Water-Soluble Polymers

    DEFF Research Database (Denmark)

    Malmstrøm, Torsten; Andersson, Carlaxel; Hjortkjær, Jes

    1999-01-01

    Coupling of the triphenylphosphine moiety to poly-acrylic acid and poly-ethyleneimine respectively afford the macromolecular ligands PAA-PNH and PEI-PNH. Reaction of the ligands with Rh(CO)2(acac) give water-soluble complexes that are active as catalysts in the hydroformylation ofdifferent olefins...

  10. Study on Phosphine Fumigation Effects on Late Indica Rice of Different Water Contents%磷化氢对不同含水量晚籼稻谷的熏蒸效果研究

    Institute of Scientific and Technical Information of China (English)

    郭兴海; 郭均钧

    2012-01-01

    针对不同含水量晚籼稻谷对磷化氢的吸附性差异开展试验研究,探讨磷化氢对不同含水量晚籼稻谷环流熏蒸有效浓度的维持时间,精准施药,取得理想的熏蒸效果,指导科学实施磷化氢环流熏蒸具有现实意义。%According to the test and study of the adsorption difference of phosphine on late indica rice grain with different water content, examine the circulation fumigation effective concentration time of maintaining the water content of late indi- ca rice in different phosphine, and spray medicine accurately,to achieve the desired effect of fumigation,and it has the practical significance of guiding scientific implementation of phosphine circulation fumigation.

  11. A high-throughput hydrophilic interaction liquid chromatography coupled with a charged aerosol detector method to assess trisulfides in IgG1 monoclonal antibodies using tris(2-carboxyethyl)phosphine reaction products: Tris(2-carboxyethyl)phosphine-oxide and tris(2-carboxyethyl)phosphine-sulfide.

    Science.gov (United States)

    Cornell, Christopher; Karanjit, Amish; Chen, Yan; Jacobson, Fredric

    2016-07-29

    A robust, high-throughput method using hydrophilic interaction liquid chromatography (HILIC) coupled with a charged aerosol detector (CAD) is reported as a novel approach for trisulfide quantitation in monoclonal antibodies (mAbs). The products of mAb reduction using tris(2-carboxyethyl)phosphine (TCEP) include a species (TCEP(S)) that is stoichiometrically produced from trisulfides. The TCEP reaction products are chromatographically separated, detected, and quantified by the HILICCAD method. The method was qualified to quantify trisulfides across a range of 1-40% (mol trisulfide/mol mAb). In all tested matrix components, assay linearity and intermediate precision were established with correlation coefficients (R(2))>0.99, and relative standard deviations (RSD)value of LC-MS with 95% confidence. Applications of the HILICCAD method include trisulfide determination in purified mAbs to be used in the production of cysteine-linked antibody-drug conjugates, and in cell culture development studies to understand sources of, and strategies for control of, trisulfides.

  12. Biphasic and SAPC Hydroformylation Catalyzed by Rh-phosphines Bound to Water-Soluble Polymers

    DEFF Research Database (Denmark)

    Malmstrøm, Torsten; Andersson, Carlaxel; Hjortkjær, Jes

    1999-01-01

    Coupling of the triphenylphosphine moiety to poly-acrylic acid and poly-ethyleneimine respectively afford the macromolecular ligands PAA-PNH and PEI-PNH. Reaction of the ligands with Rh(CO)2(acac) give water-soluble complexes that are active as catalysts in the hydroformylation ofdifferent olefin...... PEI-PNH as ligands show lower stability and activity in both SAPC and biphasic applications....

  13. 高大平房仓储粮磷化氢熏蒸散气后残留量变化研究%STUDY ON CHANGES OF PHOSPHINE RESIDUE AFTER FUMIGATION DEGASSING OF STORED GRAIN IN LARGE WAREHOUSE

    Institute of Scientific and Technical Information of China (English)

    周天智; 吴秋蓉; 许建华; 邱艳; 朱全林

    2012-01-01

    The change rules of the phosphine residue had been studied, when different ventilation methods were used after phosphine fumigation in stored paddy and wheat, then the residue of phosphine was inspected termly by taking sample. The results showed that all the residue of phosphine were tend to decrease apparently when degassing. The average residue of phosphine in the whole stored grain was 0.031 mg/kg, and every sample's residue had decreased to safety standards atter degassing for 8 days in the wheat warehouse. The residue of every samples had decreased to 0.02 mg/kg after degassing for 5 days in paddy warehouse. The phosphine residue in paddy warehouse were lower than in the wheat warehouse. The whole study was beneficial to guide the grain safety in the future.%对储藏稻谷和小麦用磷化氢熏蒸后采取了不同的通风方式散气,并定期分区、分点进行跟踪检测磷化氢残留量,研究其变化规律.试验表明:随着通风散气时间的延长,磷化氢残留量均有明显降低趋势.小麦仓散气8d后,整仓储粮磷化氢平均残留量降至0.031 mg/kg,各扦样点磷化氢残留量也均降至安全标准以内.稻谷仓通风散气5d后,各区、各点磷化氢残留量均已降至0.02mg/kg以内,且磷化氢残留量明显低于小麦仓,有利于指导今后出库粮食食用安全.

  14. Higher coordinate gold(I) complexes with the weak Lewis base tri(4-fluorophenyl) phosphine. Synthesis, structural, luminescence, and DFT studies

    Science.gov (United States)

    Agbeworvi, George; Assefa, Zerihun; Sykora, Richard E.; Taylor, Jared; Crawford, Carlos

    2016-03-01

    The structures and spectroscopic properties of two high coordinate gold(I) phosphine complexes with the TFFPP=tri(4-fluorophenyl)phosphine ligand are reported. Synthesis in a 1:3 metal to ligand ratio provided the compound [AuCl(TFFPP)3] (2) that crystallize in the P 1 bar space group, where the asymmetric unit consists of three independent molecules. In all three sites, two sets of bond angles display distinctly different ranges. The three P-Au-P angles have average values of 117.92°, 117.57°, and 114.78° for sites A, B, and C, with the corresponding P-Au-Cl angles of 98.31°, 99.05°, and 103.38°, respectively. The chloride ion coordinates as the fourth ligand, at the corresponding Au-Cl distance of 2.7337, 2.6825, and 2.6951 Å for the three sites. This distance is longer by 0.40-0.45 Å than the Au-Cl distance found in the mono TFFPP complex 1 (2.285 Å) indicating a weakening of the Au-Cl interaction as the coordination number increases. In compound 3, [Au(TFFPP)3]Cl·½CH2Cl2·H2O, the structure consists of three phosphine ligands bound to the gold(I) atom, but the Cl- exists as uncoordinated counter anion. The structural differences observed in the two complexes are attributable to crystal-packing effects caused by the introduction of H-bonding as well as enhanced intra and inter-molecular π-interaction in 3. The photoluminescence of the complexes compared with that of the ligand show ligand centered emission perturbed by the metal coordination. Theoretical DFT studies conducted on these complexes supports assignments of the electronic transitions observed in these systems.

  15. Probing the Carbon-phosphorus Bond Coupling in Low-temperature Phosphine PH3—Methane CH4 Interstellar Ice Analogues

    Science.gov (United States)

    Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I.

    2016-03-01

    Phosphine, which has now been confirmed around the carbon-rich star IRC+10216, provides the first example of a phosphorus-containing single bond in interstellar or circumstellar media. While four compounds containing both phosphorus and carbon have been discovered, none contain a carbon-phosphorus single bond. Here, we show that this moiety is plausible from the reaction of phosphine with methane in electron-irradiated interstellar ice analogues. Fractional sublimation allows for detection of individual products at distinct temperatures using reflectron time-of-flight mass spectrometry (ReTOF) coupled with vacuum ultraviolet photoionization. This method produced phosphanes and methylphosphanes as large as P8H10 and CH3P8H9, which demonstrates that a phosphorus-carbon bond can readily form and that methylphosphanes sublime at 12-17 K higher temperatures than the non-organic phosphanes. Also, irradiated ices of phosphine with deuterated-methane untangle the reaction pathways through which these methylphosphanes were formed and identified radical recombination to be preferred over carbene/phosphinidene insertion reactions. In addition, these ReTOF results confirm that CH3PH2 and CH6P2 can form via insertion of carbene and phosphinidene and that the methylenediphosphine (PH2CH2PH2) isomer forms in the ices, although methylphosphine (CH3P2H3) is likely the more abundant isomer and that phosphanes and organophosphanes preferentially fragment via the loss of a phosphino group when photoionized. While the formation of methylphosphine is overall endoergic, the intermediates produced by interactions with energetic electrons proceed toward methylphosphine favorably and barrierlessly and provide plausible mechanisms toward hitherto unidentified interstellar compounds.

  16. PROBING THE CARBON–PHOSPHORUS BOND COUPLING IN LOW-TEMPERATURE PHOSPHINE (PH{sub 3})–METHANE (CH{sub 4}) INTERSTELLAR ICE ANALOGUES

    Energy Technology Data Exchange (ETDEWEB)

    Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I. [W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States)

    2016-03-10

    Phosphine, which has now been confirmed around the carbon-rich star IRC+10216, provides the first example of a phosphorus-containing single bond in interstellar or circumstellar media. While four compounds containing both phosphorus and carbon have been discovered, none contain a carbon–phosphorus single bond. Here, we show that this moiety is plausible from the reaction of phosphine with methane in electron-irradiated interstellar ice analogues. Fractional sublimation allows for detection of individual products at distinct temperatures using reflectron time-of-flight mass spectrometry (ReTOF) coupled with vacuum ultraviolet photoionization. This method produced phosphanes and methylphosphanes as large as P{sub 8}H{sub 10} and CH{sub 3}P{sub 8}H{sub 9}, which demonstrates that a phosphorus–carbon bond can readily form and that methylphosphanes sublime at 12–17 K higher temperatures than the non-organic phosphanes. Also, irradiated ices of phosphine with deuterated-methane untangle the reaction pathways through which these methylphosphanes were formed and identified radical recombination to be preferred over carbene/phosphinidene insertion reactions. In addition, these ReTOF results confirm that CH{sub 3}PH{sub 2} and CH{sub 6}P{sub 2} can form via insertion of carbene and phosphinidene and that the methylenediphosphine (PH{sub 2}CH{sub 2}PH{sub 2}) isomer forms in the ices, although methylphosphine (CH{sub 3}P{sub 2}H{sub 3}) is likely the more abundant isomer and that phosphanes and organophosphanes preferentially fragment via the loss of a phosphino group when photoionized. While the formation of methylphosphine is overall endoergic, the intermediates produced by interactions with energetic electrons proceed toward methylphosphine favorably and barrierlessly and provide plausible mechanisms toward hitherto unidentified interstellar compounds.

  17. Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans-Bis(para-ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives.

    Science.gov (United States)

    Wong, Wai-Yeung; Harvey, Pierre D

    2010-04-20

    This review article surveys the electronic and photophysical properties of conjugated organometallic polymers built upon the title compound and its related derivatives focussing primarily on systems investigated in our laboratories. The general structure of the polymers is (trans-bis(para-ethynylbenzene)bis(phosphine)platinum(II)-G)(n) where G is a conjugated group such as thiophene, fluorene, carbazole, substituted silole, quinone derivative, and metalloporphyrin residue, or a non-conjugated main-group moiety. Systems based on substituted phenylene units and other related fused rings are also discussed. The phosphine ligands are generally triethyl- or tri-n-butylphosphine groups. These trans-platinum(II) polymers and the corresponding model compounds are compared to the corresponding ortho-derivatives in the quinone series, and the newly prepared paracyclophane-containing polymers. For the porphyrin series, a comparison of fully conjugated oligomers exhibiting the general structure (trans-bis(para-ethynyl(zinc(porphyrin)))bis(phosphine)platinum(II))(n) (i.e., the C(6) H(4) group is absent from the main chain) will be made. This contribution also includes a description of the properties of the mononuclear chromophore itself, properties that define those of the polymers. Potential applications with regard to electronic and optical devices will be highlighted. These soluble and stable materials feature both the processing advantages of polymers and the functionality provided by the presence of metal centers. These multifunctional organometallic polyyne polymers exhibit convenient structural variability as well as optical and electronic properties, which renders them important for use in different research domains as chemical sensors and sensor protectors, as converters for light/electricity signals, and as patternable precursors to magnetic metal alloy nanoparticles.

  18. PCN pincer palladium(II) complex catalyzed enantioselective hydrophosphination of enones: synthesis of pyridine-functionalized chiral phosphine oxides as NC(sp(3))O pincer preligands.

    Science.gov (United States)

    Hao, Xin-Qi; Huang, Juan-Juan; Wang, Tao; Lv, Jing; Gong, Jun-Fang; Song, Mao-Ping

    2014-10-17

    A series of chiral PCN pincer Pd(II) complexes VI-XIII with aryl-based aminophosphine-imidazoline or phosphinite-imidazoline ligands were synthesized and characterized. They were examined as enantioselective catalysts for the hydrophosphination of enones. Among them, complex IX, which features a Ph2PO donor as well as an imidazoline donor with (4S)-phenyl and N-Tol-p groups, was found to be the optimal catalyst. Thus, in the presence of 2-5 mol % of complex IX a wide variety of enones reacted smoothly with diarylphosphines to give the corresponding chiral phosphine derivatives in high yields with enantioselectivities of up to 98% ee. In particular, heteroaryl species such as 2-thienyl-, 2-furyl-, and 2-pyridinyl-containing enones that have a strong coordination ability to the Pd center were also appropriate substrates for the current catalytic system. For example, hydrophosphination of 2-alkenoylpyridines with diphenylphosphine followed by oxidation with H2O2 afforded the corresponding pyridine-functionalized chiral phosphine oxides in good yields with good to excellent enantioselectivities (10 examples, up to 95% ee). Furthermore, it had been demonstrated that the obtained pyridine-containing phosphine oxide acted as a tridentate ligand in the reaction with PdCl2 to form an intriguing NCsp(3)O pincer Pd(II) complex via Csp(3)-H bond activation, which to our knowledge is the first example of a chiral DCsp(3)D' Pd pincer (D ≠ D'; D and D' denote donor atoms such as P, N, etc.).

  19. Cytotoxicity in human cancer cells and mitochondrial dysfunction induced by a series of new copper(I) complexes containing tris(2-cyanoethyl)phosphines.

    Science.gov (United States)

    Zanella, Alessandro; Gandin, Valentina; Porchia, Marina; Refosco, Fiorenzo; Tisato, Francesco; Sorrentino, Francesca; Scutari, Guido; Rigobello, Maria Pia; Marzano, Cristina

    2011-12-01

    Over the last few years a lot of research has been done to develop novel metal-based anti-cancer drugs, with the aim of improving clinical effectiveness, reducing general toxicity, and broadening the spectrum of activity. The search for novel metal-based antitumour drugs other than Pt agents includes the investigation of the cytotoxic activity of copper(I/II) compounds. Among these copper agents, particular attention has been recently devoted to hydrophilic copper(I) species bearing phosphines because of their noteworthy stability in aqueous media together with their remarkable in vitro cytotoxic activity. In this study we report on the synthesis, characterization and cytotoxic assays of a series of Cu(I) complexes with tris(2-cyanoethyl)phosphine (PCN) and bis(2-cyanoethyl)phenylphosphine (PCNPh). They were prepared by reaction of [Cu(CH(3)CN)(4)](+) or CuX(2) precursors with the pertinent phosphine in acetone or acetonitrile solutions producing compounds of the following formulation: [Cu(PCN)(2)](+) 2, [Cu(CH(3)CN)(PCN)](+) 3, [Cu(X)(PCN)] (X = Cl, 4; Br, 5), and [Cu(PCNPh)(2)](+) 6. The new copper(I) complexes were tested for their cytotoxic properties against a panel of several human tumour cell lines. Cellular copper uptake rate was correlated with cell growth inhibition in 2008 human ovarian cancer cells. Moreover, copper(I)-PCN complexes were evaluated for their ability to alter the most relevant mitochondrial pathophysiological parameters such as respiration, coupling, ATP-synthetase activity and membrane potential in isolated mitochondria. These data were correlated with changes in mitochondrial membrane potential and production of reactive oxygen species (ROS) in drug-treated 2008 cells.

  20. Tris(hydroxymethyl)phosphine, P(CH2OH)3 - A convenient and effective new reagent for the fixation of protein samples for SEM imaging.

    Science.gov (United States)

    Wyllie, Megan J; Turner, Helen; Henderson, William

    2016-10-01

    Tris(hydroxymethyl)phosphine [P(CH2OH)3, THP] is demonstrated to be an alternative fixative to glutaraldehyde for preparation of proteinaceous specimens for SEM analysis. THP is easily prepared from commercially-available [P(CH2OH)4]Cl, and unlike many other alkylphosphines, is reasonably air-stable [>7days at pH 7-8]. Experiments carried out with chicken breast muscle, cross-sectioned perpendicular to the muscle fibres and imaged using SEM, indicate that THP effectively fixes the muscle structure with minimal discolouration of the sample.

  1. Nucleophilic phosphine-catalyzed intramolecular Michael reactions of N-allylic substituted α-amino nitriles: construction of functionalized pyrrolidine rings via 5-endo-trig cyclizations.

    Science.gov (United States)

    En, Da; Zou, Gong-Feng; Guo, Yuan; Liao, Wei-Wei

    2014-05-16

    Pyrrolidine rings are common moieties for pharmaceutical candidates and natural compounds, and the construction of these skeletons has received much attention. α-Amino nitriles are versatile intermediates in synthetic chemistry and have been widely used in the generation of multiple polyfunctional structures. Herein, a novel nucleophilic phosphine-catalyzed intramolecular Michael reaction of N-allylic substituted α-amino nitriles has been developed for the efficient construction of functionalized 2,4-disubstituted pyrrolidines (N-heterocyclic α-amino nitriles) via 5-endo-trig cyclization. Furthermore, the one-pot sequence of the synthesis of pyrrolidine and the subsequent transformations of the functionalized products have also been demonstrated.

  2. Synthesis of MnP nanocrystals by treatment of metal carbonyl complexes with phosphines: a new, versatile route to nanoscale transition metal phosphides.

    Science.gov (United States)

    Perera, Susanthri C; Tsoi, Georgy; Wenger, Lowell E; Brock, Stephanie L

    2003-11-19

    The reaction of Mn2(CO)10 with P(SiMe3)3 in coordinating solvents at T >/= 220 degrees C yields low polydispersity, highly crystalline MnP nanoparticles for the first time. The effect of dimensional limiting has resulted in the stabilization of a ferromagnetic ground state at low temperatures, rather than the metamagnetic state observed in bulk (microcrystalline) MnP. The synthetic methodology reported here is demonstrated to be general for a number of different metals and phosphine sources.

  3. Synthesis, structural, and electron topographical analyses of a dialkylbiaryl phosphine/arene-ligated palladium(I) dimer: enhanced reactivity in Suzuki-Miyaura coupling reactions.

    Science.gov (United States)

    Barder, Timothy E

    2006-01-25

    The treatment of bis(2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl)PdCl2 with AgBF4 produces an air-stable phosphine/arene-ligated Pd(I) dimer with two seemingly identical Pd-arene interactions by X-ray crystallography. However, NMR and theoretical electron topographical analyses of this complex distinguish between these two interactions. One interaction is classified as an arenium-like complex, while the other is classified as a pi-interaction. Additionally, this complex is a suitable precatalyst for high yielding Suzuki-Miyaura coupling reactions in short reaction times.

  4. Solid state luminescence of CuI and CuNCS complexes with phenanthrolines and a new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine

    Energy Technology Data Exchange (ETDEWEB)

    Starosta, Radosław, E-mail: radoslaw.starosta@chem.uni.wroc.pl; Komarnicka, Urszula K.; Puchalska, Małgorzata

    2014-01-15

    A new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine P(CH{sub 2}N(CH{sub 3})CH{sub 2}CH{sub 2}Ph){sub 3} (1) has been synthesized and characterized by the NMR spectra. Also, three new copper(I) iodide or isothiocyanate complexes with 1 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp) [CuI(phen)P(CH{sub 2}N(CH{sub 3})CH{sub 2}CH{sub 2}Ph){sub 3}] (1P) CuI(dmp)P(CH{sub 2}N(CH{sub 3})CH{sub 2}CH{sub 2}Ph){sub 3}] (1I) and [CuNCS(dmp)P(CH{sub 2}N(CH{sub 3})CH{sub 2}CH{sub 2}Ph){sub 3}] (1T), have been synthesized and characterized by elemental analysis as well as studied by NMR, UV–vis, IR and luminescence spectroscopies. An X-ray structure of 1P complex revealed that the geometry around Cu(I) center in this complex is distorted pseudo-tetrahedral. Investigated complexes exhibit orange, rather weak photoluminescence in the solid state. This relatively low intensity may be related to the high flattening deformations of the molecular geometries in the excited triplet states On the basis of TDDFT calculations we confirmed that the absorbance and luminescence bands of (MX,MPR{sub 3})LCT as well as of (MX)LCT types result mainly from the transitions from the copper–iodine (or isothiocyanate) bonds and a small admixture of copper–phosphine bonds to antibonding orbitals of phen or dmp diimines. -- Highlights: • A novel tris(aminomethyl)phosphine is obtained from N-methyl-2-phenylethanamine. • Three new CuI and CuNCS complexes with phen or dmp and a novel phosphine are presented. • The obtained complexes are luminescent in the solid state. • Main absorbance and luminescence bands are of (MX,MPR{sub 3})LCT as well as (MX)LCT types.

  5. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond

    2013-01-01

    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  6. Synthesis and Characterization of Phosphine and Arsine Complexes of Ruthenium (Ii & Iii Ligated With 3-(4-Pyridyl-4-Substituted-Triazoline-5-Thione

    Directory of Open Access Journals (Sweden)

    R. N. Pandey

    2014-12-01

    Full Text Available Organometallic complexes of ruthenium (II & III with the formula [RuH(CO(Ef32L] and [RuCl2(Ef32L] (E = P/As; L = deprotonated mononegative bidentate 3-(4-pyridyl-triazoline-5-thione and its 4-phenyl substituted derivative were synthesized and characterized by elemental analysis, physico-chemical and spectroscopic methods. All new compounds were iso-structural with precursor complexes. Two triphenyl phosphine or triphenylarsine molecules are at trans-disposition and thioamide ligands behaves as bidentate (N, S donor in assigned octahedral structure.

  7. Zwitterionic and Cationic Bis(phosphine) Platinum(II) Complexes:  Structural, Electronic, and Mechanistic Comparisons Relevant to Ligand Exchange and Benzene C−H Activation Processes

    OpenAIRE

    Thomas, J. Christopher; Peters, Jonas C.

    2003-01-01

    Structurally similar but charge-differentiated platinum complexes have been prepared using the bidentate phosphine ligands [Ph_(2)B(CH_(2)PPh_(2))_(2)], ([Ph_(2)BP_(2)], [1]), Ph_(2)Si(CH_(2)PPh_(2))_(2), (Ph_(2)SiP_(2), 2), and H_(2)C(CH_(2)PPh_(2))_(2), (dppp, 3). The relative electronic impact of each ligand with respect to a coordinated metal center's electron-richness has been examined using comparative molybdenum and platinum model carbonyl and alkyl complexes. Complexes supported by an...

  8. Preparation and Characterization of Mono-cyclopentadienylvanadium Dihalide Bis-phosphine Complexes; Crystal Structure of (η5-C5H5)VCl2(PMe3)2

    NARCIS (Netherlands)

    Nieman, J.; Teuben, J.H.; Huffman, J.C.; Caulton, K.G.

    1983-01-01

    Mono-cyclopentadienyl complexes CpVX2(PR3)2 and Cp´VX2(PR3)2 (Cp = η5-C5H5; Cp´ = η5-C5H4Me; R = Me, Et; X = Cl, Br) have been prepared by reaction of VX3(PR3)2 with CpM (M = Na, Tl, SnBun3, 1/2 Mg) or Cp´Na. Attempts to prepare analogous complexes with other phosphine ligands, PPh3, PPh2Me, PPhMe2,

  9. Reduction of dehydroascorbic acid at low pH.

    Science.gov (United States)

    Wechtersbach, Luka; Cigić, Blaz

    2007-08-01

    Ascorbic acid and dehydroascorbic acid are unstable in aqueous solution in the presence of copper and iron ions, causing problems in the routine analysis of vitamin C. Their stability can be improved by lowering the pH below 2, preferably with metaphosphoric acid. Dehydroascorbic acid, an oxidised form of vitamin C, gives a relatively low response on the majority of chromatographic detectors, and is therefore routinely determined as the increase of ascorbic acid formed after reduction. The reduction step is routinely performed at a pH that is suboptimal for the stability of both forms. In this paper, the reduction of dehydroascorbic acid with tris-[2-carboxyethyl] phosphine (TCEP) at pH below 2 is evaluated. Dehydroascorbic acid is fully reduced with TCEP in metaphosphoric acid in less than 20 min, and yields of ascorbic acid are the same as at higher pH. TCEP and ascorbic acid formed by reduction, are more stable in metaphosphoric acid than in acetate or citrate buffers at pH 5, in the presence of redox active copper ions. The simple experimental procedure and low probability of artefacts are major benefits of this method, over those currently applied in a routine assay of vitamin C, performed on large number of samples.

  10. Electrophysiological and molecular mechanisms of protection by iron sucrose against phosphine-induced cardiotoxicity: a time course study.

    Science.gov (United States)

    Solgi, Reza; Baghaei, Amir; Golaghaei, Ali; Hasani, Shokoufeh; Baeeri, Maryam; Navaei, Mona; Ostad, Seyyed Nasser; Hosseini, Rohollah; Abdollahi, Mohammad

    2015-01-01

    The present study was designed for determining the exact mechanism of cytotoxic action of aluminum phosphide (AlP) in the presence of iron sucrose as the proposed antidote. Rats received AlP (12 mg/kg) and iron sucrose (5-30 mg/kg) in various sets and were connected to cardiovascular monitoring device. After identification of optimum doses of AlP and iron sucrose, rats taken in 18 groups received AlP (6 mg/kg) and iron sucrose (10 mg/kg), treated at six different time points, and then their hearts were surgically removed and used for evaluating a series of mitochondrial parameters, including cell lipid peroxidation, antioxidant power, mitochondrial complex activity, ADP/ATP ratio and process of apoptosis. ECG changes of AlP poisoning, including QRS, QT, P-R, ST, BP and HR were ameliorated by iron sucrose (10 mg/kg) treatment. AlP initiated its toxicity in the heart mitochondria through reducing mitochondrial complexes (II, IV and V), which was followed by increasing lipid peroxidation and the ADP/ATP ratio and declining mitochondrial membrane integrity that ultimately resulted in cell death. AlP in acute exposure (6 mg/kg) resulted in an increase in hydroxyl radicals and lipid peroxidation in a time-dependent fashion, suggesting an interaction of delivering electrons of phosphine with mitochondrial respiratory chain and oxidative stress. Iron sucrose, as an electron receiver, can compete with mitochondrial respiratory chain complexes and divert electrons to another pathway. The present findings supported the idea that iron sucrose could normalize the activity of mitochondrial electron transfer chain and cellular ATP level as vital factors for cell escaping from AlP poisoning.

  11. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    Science.gov (United States)

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G

    2014-06-01

    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

  12. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Directory of Open Access Journals (Sweden)

    Marcia E. Richard

    2013-10-01

    Full Text Available A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

  13. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Science.gov (United States)

    Richard, Marcia E; Fraccica, Daniel V; Garcia, Kevin J; Miller, Erica J; Ciccarelli, Rosa M; Holahan, Erin C; Resh, Victoria L; Shah, Aakash; Findeis, Peter M

    2013-01-01

    Summary A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers. PMID:24204410

  14. B类滤毒罐防护磷化氢性能评价探讨%Evaluation of B-Type Canister Protective Performance against Phosphine

    Institute of Scientific and Technical Information of China (English)

    汪东旺; 李泽; 赵鑫华; 尹维东; 李志坚; 元以栋

    2012-01-01

    磷化氢是粮食仓储企业使用效果最好的杀虫剂,是一种剧毒的气体熏蒸剂。所以对于从业人员来讲,安全防护就显得格外重要。长期以来粮食仓储企业一直使用自吸过滤式防毒面具(配套选用B类滤毒罐)为首选器材。近期业内对B类滤毒罐防护磷化氢的有效性提出质疑,为此,本文通过性能评价试验,说明B类滤毒罐防护磷化氢是有效的,并从理论上说明B类滤毒罐防护磷化氢是有科学依据的。%Phosphine is the best pesticides of the grain storage enterprise, and is the toxic gaseous fumigant. For users, it is important for the security. For a long time, the grain storage enterprise uses the serf-absorption filtering gas mask (selecting the B-type canister) . Recently, the protective performance against phosphine of B-type canister is doubted, through the test, this paper will explain the effective and scientific theory of B-type canister.

  15. Genetic linkage analysis of the lesser grain borer Rhyzopertha dominica identifies two loci that confer high-level resistance to the fumigant phosphine.

    Science.gov (United States)

    Schlipalius, David I; Cheng, Qiang; Reilly, Paul E B; Collins, Patrick J; Ebert, Paul R

    2002-01-01

    High levels of inheritable resistance to phosphine in Rhyzopertha dominica have recently been detected in Australia and in an effort to isolate the genes responsible for resistance we have used random amplified DNA fingerprinting (RAF) to produce a genetic linkage map of R. dominica. The map consists of 94 dominant DNA markers with an average distance between markers of 4.6 cM and defines nine linkage groups with a total recombination distance of 390.1 cM. We have identified two loci that are responsible for high-level resistance. One provides approximately 50x resistance to phosphine while the other provides 12.5x resistance and in combination, the two genes act synergistically to provide a resistance level 250x greater than that of fully susceptible beetles. The haploid genome size has been determined to be 4.76 x 10(8) bp, resulting in an average physical distance of 1.2 Mbp per map unit. No recombination has been observed between either of the two resistance loci and their adjacent DNA markers in a population of 44 fully resistant F5 individuals, which indicates that the genes are likely to reside within 0.91 cM (1.1 Mbp) of the DNA markers. PMID:12072472

  16. Novel gold(I) complexes with 5-phenyl-1,3,4-oxadiazole-2-thione and phosphine as potential anticancer and antileishmanial agents.

    Science.gov (United States)

    Chaves, Joana Darc S; Tunes, Luiza Guimarães; de J Franco, Chris Hebert; Francisco, Thiago Martins; Corrêa, Charlane Cimini; Murta, Silvane M F; Monte-Neto, Rubens Lima; Silva, Heveline; Fontes, Ana Paula S; de Almeida, Mauro V

    2017-02-15

    The current anticancer and antileishmanial drug arsenal presents several limitations concerning their specificity, efficacy, costs and the emergence of drug-resistant cells lines, which encourages the urgent need to search for new alternatives. Inspired by the fact that gold(I)-based compounds are promising antitumoral and antileishmanial drug candidates, we synthesized novel gold(I) complexes containing phosphine and 5-phenyl-1,3,4-oxadiazole-2-thione and evaluated their anticancer and antileishmanial activities. Synthesis was performed by reacting 5-phenyl-1,3,4-oxadiazole-2-thione derivatives with chloro(triphenylphosphine)gold(I) and chloro(triethylphosphine)gold(I). The novel compounds were characterized by infrared, Raman, (1)H, (13)C nuclear magnetic resonance, high-resolution mass spectra, and x-ray crystallography. The coordination of the ligands to gold(I) occurred through the exocyclic sulfur atom. All gold(I) complexes were active at low micromolar or nanomolar range with IC50 values ranging from gold(I) complexes were more active than the conterparts triphenylphosphine derivatives for both anticancer and antileishmanial activities. Triethylphosphine gold(I) derivatives presented antimony cross-resistance in L. guyanensis demonstrating their potential to be used as chemical tools to better understand mechanisms of drug resistance and action. These findings revealed the anticancer and antileishmanial potential of gold(I) oxadiazole phosphine derivatives. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  17. Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

    Energy Technology Data Exchange (ETDEWEB)

    Raj, Joe Gerald Jesu [Institut National de la Recherche Scientifique, Quebec (China); Pathak, Devendra Deo [Indian School of Mines, Dhanbad (India); Kapoor, Pramesh N. [Univ. of Delhi, Delhi (India)

    2013-12-15

    Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong σ-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, {sup 1}HNMR, {sup 31}PNMR and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

  18. The influence of carboxilate, phosphinate and seleninate groups on luminescent properties of lanthanides complexes

    Energy Technology Data Exchange (ETDEWEB)

    Monteiro, Jorge H.S.K.; Formiga, André L.B.; Sigoli, Fernando A., E-mail: fsigoli@iqm.unicamp.br

    2014-10-15

    changing the triplet state energy in the range of ∼2000 cm{sup −1}. The changes in the energy transfer rates from triplet state to europium(III) levels are not sufficient to significantly modify the population of the europium(III) {sup 5}D{sub 0,1} levels and therefore the emission quantum yield. - Highlights: • Influences of ligands on luminescence of europium(III) and terbium(III) complexes. • Ligands: benzoic acid, phenylseleninic acid, and phenylphosphinic acid. • Ground state geometries were obtained from semi-empirical methods. • Theoretical values of JO parameters are compared to experimental ones. • Nature of chemical bonds, energy transfer rates and emission quantum yields.

  19. Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters.

    Science.gov (United States)

    Li, Yuehui; Topf, Christoph; Cui, Xinjiang; Junge, Kathrin; Beller, Matthias

    2015-04-20

    Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 催化氧化活性炭法净化磷化氢熏蒸尾气综述%Purification of exhausted gas from phosphine fumigation with catalytic oxidation activated carbon

    Institute of Scientific and Technical Information of China (English)

    李云玲; 黄健翔

    2016-01-01

    在磷化氢进行熏蒸保护粮食、烟草仓储过程中,会产生有剧毒的磷化氢熏蒸尾气,对周围人和环境产生重大影响,催化氧化活性炭是解决这一问题最有效的方法之一。简述了历来磷化氢气体净化技术的优缺点,较详细的论述了催化氧化活性炭净化磷化氢工作原理、处理工艺及再生方法。%In the process of fumigation with phosphine for protecting food and tobacco in store,highly toxic exhausted gas containing phosphine is likely to be produced,which may produce significant im-pact on the surrounding environment. Catalytic oxidation activated carbon is one of the most effective ways to solve this problem. The paper mainly introduces the advantages and disadvantages of tradi-tionally phosphine gas purification technology ,with more detailed discussion on the principles of work,treatment process and regeneration methods for catalytic oxidation activated carbon purification of phosphine.

  1. Toxicity of phosphine fumigation western flower thrips, Frankliniella occidentalis (Thysanoptera: Thripidae)%磷化氢熏蒸对西花蓟马的毒力作用研究

    Institute of Scientific and Technical Information of China (English)

    张凡华; 王跃进; 刘涛; 李丽

    2013-01-01

    The toxicity of phosphine fumigation on western flower thrips (Frankliniella occidentalis) at different temperatures was investigated in this study. The results showed 3 days egg was the most tolerant among all life stages- Phosphine fumigation could influence the development of western fiower thrips. The time of treatments required for the same mortality at same dose decreased remarkably as fumigation temperature increased from 15℃ to 25℃, and exposure duration was the critical factor affecting the toxicity of phosphine. Phosphine could be a potential alternative for quarantine treatment of western flower thrips.%本文研究了不同温度下磷化氢熏蒸处理对西花蓟马的毒力作用.结果表明:在西花蓟马各虫态中,3d卵对磷化氢熏蒸耐受性最强;磷化氢熏蒸会影响西花蓟马的生长发育;在15、25℃下,随着熏蒸温度的提高,以相同浓度处理达到相同死亡率水平所需的时间明显缩短,熏蒸时间为影响磷化氢毒力作用的关键因素.磷化氢是一种潜在的可以用于西花蓟马检疫处理的熏蒸剂.

  2. Ir-Catalyzed Enantioselective Hydrogenation of 2H-1,4-Benzoxazines with a Chiral 1,2,3,4- Tetrahydro-l-naphthylamine Derived Phosphine-aminophosphine Ligand

    Institute of Scientific and Technical Information of China (English)

    胡娟; 王道永; 郑卓; 胡向平

    2012-01-01

    Unsymmetrical hybrid chiral phosphine-aminophosphine ligand derived from 1,2,3,4-tetrahydro-l-naphthyl- amine has been found to be highly efficient in the Ir-catalyzed asymmetric hydrogenation of various 3-aryl-2H-1,4-benzoxazines, providing good enantioselectivities (up to 95% ee) and high catalytic activity (S/C up to 5000).

  3. MECHANISMS AND MOLECULAR MONITORING OF PHOSPHIN RESISTANCE IN STORE D GRAIN PESTS%储粮害虫PH3抗性机理及分子监测研究进展

    Institute of Scientific and Technical Information of China (English)

    吴芳; 严晓平

    2011-01-01

    Resistance of stored grain pests to phosphine has attracted much attention. Mechanisms of phosphine resistance in stored grain pests has been researched extensively in the past several decades, but inconclu-siveness yet. With the development of molecular biology in recent years, molecular monitoring of stored grain pest resistance of phosphine are more and more concerned. In this paper, advances in mechanisms and molecular monitoring of phosphine resistance in stored grain pests are reviewed.%储粮害虫PH3抗性一直倍受关注.在过去几十年中,人们对储粮害虫PH3抗性产生的生化机理进行了广泛的研究,但尚无定论.近年来,随着分子生物学的发展,储粮害虫PH3抗性分子监测方面的研究也日益受到重视.综述了储粮害虫PH3抗性产生的生化机制及PH3抗性分子监测方面的研究进展.

  4. Synthesis, Structure and Luminescent Properties of Polymeric Copper(Ⅰ) Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Three polymeric copper(Ⅰ) halide complexes bearing phosphine and N-donor bridging ligands, [(PPh3)2Cu2(μ-Br)2(μ-4,4'-bipy)]∞ 1 (bipy=bipyridine), [(PPh3)2Cu2(μ-Br)2(μ-bpe)]∞ 2 (bpe=trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P-1 with a=9.122(3), b=9.322(3), c=13.201(4) (A),α=106.440(4), β=105.965(5), γ=94.167(5)°, V=1021.3(6) (A), Mr=967.62, Z=1,Dc=1.573 g/cm3, F(000)=486,μ=3.111 mm-1, the final R=0.0383 and wR=0.0960 for 2792observed reflections (I > 2σ(Ⅰ)). Complex 2 crystallizes in triclinic, space group P-1 with a=9.420(3), b=10.209(4), c=12.407(4)(A), α=104.136(6), β=108.132(5), γ=95.338(6)°, V=1081.0(7)(A), Mr=496.83, Z=2, Dc=1.526 g/cm3, F(000)=500,μ=2.941 mm-1, the final R=0.0445 and wR=0.1117 for 3251 observed reflections (I> 2σ(Ⅰ)). Complex 3 crystallizes in triclinic,space group P-1 with a=8.32(1), b=11.53(2), c=13.94(3)(A), α=109.57(3), β=93.85(3), γ=97.28(3)°, V=1242(4)(A)3, Mr=1074.59, Z=1, Dc=1.436 g/cm3, F(000)=548,μ=1.279 mm-1,the final R=0.0786 and wR=0.1586 for 2266 observed reflections (I > 2σ(Ⅰ)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.

  5. Toxicity of pure phosphine to Carposina sasakii Matsumura (Lepidoptera:Carposinadae)%纯磷化氢熏蒸对桃小食心虫的毒力作用

    Institute of Scientific and Technical Information of China (English)

    刘波; 詹国平; 任荔荔; 李柏树; 牛墨; 王跃进

    2016-01-01

    Carposina sasakii Matsumura (Lepidoptera:Carposinadae),widely distributed in pome fruit production areas in China,seriously threatens fruit export industry.In order to determinate the eliminated doses of pure phosphine against these pests for quarantine purpose,1-d,2-d,3-d-old eggs and the first to fifth instar of C . sasakii larvae were fumigated with pure phosphine.The results showed that mature fifth instar were the most tol-erant stage at room temperature.Then the mature fifth instar larvae of C .sasakii was fumigated over phosphine at different concentrations under different temperatures.0.14,0.28,0.42,0.56,0.70 mg/L phosphine fumiga-tion with 81-199 h period was required and 0.28,0.42,0.56,0.70,0.84 mg/L phosphine fumigation with 136-166 h period was required to achieve 99% mortality at 25℃ and 15℃,respectively.The expressions of k =C 0.5 T and k =C 0.2 T were obtained at 25℃ and 15℃,which indicated that exposure time was much more important than the concentration of phosphine to mortality of mature larvae of C .sasakii .In the similar conditions,higher temperature in environment was more effective to fumigation than lower temperature.All the results suggested that pure phosphine fumigation demonstrated promising application in C .sasakii control in fruit industry.%桃小食心虫在我国温带水果主产区广泛分布,严重威胁水果出口贸易。为明确纯磷化氢熏蒸处理桃小食心虫的可能性,本文系统研究了纯磷化氢在不同温度条件下对桃小食心虫的毒力。耐受性分析结果表明,桃小食心虫各虫态对磷化氢的耐受力有很大差别,1~2龄幼虫耐受性最弱,5龄老熟幼虫耐受性最强。室内毒力试验结果表明,25℃,0.14~0.70 mg/L 磷化氢熏蒸5龄老熟幼虫81~199 h 或15℃,0.28~0.84 mg/L 磷化氢熏蒸136~166 h,桃小食心虫死亡率可达99%;在25℃和15℃下,试虫达到一定死亡率的气体浓度、时间乘

  6. Two Triazole-Based Phosphine Ligands Prepared via Temperature-Mediated Li/H Exchange: Cu(I) and Au(I) Complexes and Structural Studies.

    Science.gov (United States)

    Choubey, Bimba; Radhakrishna, Latchupatula; Mague, Joel T; Balakrishna, Maravanji S

    2016-09-06

    The kinetically favored triazole-based phosphine 1-(2-(diphenylphosphino)phenyl)-4-phenyl-1H-1,2,3-triazole (2, L1) and its thermodynamically preferred isomer, 5-(diphenylphosphino)-1,4-diphenyl-1H-1,2,3-triazole (3, L2), were obtained by the temperature-controlled lithiation of 2-bromotriazole followed by the reaction with chlorodiphenylphosphine. The structures of phosphines 2 and 3 were determined by X-ray diffraction. Upon reaction with late transition-metal derivatives (Cu(I), Ag(I), and Au(I)), phosphines 2 and 3 form complexes with monodentate (Cu(I), Ag(I), and Au(I); κ(1)-P), chelate (Cu(I); κ(2)-P,N), bridged bidentate (Cu(I); μ(2)-P,N), and tridentate (Cu(I); μ(2),κ(2)-P,N,N) modes of coordination. Reactions with copper(I) halides produced mono-, di-, and tetranuclear complexes, whereas the reaction of 2 with [Cu(NCCH3)4]BF4 yielded the binuclear complex [Cu2(CH3CN)2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-μ-(κ-P,κ-N),κ-N}2](BF4)2 (10) with the ligand acting as a six-electron donor involving phosphorus and two triazole nitrogen atoms. The copper complexes of 2 and 3 containing rhomboid Cu2X2 units, [(Cu)2(μ-X)2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-κ-P}2] (4, X = Cl; 5, X = Br), on treatment with 1,10-phenanthroline and 2,2'-bipyridine gave mixed-ligand complexes of the type [(CuX)(N∩N-κ(2)-N,N){o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-κ-P}] (N∩N = 1,10-phen and 2,2'-bipy; X = Cl, Br, and I).

  7. Perfluorooctanoic acid for shotgun proteomics.

    Directory of Open Access Journals (Sweden)

    Chandra Sekhar Rao Kadiyala

    Full Text Available Here, we describe the novel use of a volatile surfactant, perfluorooctanoic acid (PFOA, for shotgun proteomics. PFOA was found to solubilize membrane proteins as effectively as sodium dodecyl sulfate (SDS. PFOA concentrations up to 0.5% (w/v did not significantly inhibit trypsin activity. The unique features of PFOA allowed us to develop a single-tube shotgun proteomics method that used all volatile chemicals that could easily be removed by evaporation prior to mass spectrometry analysis. The experimental procedures involved: 1 extraction of proteins in 2% PFOA; 2 reduction of cystine residues with triethyl phosphine and their S-alkylation with iodoethanol; 3 trypsin digestion of proteins in 0.5% PFOA; 4 removal of PFOA by evaporation; and 5 LC-MS/MS analysis of the resulting peptides. The general applicability of the method was demonstrated with the membrane preparation of photoreceptor outer segments. We identified 75 proteins from 1 µg of the tryptic peptides in a single, 1-hour, LC-MS/MS run. About 67% of the proteins identified were classified as membrane proteins. We also demonstrate that a proteolytic (18O labeling procedure can be incorporated after the PFOA removal step for quantitative proteomic experiments. The present method does not require sample clean-up devices such as solid-phase extractions and membrane filters, so no proteins/peptides are lost in any experimental steps. Thus, this single-tube shotgun proteomics method overcomes the major drawbacks of surfactant use in proteomic experiments.

  8. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    Energy Technology Data Exchange (ETDEWEB)

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  9. 磷化氢环流熏蒸生产性应用研究%Application of circumfluent fumigation with phosphine

    Institute of Scientific and Technical Information of China (English)

    汪宁; 王旭峰

    2011-01-01

    The technique of phosphine circumfluent fumigation was applied to wheat stored in high large warehouse.The test included three modes of apply drug,outside warehouse,combination of outside warehouse with grain surface and combination of outside warehouse w%以高大房式仓散存硬麦为实验对象,运用磷化氢环流熏蒸装备,分别采用仓外施药、仓外与粮面施药相结合、仓外与粮面间歇投药法不同方式生产性应用。根据不同区域和厂房条件,可以制定经济、安全、有效的熏蒸工艺,节省熏蒸时间,且浓度均匀,杀虫效果好。

  10. Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

    KAUST Repository

    Wappel, Julia

    2016-01-28

    A straightforward synthesis utilizing the ring-opening metathesis polymerization (ROMP) reaction is described for acid-triggered N,O-chelating ruthenium-based pre-catalysts bearing one or two 8-quinolinolate ligands. The innovative pre-catalysts were tested regarding their behavior in ROMP and especially for their use in the synthesis of poly(dicyclopentadiene) (pDCPD). Bearing either the common phosphine leaving ligand in the first and second Grubbs olefin metathesis catalysts, or the Ru–O bond cleavage for the next Hoveyda-type catalysts, this work is a step forward towards the control of polymer functionalization and living or switchable polymerizations.

  11. Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

    Science.gov (United States)

    Wappel, Julia; Fischer, Roland C; Cavallo, Luigi; Slugovc, Christian

    2016-01-01

    Summary A straightforward synthesis utilizing the ring-opening metathesis polymerization (ROMP) reaction is described for acid-triggered N,O-chelating ruthenium-based pre-catalysts bearing one or two 8-quinolinolate ligands. The innovative pre-catalysts were tested regarding their behavior in ROMP and especially for their use in the synthesis of poly(dicyclopentadiene) (pDCPD). Bearing either the common phosphine leaving ligand in the first and second Grubbs olefin metathesis catalysts, or the Ru–O bond cleavage for the next Hoveyda-type catalysts, this work is a step forward towards the control of polymer functionalization and living or switchable polymerizations. PMID:26877818

  12. Effect of diluents on the extraction of praseodymium and samarium by Cyanex 923 from acidic nitrate medium

    Institute of Scientific and Technical Information of China (English)

    YA; El-Nadi

    2010-01-01

    The solvent extraction of Pr(Ⅲ) and Sm(Ⅲ) with trialkyl phosphine oxide(Cyanex 923) in chloroform,carbon tetrachloride,n-octane,cyclohexane,1,2-dichloroethane,benzene,toluene,xylene and nitrobenzene from acidic nitrate medium was investigated.On the basis of slope analysis data,the composition of the extracted species was determined as(M(NO3)3?2CY923),CY923 refers to Cyanex 923.The values of the equilibrium constants and the separation factors were calculated.The effect of the diluents on the metal extracti...

  13. Building new discrete supramolecular assemblies through the interaction of iso-tellurazole N-oxides with Lewis acids and bases.

    Science.gov (United States)

    Ho, Peter C; Jenkins, Hilary A; Britten, James F; Vargas-Baca, Ignacio

    2017-07-21

    The supramolecular macrocycles spontaneously assembled by iso-tellurazole N-oxides are stable towards Lewis bases as strong as N-heterocyclic carbenes (NHC) but readily react with Lewis acids such as BR3 (R = Ph, F). The electron acceptor ability of the tellurium atom is greatly enhanced in the resulting O-bonded adducts, which consequently enables binding to a variety of Lewis bases that includes acetonitrile, 4-dimethylaminopyridine, 4,4'-bipyridine, triphenyl phosphine, a N-heterocyclic carbene and a second molecule of iso-tellurazole N-oxide.

  14. Soft-electron beam and gamma-radiation sensitivity and DNA damage in phosphine-resistant and -susceptible strains of Rhyzopertha dominica.

    Science.gov (United States)

    Hasan, Md Mahbub; Todoriki, Setsuko; Miyanoshita, Akihiro; Imamura, Taro; Hayashi, Toru

    2006-10-01

    The soft-electron beam (low-energy electrons) and gamma-radiation sensitivities of phosphine-resistant (PHR) and -susceptible (PHS) strains of adults lesser grain borer Rhyzopertha dominica (F.) were studied, with particular reference to DNA damage assessed using single-cell electrophoresis (comet assay). Results showed that mortality in adult R. dominica varied significantly between both PHR and PHS strains. Adults of the PHR strain were found to be more tolerant toward soft-electron and gamma radiation than adults of the PHS strain. Studies on the longevity of strains showed that mean survival time and dose rate were highly correlated with both strains and treatments. Results also showed that adults of the PHR strain lived longer than adults of PHS strain for both treatments. Radiation sensitivity indices, however, decreased as radiation dose increased in both strains. Analysis of DNA damage, after 40- and 160-Gy gamma radiation, was carried out using cells obtained from both strains. Gamma-irradiated adults of both strains showed typical DNA fragmentation, compared with cells from nonirradiated adults, which showed more intact DNA. Investigations using the comet assay showed that tail length, moment, olive-tail moment, percentage of tail DNA, and percentage of DNA damage were all greater in the PHS strain compared with the PHR strain and the control insects. Results also showed that DNA damage remained at a constant level for up to 24 h after irradiation. The results have been discussed in relation to the observed strain differences in radiation sensitivity and resistance to phosphine.

  15. Scales of Lewis basicities toward C-centered Lewis acids (carbocations).

    Science.gov (United States)

    Mayr, Herbert; Ammer, Johannes; Baidya, Mahiuddin; Maji, Biplab; Nigst, Tobias A; Ofial, Armin R; Singer, Thomas

    2015-02-25

    Equilibria for the reactions of benzhydryl cations (Ar2CH(+)) with phosphines, tert-amines, pyridines, and related Lewis bases were determined photometrically in CH2Cl2 and CH3CN solution at 20 °C. The measured equilibrium constants can be expressed by the sum of two parameters, defined as the Lewis Acidity (LA) of the benzhydrylium ions and the Lewis basicity (LB) of the phosphines, pyridines, etc. Least-squares minimization of log K = LA + LB with the definition LA = 0 for (4-MeOC6H4)2CH(+) gave a Lewis acidity scale for 18 benzhydrylium ions covering 18 orders of magnitude in CH2Cl2 as well as Lewis basicities (with respect to C-centered Lewis acids) for 56 bases. The Lewis acidities correlated linearly with the quantum chemically calculated (B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G(d,p) level) methyl anion affinities of the corresponding benzhydrylium ions, which can be used as reference compounds for characterizing a wide variety of Lewis bases. The equilibrium measurements were complemented by isothermal titration calorimetry studies. Rates of SN1 solvolyses of benzhydryl chlorides, bromides, and tosylates derived from E(13-33)(+), i.e., from highly reactive carbocations, correlate excellently with the corresponding Lewis acidities and the quantum chemically calculated methyl anion affinities. This correlation does not hold for solvolyses of derivatives of the better stabilized amino-substituted benzhydrylium ions E(1-12)(+). In contrast, the correlation between electrophilic reactivities and Lewis acidities (or methyl anion affinities) is linear for all donor-substituted benzhydrylium ions E(1-21)(+), while the acceptor-substituted benzhydrylium ions E(26-33)(+) react more slowly than expected from their thermodynamic stabilities. The boundaries of linear rate-equilibrium relationships were thus defined.

  16. 磷化氢环流熏蒸技术应用中需注意的几个问题%SOME ISSUES ON APPLICATION OF RECIRCULATION FUMIGATION OF PHOSPHINE

    Institute of Scientific and Technical Information of China (English)

    王殿轩

    2001-01-01

    In this paper some issues about recirculation fumigation of phosphine are discussed, those include demand for gastight , the relationship between dosage of aluminium phophide, phosphine concentration and effectiveness of killing pests, several manners of phospine application, monitoring and evaluation of effectiveness. And several cases are indicated that phosphine is unsuitable to recirculate in the warehouse equipped with recirculation fumigation system.%本文从仓房的气密性、用药量浓度和密闭时间与杀虫效果的关系、磷化氢环流熏蒸中可采用的几种方式、熏蒸效果的检查与评价等几个方面阐述了磷化氢环流熏蒸中应注意的若干问题,并对几种不宜进行整仓环流熏蒸的情况进行了说明。

  17. Phosphine-free Stille-Migita chemistry for the mild and orthogonal modification of DNA and RNA.

    Science.gov (United States)

    Krause, André; Hertl, Alexander; Muttach, Fabian; Jäschke, Andres

    2014-12-08

    An optimized catalyst system of [Pd2 (dba)3 ] and AsPh3 efficiently catalyzes the Stille reaction between a diverse set of functionalized stannanes and halogenated mono-, di- and oligonucleotides. The methodology allows for the facile conjugation of short and long nucleic acid molecules with moieties that are not compatible with conventional chemical or enzymatic synthesis, among them acid-, base-, or fluoride-labile protecting groups, fluorogenic and synthetically challenging moieties with good to near-quantitative yields. Notably, even azides can be directly introduced into oligonucleotides and (deoxy)nucleoside triphosphates, thereby giving direct access to "clickable" nucleic acids.

  18. Synthesis and enzymic evaluation of 4-mercapto-6-oxo-1, 4-azaphosphinane-2-carboxylic acid 4-oxide as an inhibitor of mammalian dihydroorotase.

    Science.gov (United States)

    Manthey, M K; Huang, D T; Bubb, W A; Christopherson, R I

    1998-11-05

    The design, synthesis, and enzymic evaluation of cis- and trans-4-mercapto-6-oxo-1,4-azaphosphinane-2-carboxylic acid 4-oxide 5 against mammalian dihydroorotase is presented. The design strategy for 5 was based on the strong affinity of phosphinothioic acids for zinc and that 5 also resembles the postulated tetrahedral transition state for the enzyme-catalyzed reaction. The synthesis of 5 utilized a novel protection/deprotection sequence upon 4-hydroxy-6-oxo-1, 4-azaphosphinane-2-carboxylic acid 4-oxide 4, followed by incorporation of alpha-phenyl benzenemethanethiol and exhaustive deprotection to afford 5 in 40% overall yield from 4. The activities of both isomers of 5 as inhibitors of mammalian dihydroorotase were marginally greater than that of the parent phosphinic acid 4, indicating a weak binding enhancement due to the phosphinothioic acid moiety.

  19. The Effect of Extending Expose Time of Phosphine on Grain Pests%延长磷化氢熏蒸有效时间对储粮害虫熏蒸效果的影响

    Institute of Scientific and Technical Information of China (English)

    周晓军; 王凯; 代永; 司雪梅

    2016-01-01

    Effective concentration and fumigation time of phosphine are key factors in phosphine fumigation techniques controlling the stored grain pests successfully. For the limitation of poor storage airtightness in practices, half life of pressure is not accord with the fumigation warehouse criteria, and it is the most challenge of control pests in grain storage. With a complementary application technology of phosphine, phosphine tables will be input when phosphine concentration is less than 250 mL/m3 and exposure time is 40 days in stored wheat warehouses under a whole-warehouse fumigation. The results as follow:(1)the expose time of phosphine concentration more than 200 mL/m3 and 250 mL/m3 were 35 days and 25 days under the complementary application technology, respectively; (2)Tribolium castaneum and Cryptolestes ferrugineus were all killed after expose 22 days. It showed that expose time of effective concentration was extended with a complementary application technology, it is a available way to controlling stored grain pests with phosphine fumigation.%维持磷化氢的有效熏蒸浓度和有效熏蒸时间是磷化氢熏蒸技术成功防治储粮害虫的决定性因素。实践中,由于储粮维护结构的气密性较差,仓房气密性的压力半衰期往往无法达到熏蒸仓的标准,给储粮害虫的防治带来了一定困难。本研究采用补充施药技术,当磷化氢浓度降至250 mL/m3时开始补药,延长熏蒸时间至40 d以上,采用整仓环流熏蒸的方式,在储有小麦的高大平房仓进行储粮害虫的磷化氢熏蒸防治试验,结果表明:采用补充施药至少可维持磷化氢浓度在200 mL/m3以上可达35 d,在250 mL/m3以上可达25 d;熏蒸22 d后,可全部杀死仓内的赤拟谷盗和锈赤扁谷盗。表明通过补充施药进而延长有效熏蒸时间是保障磷化氢熏蒸成功有效方法。

  20. Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids.

    Science.gov (United States)

    Martín-Sómer, Ana; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

    2015-01-21

    The intrinsic acidity of CH2[double bond, length as m-dash]CHXH2, HC[triple bond, length as m-dash]CXH2 (X = N, P, As, Sb) derivatives and of their complexes with BeH2 and BH3 has been investigated by means of high-level density functional theory and molecular orbital ab initio calculations, using as a reference the ethyl saturated analogues. The acidity of the free systems steadily increases down the group for the three series of derivatives, ethyl, vinyl and ethynyl. The association with both beryllium dihydride and borane leads to a very significant acidity enhancement, being larger for BeH2 than for BH3 complexes. This acidity enhancement, for the unsaturated compounds, is accompanied by a change in the acidity trends down the group, which do not steadily decrease but present a minimum value for both the vinyl- and the ethynyl-phosphine. When the molecule acting as the Lewis acid is beryllium dihydride, the π-type complexes in which the BeH2 molecules interact with the double or triple bond are found, in some cases, to be more stable, in terms of free energies, than the conventional complexes in which the attachment takes place at the heteroatom, X. The most important finding, however, is that P, As, and Sb ethynyl complexes with BeH2 do not behave as P, As, or Sb Brønsted acids, but unexpectedly as Be acids.

  1. Evaluation of microwave irradiation for analysis of carbonyl sulfide, carbon disulfide, cyanogen, ethyl formate, methyl bromide, sulfuryl fluoride, propylene oxide, and phosphine in hay.

    Science.gov (United States)

    Ren, Yonglin; Mahon, Daphne

    2007-01-10

    Fumigant residues in hay were "extracted" by microwave irradiation. Hay, in gastight glass flasks, was placed in a domestic microwave oven, and fumigants were released into the headspace by microwave irradiation. Power settings for maximum release of fumigants were determined for carbonyl sulfide (COS), carbon disulfide (CS(2)), cyanogen (C(2)N(2)), ethyl formate (EF), methyl bromide (CH(3)Br), sulfuryl fluoride (SF), propylene oxide (PPO), and phosphine (PH(3)). Recoveries of fortified samples were >91% for COS, CS(2), CH(3)Br, SF, PPO, and PH(3) and >76% for C(2)N(2) and EF. Completeness of extraction was assessed from the amount of fumigant retained by the microwaved hay. This amount was determined from further microwave irradiation and was always small (<5% of the amount obtained from the initial procedure). Limits of quantification were <0.1 mg/kg for COS, CS(2), C(2)N(2), EF, and PH(3) and <0.5 mg/kg for CH(3)Br, SF, and PPO. These low limits were essentially due to the absence of interference from solvents and no necessity to inject large-volume gas samples. The microwave method is rapid and solvent-free. However, care is required in selecting the appropriate power setting. The safety implications of heating sealed flasks in microwave ovens should be noted.

  2. Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

    Science.gov (United States)

    Yao, Hiroshi; Iwatsu, Mana

    2016-04-05

    Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

  3. Animal and human studies of a new /sup 99m/Tc labelled phosphine-isocyanide complex with possible applications to radionuclide ventriculography

    Energy Technology Data Exchange (ETDEWEB)

    Zanelli, G.D; Patel, N.; Smith, T.; Crawley, J.C.W.; Lahiri, A.; Brady, F.; Radfar, G.; Silvester, D.J.; Cook, N.D.

    1987-04-01

    A new /sup 99m/Tc-phosphine-isocyanide complex with the general structure (/sup 99m/Tc (DEPE)/sub 2/(CNR)/sub 2/)/sup +/ has been synthesised and tested in animals and one human. In three animal species (rat, rabbit, dog), the complex is an efficient myocardial imaging agent, while in humans it remains in the blood pool. The complex is 100% protein bound in animals and humans, but whereas in humans it is attached to a 51.5 kdalton protein (probably prealbumin), in rabbits it appears to be bound to a larger macromolecule (M.W.>100 kdalton). The efficiency of the complex for blood pool labelling was tested in a human volunteer and compared with the standard in vivo red cell labelling technique with stannous pyrophosphate. A satisfactory radionuclide angiogram could be performed with less than 370 MBq of the complex. The count rate for the complex (cps/MBq) was 15% higher than that obtained with the labelled red cells and the absence of splenic activity was notable. In humans this complex appears to be an efficient blood pool labelling agent which might be useful for radionuclide ventriculography.

  4. Tris(3-hydroxypropyl)phosphine is superior to dithiothreitol for in vitro assessment of vitamin K 2,3-epoxide reductase activity.

    Science.gov (United States)

    Krettler, Christoph; Bevans, Carville G; Reinhart, Christoph; Watzka, Matthias; Oldenburg, Johannes

    2015-04-01

    Use of the reductant dithiothreitol (DTT) as a substrate for measuring vitamin K 2,3-epoxide reductase (VKOR) activity in vitro has been reported to be problematic because it enables side reactions involving the vitamin K1 2,3-epoxide (K1>O) substrate. Here we characterize specific problems when using DTT and show that tris(3-hydroxypropyl)phosphine (THPP) is a reliable alternative to DTT for in vitro assessment of VKOR enzymatic activity. In addition, the pH buffering compound imidazole was found to be problematic in enhancing DTT-dependent non-enzymatic side reactions. Using THPP and phosphate-based pH buffering, we measured apparent Michaelis-Menten constants of 1.20 μM for K1>O and 260 μM for the active neutral form of THPP. The Km value for K1>O is in agreement with the value that we previously obtained using DTT (1.24 μM). Using THPP, we successfully eliminated non-enzymatic production of 3-hydroxyvitamin K1 and its previously reported base-catalyzed conversion to K1, both of which were shown to occur when DTT and imidazole are used as the reductant and pH buffer, respectively, in the in vitro VKOR assay. Accordingly, substitution of THPP for DTT in the in vitro VKOR assay will ensure more accurate enzymatic measurements and assessment of warfarin and other 4-hydroxycoumarin inhibition constants.

  5. Origin of the chemical stability of phosphine-phosphoramidites: structural study of an UPPhos-type crystal and application of UPPhos in the asymmetric hydrogenation of imines.

    Science.gov (United States)

    Balogh, Szabolcs; Farkas, Gergely; Holczbauer, Tamás; Bakos, József

    2017-08-01

    Phosphine-phosphoramidites (PPAs) are heterobidentate ligands that have been developed in the last two decades and have been used successfully in asymmetric catalytic reactions. A single crystal of the PPA (11bS)-N-[(2S,4S)-4-(diphenylphosphanyl)pentan-2-yl]-N-methyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine, C38H35NO2P2, was prepared and structurally characterized by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Structure elucidation revealed unique features which might have a significant effect in the excellent chemical stability of this type of molecule. The conformation of the molecule provides an optimal chelating structure. Iridium complexes of UPPhos were found to be efficient catalysts in the asymmetric hydrogenation of imines {UPPhos is (11bS)-N-[(2S,4S)-4-(diphenylphosphanyl)pentan-2-yl]-N-(propan-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine}.

  6. Acidic deposition ("acid rain")

    Science.gov (United States)

    Schreiber, R. Kent; LaRoe, Edward T.; Farris, Gaye S.; Puckett, Catherine E.; Doran, Peter D.; Mac, Michael J.

    1995-01-01

    Acidic deposition, or "acid rain," describes any form of precipitation, including rain, snow, and fog, with a pH of 5.5 or below (Note: pH values below 7 are acidic; vinegar has a pH of 3). It often results when the acidity of normal precipitation is increased by sulfates and nitrates that are emitted into the atmosphere from burning fossil fuels. This form of airborne contamination is considered harmful, both directly and indirectly, to a host of plant and animal species.Although acid rain can fall virtually anywhere, ecological damages in environmentally sensitive areas downwind of industrial and urban emissions are a major concern. This includes areas that have a reduced capacity to neutralize acid inputs because of low alkalinity soils and areas that contain species with a low tolerance to acid conditions. To determine the distribution of acidic deposition and evaluate its biological effects, research and monitoring are being conducted by the federal government with support from states, universities, and private industry.            The national extent of the acid rain problem has been estimated by sampling water from 3,000 lakes and 500 streams (Irving 1991), representing more than 28,000 lakes and 56,000 stream reaches with a total of 200,000 km (125,000 mi). Some particularly sensitive areas, such as the Adirondack Mountain region, have been more intensively sampled and the biota examined in detail for effects from acidity.         To identify trends in aquatic ecosystems, present and historical survey data on water chemistry and associated biota are compared. In lakes, the chemical and biological history and pH trends may be inferred or reconstructed in some cases by examining assemblages of fossil diatoms and aquatic invertebrates in the sediment layers. In terrestrial ecosystems, vegetation damage is surveyed and effects of acidic deposition to plants and animals are determined from laboratory and field exposure experiments. Natural

  7. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids%有机磷(膦)酸对碱土金属的萃取

    Institute of Scientific and Technical Information of China (English)

    许新; 朱屯

    2002-01-01

    Solvent extraction equilibria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester,di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent on the e/r value and hydration energy of the metal ions. The minor shift of the P-O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P-O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compounds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effect is explained by using IR spectra of the loaded organic phase.

  8. CONTROL OF LIPOSCELISH BOSTRYCHOPHILUS BADONNEL BY SUPPLEMENTING PHOSPHINE AND MAINTAINING CONCENTRATION IN AN AYCH STORAGE%补充施药保持磷化氢浓度熏蒸抗性书虱实仓试验

    Institute of Scientific and Technical Information of China (English)

    刘合存; 王殿轩; 王法林; 陈合印; 韩建平; 陈吉汉

    2011-01-01

    A phosphine fumigation trial against Liposcelish bostrychophilus Badonnel with 488 times of phosphine resistance was carried out in an arch storage of 30 seconds half time at 500 Pa pressure. The test included test cage monitoring, applying aluminium tablet on trays, gas recirculation, phosphine concentration monitoring, fumigant supplement etc.. Phosphine concentration decreased quickly after applying 44 kg of the aluminium phosphide tablet, but for maintaining the concentration above 200 ppm for 45 days, 6 kg, 12 kg and 12 kg tablet was supplied on the 14th day, 19th day and 37th day respectively. The pests in the cage would not be killed completely until 45 days at the 200~500 mL/m3 of phosphine concentration exposure. By making up tablet, no Liposcelish bostrychophilus Badonnel has been detected after 180 days in test granary. The results indicated that it was necessary to supplement in granary with poor airtightness performance to keep effective pbosphine concentration, and Liposcelish bostrychophilus Badonnel could be killed completely at the 200~500 mL/m3 of phosphine concentration for enough time.%在500 Pa正压半衰期为30 s的拱板仓中对储藏小麦中抗性488倍的嗜卷书虱Liposcelish bostrychophilus Badonnel进行磷化氢熏蒸,包括预置试虫虫笼、潮解施药、气体环流、检测浓度、补充药剂、检查效果、熏蒸后防护等.主要结果为:初次施入磷化铝片剂44 kg后,仓内磷化氢浓度下降很快,以后分别于第14 d、第19 d和第37 d先后补充施药6 kg、12 kg、12 kg,仓内磷化氢浓度保持在200 mL/m3以上的时间维持45d.在大部分时间保持磷化氢浓度200 mL/m3~500 mL/m3的情况下,虫笼中的害虫到第45 d才全部死亡,试验仓在后期隔离防护的情况下180 d没有检测到书虱.结果说明,密闭较差的仓房熏蒸中补充施药才可能有效保持磷化氢浓度,在200 mL/m3~500 mL/m3的浓度下熏蒸需要很长的时间才能完全杀死抗性嗜卷书虱.

  9. Toxicidade da combinação de dióxido de carbono e fosfina sob diferentes temperaturas para Tribolium castaneum Toxicity of the carbon dioxide and phosphine combination to Tribolium castaneum under different temperatures

    Directory of Open Access Journals (Sweden)

    Raimundo W. S. Aguiar

    2010-01-01

    Full Text Available O objetivo deste trabalho foi avaliar o efeito da temperatura sobre a toxicidade da combinação de dióxido de carbono e fosfina, para os estágios de desenvolvimento de Tribolium castaneum (Herbst (Coleoptera: Tenebrionidae. A toxicidade da combinação de 5% de dióxido de carbono e 1 g m-3 de fosfina para os estágios de ovo, larvas de 5, 10 e 15 dias, pupa e adulto de T. castaneum, foi estudada nas temperaturas de 25, 30, 35, 40 e 45 °C, por meio de estimativas dos tempos de exposição letais para 50 e 95% dos insetos (TL50 e TL95. Curvas tempo-resposta foram estabelecidas mediante bioensaios com períodos crescentes de exposição à combinação do dióxido de carbono com a fosfina. Observou-se que os TL50 e TL95 reduziram com a elevação da temperatura em todos os estágios de T. castaneum avaliados. O estágio de larva de cinco dias foi a mais susceptível à combinação de dióxido de carbono e fosfina. De acordo com os resultados, a combinação do dióxido de carbono com a fosfina é alternativa potencial para diminuir a quantidade de fosfina aplicada em produtos armazenados, por apresentar alta toxicidade para todos os estágios de T. castaneum sob diferentes temperaturas.The objective of this work was to assess the effect of temperature on the toxicity of the carbon dioxide-phosphine combination for the developmental stages of Tribolium castaneum (Herbst (Coleoptera: Tenebrionidae. The toxicity of combination of 5% carbon dioxide and 1 g m-3 phosphine in the developmental stages of egg, larvae of 5, 10 and 15 days, pupae and adult of T. castaneum was studied under the temperatures of 25, 30, 35, 40 and 45 °C, through the estimation of lethal insect exposure times of 50 and 95% (LT50 and LT95. For that, time-response curves were established through bioassays with increasing periods of exposure to the combination of carbon dioxide and phosphine. A reduction of LT50 and LT95 was observed with temperature increase in all

  10. Low temperature phosphine fumigation for phytosanitary treatment of oriental fruit fly on navel oranges%脐橙携带桔小实蝇低温磷化氢检疫熏蒸技术研究

    Institute of Scientific and Technical Information of China (English)

    刘涛; 张凡华; 李丽; 董书军; 王跃进

    2012-01-01

    桔小实蝇(Bactrocera dorsalis Hendel)广泛危害柑橘等经济水果,是重要的检疫性有害生物之一。本文探讨了低温磷化氢熏蒸对桔小实蝇的杀灭效果及对脐橙(Citrussinensis)的药害。耐受性分析实验表明,3龄幼虫是对磷化氢的最耐受虫态;室内毒力实验表明,熏蒸时间是影响磷化氢毒性的主要因素,低温磷化氢熏蒸桔小实蝇3龄幼虫2~5d的LD99分别为2.147,1.312,0.873和0.628mg/L;根据室内毒力测定结果,我们选择3.80mg/L3d、2.28mg/L4d和1.52mg/L5d对带虫脐橙在5℃下进行了熏蒸实验,结果表明,5℃下,1.52mg/L磷化氢熏蒸5d可完全杀灭脐橙中的桔小实蝇幼虫且对脐橙无药害,可作为实际检疫处理的候选。%The oriental fruit fly (Bactrocera dorsalis Hendel) is one of the most serious pest in citrus and other fruits, thus concerned by many countries for quarantine purpose. The toxicity of low temperature phosphine fumigation against oriental fruit fly and the influence on navel oranges ( Citrus sinensis) were studied in this study. Our results showed that the 3rd - instar larvae tolerated most to phosphine fumigation. The LD99 were 2. 147, 1. 312, 0. 873 and 0. 628mg/L while the exposure time was 2, 3, 4 and 5 days respectively, indicating the exposure time was more effective than doses in phosphine fumigation. Finally, 5℃ fumigation of 3.80mg/L phosphine for 3 days, 2.28mg/L phosphine for 4 days and 1.52mg/L phosphine for 5 days were performed on navel oranges infected with oriental fruit fly, and 100% mortality was achieved in the last group without any adverse effects, indicating it could be a candidate for practical use.

  11. Determination of phosphine residues in fumigated tobacco by headspace gas chromatography%顶空气相色谱法测定烟草熏蒸后的磷化氢残留量

    Institute of Scientific and Technical Information of China (English)

    卢昕博; 周国俊; 边腾飞; 肖卫强; 张云莲; 黄健; 储国海; 金光辉; 丁伟; 周小忠

    2014-01-01

    A method was developed by headspace gas chromatography to monitor trace phosphine residue in fumigated tobacco. PoraPLOT Q capillary column and pulsed flame photometric detector (PFPD) in P-mode were employed. Results showed thatR2 was 0.9998, average recovery of 98.90%, intra-day RSD of 0.5% (n=5), inter-day RSD of 2.4% (n=5), and that limit of detection and quantification of phosphine were 0.005 and 0.015μg/g, respectively. Concentration of phosphine in fumigated tobacco was less than 0.0069μg/g three days after fumigation.%建立了顶空气相色谱法测定熏蒸后烟草中的痕量磷化氢。采用PoraPLOT Q毛细管色谱柱,脉冲火焰光度检测器(PFPD) P模式检测。结果显示,方法决定系数R2为0.9998,平均加标回收率为98.90%,日内重复性RSD为0.5%(n=5),日间重复性RSD为2.4%(n=5),方法检出限为0.0050μg/g,定量限为0.015μg/g。运用本方法对熏蒸后烟草进行测试,结果显示熏蒸结束3天后烟草中磷化氢残留量均小于0.0069μg/g。

  12. Determination of phosphine and other fumigants in air samples by thermal desorption and 2D heart-cutting gas chromatography with synchronous SIM/Scan mass spectrometry and flame photometric detection.

    Science.gov (United States)

    Fahrenholtz, Svea; Hühnerfuss, Heinrich; Baur, Xaver; Budnik, Lygia Therese

    2010-12-24

    Fumigants and volatile industrial chemicals are particularly hazardous to health when a freight container is fumigated or the contaminated material is introduced into its enclosed environment. Phosphine is now increasingly used as a fumigant, after bromomethane--the former fumigant of choice--has been banned by the Montreal Protocol. We have enhanced our previously established thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method by integrating a second gas chromatographic dimension and a flame photometric detector to allow the simultaneous detection of phosphine and volatile organic compounds (VOCs), providing a novel application. A thermal desorption system is coupled to a two dimensional gas chromatograph using both mass spectrometric and flame photometric detection (TD-2D-GC-MS/FPD). Additionally, the collection of mass spectrometric SIM and Scan data has been synchronised, so only a single analysis is now sufficient for qualitative scanning of the whole sample and for sensitive quantification. Though detection limits for the herewith described method are slightly higher than in the previous method, they are in the low μL m(-3) range, which is not only below the respective occupational exposure and intervention limits but also allows the detection of residual contamination after ventilation. The method was developed for the separation and identification of 44 volatile substances. For 12 of these compounds (bromomethane, iodomethane, dichloromethane, 1,2-dichlorethane, benzene, tetrachloromethane, 1,2-dichloropropane, toluene, trichloronitromethane, ethyl benzene, phosphine, carbon disulfide) the method was validated as we chose the target compounds due to their relevance in freight container handling.

  13. The absorbability variation test for late indica rice of different moisture content and phosphine%不同含水量晚籼稻谷对磷化氢的吸附性差异试验

    Institute of Scientific and Technical Information of China (English)

    郭兴海; 郭均钧

    2012-01-01

    Fumigated by phosphine,the absorbability of the late indica rice with different moisture content has big disparity.Fumigation maintains different effective concentration according to different dosage of unit grain.During the circulation fumigation of phosphine,based on the fumigation concentration set,with full consideration of the absorbability variation of late indica rice in various moisture content,we can not only determine accurately the fumigation dosage of unit grain,but also be conductive to an accurate grasp of the fumigation effective concentration lasting time of late indica rice with different moisture content in the circulation fumigation of phosphine,and help to maintain a reasonable and appropriate effective concentration and sufficient time sealed,to achieve a good fumigation effect.%不同含水量的晚籼稻谷磷化氢熏蒸,吸附性存在较大差异,单位粮食用药量不同,熏蒸有效浓度维持的时间不同。磷化氢环流熏蒸时,根据设定的熏蒸浓度,充分考虑不同含水量晚籼稻谷的吸附性差异,不仅能够准确确定单位粮食熏蒸用药量,而且有利于准确把握不同含水量晚籼稻谷磷化氢环流熏蒸有效浓度的维持时间,有利于合理保持合适的有效浓度和足够的密闭时间,熏蒸效果好。

  14. Computational study of the reaction of C6F6 with [IrMe(PEt3)3]: identification of a phosphine-assisted C-F activation pathway via a metallophosphorane intermediate.

    Science.gov (United States)

    Erhardt, Stefan; Macgregor, Stuart A

    2008-11-19

    Density functional theory calculations have been used to model the reaction of C6F6 with [IrMe(PEt3)3], which proceeds with both C-F and P-C bond activation to yield trans-[Ir(C6F5)(PEt3)2(PEt2F)], C2H4, and CH4 (Blum, O.; Frolow, F.; Milstein, D. J. Chem. Soc., Chem. Commun. 1991, 258). Using a model species, trans-[IrMe(PH3)2(PH2Et)], a low-energy mechanism involving nucleophilic attack of the electron-rich Ir metal center at C6F6 with displacement of fluoride has been identified. A novel feature of this process is the capture of fluoride by a phosphine ligand to generate a metallophosphorane intermediate [Ir(C6F5)(Me)(PH3)2(PH2EtF)]. These events occur in a single step via a 4-centered transition state, in a process that we have termed "phosphine-assisted C-F activation". Alternative mechanisms based on C-F activation via concerted oxidative addition or electron-transfer processes proved less favorable. From the metallophosphorane intermediate the formation of the final products can be accounted for by facile ethyl group transfer from phosphorus to iridium followed by beta-H elimination of ethene and reductive elimination of methane. The interpretation of phosphine-assisted C-F activation in terms of nucleophilic attack is supported by the reduced activation barriers computed with the more electron-rich model reactant trans-[IrMe(PMe3)2(PMe2Et)] and the higher barriers found with lesser fluorinated arenes. Reactivity patterns for a range of fluoroarenes indicate the dominance of the presence of ortho-F substituents in promoting phosphine-assisted C-F activation, and an analysis of the charge distribution and transition state geometries indicates that this process is controlled by the strength of the Ir-aryl bond that is being formed.

  15. Oligo-nuclear silver thiocyanate complexes with monodentate tertiary phosphine ligands, including novel 'cubane' and 'step' tetramer forms of AgSCN : PR3 (1:1)4.

    Science.gov (United States)

    Bowmaker, Graham A; Di Nicola, Corrado; Effendy; Hanna, John V; Healy, Peter C; King, Scott P; Marchetti, Fabio; Pettinari, Claudio; Robinson, Ward T; Skelton, Brian W; Sobolev, Alexandre N; Tăbăcaru, Aurel; White, Allan H

    2013-01-07

    Adducts of a number of tertiary pnicogen ligands ER(3) (triphenyl-phosphine and -arsine (PPh(3),AsPh(3)), diphenyl,2-pyridylphosphine (PPh(2)py), tris(4-fluorophenyl)phosphine (P(C(6)H(4)-4F)(3)), tris(2-tolyl)phosphine (P(o-tol)(3)), tris(cyclohexyl)phosphine (PCy(3))), with silver(I) thiocyanate, AgSCN are structurally and spectroscopically characterized. The 1:3 AgSCN : ER(3) complexes structurally defined (for PPh(3),AsPh(3) (diversely solvated)) take the form [(R(3)E)(3)AgX], the thiocyanate X = NCS being N-bound, thus [(Ph(3)E)Ag(NCS)]. A 1:2 complex with PPh(2)py, takes the binuclear form [(pyPh(2)P)(2)Ag()Ag(PPh(2)py)(2)] with an eight-membered cyclic core. 1:1 complexes are defined with PPh(2)py, P(o-tol)(3) and PCy(3); binuclear forms [(R(3)P)Ag()Ag(PR(3))] are obtained with P(o-tol)(3) (two polymorphs), while novel isomeric tetranuclear forms, which may be envisaged as dimers of dimers, are obtained with PPh(2)py, and, as further polymorphs, with PCy(3); these latter may be considered as extensions of the 'cubane' and 'step' forms previously described for [(R(3)E)AgX](4) (X = halide) complexes. Solvent-assisted mechanochemical or solvent-assisted solid-state synthesis methods were employed in some cases, where complexes could not be obtained by conventional solution methods, or where such methods yielded a mixture of polymorphs unsuitable for solid-state spectroscopy. The wavenumbers of the ν(CN) bands in the IR spectra are in broad agreement with the empirical rule that distinguishes bridging from terminal bonding, but exceptions occur for compounds that have a double SCN bridged dimeric structure, and replacement of PPh(3) with PPh(2)py apparently causes a significant decrease in ν(CN) to well below the range expected for bridging SCN in these structures. (31)P CP MAS NMR spectra yield additional parameters that allow a correlation between the structures and spectra.

  16. New and versatile ternary ligand system for technetium radiopharmaceuticals: water soluble phosphines and tricine as coligands in labeling a hydrazinonicotinamide-modified cyclic glycoprotein IIb/IIIa receptor antagonist with 99mTc.

    Science.gov (United States)

    Edwards, D S; Liu, S; Barrett, J A; Harris, A R; Looby, R J; Ziegler, M C; Heminway, S J; Carroll, T R

    1997-01-01

    A hydrazinonicotinamide-functionalized cyclic platelet glycoprotein IIb/IIIa (GPIIb/IIIa) receptor antagonist [cyclo(D-Val-NMeArg-Gly-Asp-Mamb(5-(6-(6-hydrazinonicotin amido) hexanamide))) (HYNIC-tide)] was labeled with 99mTc using tricine and a water soluble phosphine (TPPTS, trisodium triphenylphosphine-3,3',3"-trisulfonate; TPPDS, disodium triphenylphosphine-3,3'-disulfonate; or TPPMS, sodium triphenylphosphine-3-monosulfonate] as coligands. The synthesis of technetium complexes, [99mTc(HYNICtide)(L)(tricine)] (1, L = TPPTS; 2, L = TPPDS; 3, L = TPPMS), can be performed in one or two steps in high yield and with high specific activity (> or = 20,000 Ci/mmol). For example, the reaction of the HYNICtide, [99mTc]pertechnetate, stannous chloride, and tricine at pH 4-5 and room temperature results in the complex [99mTc(HYNICtide)(tricine)2], which reacts with TPPTS (50 degrees C for 30 min) to give complex 1 in > or = 90% yield as determined by radio-HPLC. Complexes 1-3 are formed as equal mixtures of two isomeric forms and are stable for > or = 6 h in the reaction mixture and in dilute solution. Both isomeric forms of complex 1 were found by a platelet-binding assay to contain the 99mTc-labeled HYNICtide and possess biological activity. The composition of these complexes was determined to be 1:1:1:1 for Tc:HYNICtide:L:tricine through a series of mixed ligand experiments on the tracer (99mTc) level. Surprisingly, this composition is maintained over a wide range of relative ligand ratios. The relative bonding capability of the three phosphine coligands to the Tc was determined by spiking various amounts of TPPDS or TPPMS into TPPTS and falls in the order TPPMS > TPPDS > TPPTS. The lipophilicity of the [99m Tc]HYNICtide complexes can be systematically varied by the choice of the phosphine and aminocarboxylate coligands. Using the combination of tricine and a phosphine ligand, HYNIC-derivatized peptides or other small molecules can be labeled with 99mTc in high specific

  17. Recyclable nickel catalysed Suzuki-Miyaura reaction in the presence of polyethyleneimine under phosphine-free conditions in ethylene glycol

    Indian Academy of Sciences (India)

    Nooredin Goudarzian; Mohammad Gholinejad; Parisa Ghahramani

    2011-07-01

    In this report, Suzuki-Miyaura coupling reaction was performed in the presence of polyethyleneimine (PEI) as ligand, NiCl2·6H2O and K2CO3 in ethylene glycol at 80-100°C under phosphinefree conditions. By this method, structurally different aryl bromides and iodides were reacted with phenylboronic acid and potassium phenyltrifluoroborate. Under these simple reaction conditions a different biaryl derivatives have been prepared in high to excellent yields. Recycling experiments showed that catalyst can be used as recyclable catalyst in the Suzuki-Miyaura cross-coupling reactions.

  18. Zwitterionic and cationic bis(phosphine) platinum(II) complexes: structural, electronic, and mechanistic comparisons relevant to ligand exchange and benzene C-H activation processes.

    Science.gov (United States)

    Thomas, J Christopher; Peters, Jonas C

    2003-07-23

    Structurally similar but charge-differentiated platinum complexes have been prepared using the bidentate phosphine ligands [Ph(2)B(CH(2)PPh(2))(2)], ([Ph(2)BP(2)], [1]), Ph(2)Si(CH(2)PPh(2))(2), (Ph(2)SiP(2), 2), and H(2)C(CH(2)PPh(2))(2), (dppp, 3). The relative electronic impact of each ligand with respect to a coordinated metal center's electron-richness has been examined using comparative molybdenum and platinum model carbonyl and alkyl complexes. Complexes supported by anionic [1] are shown to be more electron-rich than those supported by 2 and 3. A study of the temperature and THF dependence of the rate of THF self-exchange between neutral, formally zwitterionic [Ph(2)BP(2)]Pt(Me)(THF) (13) and its cationic relative [(Ph(2)SiP(2))Pt(Me)(THF)][B(C(6)F(5))(4)] (14) demonstrates that different exchange mechanisms are operative for the two systems. Whereas cationic 14 displays THF-dependent, associative THF exchange in benzene, the mechanism of THF exchange for neutral 13 appears to be a THF independent, ligand-assisted process involving an anchimeric, eta(3)-binding mode of the [Ph(2)BP(2)] ligand. The methyl solvento species 13, 14, and [(dppp)Pt(Me)(THF)][B(C(6)F(5))(4)] (15), each undergo a C-H bond activation reaction with benzene that generates their corresponding phenyl solvento complexes [Ph(2)BP(2)]Pt(Ph)(THF) (16), [(Ph(2)SiP(2))Pt(Ph)(THF)][B(C(6)F(5))(4)] (17), and [(dppp)Pt(Ph)(THF)][B(C(6)F(5))(4)] (18). Examination of the kinetics of each C-H bond activation process shows that neutral 13 reacts faster than both of the cations 14 and 15. The magnitude of the primary kinetic isotope effect measured for the neutral versus the cationic systems also differs markedly (k(C(6)H(6))/k(C(6)D(6)): 13 = 1.26; 14 = 6.52; 15 approximately 6). THF inhibits the rate of the thermolysis reaction in all three cases. Extended thermolysis of 17 and 18 results in an aryl coupling process that produces the dicationic, biphenyl-bridged platinum dimers [[(Ph(2)SiP(2))Pt](2

  19. Potent suppression of Kv1.3 potassium channel and IL-2 secretion by diphenyl phosphine oxide-1 in human T cells.

    Directory of Open Access Journals (Sweden)

    Ning Zhao

    Full Text Available Diphenyl phosphine oxide-1 (DPO-1 is a potent Kv1.5 channel inhibitor that has therapeutic potential for the treatment of atrial fibrillation. Many other Kv1.5 channel blockers also potently inhibit the Kv1.3 channel, but whether DPO-1 blocks Kv1.3 channels has not been investigated. The Kv1.3 channel is highly expressed in activated T cells, which is considered a favorable target for immunomodulation. Accordingly, we hypothesized that DPO-1 may exert immunosuppressive and anti-inflammatory effects by inhibiting Kv1.3 channel activity. In this study, DPO-1 blocked Kv1.3 current in a voltage-dependent and concentration-dependent manner, with IC₅₀ values of 2.58 µM in Jurkat cells and 3.11 µM in human peripheral blood T cells. DPO-1 also accelerated the inactivation rate and negatively shifted steady-state inactivation. Moreover, DPO-1 at 3 µM had no apparent effect on the Ca²⁺ activated potassium channel (K(Ca current in both Jurkat cells and human peripheral blood T cells. In Jurkat cells, pre-treatment with DPO-1 for 24 h decreased Kv1.3 current density, and protein expression by 48±6% and 60±9%, at 3 and 10 µM, respectively (both p<0.05. In addition, Ca²⁺ influx to Ca²⁺-depleted cells was blunted and IL-2 production was also reduced in activated Jurkat cells. IL-2 secretion was also inhibited by the Kv1.3 inhibitors margatoxin and charybdotoxin. Our results demonstrate for the first time that that DPO-1, at clinically relevant concentrations, blocks Kv1.3 channels, decreases Kv1.3 channel expression and suppresses IL-2 secretion. Therefore, DPO-1 may be a useful treatment strategy for immunologic disorders.

  20. Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect.

    Science.gov (United States)

    Cano, Israel; Huertos, Miguel A; Chapman, Andrew M; Buntkowsky, Gerd; Gutmann, Torsten; Groszewicz, Pedro B; van Leeuwen, Piet W N M

    2015-06-24

    Air-stable and homogeneous gold nanoparticles (AuNPs, 1a-5a) ligated by various secondary phosphine oxides (SPOs), [R(1)R(2)P(O)H] (R(1) = Naph, R(2) = (t)Bu, L1; R(1) = R(2) = Ph, L2; R(1) = Ph, R(2) = Naph, L3; R(1) = R(2) = Et, L4; R(1) = R(2) = Cy, L5; R(1) = R(2) = (t)Bu, L6), with different electronic and steric properties were synthesized via NaBH4 reduction of the corresponding Au(I)-SPO complex. These easily accessible ligands allow the formation of well dispersed and small nanoparticles (size 1.2-2.2 nm), which were characterized by the use of a wide variety of techniques, such as transmission electron microscopy, thermogravimetric analysis, UV-vis, energy-dispersive X-ray, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR), and cross polarization magic angle spinning (CP MAS) NMR spectroscopy. A pronounced ligand effect was found, and CP MAS NMR experiments enabled us to probe important differences in the polarity of the P-O bond of the SPOs coordinated to the nanoparticle surface depending on the type of substituents in the ligand. AuNPs containing aryl SPOs carry only SPO anions and are highly selective for aldehyde hydrogenation. AuNPs of similar size made with alkyl SPOs contain also SPOH, hydrogen bonded to SPO anions. As a consequence they contain less Au(I) and more Au(0), as is also evidenced by XPS. They are less selective and active in aldehyde hydrogenation and now show the typical activity of Au(0)NPs in nitro group hydrogenation.