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Sample records for phosphines

  1. Phosphine

    Integrated Risk Information System (IRIS)

    Phosphine ; CASRN 7803 - 51 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  2. Silylated Phosphines and Phosphoranimines.

    DTIC Science & Technology

    1986-10-10

    react smoothly with both substrates. Cyclopentadlene, for example, affords a .. ,. Diels - Alder adduct in each case. - *..:*. V.., 7., 7 NSiNe 3 PhPC1 2... condensation with ELECTEm LU ractie phsphies.Some new 2,2-addition and --J oxidation reactions of the P-C systems. Nf-HR.O 2318 LA... R NP(-NR)=CHR...groups, transilylation, and condensation with .. reactive phosphines. Some new 1,2-addition and oxidation reactions of the P=C systems, R2 NP=CHR,R NP(=NR

  3. CONFIRMATION OF CIRCUMSTELLAR PHOSPHINE

    SciTech Connect

    Agúndez, M.; Cernicharo, J.; Encrenaz, P.; Teyssier, D.

    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.

  4. Phosphonate–Phosphinate Rearrangement

    PubMed Central

    2014-01-01

    LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH3O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH3O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate. PMID:25525945

  5. Phosphine oxide surfactants revisited.

    PubMed

    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.

  6. Chiral phosphines in nucleophilic organocatalysis

    PubMed Central

    Xiao, Yumei; Sun, Zhanhu

    2014-01-01

    Summary This review discusses the tertiary phosphines possessing various chiral skeletons that have been used in asymmetric nucleophilic organocatalytic reactions, including annulations of allenes, alkynes, and Morita–Baylis–Hillman (MBH) acetates, carbonates, and ketenes with activated alkenes and imines, allylic substitutions of MBH acetates and carbonates, Michael additions, γ-umpolung additions, and acylations of alcohols. PMID:25246969

  7. Phosphine Catalysis of Allenes with Electrophiles

    PubMed Central

    Wang, Zhiming; Xu, Xingzhu; Kwon, Ohyun

    2014-01-01

    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 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. PMID:24663290

  8. Matrix-bound phosphine in Antarctic biosphere.

    PubMed

    Zhu, Renbin; Sun, Liguang; Kong, Deming; Geng, Jinju; Wang, Ning; Wang, Qiang; Wang, Xiaorong

    2006-08-01

    Phosphine (PH(3)) is a natural gaseous carrier of phosphorus in its geochemical cycles, and it might be of importance to the phosphorus balance of natural ecosystem. For the first time phosphine levels were investigated in the Earth's coldest, driest, and most southerly Antarctic biosphere. Matrix-bound phosphine (MBP) was found in sea animal guanos, ornithogenic sediments and soils. Phosphine concentrations varied with different sea animal guanos. Average phosphine concentrations in empire penguin, gentoo penguin, sea lion, skua and gull guanos were 2.54+/-1.28 ng kg(-1), 6.21+/-2.15 ng kg(-1), 9.12+/-4.66 ng kg(-1), 11.90+/-1.29 ng kg(-1) and 14.55+/-6.74 ng kg(-1), respectively. The contents of phosphorus in these various matrixes have an important effect on MBP concentrations. The levels of phosphine appeared an increasing tendency with the content of TP, IP and OP in sea animal guanos, ornithogenic sediments or soils. The correlation between PH(3) and Fe, Mn, Al in these matrixes was also analyzed and discussed. Phosphine showed an obviously positive correlation with Fe in sea animal guanos. However, excessively high Fe, Al and Mn may inhibit the formation of PH(3) in the ornithogenic soils or sediments in the Antarctic biosphere.

  9. Phosphine gas in the upper troposphere

    NASA Astrophysics Data System (ADS)

    Glindemann, Dietmar; Edwards, Marc; Kuschk, Peter

    The gas phosphine (PH 3) is a part of an atmospheric link of the phosphorus cycle on earth. Phosphine was reported elsewhere to be found worldwide in remote air samples in the lower troposphere in the low ng/m 3 range during the night, when oxidation is inhibited. But much less phosphine (pg/m 3 range) was found during daylight around noon in this reactive contaminated atmosphere. Here we found for the first time gaseous phosphine in remote air samples (0.39-2.45 ng/m 3, 16 locations) in the high troposphere above the North-Atlantic in November 1995 during daylight around noontime. The maximum concentration was measured at the highest altitude of 12,500 m. No night measurements could be conducted to compare day and night values. The finding of the reactive phosphine under the sunlight in the high troposphere far from possible terrestric sources is strange. A model experiment shows that phosphine could possibly survive the daylight much longer at high altitudes because of a lack of UV-induced oxidants in the clean and dry air. Additional model experiments indicate that phosphine can easier sustain its mobile gaseous state in the atmosphere compared to gases like hydrogen sulfide and ammonia which stick easier to aerosol and are subject to faster washout and return to Earth's surface. However, the ultimate fate of phosphine is the oxidation to form phosphoric acid as a low pH agent and as possible condensation nuclei for clouds at very high altitudes. The potent sources and atmospheric chemistry which allow phosphine to accumulate in the upper troposphere are still to be discovered.

  10. Phosphine photochemistry in Saturn's atmosphere

    NASA Technical Reports Server (NTRS)

    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.

  11. Phosphine photochemistry in Saturn's atmosphere

    NASA Astrophysics Data System (ADS)

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

    1983-10-01

    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.

  12. Spontaneous ignition limits of silane and phosphine

    SciTech Connect

    Kondo, Shigeo; Tokuhashi, Kazuaki; Nagai, Hidekazu; Iwasaka, Masaji; Kaise, Masahiro

    1995-04-01

    Spontaneous ignition limits of silane and phosphine have been investigated at relatively low concentrations. For silane, the spontaneous ignition occurs if the mixture concentration is such that the silane/oxygen ratio is higher than a certain threshold limit value. In other words, the mixture is not stable if the ratio is higher than a certain value. On the other hand. in the case of phosphine the threshold limit line has been found to be a little curved, though the reason for the fact is not clear. At any rate, it is concluded that the spontaneous ignition of both silane and phosphine occurs as a result of a competition of chain branching and chain breaking reactions, in a way that is qualitatively similar to that in hydrogen oxidation.

  13. Thiazoyl phosphines. Design, reactivity, and complexation.

    PubMed

    Zablocka, Maria; Oshovsky, Gennady; Duhayon, Carine; Ladeira, Sonia; Caminade, Anne-Marie; Mignani, Serge; Majoral, Jean-Pierre

    2016-06-21

    In spite of the numerous possible applications of thiazoles as ligands for catalysis and as active molecules in medicinal chemistry, only a few studies have dealt with their versatile chemistry. Several selective modifications of the structure of these derivatives and mainly of thiazoyl phosphines are detailed, thus illustrating the great possibilities to tailor at will their structures and therefore their properties. The formation of Ru and Au complexes is reported. Six of these new thiazoyl phosphines were characterized by X-ray crystallography as well as two of their gold complexes.

  14. Hydrophosphorylation of alkynes with phosphinous acids

    SciTech Connect

    Nifant'ev, E.E.; Solovetskaya, L.A.; Magdeeva, R.K.

    1986-03-20

    A feature of the homolytic hydrophosphorylation of alkynes, as compared with alkenes, is more ready addition of phosphinous acids in presence of benzoyl peroxides. A difference was found in the hydrophosphorylation of acetylenes with dibutylphosphinous acid and with diarylphosphinous acids: the latter tend to form diaddition products.

  15. Disruption of iron homeostasis increases phosphine toxicity in Caenorhabditis elegans.

    PubMed

    Cha'on, Ubon; Valmas, Nicholas; Collins, Patrick J; Reilly, Paul E B; Hammock, Bruce D; Ebert, Paul R

    2007-03-01

    The aim of this study is to identify the biochemical mechanism of phosphine toxicity and resistance, using Caenorhabditis elegans as a model organism. To date, the precise mode of phosphine action is unclear. In this report, we demonstrate the following dose-dependent actions of phosphine, in vitro: (1) reduction of ferric iron (Fe3+) to ferrous iron (Fe2+), (2) release of iron from horse ferritin, (3) and the peroxidation of lipid as a result of iron release from ferritin. Using in situ hybridization, we show that the ferritin genes of C. elegans, both ferritin-1 and ferritin-2, are expressed along the digestive tract with greatest expression at the proximal and distal ends. Basal expression of the ferritin-2 gene, as determined by quantitative PCR, is approximately 80 times that of ferritin-1. However, transcript levels of ferritin-1 are induced at least 20-fold in response to phosphine, whereas there is no change in the level of ferritin-2. This resembles the reported pattern of ferritin gene regulation by iron, suggesting that phosphine toxicity may be related to an increase in the level of free iron. Indeed, iron overload increases phosphine toxicity in C. elegans at least threefold. Moreover, we demonstrate that suppression of ferritin-2 gene expression by RNAi, significantly increases sensitivity to phosphine. This study identifies similarities between phosphine toxicity and iron overload and demonstrates that phosphine can trigger iron release from storage proteins, increasing lipid peroxidation, leading to cell injury and/or cell death.

  16. Cationic ruthenium alkylidene catalysts bearing phosphine ligands.

    PubMed

    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.

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

    PubMed

    Beaud, Rodolphe; Phipps, Robert J; Gaunt, Matthew J

    2016-10-12

    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.

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

    PubMed Central

    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

  19. Preparation of phosphines through C–P bond formation

    PubMed Central

    Wauters, Iris; Debrouwer, Wouter

    2014-01-01

    Summary 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. PMID:24991257

  20. Searching for Practically Useful P-Chirogenic Phosphine Ligands.

    PubMed

    Imamoto, Tsuneo

    2016-12-01

    In this account, the design, synthesis, and application of P-chirogenic phosphine ligands that have been mainly carried out in our laboratory over the last three decades are described. Various enantiopure P-chirogenic phosphine ligands have been efficiently prepared by using phosphine boranes as intermediates. Conformationally rigid and electron-rich P-chirogenic phosphine ligands possessing C2 symmetry as well as a bulky alkyl group and a small group at the phosphorus atoms exhibit excellent enantioselectivities and catalytic efficiency in a variety of transition-metal-catalyzed asymmetric reactions. Enantiopure 2,3-bis(tert-butylmethylphosphino)quinoxaline (QuinoxP*) is an air-stable crystalline solid that shows superior enantioinduction ability in catalytic asymmetric syntheses. Mechanistic studies of Rh-catalyzed asymmetric hydrogenation using structurally simple P-chirogenic phosphine ligands, such as tBu-BisP*, are briefly described.

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

    PubMed

    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 degrees C and the optimal digestion time was about 20 min. Acidic conditions were more favorable for the release of matrix-bound phosphine compared to the neutral conditions. A proper water dilution can increase the production and emission of phosphine from the Antarctic penguin guanos.

  2. Hydroxyalkyl phosphine compounds for use as diagnostic and therapeutic pharmaceuticals

    DOEpatents

    Katti, K.V.; Singh, P.R.; Reddy, V.S.; Katti, K.K.; Volkert, W.A.; Ketring, A.R.

    1999-03-02

    This research discloses a compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical comprises a functionalized hydroxyalkyl phosphine ligand and a metal combined with the ligand. 16 figs.

  3. Nucleophilic Chiral Phosphines: Powerful and Versatile Catalysts for Asymmetric Annulations

    PubMed Central

    Xiao, Yumei; Guo, Hongchao; Kwon, Ohyun

    2016-01-01

    Recent advances in chiral-phosphine-catalyzed asymmetric annulation reactions; including annulations of allenes, alkynes, Morita–Baylis–Hillman (MBH) carbonates, and ketenes; and their applications in the synthesis of bioactive molecules and natural products are reviewed. PMID:28077882

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 major stored-cereal pests worldwide. To understand the molecular bases of phosphine resistance in insects, we used RNA-...

  7. Unintentional poisoning by phosphine released from aluminum phosphide.

    PubMed

    Shadnia, S; Mehrpour, O; Abdollahi, M

    2008-01-01

    Aluminum phosphide as a releaser of phosphine gas is used as a grain preservative. In this case report, we describe an accidental severe poisoning in a 35-year-old woman, her 18-year-old daughter, and 6-year-old son caused by inhalation of phosphine gas released from 20 tablets of aluminum phosphide stored in 15 rice bags. The boy died 2 days after exposure before admission to hospital and any special treatment, but the others were admitted 48 h after exposure. They had signs and symptoms of severe toxicity, and their clinical course included metabolic acidosis, electrocardiographic changes, and hypotension. They were treated by intravenous administration of sodium bicarbonate, magnesium sulfate, and calcium gluconate. The patients were discharged after 3 days and followed up for 1 week after discharge. Rapid absorption of phosphine by inhalation, induction of hyperglycemia, and surviving of patients are interesting issues of this case report.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Studies of Polymer-Bound Macrocyclic Polytertiary Phosphines.

    DTIC Science & Technology

    1983-07-31

    Polymer-Bound ?4acrocyclic Polytertiary Fnl c~//q 73, Phosphines 6.PERFORMING o-46. REponR NUMBER 7. AUTI4OR(s) 6. CONTRACT OR GRANT NUMBER(s) tt 2P...Macrocyclic Polytertiary Phosphines 2/1/79 - 7/31/83 P.I., Evan P. Kyba Department of Chemistry University of Texas at Austin Austin, Texas 78712 Approved...transformed into 22 (L = HOMe), which is the operating catalyst in asymmetric hydrogenations of enamides. 1 3 More recently we have described the structure of

  10. Extraction of uranium by macroporous bifunctional phosphinic acid resin

    SciTech Connect

    Sabharwal, K.N.; Rao, P.R.V.; Srinivasan, M.

    1995-05-01

    The extraction of U(VI), Th(IV) and a number of fission products from nitric acid medium by a newly synthesised macroporous bifunctional phosphinic acid resin has been studied. The extraction of uranium from sulphuric acid medium has also been studied. While the gel type phosphinic acid resins seems to pose a number of problems in practical applications, the macroporous type resins are shown to be suitable for a variety of applications where conventional ion exchange resins are of limited use. 12 refs., 5 figs., 3 tabs.

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

    PubMed

    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.

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

    PubMed

    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.

  13. Advances in Nucleophilic Phosphine Catalysis of Alkenes, Allenes, Alkynes, and MBHADs

    PubMed Central

    Fan, Yi Chiao

    2014-01-01

    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. PMID:24196409

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

    PubMed

    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.

  15. Retrievals of Jovian Tropospheric Phosphine from Cassini/CIRS

    NASA Technical Reports Server (NTRS)

    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.

  16. Phosphine-boronates: efficient bifunctional organocatalysts for Michael addition.

    PubMed

    Baslé, Olivier; Porcel, Susana; Ladeira, Sonia; Bouhadir, Ghenwa; Bourissou, Didier

    2012-05-11

    Phosphine-boronates R(2)P(o-C(6)H(4))B(OR')(2) have been evaluated as bifunctional organocatalysts for the Michael addition of malonate pronucleophiles to methylvinylketone. The presence of the Lewis acidic boron center adjacent to phosphorus significantly improves catalytic performance. Isolation and complete characterization of a key intermediate, namely a β-phosphonium enolate, substantiate the role of the Lewis acidic moiety in the catalytic process.

  17. Toward the formation of alkylphosphonic acids in phosphine ices

    NASA Astrophysics Data System (ADS)

    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.

  18. Biaryl Phosphine Ligands in Palladium-Catalyzed Amination

    PubMed Central

    Surry, David S.

    2012-01-01

    Palladium-catalyzed amination of aryl halides has undergone rapid development in the last 12 years. This has been largely driven by implementation of new classes of ligands. Biaryl phosphines have proven to provide especially active catalysts in this context. This review discusses the applications that these catalysts have found in C-N cross-coupling in heterocycle synthesis, pharmaceuticals, materials science and natural product synthesis. PMID:18663711

  19. Electrochemical Properties of Palladium and Platinum Phosphine Complexes.

    DTIC Science & Technology

    1985-09-30

    19 .3 Molecular orbital Energy Diagram for Square Planar Pd-Phosphine Complexes.......................... 20 4 Cyclic Voltammogram...hydrogen, and therefore cause reaction 6 and 7 to be more difficult than reaction 1. Similar results have been observed with lead, indium, cadmium ... voltammetry : trans-PdIIL 2x2 , where L = PPh 3, PBu 3, PCy3, NHMe 2 (Ph - phenyl, Bu = n-butyl, Cy = cyclohexyl, Me methyl) and X = Cl or I; cis-PdII(LL)X2

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

    PubMed

    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.

  1. Experiments in Thermodynamics and Kinetics of Phosphine Substitution in (p-Cymene)RuCl[subscript 2](PR[subscript 3])

    ERIC Educational Resources Information Center

    Ozerov, Oleg V.; Fafard, Claudia M.; Hoffman, Norris W.

    2007-01-01

    This manuscript describes a set of three experiments that investigates the thermodynamic and kinetic aspects of phosphine substitution at a Ru center. In the first experiment, the students synthesize a Ru organometallic complex containing a phosphine ligand. In the second, equilibria for phosphine substitution involving several different…

  2. Ab initio post-hartree-fock study of molecular structures and vibrational spectra of phosphine oxide, phosphinous acid, and their thio analogs

    SciTech Connect

    Kwiatkowski, J.S.; Leszczynski, J.

    1992-08-06

    This paper discusses how MP2 theory is used to predict the vibrational IR spectra and molecular parameters of phosphine oxide, phosphinous acid, and their thio analogs. This spectral data agrees well with experimental data, and might be applied to identification of the sulfur species. The calculations also correctly predict the observed shifts of the IR wavenumbers upon isotopic substitution of the molecules. 17 refs., 5 tabs.

  3. Polyimides Containing Pendent Phosphine Oxide Groups for Space Applications

    NASA Technical Reports Server (NTRS)

    Thompson, C. M.; Smith, J. G., Jr.; Watson, K. A.; Connell, J. W.

    2002-01-01

    As part of an ongoing materials development activity to produce high performance polymers that are durable to the space environment, phosphine oxide containing polyimides have been under investigation. A novel dianhydride was prepared from 2,5-dihydroxyphenyldiphenylphosphine oxide in good yield. The dianhydride was reacted with commercially available diamines, and a previously reported diamine was reacted with commercially available dianhydrides to prepare isomeric polyimides. The physical and mechanical properties, particularly thermal and optical properties, of the polymers were determined. One material exhibited a high glass transition temperature, high tensile properties, and low solar absorptivity. The chemistry, physical, and mechanical properties of these resins will be discussed.

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

    DTIC Science & Technology

    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

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

    PubMed

    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.

  6. Unsaturated phosphinic analogues of gamma-aminobutyric acid as GABA(C) receptor antagonists.

    PubMed

    Chebib, M; Vandenberg, R J; Froestl, W; Johnston, G A

    1997-06-25

    The phosphinic and methylphosphinic analogues of gamma-aminobutyric acid (GABA) are potent GABA(C) receptor antagonists but are even more potent as GABA(B) receptor agonists. Conformationally restricted unsaturated phosphinic and methylphosphinic analogues of GABA and some potent GABA(B) receptor phosphonoamino acid antagonists were tested on GABA(C) receptors in Xenopus oocytes expressing human retinal rho1 mRNA. 3-Aminopropyl-n-butyl-phosphinic acid (CGP36742), an orally active GABA(B) receptor antagonist, was found to be a moderately potent GABA(C) receptor antagonist (IC50 = 62 microM). The unsaturated methylphosphinic and phosphinic analogues of GABA were competitive antagonists of the GABA(C) receptors, the order of potency being [(E)-3-aminopropen-1-yl]methylphosphinic acid (CGP44530, IC50 = 5.53 microM) > [(E)-3-aminopropen-1-yl]phosphinic acid (CGP38593, IC50 = 7.68 microM) > [(Z)-3-aminopropen-1-yl]methylphosphinic acid (CGP70523, IC50 = 38.94 microM) > [(Z)-3-aminopropen-1-yl]phosphinic acid (CGP70522, IC50 > 100 microM). This order of potency differs from that reported for these compounds as GABA(B) receptor agonists, where the phosphinic acids are more potent than the corresponding methylphosphinic acids.

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

    PubMed

    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.

  8. Acute Oral Toxicity (LD50) of 4-Nitrophenyl Monochloromethyl (Phenyl) Phosphinate (TA009) in Male Rats

    DTIC Science & Technology

    1984-10-01

    phosphinates hydrolyze readily in aqueous solutions, a vehicle which would minimize the rate of hydrolysis was required. A mixture of Tween 80 (Fisher...monochloroiethyl (phenyl) phosphinat_. formulated with Tween 80 , EtOH, and citrate buffer (LAIR SOP-OP-STX-45, Preparation of Compounds Unstable in Water...phosphinate. 16.0 ml Tween 80 8.0 ml (100 %) ethanol, 56.0 ml citrate buffer (50 mM) at a pH of 3.2. The vehicle was the same as above without phosphinate. pH

  9. Acute Oral Toxicity (LD50) of 4-Nitrophenyl Monochloromethyl (Phenyl) Phosphinate (TA009) in Female Rats

    DTIC Science & Technology

    1984-10-01

    chosen was a mixture of Tween 80 (Fisher Scientific Company, Fairlawn, NJ) ethanol and citrate buffer (pH 2.9). Additional information on the vehicle...phosphinate formulated with Tween 80 , EtOH, and citrate buffer (LAIR SOP-OP-STX-45, Preparation of Compounds Unstable in Water for SLRL Assay). A 2.0...percent phosphinate solution was prepared with 1.5 g 4- nitrophenyl monochloromethyl (phenyl) phosphinate. 15.0 ml Tween 80 7.5 ml (100 %) ethanol

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

    PubMed

    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.

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

    DOEpatents

    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.

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

    DOEpatents

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

    2000-01-01

    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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

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

    PubMed

    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 < 0.05) between respiration rate and 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.

  15. 40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting...

  16. 40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting...

  17. 40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting...

  18. 40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting...

  19. 40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting...

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

    SciTech Connect

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

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Influence of structure of the metal salts of phosphinates on the performance of the fire-retardant polymers

    NASA Astrophysics Data System (ADS)

    Liu, Xueqing; Liu, Jiyan; Guo, Yuanhao; Cakmak, Miko

    2015-05-01

    Dialkylphosphinate salts (I) and amide-containing phosphinate salts(II) with varying metal cation and organic groups were used as flame retardants for epoxy resin(EP), poly(butylene terephthalate) (PBT) correspondingly. Their flame retardancy, mechanical properties, thermal stability, compatibility between phosphinate salts and polymer, and leaching of the salts from the polymer were investigated with respect to the structure of phosphinate salts.

  3. Can a functionalized phosphine ligand promote room temperature luminescence of the [Ru(bpy)(tpy)]2+ core?

    PubMed

    Lebon, Emilie; Bastin, Stéphanie; Sutra, Pierre; Vendier, Laure; Piau, Rémi E; Dixon, Isabelle M; Boggio-Pasqua, Martial; Alary, Fabienne; Heully, Jean-Louis; Igau, Alain; Juris, Alberto

    2012-01-18

    Unexpected room temperature luminescence is observed and rationalized by highly challenging excited state calculations for a functionalized phosphine ligand coordinated on the [Ru(bpy)(tpy)](2+) core.

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

    PubMed

    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%.

  5. 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.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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 ( 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.

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

    DOEpatents

    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.

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

    PubMed

    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.

  9. Three fatalities involving phosphine gas, produced as a result of methamphetamine manufacturing.

    PubMed

    Willers-Russo, L J

    1999-05-01

    In August of 1996, Sheriff's deputies investigated the deaths of three individuals suspected to have been overcome by phosphine gas. Phosphine is an extremely toxic gas, and is generally seen in the farming industry where it is used as a grain fumigant. It can also be generated as a by-product during the manufacturing of methamphetamine. Chemicals and equipment consistent with the manufacturing of methamphetamine were noted at the location, as well as an apparent reaction mixture heated to near dryness. Dräger tubes detected an atmospheric phosphine concentration in excess of 0.3 parts per million (ppm), the Threshold Limit Value. Deputies had initially assessed the scene with no protective equipment, raising concerns about phosphine toxicity and the effects of exposure. The objectives of this paper are to describe how phosphine is formed during the manufacture of methamphetamine, to review the toxicity, health effects and symptoms of exposure, to address the safety concerns regarding potential exposure to law enforcement personnel, and to describe the protective equipment available for personnel who respond to clandestine laboratories.

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

    PubMed

    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.

  11. Occupational exposure to aluminium phosphide and phosphine gas? A suspected case report and review of the literature.

    PubMed

    Sudakin, D L

    2005-01-01

    The manufacture and application of aluminium phosphide fumigants pose risks of inhalation exposure to phosphine gas. This article presents a case report of suspected inhalation exposure to phosphine gas in a manufacturing facility for aluminium phosphide fumigants, which was associated with acute dyspnoea, hypotension, bradycardia and other signs of intoxication. These symptoms resolved within several hours after removal from exposure. A review of the data on human exposures to phosphide fumigants identifies both pesticide applicators and individuals in the vicinity of application to be at risk of accidental exposure and injury from phosphine inhalation. More recent reports have identified risks of phosphine gas inhalation in association with the clandestine production of methamphetamine. Toxicodynamic effects of phosphine result from the inhibition of cytochrome c oxidase and subsequent generation of reactive oxygen species. There remain unanswered questions relating to the toxicokinetics of phosphine, as well as the assessment of human exposure utilizing biomarkers. As initial signs and symptoms of intoxication from phosphine gas may be nonspecific and transient, there is a need for improved recognition of the potential hazards associated with phosphide fumigants and phosphine gas.

  12. Phosphine derivatives of sparfloxacin - Synthesis, structures and in vitro activity

    NASA Astrophysics Data System (ADS)

    Komarnicka, Urszula K.; Starosta, Radosław; Guz-Regner, Katarzyna; Bugla-Płoskońska, Gabriela; Kyzioł, Agnieszka; Jeżowska-Bojczuk, Małgorzata

    2015-09-01

    We synthesized two derivatives of sparfloxacin (HSf): aminomethyl(diphenyl)phosphine (PSf) and its oxide (OPSf). The compounds were characterized by NMR spectroscopy, MS and elemental analysis. In addition, the molecular structures of the compounds were determined using DFT and X-ray (OPSf) analysis. The antibacterial activity of HSf and both derivatives was tested against four reference and fifteen clinical Gram-positive and Gram-negative strains of bacteria (sensitive or resistant to fluoroquinolones). The results showed that the activity of PSf was similar to or higher than the activity of HSf, while OPSf was found significantly less active. The compounds were also tested in vitro toward the following cancer cell lines: mouse colon carcinoma (CT26) and human lung adenocarcinoma (A549). Regardless of the cancer cell line, derivatization of HSf resulted in the gradual increase of cytotoxicity. OPSf exhibited the highest one (4 h - incubation time: IC50(CT26) = 51.0 ± 1.2; IC50(A549) = 74.9 ± 1.4 and 24 h: IC50(CT26) = 109.2 ± 8.8; IC50(A549) = 52.7 ± 9.2).

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

    PubMed

    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.

  14. Recent Developments in the Chemistry of N-Heterocyclic Phosphines

    NASA Astrophysics Data System (ADS)

    Gudat, Dietrich

    This chapter gives a survey on five- and six-membered phosphorus-nitrogen heterocyclic compounds whose rings combine a phosphazene (>N-P = N-) or phosphazane (>N-P(X)-N<) unit with an unsaturated C2 or C3 building block. Representatives contain structurally diverse species like aromatic 1,3,2-diazaphosphinines and (benzo)-1,3,2-diazaphospholes, cationic counterparts of subvalent main-group carbene analogues like 1,3,2-diazaphospholenium ions and phosphenium-diketiminates, and neutral heterocycles like 1,3,2-diazaphospholenes featuring unusual structures and reactivities. The exploration of these species developed rapidly in the last two decades in the wake of cutting edge research on multiple bonding and low coordination in the chemistry of heavier main-group elements, and the discovery of stable carbenes. This review summarizes the elaboration of synthetic approaches for different types of N-heterocyclic phosphine derivatives, discusses their characterization by physical and computational methods which furnished a thorough understanding of structure and bonding, and finally highlights accomplishments in the exploration of the chemical properties at the border of classical organic heterocyclic chemistry and molecular inorganic chemistry.

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

    NASA Technical Reports Server (NTRS)

    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.

  16. Bis(aminomethyl)phosphinic Acid, a Highly Promising Scaffold for the Development of Bacterial Urease Inhibitors

    PubMed Central

    2014-01-01

    Inhibitors of bacterial ureases are considered to be promising compounds in the treatment of infections caused by Helicobacter pylori in the gastric tract and/or by urealytic bacteria (e.g., Proteus species) in the urinary tract. A new, extended transition state scaffold, bis(aminomethyl)phosphinic acid, was successfully explored for the construction of effective enzyme inhibitors. A reliable methodology for the synthesis of phosphinate analogues in a three-component Mannich-type reaction was elaborated. The obtained molecules were assayed against ureases purified from Sporosarcina pasteurii and Proteus mirabilis, and aminomethyl(N-n-hexylaminomethyl)phosphinic acid was found to be the most potent inhibitor, with a Ki = 108 nM against the S. pasteurii enzyme. PMID:25699141

  17. Phosphine on Jupiter and Saturn from Cassini/CIRS

    NASA Astrophysics Data System (ADS)

    Fletcher, L. N.; Orton, G. S.; Teanby, N. A.; Irwin, P. G. J.

    2009-08-01

    The global distribution of phosphine (PH 3) on Jupiter and Saturn is derived using 2.5 cm -1 spectral resolution Cassini/CIRS observations. We extend the preliminary PH 3 analyses on the gas giants [Irwin, P.G.J., and 6 colleagues, 2004. Icarus 172, 37-49; Fletcher, L.N., and 9 colleagues, 2007a. Icarus 188, 72-88] by (a) incorporating a wider range of Cassini/CIRS datasets and by considering a broader spectral range; (b) direct incorporation of thermal infrared opacities due to tropospheric aerosols and (c) using a common retrieval algorithm and spectroscopic line database to allow direct comparison between these two gas giants. The results suggest striking similarities between the tropospheric dynamics in the 100-1000 mbar regions of the giant planets: both demonstrate enhanced PH 3 at the equator, depletion over neighbouring equatorial belts and mid-latitude belt/zone structures. Saturn's polar PH 3 shows depletion within the hot cyclonic polar vortices. Jovian aerosol distributions are consistent with previous independent studies, and on Saturn we demonstrate that CIRS spectra are most consistent with a haze in the 100-400 mbar range with a mean optical depth of 0.1 at 10 μm. Unlike Jupiter, Saturn's tropospheric haze shows a hemispherical asymmetry, being more opaque in the southern summer hemisphere than in the north. Thermal-IR haze opacity is not enhanced at Saturn's equator as it is on Jupiter. Small-scale perturbations to the mean PH 3 abundance are discussed both in terms of a model of meridional overturning and parameterisation as eddy mixing. The large-scale structure of the PH 3 distributions is likely to be related to changes in the photochemical lifetimes and the shielding due to aerosol opacities. On Saturn, the enhanced summer opacity results in shielding and extended photochemical lifetimes for PH 3, permitting elevated PH 3 levels over Saturn's summer hemisphere.

  18. Analogues of acyclic nucleosides derived from tris-(hydroxymethyl)phosphine oxide or bis-(hydroxymethyl)phosphinic acid coupled to DNA nucleobases.

    PubMed

    Nawrot, Barbara; Michalak, Olga; De Clercq, Erik; Stec, Wojciech J

    2004-11-01

    A series of novel acyclic nucleoside analogues containing bis-(hydroxymethyl)phosphinic acid (BHPA) or tris(hydroxymethyl)phosphine oxide (THPO) coupled with DNA nucleobases or with 5-fluorouracil were prepared and their antiviral activity was studied against cytomegalovirus (CMV), varicella-zoster virus (VZV), parainfluenza-virus type 3, reovirus-type 1, sindbis, coxsackie B4, punta toro, vesicular stomatitis and respiratory syncytial virus, herpes simplex virus-type 1 (KOS) and type 2 (G), vaccinia virus and herpes simplex virus-1 (TK- KOS ACVr). No specific antiviral effects were noted for any of test compounds against viruses evaluated, except thymine, cytosine and adenine derivatives of BHPA exerting borderline activity against respiratory syncytial virus at the 80 mg/ml concentration.

  19. Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles generated highly substituted cyclopentenes through an unexpected phosphine α-addition-δ-evolvement of an anion pathway.

    PubMed

    Chuang, Shih-Ching; Sung, Shih-Ping; Deng, Jie-Cheng; Chiou, Mong-Feng; Hsu, Day-Shin

    2016-02-21

    Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles provide highly substituted syn-selective cyclopentenes appending the phosphorus ylide moiety in good yield with a diastereoselectivity of up to 100% through resonance-derived 1,5-dipolar species as the key intermediates, via the nucleophilic α(δ')-attack of phosphines toward enynedioates followed by addition to benzylidene malononitriles and 5-exo-dig cyclization. Through computational analyses, the overall reactions for the formation of syn- and anti-diastereomers are both exothermic with 65.6 and 66.3 kcal mol(-1) at the B3LYP-D3/6-31G(d) level of theory and were found to be kinetically controlled, which favours the formation of syn-diastereomers.

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

    PubMed

    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.

  1. Synthesis, physicochemical analysis of two new hemilabile ether-phosphine ligands and their first stable bis-ether-phosphine/cobalt(II) tetrahedral complexes

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; Barakat, Assem

    2017-04-01

    New tridentate ether-phosphine {P, 2O} and ether-phosphine oxide {OP, 2O} ligands with P and O donor-atoms have been synthesized starting from ClCH2CH(OCH3)2. The oxidation process of Ph2PCH2CH(OCH3)2 to its oxide derivative Ph2P(dbnd O)CH2CH(OCH3)2 was monitored by 31P NMR for the first time. The desired ligands and their Co(II) complexes structures were deduced from IR, EA, MS, NMR, UV-Vis., TG/DTG and XRD physical measurements. The tridentate chelating coordination behavior of the ether-phosphine wasn't detected leading only to the mono-dentate coordination mode through the phosphorous atoms to set up a X2Co[η1-Ph2PCH2CH(OCH3)2]2 as final isomer formula (X = Cl or Br). The Cl2Co[η1-Ph2PCH2CH(OCH3)2]2 isomer belongs to complex 1 was supported by single crystal measurement. Polar/non-polar intermolecular short contacts were detected by XRD and Hirshfeld surface theoretical analysis.

  2. Matrix bound phosphine formation and depletion in eutrophic lake sediment fermentation-simulation of different environmental factors.

    PubMed

    Geng, Jinju; Jin, Xiangcan; Wang, Qiang; Niu, Xiaojun; Wang, Xiaorong; Edwards, Marc; Glindemann, Dietmar

    2005-10-01

    Closed anaerobic batch-fermentation of eutrophic lake sediment samples was performed under variation of four environmental fermentation factors (pH, temperature, water/sediment ratio and disturbance) to learn how the quantity of phosphine will change and if the quantity of phosphine can increase. The fermentation conditions where matrix bound phosphine (MBP) increased (doubled from 3193+/-520 to about 7982+/-1003 ng/kg) were: a pH of 8 and of 10 (as compared to 1, 2, 4, 6, 12), a temperature of 20 and 30 degrees C (as compared to 4 and 40 degrees C), a water/sediment ratio of 3:1 (as compared to 1:1, 2:1, 5:1) and a disturbance of 100 r/min (as compared to 0 r/min), respectively. Although, over the full time course of fermentation, the balance of phosphine production became negative again or did remain almost unchanged under most conditions. A pH of 1 or disturbance of 150 r/min was significant factors to decrease phosphine over the long term. Free phosphine had been detected but was of minor importance (in the order of 60.9+/-10.1 ng/m(3)). Overall, the fermentation conditions which had been most favorable for microbial life (moderate temperature (20 and 30 degrees C) and pH 8) were also most favorable for a positive phosphine balance. This is an indication, but no biochemical proof that a natural (biogenic, microbial, biochemical) NET PRODUCTION of phosphine or DE NOVO PRODUCTION of phosphine has occurred. MBP concentrations in lake sediments were discussed as to be strongly dependent on a balance of natural generation and depletion processes, dependent of the simulated parameters.

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

    ERIC Educational Resources Information Center

    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…

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

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

    PubMed

    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.

  6. High temperature partition functions and thermodynamic data for ammonia and phosphine

    NASA Astrophysics Data System (ADS)

    Sousa-Silva, Clara; Hesketh, Nicholas; Yurchenko, Sergei N.; Hill, Christian; Tennyson, Jonathan

    2014-07-01

    The total internal partition function of ammonia (14NH3) and phosphine (31PH3) are calculated as a function of temperature by explicit summation of 153 million (for PH3) and 7.5 million (for NH3) theoretical rotation-vibrational energy levels. High accuracy estimates are obtained for the specific heat capacity, Cp, the Gibbs enthalpy function, gef, the Helmholtz function, hcf, and the entropy, S, of gas phase molecules as a function of temperature. In order to reduce the computational costs associated with the high rotational excitations, only the A-symmetry energy levels are used above a certain threshold of the total angular momentum number J. With this approach levels are summed up to dissociation energy for values of Jmax=45 and 100 for ammonia (Emax=41 051 cm-1) and phosphine (Emax=28 839.7 cm-1), respectively. Estimates of the partition function are converged for all temperatures considered for phosphine and below 3000 K for ammonia. All other thermodynamic properties are converged to at least 2000 K for ammonia and fully converged for phosphine.

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

    PubMed

    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.

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

    PubMed Central

    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

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

    PubMed

    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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  11. Dialkylbiaryl Phosphines in Pd-Catalyzed Amination: A User’s Guide

    PubMed Central

    Surry, David S.

    2012-01-01

    Dialkylbiaryl phosphines are a valuable class of ligand for Pd-catalyzed amination reactions and have been applied in a range of contexts. This review attempts to aid the reader in the selection of the best choice of reaction conditions and ligand of this class for the most commonly encountered and practically important substrate combinations. PMID:22432049

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

    PubMed

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

    2017-01-09

    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.

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

    DOEpatents

    Katti, K.V.; Karra, S.R.; Berning, D.E.; Smith, C.J.; Volkert, W.A.; Ketring, A.R.

    1999-01-05

    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. 21 figs.

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

    DOEpatents

    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.

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

    DOEpatents

    Katti, K.V.; Berning, D.E.; Volkert, W.A.; Ketring, A.R.

    1998-12-01

    A complex and method for making 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. 20 figs.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  17. Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: development of the method and mechanistic investigations.

    PubMed

    Harris, Jason R; Haynes, M Taylor; Thomas, Andrew M; Woerpel, K A

    2010-08-06

    A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with (17)O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

  18. A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands.

    PubMed

    Chen, Weiping; Mbafor, William; Roberts, Stanley M; Whittall, John

    2006-03-29

    A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands has been developed. On the basis of this new methodology, several new families of ferrocene-based phosphine ligands have been prepared coupling chirality at phosphorus with other, more standard stereogenic features. The introduction of P-chirality into ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding Rh catalyst when a matching among the planar chirality, carbon chirality, and the chirality of phosphorus is achieved.

  19. Phosphinic peptides, the first potent inhibitors of astacin, behave as extremely slow-binding inhibitors.

    PubMed Central

    Yiallouros, I; Vassiliou, S; Yiotakis, A; Zwilling, R; Stöcker, W; Dive, V

    1998-01-01

    A series of phosphinic pseudo-peptides varying in length and composition have been designed as inhibitors of the crayfish zinc endopeptidase astacin, the prototype of the astacin family and of the metzincin superfamily of metalloproteinases. The most efficient phosphinic peptide, fluorenylmethyloxycarbonyl-Pro-Lys-PhePsi(PO2CH2)Ala-P ro-Leu-Val, binds to astacin with a Ki value of 42 nM, which is about three orders of magnitude below the corresponding values for previously used hydroxamic acid derivatives. However, the rate constants for association (kon = 96.8 M-1.s-1) and dissociation (koff = 4.1 x 10(-6) s-1) are evidence for the extremely slow binding behaviour of this compound. N-terminally or C-terminally truncated phosphinic analogues of this parent molecule are much less potent, indicating a critical role of the peptide size on the potency. In particular, omission of the N-terminal proline residue leads to a 40-fold increase in Ki which is mostly due to a 75-fold higher koff value. These findings are consistent with the previously solved crystal structure of astacin complexed with one of the phosphinic peptides, benzyloxycarbonyl-Pro-Lys-PhePsi(PO2CH2)Ala-Pro-O-methyl, Ki = 14 microM [Grams, Dive, Yiotakis, Yiallouros, Vassiliou, Zwilling, Bode and Stöcker (1996) Nature Struct. Biol. 3, 671-675]. This structure also reveals that the phosphinic group binds to the active site as a transition-state analogue. The extremely slow binding behaviour of the phosphinic peptides is discussed in the light of the conformational changes involving a unique 'tyrosine switch' in the structure of astacin upon inhibitor binding. The phosphinic peptides may provide a rational basis for the design of drugs directed towards other members of the astacin family which, like bone morphogenetic protein 1 (BMP1; i.e. the procollagen C-proteinase), have become targets of pharmacological research. PMID:9531473

  20. An Entry to Stable Mixed Phosphine-Osmium-NHC Polyhydrides.

    PubMed

    Buil, María L; Cardo, Juan J F; Esteruelas, Miguel A; Fernández, Israel; Oñate, Enrique

    2016-05-16

    An entry to mixed phosphine-osmium-NHC polyhydride complexes is described, starting from the five-coordinate hydrido-alkylidyne compounds [OsHCl(≡CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene; OTf = CF3SO3; PR3 = P(i)Pr3 (1), PPh3 (2)). The experimental procedure involves the borylation of the Os-C triple bond of 1 and 2 with NaBH4 and the subsequent alcoholysis of the borylation products OsH2Cl(η(2)-H-BCH2Ph)(IPr)(PR3) (PR3 = P(i)Pr3 (3), PPh3 (4)) or OsH2(η(2):η(2):H2BCH2Ph)(IPr)(P(i)Pr3) (5). Stirring of 3 in 2-propanol affords the five coordinate chloride-trihydride OsH3Cl(IPr)(P(i)Pr3)2 (6), which reacts with NaBH4 to give OsH3(κ(2)-H2BH2)(IPr)(P(i)Pr3) (7). This trihydride-tetrahydrideborate derivative and its PPh3 counterpart OsH3(κ(2)-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at -60 °C instead of 2-propanol as alcoholysis agent. The bonding situation in 7 and 8, analyzed by DFT calculations using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-borane derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d(2)-hexahydride derivatives OsH6(IPr)(PR3) (PR3 = P(i)Pr3 (9), PPh3 (10)), which reduce the C≡N triple bond of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine, to form the trihydride compounds OsH3{κ(2)-N,C-(NH═CH-C6H4)}(IPr)(PR3)2 (PR3 = P(i)Pr3 (11), PPh3 (12)), containing a stabilized orthometalated aldimine.

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

    NASA Astrophysics Data System (ADS)

    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

  2. Prevention of phosphine-induced cytotoxicity by nutrients in HepG2 cells

    PubMed Central

    Rashedinia, Marzieh; Jamshidzadeh, Akram; Mehrabadi, Abbas Rezaiean; Niknahad, Hossein

    2016-01-01

    Background & objectives: Phosphides used as an insecticide and rodenticide, produce phosphine (PH3) which causes accidental and intentional poisoning cases and deaths. There is no specific treatment or antidote available for PH3 poisoning. It is suggested that PH3-induced toxicity is associated with adenosine triphosphate (ATP) depletion; therefore, in this study the effect of some nutrients was evaluated on PH3 cytotoxicity in a cell culture model. Methods: PH3 was generated from reaction of zinc phosphide (10 mM) with water in the closed culture medium of HepG2 cells, and cytotoxicity was measured after one and three hours of incubation. ATP, glutathione (GSH) and lipid peroxidation were also assessed at one or three hours post-incubation. ATP suppliers including dihydroxyacetone, glyceraldehyde and fructose were added to the culture medium 10 min before PH3 generation to prevent or reduce phosphine-induced cytotoxicity. Results: Phosphine caused about 30 and 66 per cent cell death at one and three hours of incubation, respectively. ATP content of the cells was depleted to 14.7 per cent of control at one hour of incubation. ATP suppliers were able to prevent cytotoxicity and ATP depletion induced by PH3. Dihydroxyacetone, α-ketoglutarate, fructose and mannitol restored the ATP content of the cells from 14.7 per cent to about 40, 34, 32 and 30 per cent, respectively. Lipid peroxidation and GSH depletion were not significantly induced by zinc phosphide in this study. Interpretation & conclusions: The results supported the hypothesis that phosphine-induced cytotoxicity was due to decrease of ATP levels. ATP suppliers could prevent its toxicity by generating ATP through glycolysis. α-keto compounds such as dihydroxyacetone and α-ketoglutarate may bind to phosphine and restore mitochondrial respiration. PMID:28256464

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

    PubMed

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  5. Features and Application in Asymmetric Catalysis of Chiral Phosphine-Phosphite Ligands.

    PubMed

    Pizzano, Antonio

    2016-12-01

    Chiral phosphine-phosphites are a class of ligands for asymmetric catalysis characterized by two coordinating functionalities with different electronic properties. These ligands also possess a highly modular structure and, due to versatile synthetic processes, they can be tuned precisely in the catalyst optimization process. Research regarding the application of these ligands in several enantioselective catalytic processes has provided outstanding results in a good number of them. These processes include not only Rh catalyzed reactions, such as olefin hydrogenation and hydroformylation, but also other reactions, such as hydrogenation of olefins and imines by Ru complexes, of imines and N-heterocycles by Ir derivatives, allyl alkylation or conjugate addition by Cu catalysts, or hydrocyanation of olefins by Ni ones. Overall, the use of these ligands has led to the preparation of a wide variety of chiral building blocks with high enantiomeric excess. Therefore, phosphine-phosphites have become in an important class of ligands in asymmetric catalysis.

  6. Syntheses and properties of phosphine-substituted ruthenium(II) polypyridine complexes with nitrogen oxides.

    PubMed

    Nakamura, Go; Kondo, Mio; Crisalli, Meredith; Lee, Sze Koon; Shibata, Akane; Ford, Peter C; Masaoka, Shigeyuki

    2015-10-21

    Four novel phosphine-substituted ruthenium(ii) polypyridine complexes with nitrogen oxides-trans(P,NO2)-[Ru(trpy)(Pqn)(NO2)]PF6 (trans-NO2), cis(P,NO2)-[Ru(trpy)(Pqn)(NO2)]PF6 (cis-NO2), [Ru(trpy)(dppbz)(NO2)]PF6 (PP-NO2), and cis(P,NO)-[Ru(trpy)(Pqn)(NO)](PF6)3 (cis-NO)-were synthesised (trpy = 2,2':6',2''-terpyridine, Pqn = 8-(diphenylphosphanyl)quinoline, and dppbz = 1,2-bis(diphenylphosphanyl)benzene). The influence of the number and position of the phosphine group(s) on the electronic structure of these complexes was investigated using single-crystal X-ray structural analysis, UV-vis absorption spectroscopy, and electrochemical measurements. The substitution lability of the nitrogen oxide ligand of each complex is discussed in comparison with that of the corresponding acetonitrile complexes.

  7. Diphosphine is an intermediate in the photolysis of phosphine to phosphorus and hydrogen. [Jupiter atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Benson, R.

    1980-01-01

    The photolysis of phosphine to red phosphorus (P4) and hydrogen is investigated in light of the potential significance of the reaction in the atmospheric chemistry of Jupiter. It is reported that the photolysis of PH3 at room temperature by a 206.2-nm light source gave rise to a product identified by its UV and IR spectra and gas chromatographic retention time as P2H4, the yield of which is found to increase to a maximum and then decrease to 20% of the maximum value with illumination time. A mechanism for phosphine photolysis including diphosphine formation as an intermediate step is proposed, and it is concluded that P2H4 is a likely constituent of the atmospheres of the Jovian planets.

  8. Phosphine Supported Ruthenium Nanoparticle Catalyzed Synthesis of Substituted Pyrazines and Imidazoles from α-Diketones.

    PubMed

    Ganji, Prasad; van Leeuwen, Piet W N M

    2017-02-03

    A new methodology has been developed for the synthesis of highly substituted nitrogen heterocycles such as pyrazines and imidazoles starting from α-diketones using phosphine supported ruthenium nanoparticles (RuNPs) as catalysts. Ruthenium nanoparticles Ru1-Ru4 supported with different phosphines such as dbdocphos, dppp, DPEphos, and Xantphos are screened, of which Ru1 and Ru4 are found to be the most active. Interestingly, aryl-substituted and alkyl-substituted α-diketones produced different products: namely, pyrazine and imidazoles, respectively. This reaction methodology has been applied to the synthesis of a key intermediate (2m) of the marine cytotoxic natural product Dragmacidin B and an estrogen receptor (2l). This work represents the first examples of pyrazines prepared by RuNPs.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Synthesis and Lanthanide Coordination Chemistry of Phosphine Oxide Decorated Dibenzothiophene and Dibenzothiophene Sulfone Platforms

    SciTech Connect

    Rosario-Amorin, Daniel; Ouizem, Sabrina; Dickie, D. A.; Paine, Robert T.; Cramer, Roger E.; Hay, Benjamin; Podair, Julien; Delmau, Laetitia Helene

    2014-01-01

    Syntheses for new ligands based upon dibenzothiophene and dibenzothiophene sulfone platforms, decorated with phosphine oxide and methylphosphine oxide donor groups, are described. Coordination chem. of 4, 6- bis(diphenylphosphinoylmethyl) dibenzothiophene (8) , 4, 6- bis(diphenylphosphinoylmethyl) dibenzothiophene- 5, 5- dioxide (9) and 4, 6- bis(diphenylphosphinoyl) dibenzothiophene- 5, 5- dioxide (10) with lanthanide nitrates, Ln(NO3) 3 (H2O) n is outlined, and crystal structure detns. reveal a range of chelation interactions on Ln(III) ions. The HNO3 dependence of the solvent extn. performance of 9 and 10 in 1, 2- dichloroethane for Eu(III) and Am(III) is described and compared against the extn. behavior of related dibenzofuran ligands (2, 3; R = Ph) and n- octyl(phenyl) - N, N- diisobutylcarbamoylmethyl phosphine oxide (4) measured under identical conditions.

  11. Binding of phosphinate and phosphonate inhibitors to aspartic proteases: a first-principles study.

    PubMed

    Vidossich, Pietro; Carloni, Paolo

    2006-01-26

    Phosphinate and phosphonate derivatives are potent inhibitors of aspartic proteases (APs). The affinity for the enzyme might be caused by the presence of low barrier hydrogen bonds between the ligand and the catalytic Asp dyad in the cleavage site. We have used density functional theory calculations along with hybrid quantum mechanics/molecular mechanics Car-Parrinello molecular dynamics simulations to investigate the hydrogen-bonding pattern at the binding site of the complexes of human immunodeficiency virus type-1 AP and the eukaryotic endothiapepsin and penicillopepsin. Our calculations are in fair agreement with the NMR data available for endothiapepsin (Coates et al. J. Mol. Biol. 2002, 318, 1405-1415) and show that the most stable active site configuration is the diprotonated, negatively charged form. In the viral complex both protons are located at the catalytic Asp dyad, while in the eukaryotic complexes the proton shared by the closest oxygen atoms is located at the phosphinic/phosphonic group.

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

    PubMed

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

    2017-12-01

    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.

  13. Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Pike, Sebastian D.; White, Edward R.; Shaffer, Milo S. P.; Williams, Charlotte K.

    2016-10-01

    The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.

  14. The meridional phosphine distribution in Saturn's upper troposphere from Cassini/CIRS observations

    NASA Astrophysics Data System (ADS)

    Fletcher, L. N.; Irwin, P. G. J.; Teanby, N. A.; Orton, G. S.; Parrish, P. D.; Calcutt, S. B.; Bowles, N.; de Kok, R.; Howett, C.; Taylor, F. W.

    2007-05-01

    The Cassini Composite Infrared Spectrometer (CIRS) has been used to derive the vertical and meridional variation of temperature and phosphine (PH 3) abundance in Saturn's upper troposphere. PH 3 has a significant effect on the measured radiances in the thermal infrared and between May 2004 and September 2005 CIRS recorded thousands of spectra in both the far (10-600 cm -1) and mid (600-1400 cm -1) infrared, at a variety of latitudes covering the southern hemisphere. Low spectral resolution (15 cm -1) data has been used to constrain the temperature structure of the troposphere between 100 and 500 mbar. The vertical distributions of phosphine and ammonia were retrieved from far-infrared spectra at the highest spectral resolution (0.5 cm -1), and lower resolution (2.5 cm -1) mid-infrared data were used to map the meridional variation in the abundance of phosphine in the 250-500 mbar range. Temperature variations at the 250 mbar level are shown to occur on the same scale as the prograde and retrograde jets in Saturn's atmosphere [Porco, C.C., and 34 colleagues, 2005. Science 307, 1243-1247]. The PH 3 abundance at 250 mbar is found to be enhanced at the equator when compared with mid-latitudes. At mid latitudes we see anti-correlation between temperature and PH 3 abundance at 250 mbar, phosphine being enhanced at 45° S and depleted at 25 and 55° S. The vertical distribution is markedly different polewards of 60-65° S, with depleted PH 3 at 500 mbar but a slower decline in abundance with altitude when compared with the mid-latitudes. This variation is similar to the variations of cloud and aerosol parameters observed in the visible and near infrared, and may indicate the subsidence of tropospheric air at polar latitudes, coupled with a diminished sunlight penetration depth reducing the rate of PH 3 photolysis in the polar region.

  15. Potencies of phosphine peptide inhibitors of mammalian thimet oligopeptidase and neurolysin on two bacterial pz peptidases.

    PubMed

    Sugihara, Yusuke; Kawasaki, Akio; Tsujimoto, Yoshiyuki; Matsui, Hiroshi; Watanabe, Kunihiko

    2007-02-01

    Pz peptidases A and B, from a thermophile Geobacillus collagenovorans MO-1, recognize collagen-specific tripeptide units (Gly-Pro-Xaa). They share similarities in function but extremely low identities in primary sequence with mammalian thimet oligopeptidase (TOP) and neurolysin. Three phosphine peptide inhibitors that selectively inhibit TOP and neurolysin on two bacterial Pz peptidases were investigated. They showed potent inhibition of both Pz peptidases in a range from 10 to 100 nM.

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

    PubMed

    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.

  17. Phosphine passivated gold clusters: how charge transfer affects electronic structure and stability.

    PubMed

    Mollenhauer, Doreen; Gaston, Nicola

    2016-11-02

    A systematic evaluation of small phosphine ligand-protected gold clusters with six to nine gold atoms using density functional theory with dispersion correction has been performed in order to understand the major factors determining stability, including its size, shape, and charge dependence. We show that the charge per atom of the cluster is much more important for the interaction between the ligand shell and gold cluster than the system size. Thus, strong charge transfer effects determine the binding strength between the ligand shell and cluster. The clusters in this series are all non-spherical and exhibit large HOMO-LUMO gaps (above 2.7 eV). Analysis of the delocalized nature of the electronic states at the centre of the clusters demonstrates the presence of nascent superatomic states. However the number of delocalized electrons in these systems is significantly influenced by the charge transfer from the phosphine ligands, contrary to the usual accounting rule for superatom complex systems. Thus, not only electron withdrawing but also charge transfer effects should be considered to influence the superatomic structure of charged ligand surrounded clusters. In consequence in the phosphine gold cluster series under consideration the systems Au7(PPh3)7(+) and Au8(PPh3)8(2+) exhibit nearly fully filled S and P states and the HOMO-LUMO gap increases by 0.2 eV and 0.9 eV, respectively. The interpretation for the stability of the gold phosphine systems is in agreement with experimental results and demonstrates the importance of the superatomic concept.

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

    NASA Astrophysics Data System (ADS)

    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

  19. Decomposition Products of Phosphine Under Pressure: PH 2 Stable and Superconducting?

    DOE PAGES

    Shamp, Andrew; Terpstra, Tyson; Bi, Tiange; ...

    2016-02-17

    Evolutionary algorithms (EA) coupled with Density Functional Theory (DFT) calculations have been used to predict the most stable hydrides of phosphorous (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 100-200 GPa. One of these contains five formula units in the primitive cell and has C2=m symmetry (5FU-C2=m). It is comprised of 1D periodic PH3-PH-PH2-PH-PH3 oligomers. Two structurally related phases consisting of phosphorous atomsmore » that are octahedrally coordinated by four phosphorous 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 being 70 and 76 K, respectively, via the Allen-Dynes modified McMillan formula and using a value of 0.1 for the Coulomb pseudopotential, . 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.« less

  20. Decomposition Products of Phosphine Under Pressure: PH 2 Stable and Superconducting?

    SciTech Connect

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

    2016-02-17

    Evolutionary algorithms (EA) coupled with Density Functional Theory (DFT) calculations have been used to predict the most stable hydrides of phosphorous (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 100-200 GPa. One of these contains five formula units in the primitive cell and has C2=m symmetry (5FU-C2=m). It is comprised of 1D periodic PH3-PH-PH2-PH-PH3 oligomers. Two structurally related phases consisting of phosphorous atoms that are octahedrally coordinated by four phosphorous 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 being 70 and 76 K, respectively, via the Allen-Dynes modified McMillan formula and using a value of 0.1 for the Coulomb pseudopotential, . 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.

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

    PubMed

    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.

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

    DOE PAGES

    McCann, Billy W.; Silva, Nuwan De; Windus, Theresa L.; ...

    2016-02-17

    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 themore » performance of known bis-phosphine oxide extractants. For the case where 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.« less

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

    SciTech Connect

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

    2016-02-17

    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 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.

  4. Multicomponent reactions of phosphines, diynedioates, and aryl aldehydes generated furans appending reactive phosphorus ylides through cumulated trienoates as key intermediates: a phosphine α-addition-δ-evolvement of an anion pathway.

    PubMed

    Deng, Jie-Cheng; Chuang, Shih-Ching

    2014-11-07

    Multicomponent reactions of phosphines, diynedioates, and aryl aldehydes have been demonstrated, providing trisubstituted furans appending reactive phosphorus ylides, through cumulated trienoates as key intermediates. The proposed trienoate intermediates, 1,5-dipolar species formed via nucleophilic α-attack of phosphines toward diynedioates (α-addition-δ-evolvement of an anion, abbreviated αAδE), undergo addition to aryl aldehydes followed by 5-endo-dig cyclization, proton transfer, and resonance to give trisubstituted furans. Furthermore, the phosphorus ylides are oxidized to α-keto ester furans and utilized as Wittig reagents.

  5. Thermochromic luminescence of copper iodide clusters: the case of phosphine ligands.

    PubMed

    Perruchas, Sandrine; Tard, Cédric; Le Goff, Xavier F; Fargues, Alexandre; Garcia, Alain; Kahlal, Samia; Saillard, Jean-Yves; Gacoin, Thierry; Boilot, Jean-Pierre

    2011-11-07

    Three copper(I) iodide clusters coordinated by different phosphine ligands formulated [Cu(4)I(4)(PPh(3))(4)] (1), [Cu(4)I(4)(Pcpent(3))(4)] (2), and [Cu(4)I(4)(PPh(2)Pr)(4)] (3) (PPh(3) = triphenylphosphine, Pcpent(3) = tricyclopentylphosphine, and PPh(2)Pr = diphenylpropylphosphine) have been synthesized and characterized by (1)H and (31)P NMR, elemental analysis and single crystal X-ray diffraction analysis. They crystallize in different space groups, namely, monoclinic P21/c, cubic Pa ̅3, and tetragonal I ̅42m for 1, 2, and 3, respectively. The photoluminescence properties of clusters 1 and 3 show reversible luminescence thermochromism with two highly intense emission bands whose intensities are temperature dependent. In accordance to Density Functional Theory (DFT) calculations, these two emission bands have been attributed to two different transitions, a cluster centered (CC) one and a mixed XMCT/XLCT one. Cluster 2 does not exhibit luminescence variation in temperature because of the lack of the latter transition. The absorption spectra of the three clusters have been also rationalized by time dependent DFT (TDDFT) calculations. A simplified model is suggested to represent the luminescence thermochromism attributed to the two different excited states in thermal equilibrium. In contrast with the pyridine derivatives, similar excitation profiles and low activation energy for these phosphine-based clusters reflect high coupling of the two emissive states. The effect of the Cu-Cu interactions on the emission properties of these clusters is also discussed. Especially, cluster 3 with long Cu-Cu contacts exhibits a controlled thermochromic luminescence which is to our knowledge, unknown for this family of copper iodide clusters. These phosphine-based clusters appear particularly interesting for the synthesis of original emissive materials.

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

    PubMed

    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.

  7. Copper(I)-Phosphine Polypyridyl Complexes: Synthesis, Characterization, DNA/HSA Binding Study, and Antiproliferative Activity.

    PubMed

    Villarreal, Wilmer; Colina-Vegas, Legna; Visbal, Gonzalo; Corona, Oscar; Corrêa, Rodrigo S; Ellena, Javier; Cominetti, Marcia Regina; Batista, Alzir Azevedo; Navarro, Maribel

    2017-04-03

    A series of copper(I)-phosphine polypyridyl complexes have been investigated as potential antitumor agents. The complexes [Cu(PPh3)2dpq]NO3 (2), [Cu(PPh3)2dppz]NO3 (3), [Cu(PPh3)2dppa]NO3 (4), and [Cu(PPh3)2dppme]NO3 (5) were synthesized by the reaction of [Cu(PPh3)2NO3] with the respective planar ligand under mild conditions. These copper complexes were fully characterized by elemental analysis, molar conductivity, FAB-MS, and NMR, UV-vis, and IR spectroscopies. Interactions between these copper(I)-phosphine polypyridyl complexes and DNA have been investigated using various spectroscopic techniques and analytical methods, such as UV-vis titrations, thermal denaturation, circular dichroism, viscosity measurements, gel electrophoresis, and competitive fluorescent intercalator displacement assays. The results of our studies suggest that these copper(I) complexes interact with DNA in an intercalative way. Furthermore, their high protein binding affinities toward human serum albumin were determined by fluorescence studies. Additionally, cytotoxicity analyses of all complexes against several tumor cell lines (human breast, MCF-7; human lung, A549; and human prostate, DU-145) and non-tumor cell lines (Chinese hamster lung, V79-4; and human lung, MRC-5) were performed. The results revealed that copper(I)-phosphine polypyridyl complexes are more cytotoxic than the corresponding planar ligand and also showed to be more active than cisplatin. A good correlation was observed between the cytostatic activity and lipophilicity of the copper(I) complexes studied here.

  8. Water-Soluble Iridium-NHC-Phosphine Complexes as Catalysts for Chemical Hydrogen Batteries Based on Formate.

    PubMed

    Horváth, Henrietta; Papp, Gábor; Szabolcsi, Roland; Kathó, Ágnes; Joó, Ferenc

    2015-09-21

    Molecular hydrogen, obtained by water electrolysis or photocatalytic water splitting, can be used to store energy obtained from intermittent sources such as wind and solar power. The storage and safe transportation of H2 , however, is an open and central question in such a hydrogen economy. Easy-to-synthesize, water-soluble iridium-N-heterocyclic carbene-phosphine (Ir(I) -NHC-phosphine) catalysts show unprecedented high catalytic activity in dehydrogenation of aqueous sodium formate. Fast reversible generation and storage of hydrogen can be achieved with these catalysts by a simple decrease or increase in the hydrogen pressure, respectively.

  9. Simple and rapid determination of hydrogen peroxide using phosphine-based fluorescent reagents with sodium tungstate dihydrate.

    PubMed

    Onoda, Maki; Uchiyama, Takefumi; Mawatari, Ken-Ichi; Kaneko, Kiyoko; Nakagomi, Kazuya

    2006-06-01

    A simple batch method for the fluorometric determination of hydrogen peroxide using phosphine-based fluorescent reagents has been developed. A rapid, mild and selective derivatization reaction was achieved by adding sodium tungstate dihydrate to the reaction mixture of hydrogen peroxide and a phosphine-based fluorescent reagent. When 4-diphenylphosphino-7-methylthio-2,1,3-benzoxadiazole was used as a reagent, the derivatization reaction was completed after 2 min at room temperature. The calibration curve was linear between 12.5 and 500 ng hydrogen peroxide in a 10 microL sample solution. This method is accurate and has potential for on-line applications.

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

    PubMed

    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.

  11. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  12. Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate.

    PubMed

    Ma, Yan-Na; Yang, Shang-Dong

    2016-04-01

    This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios.

  13. Recovery of uranium from acid media by macroporous bifunctional phosphinic acid resin

    SciTech Connect

    Sabharwal, K.N.; Srinivasan, T.G.; Rao, P.R.V.; Nandy, K.K.

    1996-11-01

    The extraction of uranium from various acid media such as nitric acid, sulphuric acid, hydrochloric acid, phosphoric acid and perchloric acid by a macroporous bifunctional phosphinic acid resin (MPBPA) has been studied. The distribution coefficients for the extraction of uranium by the MPBPA resin are compared with the corresponding values reported in literature for the conventional sulphonic acid resin. The results clearly indicate the suitability of the MPBPA resin to recover uranium from different types of acid solutions of widely ranging acidities. 17 refs., 6 figs., 5 tabs.

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

    NASA Astrophysics Data System (ADS)

    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.

  15. Transition metal-free stereospecific access to (E)-(1-fluoro-2-arylvinyl)phosphine borane complexes.

    PubMed

    Rousée, Kevin; Pannecoucke, Xavier; Gaumont, Annie-Claude; Lohier, Jean-François; Morlet-Savary, Fabrice; Lalevée, Jacques; Bouillon, Jean-Philippe; Couve-Bonnaire, Samuel; Lakhdar, Sami

    2017-02-07

    This work describes the first transition metal-free stereospecific synthesis of (E)-(1-fluoro-2-arylvinyl)phosphine boranes through the addition of diarylphosphine-boranes to gem-bromofluoroalkenes in the presence of a base at room temperature. The reaction proceeds well under very mild conditions and tolerates a variety of functionalities. Scope and limitations of the reaction are discussed. Mechanistic investigations have been undertaken and revealed that the reaction takes place through an SRN1 mechanism. The formation of the fluorinated vinyl radical has been evidenced by electron paramagnetic resonance (EPR) experiment.

  16. Fourteen-Day Subchronic Oral Toxicity Study of 4-Nitrophenyl Monochloromethyl (Phenyl) Phosphinate in Male Rats.

    DTIC Science & Technology

    1988-02-01

    reativaed usnrtnadatdtlteay(-) Lewis--2 Appendix A. Vehicle The vehicle contained 20% Tween 80 - (Fisher Scientific Company, Fairlawn, NJ), 10...34Preparation - -[ of Phosphinate Compounds for Oral Toxicity Studies", except that the concentrations of Tween 80 ", ethanol, water, and citrate...the vhcewas to be 21.5% Tween 80 ’, 18.5% ethanol, 37.5% 50mM citrate buffer (pH 3.2), and 22.5% water. The test compound was more susceptible to

  17. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

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

    SciTech Connect

    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.

  19. Bis(allyl)-ruthenium(iv) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions.

    PubMed

    Tomás-Mendivil, Eder; Francos, Javier; González-Fernández, Rebeca; González-Liste, Pedro J; Borge, Javier; Cadierno, Victorio

    2016-09-14

    Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η(3):η(3)-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η(3):η(3)-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P([double bond, length as m-dash]O)H. The compounds [RuCl2(η(3):η(3)-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η(3):η(3)-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η(3):η(3)-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η(3):η(3)-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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. Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

    PubMed Central

    Pike, Sebastian D.; White, Edward R.; Shaffer, Milo S. P.; Williams, Charlotte K.

    2016-01-01

    The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2–4 nm) nanoparticles. PMID:27734828

  3. Atomistic Simulations of Perfluoro Phosphonic and Phosphinic Acid Membranes and Comparisons to Nafion

    SciTech Connect

    Idupulapati, Nagesh B.; Devanathan, Ramaswami; Dupuis, Michel

    2011-03-31

    We used classical molecular dynamics (MD) simulations to investigate the nanoscale morphology and proton transport properties of perfluoro phosphonic (FPA) and phosphinic acid (FPA-I) membranes as they are being considered for use in low temperature fuel cells. We systematically investigated these properties as a function of the hydration level. The changes in nanostructure, in transport dynamics of water and hydronium ions, and in water network percolation were extracted from MD simulations and compared with Nafion. Phosphonic and phosphinic acid moieties in FPA and FPA-I, have lower acidity than sulfonic acid in Nafion, yet the diffusion of water was observed to be faster in FPA and FPA-I than in Nafion, particularly at low hydration levels. However this did not give rise to notable differences in hydronium ion diffusion and water network percolation for these membranes over Nafion. Similar observations were also reported by our group recently in a study of perfluoro-sulfonyl imide membranes carrying stronger super-acids than sulfonic acid of Nafion. These findings together suggest no strong apparent correlation between the acidity strength of the functional acid groups and the dynamics of water and hydronium ions in hydrated polymer electrolyte membranes (PEMs) with similar fluorocarbon backbones and acidic group-carrying side chains. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  5. Complexation of phosphine ligands with peracetylated beta-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium constants.

    PubMed

    Galia, Alessandro; Navarre, Edward C; Scialdone, Onofrio; Ferreira, Michel; Filardo, Giuseppe; Tilloy, Sebastien; Monflier, Eric

    2007-03-15

    The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphine, which is rationalized on the basis of the excellent fit of the phosphine in the cyclodextrin cavity, leading to enhanced host-guest van der Waals interactions. This study can be considered the first step toward the comprehension of the complexation thermodynamics of modified cyclodextrins soluble in scCO2.

  6. Enantioselective direct Mannich reactions of cyclic β-ketoesters catalyzed by chiral phosphine via a novel dual-reagent catalysis.

    PubMed

    Lou, Yan-Peng; Zheng, Chang-Wu; Pan, Ren-Ming; Jin, Qiao-Wen; Zhao, Gang; Li, Zhong

    2015-02-06

    A combination of an amino acid derived chiral phosphine catalyst and methyl acrylate efficiently catalyzed the direct Mannich reaction of cyclic β-ketoesters and N-Boc-aldimines. The dual-reagent catalysis was presumed to function through the formation of a zwitterion, which catalyzed the reaction with excellent stereocontrol via a hydrogen-bonding assisted chiral ion-pair pathway.

  7. Phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates: synthesis of 2-pyrrolines.

    PubMed

    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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  10. Alkali-metal-catalyzed addition of primary and secondary phosphines to carbodiimides. A general and efficient route to substituted phosphaguanidines.

    PubMed

    Zhang, Wen-Xiong; Nishiura, Masayoshi; Hou, Zhaomin

    2006-09-28

    Organo alkali metal compounds such as (n)BuLi and (Me3Si)2NK act as excellent catalyst precursors for the addition of phosphine P-H bonds to carbodiimides, offering a general and atom-economical route to substituted phosphaguanidines, with excellent tolerability to aromatic C-Br and C-Cl bonds.

  11. Studies on the effects of phosphine on Salmonella enterica serotype Enteritidis in culture medium and in black pepper (Piper nigrum).

    PubMed

    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.

  12. Microstructure degradation of YSZ in Ni/YSZ anodes of SOFC operated in phosphine-containing fuels

    SciTech Connect

    Chen, Yun; Chen, Song; Hackett, Gregory; Finklea, Harry; Zondlod, John; Celik, Ismail; Song, Xueyan; Gerdes, Kirk

    2013-03-07

    The interaction of trace (ppm) phosphine with the nickel/yttria stabilized zirconia (YSZ) anode of commercial solid oxide fuel cells has been investigated and evaluated for both synthesis gas and hydrogen fuels in an effort to examine P–Y reactions. The Ni poisoning effects reported in literature were confirmed and degradation was examined by electrochemical methods and post-test microstructural and chemical analyses. The results indicate that P-induced degradation rates and mechanisms are fuel dependent and that degradation of cells operated in synthesis gas (syngas) with phosphine is more severe than that of cells operated in hydrogen with phosphine. As reported in published literature, a cell operated in syngas containing 10 ppm phosphine demonstrated significant microstructural degradation within the Ni phase, including formation of Ni–P phases concentrated on the outer layer of the anode and significant pitting corrosion in the Ni grains. In this research, a previously undetected YPO{sub 4} phase is observed at the YSZ/YSZ/Ni triple grain junctions located at the interface with the YSZ electrolyte. Tetragonal YSZ (t-YSZ) and cubic-YSZ (c-YSZ) domains with sizes of several tens of nanometers are also newly observed along the Ni/YSZ interface. These observations contrast with data obtained for a cell operated in dry hydrogen with phosphine, where no YPO{sub 4} phase is observed and the alternating t-YSZ and c-YSZ domains at the Ni/YSZ interface are smaller with typical sizes of 5–10 nm. The data imply that electrolyte attack by P is a potentially debilitating mode of degradation in SOFC anodes, and that the associated reaction mechanisms and rates are worthy of further examination.

  13. Low temperature phosphine fumigation of pre-chilled iceberg lettuce under insulation cover for postharvest control of western flower thrips, Frankliniella occidentalis (Thysanoptera: Thripidae).

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  14. Symmetry and magnetism in Ni9Te6 clusters ligated by CO or phosphine ligands.

    PubMed

    Reber, Arthur C; Chauhan, Vikas; Khanna, Shiv N

    2017-01-14

    The removal of a single ligand from the magnetic Ni9Te6(L)8 (L = P(CH3)3, CO) clusters is found to quench the magnetic moment. The reduction in magnetic moment is caused by a geometric deformation of the Ni9Te6 core that breaks the octahedral symmetry of the cluster. This effect is observed in both the CO and phosphine based ligands. The octahedral symmetry bare cluster is also found to have a large magnetic moment. These results highlight the dilemma faced by magnetic ligand protected clusters whose symmetry has been broken: whether to break the spin symmetry as in Hund's rules or to break the spatial symmetry as in the Jahn-Teller effect. The spatial symmetry breaking is found to be an oblate distortion that forms additional Ni-Te bonds resulting in the enhanced stability of the cluster.

  15. Flotation performances and adsorption mechanism of α-hydroxyoctyl phosphinic acid to cassiterite

    NASA Astrophysics Data System (ADS)

    Li, Fangxu; Zhong, Hong; Zhao, Gang; Wang, Shuai; Liu, Guangyi

    2015-10-01

    In this paper, the flotation performances and adsorption mechanism of α-hydroxyoctyl phosphinic acid (HPA) to cassiterite were investigated by adsorption experiments, micro-flotation tests, zeta potential measurements, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses. The micro-flotation results indicated that compared with styrene phosphonic acid (SPA), diphosphonic acid (DPA), benzohydroxamic acid (BHA) and salicylhydroxamic acid (SHA), HPA exhibited excellent collecting power to cassiterite and superior selectivity against magnetite or hematite over a wide pH range. The results of adsorption experiments and zeta potential deduced that HPA chemisorb on cassiterite surfaces. The results of FTIR inferred HPA chemisorb onto cassiterite surfaces through its P and O atoms with the P-H and O-H bonds broken. XPS analysis further demonstrated HPA react with Sn species by formation of Sn-O-P and Sn-P bond.

  16. Nickel Phosphine Catalysts with Pendant Amines for Electrocatalytic Oxidation of Alcohols

    SciTech Connect

    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.

  17. Preparation of cadmium selenide-polyolefin composites from functional phosphine oxides and ruthenium-based metathesis.

    PubMed

    Skaff, Habib; Ilker, M Firat; Coughlin, E Bryan; Emrick, Todd

    2002-05-22

    Cadmium selenide nanoparticles, prepared by known methods, were stabilized with functional phosphine oxide 1, then used to support the polymerization of cyclic olefins radially outward from the surface by ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The conversion of compound 1 into the new metathesis catalyst 3 by carbene exchange and the subsequent polymerization of cyclic olefins were observed spectroscopically by (1)H NMR to afford for example CdSe-polycyclooctene composite 6. Transmission electron micrographs on thin films of these composites showed good nanoparticle dispersion. This is in stark contrast to the substantial nanoparticle aggregation observed when similar polymerizations were performed in the presence of conventional TOPO-covered nanoparticles. The methods reported here to prepare composite product 6 are applicable to other cyclic olefins, and suggest that this chemistry will be useful for incorporating CdSe nanoparticles into a wide variety of polymer matrices.

  18. Comparison of Aromatic Dithiophoshinic and Phosphinic Acid Derivatives for Minor Actinide Extraction

    SciTech Connect

    John R. Klaehn; Dean R. Peterman; Mason K. Harrup; Richard D. Tillotson; Mitchell R. Greenhalgh; Thomas A. Luther; Jack D. Law; Lee M. Daniels

    2008-03-01

    A new extractant for the separation of actinide(III) and lanthanide(III), bis(otrifluoromethylphenyl) phosphinic acid (O-PA) was synthesized. The synthetic route employed mirrors one that was employed to produce the sulfur containing analog bis(otrifluoromethylphenyl) dithiophosphinic acid (S-PA). Multinuclear NMR spectroscopy was used for elementary characterization of the new O-PA derivative. This new O-PA extractant was used to perform Am(III)/Eu(III) separations and the results were directly compared to those obtained in identical separation experiments using S-PA, an extractant that is known to exhibit separation factors of ~100,000 at low pH. The separations data are presented and discussed in terms comparing the nature of the oxygen atom as a donor to that of the sulfur atom in extractants that are otherwise identical.

  19. Comparison of Dithiophosphinic and Phosphinic Acid Derivatives for Minor Actinide Extraction

    SciTech Connect

    Mason K Harrup; Dean R. Peterman; Thomas A. Luther; Mitchell R. Greenhalgh; John R. Klaehn

    2008-03-01

    A new extractant for the separation of actinide(III) and lanthanide(III), bis(otrifluoromethylphenyl) phosphinic acid (O-PA) was synthesized. The synthetic route employed mirrors one that was employed to produce the sulfur containing analog bis(otrifluoromethylphenyl) dithiophosphinic acid (S-PA). Multinuclear NMR spectroscopy was used for elementary characterization of the new O-PA derivative. This new O-PA extractant was used to perform Am(III)/Eu(III) separations and the results were directly compared to those obtained in identical separation experiments using S-PA, an extractant that is known to exhibit separation factors of ~100,000 at low pH. The separations data are presented and discussed in terms comparing the nature of the oxygen atom as a donor to that of the sulfur atom in extractants that are otherwise identical.

  20. High solubilities of small hydrocarbons in trihexyl tetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate.

    PubMed

    Liu, Xiangyang; Afzal, Waheed; Yu, Guangren; He, Maogang; Prausnitz, John M

    2013-09-12

    Experimental solubilities are reported for methane, ethane, ethylene, propane, and propylene in trihexyl tetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate [P(14)666][TMPP] from 313 to 353 K up to 6.7 MPa. A literature review on solubilities of small hydrocarbons in ionic liquids shows that solubilities in [P(14)666][TMPP] are appreciably larger than those in other ionic liquids. Contrary to solubilities in ionic liquids studied earlier, solubilities of paraffins (ethane and propane) in [P(14)666][TMPP] are larger than those of the corresponding olefins (ethylene and propylene). Because, at fixed temperature, the vapor pressure of an olefin is larger than that of the corresponding paraffin, the relative volatility of the olefin exceeds that of the corresponding paraffin, contrary to the relative volatility observed in conventional extractive distillation with polar solvents where the volatility of the paraffin exceeds that of the corresponding olefin.

  1. Synthesis and characterization of aryl phosphine oxide containing thermoplastic polyimides and thermosetting polyimides with controlled reactivity

    NASA Astrophysics Data System (ADS)

    Zhuang, Hong

    1998-11-01

    Phosphorus containing monomers, bis(3-aminophenyl)methyl phosphine oxide (m-DAMPO) and bis(3-aminophenyl)phenyl phosphine oxide (m-DAPPO), were synthesized and incorporated into a thermoplastic poly(arylene ether imide) based upon 2,2sp'-bis (4-(3,4-dicarboxyphenoxy)phenyl) propane dianhydride and 1,3-phenylene diamine, in order to study their influence on flame resistance and other properties. DAMPO or DAPPO were quantitatively incorporated in concentrations of 25, 50, 75 and 100 mole percent, using the "one pot" ester-acid method. The number average molecular weights of the prepared materials were controlled to 20,000g/mol by off-setting the stoichiometry and endcapping with phthalic anhydride. This strategy enabled one to distinguish the effects of the phosphine oxide incorporation from the influence of molecular weight. The resulting copolymers demonstrated a significant increase in char yield as a function of the phosphine oxide content, thus suggesting improved fire resistance. Glass transition temperatures similar to the control were determined by DSC analysis. Analysis of the mechanical behavior of the DAMPO system at room temperature showed that tensile strength and elongation at failure values were comparable to the control system, while the DAPPO containing copolymers were surprisingly brittle. The influence of the reactive endgroup on the synthesis, cure behavior and network properties of thermosetting polyetherimides was investigated. Reactive phenylacetylene, acetylene and maleimide terminated poly(ether imide) oligomers were prepared and characterized. Optimal reaction conditions were established to produce fully endcapped oligomers with imidized structures and controlled molecular weight. The phenylacetylene endcapped system was synthesized by a conventional ester-acid method. The acetylene endcapped system was prepared via modified ester-acid method and the maleimide endcapped system was fabricated utilizing an amic-acid route. It was determined

  2. Observations of the J = 10 manifold of the pure rotational band of phosphine on Saturn

    NASA Technical Reports Server (NTRS)

    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.

  3. Observations of the J = 10 manifold of the pure rotational band of phosphine on Saturn

    NASA Technical Reports Server (NTRS)

    Haas, M. R.; Erickson, E. F.; Goorvitch, D.; Mckibbin, D. D.; Rank, D. M.

    1985-01-01

    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 constraints 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.

  4. Synthesis and fuel cell characterization of blend membranes from phenyl phosphine oxide containing flourinated novel polymers

    NASA Astrophysics Data System (ADS)

    Gürtekin Seden, Merve; Baştürk, Emre; Inan, Tülay Y.; Kayaman Apohan, Nilhan; Güngör, Atilla

    2014-12-01

    Novel fluorinated poly(arylene ether)'s are synthesized from polycondensation of bis (p-hydroxy-tetrafluoro) phenyl) phenyl phosphine oxide (PFPPO-OH) with 4,4‧-dichlorodiphenyl sulfone (DCDPS) and 2,2-bis(4-hydroxyphenyl)propane (Bisfenol A) (Copolymer 1a) or 2,2-bis(4-hydroxyphenyl) hexafluoropropane (Bisphenol AF) (Copolymer 1b). The fluorinated copolymers have been blended with sulphonated poly(ether ether ketone)-SPEEK by solvent casting method. The water uptake and proton conductivity of the blend membranes decreases with the increase of copolymer content as expected, but proton conductivity values are still comparable to that of Nafion117® membrane. Addition of hydrophobic copolymer 1b to the SPEEK caused increase in water vapor transmission. Methanol permeability of the membranes is decreased to 8.2 × 10-8 cm2 s-1 and 1.3 × 10-9 cm2 s-1 by addition of Copolymer 1a and 1b, respectively and they are much lower than that of Nafion® 117 (1.21E-06 (cm2 s-1). The blend membranes endure up to 6.5 h before it starts to dissolve. Hydrogen and oxygen permeability of the blend membranes is one-hundredth of the Nafion®. Fluorinated polymer improved chemical, mechanical, and hydrolytic stability and also phenyl phosphine oxide structure in the ionomer increased the thermal stability, gas and methanol permeability and overcomed the drawbacks of the Nafion® type membranes.

  5. Synthesis, characterization, and crystal structure of mercury(II) complex containing new phosphine oxide salt

    NASA Astrophysics Data System (ADS)

    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.

  6. Sterically crowded peri-substituted naphthalene phosphines and their PV derivatives.

    PubMed

    Knight, Fergus R; Fuller, Amy L; Bühl, Michael; Slawin, Alexandra M Z; Woollins, J Derek

    2010-07-05

    Three sterically crowded peri-substituted naphthalene phosphines, Nap[PPh(2)][ER] (Nap=naphthalene-1,8-diyl; ER=SEt, SPh, SePh) 1-3, which contain phosphorus and chalcogen functional groups at the peri positions have been prepared. Each phosphine reacts to form a complete series of P(V) chalcogenides Nap[P(E')(Ph(2))(ER)] (E'=O, S, Se). The novel compounds were fully characterised by using X-ray crystallography and multinuclear NMR spectroscopy, IR spectroscopy and MS. X-ray data for 1, 2, nO, nS, nSe (n=1-3) are compared. Eleven molecular structures have been analysed by naphthalene ring torsions, peri-atom displacement, splay angle magnitude, X...E interactions, aromatic ring orientations and quasi-linear arrangements. An increase in the congestion of the peri region following the introduction of heavy chalcogen atoms is accompanied by a general increase in naphthalene distortion. P...E distances increase for molecules that contain bulkier atoms at the peri positions and also when larger chalcogen atoms are bound to phosphorus. The chalcogenides adopt similar conformations that contain a quasi-linear E...P-C fragment, except for 3O, which displays a twist-axial-twist conformation resulting in the formation of a linear O...Se-C alignment. Ab initio MO calculations performed on 2O, 3O, 3S and 3Se reveal Wiberg bond index values of 0.02 to 0.04, which indicates only minor non-bonded interactions; however, calculations on radical cations of 3O, 3S and 3Se reveal increased values (0.14-0.19).

  7. Unmasking the Action of Phosphinous Acid Ligands in Nitrile Hydration Reactions Catalyzed by Arene-Ruthenium(II) Complexes.

    PubMed

    Tomás-Mendivil, Eder; Cadierno, Victorio; Menéndez, María I; López, Ramón

    2015-11-16

    The catalytic hydration of benzonitrile and acetonitrile has been studied by employing different arene-ruthenium(II) complexes with phosphinous (PR2OH) and phosphorous acid (P(OR)2OH) ligands as catalysts. Marked differences in activity were found, depending on the nature of both the P-donor and η(6)-coordinated arene ligand. Faster transformations were always observed with the phosphinous acids. DFT computations unveiled the intriguing mechanism of acetonitrile hydration catalyzed by these arene-ruthenium(II) complexes. The process starts with attack on the nitrile carbon atom of the hydroxyl group of the P-donor ligand instead of on a solvent water molecule, as previously suggested. The experimental results presented herein for acetonitrile and benzonitrile hydration catalyzed by different arene-ruthenium(II) complexes could be rationalized in terms of such a mechanism.

  8. Diphen­yl[2-(2-pyridylamino­meth­yl)phen­yl]phosphine oxide

    PubMed Central

    Hernández-Ortega, Simón; Cuenu Cabeza, Fernando; Cabrera-Ortiz, Armando

    2010-01-01

    The title compound, C24H21N2OP, was obtained by reacting 2-amino­pyridine and 2-(diphenyl­phosphin­yl)benzaldehyde 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. PMID:21579222

  9. The reductive P-P coupling of primary and secondary phosphines mediated by N-heterocyclic carbenes.

    PubMed

    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.

  10. Hydrogen sulphide and phosphine interactions with human skin in vitro: Application to hazardous material incident decision making for skin decontamination.

    PubMed

    Gaskin, Sharyn; Heath, Linda; Pisaniello, Dino; Evans, Richard; Edwards, John W; Logan, Michael; Baxter, Christina

    2016-03-03

    Accidental or intentional releases of toxic gases can have significant public health consequences and emergency resource demands. Management of exposed individuals during hazardous material incidents should be risk and evidence based, but there are knowledge gaps in relation to dermal absorption of gases and management advice for potentially exposed individuals. Using a modified Organization for Economic Co-operation and Development (OECD) in vitro toxicology protocol with human donor skin, this article reports on two common and odorous chemicals, hydrogen sulphide and phosphine. Results show that undamaged human skin provides a good barrier to hydrogen sulphide (up to 800 ppm) and phosphine (up to 1000 ppm) penetration for up to 30 min exposures, with little variability in the presence of clothing or in elevated temperature and humidity conditions. A practical guideline template for skin decontamination has been developed, and implications of the research for first responders are outlined.

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

    PubMed

    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.

  12. Phosphinate chemistry in the 21st century: a viable alternative to the use of phosphorus trichloride in organophosphorus synthesis.

    PubMed

    Montchamp, Jean-Luc

    2014-01-21

    Organophosphorus compounds are important in everyday applications ranging from agriculture to medicine and are used in flame retardants and other materials. Although organophosphorus chemistry is known as a mature and specialized area, researchers would like to develop new methods for synthesizing organophosphorus compounds to improve the safety and sustainability of these chemical processes. The vast majority of compounds that contain a phosphorus-carbon bond are manufactured using phosphorus trichloride (PCl3) as an intermediate. However, these reactions require chlorine, and researchers would like to avoid the use of PCl3 and develop safer chemistry that also decreases energy consumption and minimizes waste. Researchers have already proposed and discussed two primary strategies based on elemental phosphorus (P4 or Pred) or on phosphine (PH3) as alternatives to PCl3. However, phosphinates, an important class of phosphorus compounds defined as any compound with a phosphorus atom attached to two oxygens, R(1)R(2)P(O)(OR) (R(1)/R(2) = hydrogen/carbon), offer another option. This Account discusses the previously neglected potential of these phosphinates as replacements of PCl3 for the preparation of organophosphorus compounds. Because of their strong reductive properties, industry currently uses the simplest members of this class of compounds, hypophosphites, for one major application: electroless plating. In comparison with other proposed PCl3 surrogates, hypophosphorous derivatives can offer improved stability, lower toxicity, higher solubility, and increased atom economy. When their reducing power is harnessed to form phosphorus-carbon or phosphorus-oxygen bonds, these compounds are also rich and versatile precursors to organophosphorus compounds. This Account examines the use of transition metal-catalyzed reactions such as cross-coupling and hydrophosphinylation for phosphorus-carbon bond formation. Because the most important industrial organophosphorus compounds

  13. Synthesis of 2-azaspiro[4.4]nonan-1-ones via phosphine-catalysed [3+2]-cycloadditions

    SciTech Connect

    Yong, Sarah R.; Williams, Morwenna C.; Pyne, Stephen G.; Ung, Alison T.; Skelton, Brian W.; White, Allan H.; Turner, Peter

    2008-10-03

    The phosphine-catalyzed [3+2]-cycloaddition of the 2-methylene {gamma}-lactams 4 and 5 and the acrylate 6 with the ylides derived from the ethyl ester, the amide or the chiral camphor sultam derivative of 2-butynoic acid (7a-c) give directly, or indirectly after reductive cyclization, spiro-heterocyclic products. The acid 32 underwent Curtius rearrangement and then acid hydrolysis to give two novel spiro-cyclic ketones, 41 and 42.

  14. Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

    SciTech Connect

    Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin

    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.

  15. On the origin of reversible hydrogen activation by phosphine-boranes.

    PubMed

    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.

  16. Palladium(II) complexes with tris(2-carboxyethyl)phosphine, structure, reactions and cytostatic activity.

    PubMed

    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.

  17. Cationic Gold Clusters Ligated with Differently Substituted Phosphines: Effect of Substitution on Ligand Reactivity and Binding

    SciTech Connect

    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

  18. Global Modeling of Phosphine (PH3) Spectra: 13 to 2.8 μm

    NASA Astrophysics Data System (ADS)

    Brown, Linda R.; Nikitin, A.; Champion, J.; Kleiner, I.; Butler, R. A. H.

    2008-09-01

    In order to support remote sensing of Saturn and Jupiter, the infrared spectrum of PH3 was studied using high resolution (R>360000) laboratory spectra obtained with Fourier transform spectrometers. The line positions and intensities involving up to 21 sub-vibrational states were analyzed simultaneously using theoretical models developed in France and extended in Russia. The polyads considered were the Dyad (13 - 7.3 μm), Pentad (5.9 - 3.8 μm) and Octad (3.7 - 3.1 μm). The improved quantum mechanical models were implemented using an effective Hamiltonian in the form of irreducible tensors. The global modeling permitted more extensive quantum assignments to be made for transitions arising from both from the ground state and the two lowest fundamentals. The standard deviations of the global fit represent significant improvement with respect to previous studies of phosphine spectroscopy at these wavelengths. These results will be presented. Part of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract with The National Aeronautics and Space Administration. I.K. also thanks the Programme National de Planétologie for funding part of this research.

  19. Phosphine substitution in (.eta.5-cyclopentadienyl)bis(triphenylphosphine)cobalt(I): evidence for a dissociative mechanism

    SciTech Connect

    Janowicz, Andrew H.; Bryndza, Henry E.; Bergman, Robert G.

    1981-03-01

    The substitution of trimethylphosphine for triphenylphosphine in (η5-cyclopentadienyl)bis(triphenylphosphine)cobalt(I) (1) to form (η5-cyclopentadienyl)(trimethylphosphine)(triphenylphosphine)cobalt(I) was studied at -60°C in an NMR spectrometer. Kinetic measurements show the process to be first order in 1 and zero order in PMe3; added PPh3 strongly inhibits the reaction rate. This information indicates the reaction proceeds by rapid reversible phosphine dissociation through the unsaturated CpCo(PPh3) intermediate. The rate for generation of that intermediate, k1, is 1.15 x 10-3s-1 while the ratio of rate constant k2 (for conversion of intermediate to products) to k-1 (return to starting materials) is 4 at -60°C. Possible structures for CpCo(L) are also discussed in light of recent indications that the linear structure has a triplet ground state.

  20. A Combination Treatment Using Ethyl Formate and Phosphine to Control Planococcus citri (Hemiptera: Pseudococcidae) on Pineapples.

    PubMed

    Yang, JeongOh; Park, Youngrong; Hyun, Ik-Hwa; Kim, Gil-Hah; Kim, Bong-Su; Lee, Byung-Ho; Ren, YongLin

    2016-12-01

    Citrus mealybug, Planococcus citri (Risso), is a known quarantine pest that is difficult to control with phosphine (PH3) or low concentrations of ethyl formate (EF), particularly at low temperatures. Methyl bromide (MB) is a fumigant used for quarantine and preshipment (QPS) that can eradicate target pests with short fumigation periods. However, MB, which is an ozone-depleting substance, is scheduled to be phased out in South Korea over the next decade. There is no ideal alternative fumigant to replace MB for QPS of perishable commodities. A laboratory study was conducted to compare the individual effects of EF and PH3 individually, and the effects of EF mixed with PH3 as an MB alternative for the control of P. citri adults, nymphs, and eggs. In comparison to treatments with EF and PH3 individually, EF mixed with PH3 resulted in high toxicity to all stages of P. citri. The eggs were more tolerant than the nymphs and adults. A mixed treatment of EF and PH3 achieved complete control of eggs infesting pineapples at concentrations of 25.1/1.0 (EF/PH3) mg/liter at 8 °C for 4 h of exposures. This new combined EF/PH3 fumigation technology could offer shorter exposure times and less damage to perishable commodities at low temperatures, and could potentially be extended to controlling other quarantine pests as a replacement treatment for fruit and vegetables in which methyl bromide is currently being used.

  1. Tuning luminescent properties of CdSe nanoclusters by phosphine surface passivation

    NASA Astrophysics Data System (ADS)

    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.

  2. Molecular determinants of Kv1.5 channel block by diphenyl phosphine oxide-1.

    PubMed

    Du, Yi-mei; Zhang, Xiao-xian; Tu, Dan-na; Zhao, Ning; Liu, Yan-jie; Xiao, Hua; Sanguinetti, Michael C; Zou, Anruo; Liao, Yu-hua

    2010-06-01

    Kv1.5 channels conduct the ultra-rapid delayed rectifier current (I(Kur)) that contributes to action potential repolarization of human atrial myocytes. Block of these channels has been proposed as a treatment for atrial arrhythmias. Diphenyl phosphine oxide-1 (DPO-1) is a novel and potent inhibitor of Kv1.5 potassium channels. The present study was undertaken to characterize the mechanisms and molecular determinants of channel block by DPO-1. Experiments were carried out on wild-type and mutant Kv1.5 channels expressed in Xenopus laevis oocytes using the standard two microelectrode voltage clamp technique. DPO-1 blocked Kv1.5 current in oocytes with an IC(50) of 0.78+/-0.12 microM at +40 mV. Block was enhanced by higher rates of stimulation, consistent with preferential binding of the drug to the open state of the channel. Ala-scanning mutagenesis of the pore domain of Kv1.5 identified the residues Thr480, Leu499, Leu506, Ile508, Leu510 and Val514 as components of the putative binding site for DPO-1, partially overlapping the site previously defined for the Kv1.5 channel blockers AVE0118 and S0100176. Block of Kv1.5 by DPO-1 was significantly reduced in the presence of Kvbeta1.3.

  3. Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines

    SciTech Connect

    Weiss, Charles J.; Das, Partha Pratim; Higgins, Deanna LM; Helm, Monte L.; Appel, Aaron M.

    2014-09-05

    Nickel complexes were prepared with diphosphine ligands that contain pendant amines, and these complexes catalytically oxidize primary and secondary alcohols to their respective aldehydes and ketones. Kinetic and mechanistic studies of these prospective electrocatalysts were performed to understand what influences the catalytic activity. For the oxidation of diphenylmethanol, the catalytic rates were determined to be dependent on the concentration of both the catalyst and the alcohol. The catalytic rates were found to be independent of the concentration of base and oxidant. The incorporation of pendant amines to the phosphine ligand results in substantial increases in the rate of alcohol oxidation with more electron-donating substituents on the pendant amine exhibiting the fastest rates. We thank Dr. John C. Linehan, Dr. Elliott B. Hulley, Dr. Jonathan M. Darmon, and Dr. Elizabeth L. Tyson for helpful discussions. Research by CJW, PD, DLM, and AMA was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Research by MLH 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, Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  4. Bacterial carbon-phosphorus lyase: products, rates, and regulation of phosphonic and phosphinic acid metabolism.

    PubMed Central

    Wackett, L P; Shames, S L; Venditti, C P; Walsh, C T

    1987-01-01

    Carbon-phosphorus bond cleavage activity, found in bacteria that utilize alkyl- and phenylphosphonic acids, has not yet been obtained in a cell-free system. Given this constraint, a systematic examination of in vivo C-P lyase activity has been conducted to develop insight into the C-P cleavage reaction. Six bacterial strains were obtained by enrichment culture, identified, and characterized with respect to their phosphonic acid substrate specificity. One isolate, Agrobacterium radiobacter, was shown to cleave the carbon-phosphorus bond of a wide range of substrates, including fosfomycin, glyphosate, and dialkyl phosphinic acids. Furthermore, this organism processed vinyl-, propenyl-, and propynylphosphonic acids, a previously uninvestigated group, to ethylene, propene, and propyne, respectively. A determination of product stoichiometries revealed that both C-P bonds of dimethylphosphinic acid are cleaved quantitatively to methane and, furthermore, that the extent of C-P bond cleavage correlated linearly with the specific growth rate for a range of substrates. The broad substrate specificity of Agrobacterium C-P lyase and the comprehensive characterization of the in vivo activity make this an attractive system for further biochemical and mechanistic experiments. In addition, the failure to observe the activity in a group of gram-positive bacteria holds open the possibility that a periplasmic component may be required for in vivo expression of C-P lyase activity. PMID:3804975

  5. Phosphine and methylphosphine production by simulated lightning—a study for the volatile phosphorus cycle and cloud formation in the earth atmosphere

    NASA Astrophysics Data System (ADS)

    Glindemann, Dietmar; Edwards, Marc; Schrems, Otto

    Phosphine (PH 3), was recently found worldwide even in the remote atmosphere (Naturwissenschaften83(1996a)131; Atmos. Environ. 37(2003)24 29). It is of interest to find natural mechanisms which could produce phosphine gas and drive a volatile link of the atmospheric phosphorus cycle and the formation of phosphoric acid as possible condensation nuclei for clouds. Here, we report on simulated lightning exposing sodium phosphate in a reducing medium (methane model atmosphere or organic matter) for 5 s to a spark induced by microwave. The gas product analyzed by gas chromatography contained phosphine (yield up to 0.6 g kg -1 phosphate P) and methylphosphine (CH 3)PH 2 (yield up to 0.02 g kg -1 phosphate P). We suggest a plasma-chemical formation mechanism where organic compounds or methane or secondary hydrogen thereof reduce phosphate to phosphine of which a small fraction can subsequently react with methyl radicals to form methylphosphine. A small yield of 6 mg phosphine per kg phosphate P was even obtained in methane free medium, by simple plasmatic recombination of inorganic phosphorus. We believe that methane and hydrogen are useful model substances of pyrolytic gases with high reducing power which may form if lightning strikes biomass, soil and aerosol. These results suggest evidence that phosphine and methylphosphine (detectable in the field by intense garlic odor) are produced when atmospheric lightning strikes the ground or aerosol which is containing oxidized forms of phosphorus and chemical reductants. Additional reviewed data show that laboratory lightning was able to reduce a much more significant portion of phosphate to phosphite (up to 25% yield), methylphosphonic acid (up to 8.5% yield) and traces of hypophosphite in a matter of seconds.

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

    PubMed

    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

  7. Evidence for a SN2-type pathway in the exchange of phosphines at a [PhSe]+ centre.

    PubMed

    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.

  8. IR and Raman study of Pt(II) and Pd(II) complexes of amino substituted phosphine oxides. Normal coordinate analysis

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Georgieva, I.; Bauer, G.; Varbanov, S.; Dodoff, N.

    1997-06-01

    IR and Raman spectra of Pt(dapo) 2Cl 2 and Pd(dapo) 2Cl 2 (dapo=dimethyl(aminomethyl)phosphine oxide) have been measured in the 200-4000 cm -1 frequency range. Both the IR and Raman spectra show that dimethyl(aminomethyl)phosphine oxide ligands are monodentate coordinate. The results from the normal coordinate analysis calculations confirm the monodentate coordination of the ligands in agreement with some literature data. For Pd(dapo) 2Cl 2 complex the possibility for bidentate coordination of one dapo ligand is also considered.

  9. (2,4,6-Trimethyl­phen­yl)boronic acid–triphenyl­phosphine oxide (1/1)

    PubMed Central

    Roşca, Sorin; Olaru, Marian; Raţ, Ciprian I.

    2012-01-01

    In the crystal structure of the title compound, C9H13BO2·C18H15OP, there are O—H⋯O hydrogen bonds between the O atom of triphenyl­phosphine oxide and one hy­droxy group of the boronic acid. Boronic acid mol­ecules form inversion-related hydrogen-bonded dimers in an R 2 2(8) motif. The structure is consolidated by inter­molecular C—H⋯O bonds and C—H⋯π inter­actions. PMID:22259536

  10. Single-Component Phosphinous Acid Ruthenium(II) Catalysts for Versatile C-H Activation by Metal-Ligand Cooperation.

    PubMed

    Zell, Daniel; Warratz, Svenja; Gelman, Dmitri; Garden, Simon J; Ackermann, Lutz

    2016-01-22

    Well-defined ruthenium(II) phosphinous acid (PA) complexes enabled chemo-, site-, and diastereoselective C-H functionalization of arenes and alkenes with ample scope. The outstanding catalytic activity was reflected by catalyst loadings as low as 0.75 mol %, and the most step-economical access reported to date to angiotensin II receptor antagonist blockbuster drugs. Mechanistic studies indicated a kinetically relevant C-X cleavage by a single-electron transfer (SET)-type elementary process, and provided evidence for a PA-assisted C-H ruthenation step.

  11. Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

    SciTech Connect

    Pham, Tien Q.; Pyne, Stephen G.; Skelton, Brian W.; White, Allan H.

    2010-07-20

    The phosphine-catalyzed [3 + 2]-cycloaddition of 5-methylenehydantoins 4 with the ylides 5, derived from addition of tributylphosphine to the 2-butynoic acid derivatives, 6a-d, gives spiro-heterocyclic products. The camphor sultam derivative 6b gives optically active products. Noteable was that the ylides derived from ethyl 2-butynoate and the 3-(2-butynoyl)-1,3-oxazolidin-2-one derivatives 6c and 6d gave spiro-heterocyclic products with reverse regioselectivities. The N,N-dibenzylprotected cycloadduct has been converted to carbocyclic hydantocidin and 6,7-diepi-carbocyclic hydantocidin.

  12. 31P{1H}NMR and carbonyl force constants of unsymmetrical bidentate phosphine complexes of group (VI) metal carbonyls

    NASA Astrophysics Data System (ADS)

    Jesu Raj, Joe Gerald; Pathak, Devendra Deo; Kapoor, Pramesh N.

    2015-05-01

    In our present work we report synthesis of an unsymmetrical diphos ligand, 1-diphenylphosphino-2-di-m-tolylphosphinoethane and its coordinate complexes with group (VI) metal carbonyls such as Cr(CO)6 Mo(CO)6 and W(CO)6. The synthesized ligand and its complexes have been completely characterized by elemental analyses, FTIR, 1HNMR, 31P{1H}NMR and FAB mass spectrometry methods. Special emphasis has been given to calculations of carbonyl force constants. Based on the spectroscopic evidences it has been confirmed that these metal carbonyl complexes with the ditertiary phosphine ligand showed cis geometry in their molecular structure.

  13. Apparatus for purifying arsine, phosphine, ammonia, and inert gases to remove Lewis acid and oxidant impurities therefrom

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1991-01-08

    An apparatus for purifying a gaseous mixture comprising arsine, phosphine, ammonia, and/or inert gases, to remove Lewis acid and/or oxidant impurities therefrom, comprising a vessel containing a bed of a scavenger, the scavenger including a support having associated therewith an anion which is effective to remove such impurities, such anion being selected from one or more members of the group consisting of: (i) carbanions whose corresponding protonated compounds have a pK.sub.a value of from about 22 to about 36; and (ii) anions formed by reaction of such carbanions with the primary component of the mixture.

  14. Impedance technology reveals correlations between cytotoxicity and lipophilicity of mono and bimetallic phosphine complexes.

    PubMed

    Fonteh, P; Elkhadir, A; Omondi, B; Guzei, I; Darkwa, J; Meyer, D

    2015-08-01

    Label free impedance technology enables the monitoring of cell response patterns post treatment with drugs or other chemicals. Using this technology, a correlation between the lipophilicity of metal complexes and the degree of cytotoxicity was observed. Au(L1)Cl (1), AuPd(L1)(SC4H8)Cl3 (1a) and Au(L2)Cl (2) [L1 = diphenylphosphino-2-pyridine; L2 = 2-(2-(diphenylphosphino)ethyl)-pyridine] were synthesised, in silico drug-likeness and structure-activity relationship monitored using impedance technology. Dose dependent changes in cytotoxicity were observed for the metal complexes resulting in IC50s of 12.5 ± 2.5, 18.3 ± 8.3 and 16.9 ± 0.5 µM for 1, 1a and 2 respectively in an endpoint assay. When a real time impedance assay was used, dose-dependent responses depicting patterns that suggested slower uptake (at a toxic 20 µM) and faster recovery of the cells (at the less toxic 10 µM) of the bimetallic complex (1a) compared to the monometallic complexes (1 and 2) was observed. These data agreed with the ADMET findings of lower aqueous solubility of 1a and non-ideal lipophilicity (AlogP98 of 6.55) over more water soluble 1 and 2 with ideal lipophilicity (4.91 and 5.03 respectively) values. The additional coordination of a Pd atom to the nitrogen atom of a pyridine ring, the sulfur atom of a tetrahydrothiophene moiety and two chlorine atoms in 1a could be contributing to the observed differences when compared to the monometallic complexes. This report presents impedance technology as a means of correlating drug-likeness of lipophilic phosphine complexes containing similar backbone structures and could prove valuable in filtering drug-like compounds in a drug discovery project.

  15. Ambipolar Phosphine Derivatives to Attain True Blue OLEDs with 6.5% EQE.

    PubMed

    Kondrasenko, Ilya; Tsai, Zheng-Hua; Chung, Kun-You; Chen, Yi-Ting; Ershova, Yana Yu; Doménech-Carbó, Antonio; Hung, Wen-Yi; Chou, Pi-Tai; Karttunen, Antti J; Koshevoy, Igor O

    2016-05-04

    A family of new branched phosphine derivatives {Ph2N-(C6H4)n-}3P → E (E = O 1-3, n = 1-3; E = S 4-6, n = 1-3; E = Se 7-9, n = 1-3; E = AuC6F5 4-6, n = 1-3), which are the donor-acceptor type molecules, exhibit efficient deep blue room temperature fluorescence (λem = 403-483 nm in CH2Cl2 solution, λem = 400-469 nm in the solid state). Fine tuning the emission characteristics can be achieved varying the length of aromatic oligophenylene bridge -(C6H4)n-. The pyramidal geometry of central R3P → E fragment on the one hand disrupts π-conjugation between the branches to preserve blue luminescence and high triplet energy, while on the other hand provides amorphous materials to prevent excimer formation and fluorescence self-quenching. Hence, compounds 2, 3, 5, and 12 were used as emitters to fabricate nondoped and doped electroluminescent devices. The luminophore 2 (E = O, n = 2) demonstrates excellently balanced bipolar charge transport and good nondoped device performance with a maximum external quantum efficiency (EQEmax) of 3.3% at 250 cd/m(2) and Commission International de L'Eclairage (CIE) coordinates of (0.15, 0.08). The doped device of 3 (E = O, n = 3) shows higher efficiency (EQEmax of 6.5, 6.0 at 100 cd/m(2)) and high color purity with CIE (0.15, 0.06) that matches the HDTV standard blue. The time-resolved electroluminescence measurement indicates that high efficiency of the device can be attributed to the triplet-triplet annihilation to enhance generation of singlet excitons.

  16. Ammonia, Phosphine, And Cloud Structure On Saturn Derived From 5-micron Spectra

    NASA Astrophysics Data System (ADS)

    Bjoraker, Gordon; Chanover, N.; Glenar, D.; Hewagama, T.

    2006-09-01

    The CSHELL spectrometer on NASA's Infrared Telescope Facility was used to observe Saturn at several settings between 5.07 and 5.27μm beginning in 2004 February through 2006 January at about the same time as Cassini/VIMS and CIRS were mapping the planet. At these wavelengths thermal radiation originates from the deep atmosphere (5 bars) and it is attenuated by two cloud layers considered to be composed of NH4SH and condensed NH3. In addition, there is a component of sunlight reflected from the upper (NH3) cloud that varies spatially on Saturn. CSHELL can spectrally resolve profiles of absorption lines of ammonia (NH3) and phosphine (PH3) on Saturn. These lines are very broad due to collisions with 3 to 5 bars of hydrogen. The Saturn spectrum exhibits several strong NH3 and PH3 lines, as well as Fraunhofer lines due to CO in the Sun. The spatial variation of this spectrum is dominated by the variable opacity of Saturn's cloud structure. Superimposed on this are smaller variations in the mixing ratios of NH3 and PH3. The abundances of these gases can be retrieved reliably in relatively cloud-free regions between 50 South and 65 South, which are analogous to Jupiter's belts and 5-micron hot spots. Elsewhere, it is more difficult to separate changes in cloud opacity from gas abundances. We use near-simultaneous CIRS observations which sound the 500-mbar level to provide an upper boundary condition to PH3. The 5-μm spectrum of Saturn's Equatorial Zone (10 South) is significantly different from a region near 60 South. The NH3 and PH3 lines are weaker and narrower in the EQZ, while the Fraunhofer lines are stronger. We will present synthetic spectra calculated from models which fit both regions and which explore the tradeoffs between gas mixing ratios and cloud opacity. This work was supported by NASA's Planetary Astronomy program.

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

    PubMed

    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.

  18. Discovery of Brigatinib (AP26113), a Phosphine Oxide-Containing, Potent, Orally Active Inhibitor of Anaplastic Lymphoma Kinase.

    PubMed

    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.

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

    PubMed

    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.

  20. Latitude Variations of the Abundances of Ammonia, Acetylene, and Phosphine and Vertical Mixing in the Atmospheres of Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Edgington, Scott G.

    Ultraviolet observations of Jupiter and Saturn performed in the past have typically suffered from poor spatial resolution and have therefore focused on either globally-averaged values or north-south asymmetries. Spectra taken with the Hubble Space Telescope Faint Object Spectrograph have a spatial resolution of 1 arc second, making it possible to sample the disk at several latitudes. The observations presented here were taken at latitudes along the Central Meridian of both Jupiter (65oS, 48oS, 33oS, 25oS, 12oS, 6oS, 0o, 6oN, 15oN, 20oN, 25oN, 48oN, 65oN, along with the Great Red Spot and the South Equatorial Belt) and Saturn (4oS, 4oN, 12oN, 20oN, 40oN, 48oN, 60oN, 79oN, 90oN). The wavelength interval covers a range from 180 nm to 240 nm. Albedos have been calculated by dividing the observations by intensity of the Sun at each planet. Removal of solar features reveals the presence of ammonia, acetylene, and continuum absorbers (e.g. phosphine and aerosols). With the use of a photochemical model which includes a multiple scattering radiative transfer code, the altitude profiles of these species have been generated by using the eddy diffusion coefficient as a free parameter. From the altitude profiles, synthetic spectra were calculated and compared with the observations at each latitude. This work reveals that a variation of ammonia, acetylene, phosphine, and the vertical mixing with altitude exists in both atmospheres. The presence of a strong ammonia signature in the Jovian spectra allows it to be used as a tracer for the dynamics near the tropopause. The value of the eddy mixing coefficient at 6oN increases rapidly with depth from a value of 5×102 cm2s-1 to 104 cm2s-1 between 90-150 mbar. Above the 90 mbar level, the value increases reaching a value of 8×102 cm2s-1 at 60 mbar. A latitudinal variation in the ammonia mixing ratio and eddy mixing profile is also derived from the FOS observations. In the northern hemisphere of Jupiter, the ammonia mixing ratio above

  1. Development of the first potent and selective inhibitor of the zinc endopeptidase neurolysin using a systematic approach based on combinatorial chemistry of phosphinic peptides.

    PubMed

    Jirácek, J; Yiotakis, A; Vincent, B; Checler, F; Dive, V

    1996-08-09

    A new systematic approach, based on combinatorial chemistry of phosphinic peptides, is proposed for rapid development of highly potent and selective inhibitors of zinc metalloproteases. This strategy first evaluates the effects on the inhibitory potency and selectivity of the following parameters: 1) size of the phosphinic peptides, 2) position of the phosphinic bond in the sequence, and 3) the state (free or blocked) of the peptide extremities. After this selection step, the influence of the inhibitor sequence is analyzed in order to determine the identity of the residues that optimized both the potency and the selectivity. We demonstrate the efficiency of this novel approach in rapid identification of the first potent inhibitor of the mammalian zinc endopeptidase neurolysin(24-16), able to discriminate between this enzyme and the related zinc endopeptidase thimet oligopeptidase(24-15). The most potent and selective inhibitor developed in this study, Pro-LPhePsi(PO2CH2)Gly-Pro, displays a Ki value of 4 nM for 24-16 and is 2000 times less potent on 24-15. The specific recognition of such a free phosphinic tetrapeptide by 24-16, as well as the unique specificity of the 24-16 S2 and S2' subsites for proline, unveiled by this study, are discussed in terms of their possible significance for the function of this enzyme and its related zinc endopeptidase activities.

  2. Phosphorus-containing polymers from THPS. IV: Synthesis and properties of phosphorus-containing polybenzoxazines as a green route for recycling toxic phosphine (PH3) tail gas.

    PubMed

    Tan, Zhi-Wei; Sun, Jian; Wu, Cheng-Yan; Qiu, Jin-Jun; Liu, Cheng-Mei

    2017-01-15

    A convenient route to convert the highly toxic phosphine (PH3) tail gas into high-performance polybenzoxazines was first described in this paper. Two aliphatic polyamines, namely tris(aminomethyl)phosphine oxide and bis(aminomethyl)phenylphosphine oxide, were synthesized from tetrakis(hydroxymethyl)phosphonium sulfate (THPS), a green derivative of PH3 tail gas. And then two novel phosphorus-containing benzoxazine monomers, tris(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl)phosphine oxide (TBOz) and benzylbis(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl) phosphine oxide (BBOz) were prepared by three-steps procedure. FT-IR and DSC technologies were adopted to study the thermal-initiated polymerization behaviors of two benzoxazine monomers. Thermal properties of these crosslinked polymers were studied by TGA and DMA. The results display that the polybenzoxazines (PTBOz and PBBOz) exhibite good thermal stabilities and high glass transition temperatures. The char yield of polybanzoxazine is high as 47% and indiactes that phosphorus-containing polybenzoxazines show high fire-retardancy. The surface free energies of the PTBOz and PBBOz are 37.1 and 40.4mJm(-2) by Owens two-liquid method. The dielectric properties of the PTBOz and PBBOz remaine near constant in the experimental frequency range.

  3. Phosphine-Catalyzed Enantioselective [2+4] Cycloaddition to Synthesize Pyrrolidin-2-one Fused Dihydropyrans Using α-Substituted Allenoates as C2 Synthons.

    PubMed

    Wang, Chang; Jia, Hao; Zhang, Cheng; Gao, Zhenzhen; Zhou, Leijie; Yuan, Chunhao; Xiao, Yumei; Guo, Hongchao

    2017-01-06

    A bifunctional phosphine-catalyzed highly enantioselective [2+4] cycloaddition of α-substituted allenoates with (E)-1-benzyl-4-olefinicpyrrolidine-2,3-diones has been achieved, giving pyrrolidin-2-one fused dihydropyran derivatives in moderate to good yields with excellent enantioselectivities (up to 98% ee). This reaction provides a useful catalytic asymmetric access to dihydropyran structural motifs.

  4. Phosphine-catalyzed [3+2] cycloaddition reactions of azomethine imines with electron-deficient alkenes: a facile access to dinitrogen-fused heterocycles.

    PubMed

    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.

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

    PubMed

    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.

  6. Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways

    PubMed Central

    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. A facile phosphine-free colloidal synthesis of Cu2SnS3 and Cu2ZnSnS4 nanorods with a controllable aspect ratio.

    PubMed

    Wang, Jian-Jun; Liu, Pai; Ryan, Kevin M

    2015-09-18

    Cu2SnS3 (CTS) nanorods were synthesized with a controllable aspect ratio via a facile phosphine-free colloidal synthesis. This synthesis can be readily extended to obtain Cu2ZnSnS4 (CZTS) nanorods with tunable Zn content.

  8. Synthesis of Monomeric Fe(II) and Ru(II) Complexes of Tetradentate Phosphines

    SciTech Connect

    Jana, Barun; Ellern, Arkady; Pestovsky, Oleg; Sadow, Aaron; Bakac, Andreja

    2011-03-07

    rac-Bis[{l_brace}(diphenylphosphino)ethyl{r_brace}-phenylphosphino]methane (DPPEPM) reacts with iron(II) and ruthenium(II) halides to generate complexes with folded DPPEPM coordination. The paramagnetic, five-coordinate Fe(DPPEPM)Cl{sub 2} (1) in CD{sub 2}Cl{sub 2} features a tridentate binding mode as established by {sup 31}P{l_brace}{sup 1}H{r_brace} NMR spectroscopy. Crystal structure analysis of the analogous bromo complex, Fe(DPPEPM)Br{sub 2} (2) revealed a pseudo-octahedral, cis-{alpha} geometry at iron with DPPEPM coordinated in a tetradentate fashion. However, in CD{sub 2}Cl{sub 2} solution, the coordination of DPPEPM in 2 is similar to that of 1 in that one of the external phosphorus atoms is dissociated resulting in a mixture of three tridentate complexes. The chloro ruthenium complex cis-Ru({kappa}{sup 4}-DPPEPM)Cl{sub 2} (3) is obtained from rac-DPPEPM and either [RuCl{sub 2}(COD)]{sub 2} [COD = 1,5-cyclooctadiene] or RuCl{sub 2}(PPh{sub 3}){sub 4}. The structure of 3 in both the solid state and in CD{sub 2}Cl{sub 2} solution features a folded {kappa}{sup 4}-DPPEPM. This binding mode was also observed in cis-[Fe({kappa}{sup 4}-DPPEPM)(CH{sub 3}CN){sub 2}](CF{sub 3}SO{sub 3}){sub 2} (4). Addition of an excess of CO to a methanolic solution of 1 results in the replacement of one of the chloride ions by CO to yield cis-[Fe({kappa}{sup 4}-DPPEPM)Cl(CO)](Cl) (5). The same reaction in CH{sub 2}Cl{sub 2} produces a mixture of 5 and [Fe({kappa}{sup 3}-DPPEPM)Cl{sub 2}(CO)] (6) in which one of the internal phosphines has been substituted by CO. Complexes 2, 3, 4, and 5 appear to be the first structurally characterized monometallic complexes of {kappa}{sup 4}-DPPEPM.

  9. Polymer versus phosphine stabilized Rh nanoparticles as components of supported catalysts: implication in the hydrogenation of cyclohexene model molecule.

    PubMed

    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.

  10. Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

    NASA Technical Reports Server (NTRS)

    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.

  11. Phosphine and tertiarybutylphosphine adsorption on the indium-rich InP (0 0 1)-(2 × 4) surface

    NASA Astrophysics Data System (ADS)

    Woo, R. L.; Das, U.; Cheng, S. F.; Chen, G.; Raghavachari, K.; Hicks, R. F.

    2006-11-01

    Phosphine and tertiarybutylphosphine adsorption on the indium-rich InP (0 0 1)-(2 × 4) surface at 25 °C have been studied by internal reflection infrared spectroscopy, X-ray photoelectron spectroscopy, and low energy electron diffraction. Both molecules form a dative bond to the empty dangling bonds on the In-P heterodimers and the second-layer In-In dimers and vibrate symmetrically at 2319 (2315) and 2285 (2281) cm -1 and asymmetrically at 2339 (2339) and 2327 (2323) cm -1. A fraction of these species dissociate into adsorbed PH 2 with the hydrogen and tertiarybutyl ligands transferring to nearby phosphorus sites. The calculated energy barriers for desorption (<11 kcal/mol) of these molecules is less than that for dissociation (>17 kcal/mol) and explains their low sticking probabilities at elevated temperatures under InP growth conditions.

  12. Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

    NASA Astrophysics Data System (ADS)

    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.

  13. Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

    PubMed Central

    Yamamoto, Kosuke; Shimizu, Takashi; Igawa, Kazunobu; Tomooka, Katsuhiko; Hirai, Go; Suemune, Hiroshi; Usui, Kazuteru

    2016-01-01

    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. PMID:27824074

  14. Molybdenum complexes supported by mixed NHC/phosphine ligands: activation of N2 and reaction with P(OMe)3 to the first meta-phosphite complex.

    PubMed

    Gradert, Christian; Stucke, Nadja; Krahmer, Jan; Näther, Christian; Tuczek, Felix

    2015-01-12

    Molybdenum(0) dinitrogen complexes, supported by the mixed NHC/phosphine pincer ligand PCP, exhibit an extreme activation of the N2 ligand due to a very π-electron-rich metal center. The low thermal stability of these compounds can be increased using phosphites instead of phosphines as coligands. Through an amalgam reduction of [MoCl3(PCP)] in the presence of trimethyl phosphite and N2 the highly activated and room-temperature stable dinitrogen complex [Mo(N2)(PCP)(P(OMe)3)2] is obtained. As a second product, the first transition metal complex containing the meta-phosphite ligand P(O)(OMe) originates from this reaction.

  15. Uv and radiation grafting of p-styryl diphenyl phosphine to synthetic polymers and the use of the resulting copolymers in insolubilization processes

    SciTech Connect

    Garnett, J.L.; Levot, R.; Long, M.A.

    1981-01-01

    Results of studies of ..gamma..-induced grafting of p-styryl diphenyl phosphine (SOP) to polyvinylchloride (PVC), polypropylene and crosslinked polystyrene beads are described. SOP dissolved in dioxane-methanol radiation grafts readily to PVC at close rates up to 1.5 Mrad, and a Trommsdorff peak was observed at about 28% v/v monomer concentration under experimental conditions set forth here. SOP was found to be much more efficient in radiation grafting than vinyl phosphine. A photosensitized process using uv radiation was also investigated, and SOP was found to copolymerize easily to PVC and crosslinked polystyrene. The copolymerized SOP is useful for attachment of metal ions to yield catalysts suitable for hydrogenation reactions. Data for hydrogenation of cyclohexane using such catalysts showed as much as 30% conversion of the cyclohexane using chlorocarbonyltris(triphenylphosphine) iridium as catalyst. (BLM)

  16. trans-(4-Acetyl­naphth­yl)chlorido­bis(triphenyl­phosphine-κP)nickel(II) dichloro­methane solvate

    PubMed Central

    Liu, Yu-Hua; Chen, Chen; Yang, Lian-Ming

    2008-01-01

    The title compound, [Ni(C12H9O)Cl(C18H15P)2]·CH2Cl2, was synthesized from the reaction between 1-acetyl-4-chloro­naphthalene, NiCl2·6H2O and triphenyl­phosphine (PPh3) in ethanol. The compound contains one crystallographically unique nickel ion in a pseudo-square-planar geometry. PMID:21200986

  17. A phosphine mediated sequential annulation process of 2-tosylaminochalcones with MBH carbonates to construct functionalized aza-benzobicyclo[4.3.0] derivatives.

    PubMed

    Zhang, Qinglong; Zhu, Yannan; Jin, Hongxing; Huang, You

    2017-04-04

    A novel phosphine mediated sequential annulation process to construct functionalized aza-benzobicyclo[4.3.0] derivatives has been developed involving a one-pot sequential catalytic and stoichiometric process, which generates a series of benzobicyclo[4.3.0] compounds containing one quaternary center with up to 94% yield and 20 : 1 dr value. In this reaction, MBH carbonates act as 1,2,3-C3 synthons.

  18. An Electronic Rationale for Observed Initiation Rates in Ruthenium-Mediated Olefin Metathesis: Charge Donation in Phosphine And N-Heterocyclic Carbene Ligands

    SciTech Connect

    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.

  19. Tris(3-hydroxypropyl)phosphine (THPP): A mild, air-stable reagent for the rapid, reductive cleavage of small-molecule disulfides.

    PubMed

    McNulty, James; Krishnamoorthy, Venkatesan; Amoroso, Dino; Moser, Michael

    2015-10-01

    Tris(3-hydroxypropyl)phosphine (THPP) is demonstrated to be a versatile, water-soluble and air-stable reducing agent, allowing for the rapid, irreversible reductive cleavage of disulfide bonds in both aqueous and buffered aqueous-organic media. The reagent shows exceptional stability at biological pH under which condition it permits the rapid reduction of a wide range of differentially functionalized small-molecule disulfides.

  20. Catalytic Enantioselective Carbon-Oxygen Bond Formation: Phosphine-Catalyzed Synthesis of Benzylic Ethers via the Oxidation of Benzylic C-H Bonds.

    PubMed

    Ziegler, Daniel T; Fu, Gregory C

    2016-09-21

    Benzylic alcohols and ethers are common subunits in bioactive molecules, as well as useful intermediates in organic chemistry. In this Communication, we describe a new approach to the enantioselective synthesis of benzylic ethers through the chiral phosphine-catalyzed coupling of two readily available partners, γ-aryl-substituted alkynoates and alcohols, under mild conditions. In this process, the alkynoate partner undergoes an internal redox reaction. Specifically, the benzylic position is oxidized with good enantioselectivity, and the alkyne is reduced to the alkene.

  1. Phosphine-catalyzed [4+1] annulation of 1,3-(aza)dienes with maleimides: highly efficient construction of azaspiro[4.4]nonenes.

    PubMed

    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.

  2. Selectivity control between Mizoroki-Heck and homo-coupling reactions for synthesising multinuclear metal complexes: unique addition effects of tertiary phosphines and O2.

    PubMed

    Yamazaki, Yasuomi; Ishitani, Osamu

    2017-04-05

    The addition of a tertiary phosphine and O2 to reaction solutions strongly affected the reactivity and selectivity of coupling reactions between transition metal complexes. The Mizoroki-Heck reaction between metal complexes with bromo and those with vinyl groups in the diimine ligand did not proceed using Pd(OAc)2 in the presence of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (Sphos) under Ar but proceeded selectively after injection of air into the reaction vessel. In the absence of the phosphine ligand, on the other hand, not only the Mizoroki-Heck reaction but also a homo-coupling reaction between the metal complexes with the bromo groups proceeded at the same time. Mechanistic investigation showed that nanoparticles of Pd species were produced in the absence of the phosphine ligand and worked as catalysts for both the Mizoroki-Heck and homo-coupling reactions. On the other hand, larger Pd particles, which were produced in the presence of Sphos but after addition of air for oxidising Sphos, selectively catalysed the Mizoroki-Heck reaction. 'Molecular' Pd species that were stabilised in the presence of non-oxidised Sphos could not catalyse both coupling reactions under the reaction conditions. Based on these results, reaction conditions were established for the selective progress of the Mizoroki-Heck and the homo-coupling reactions.

  3. Investigation of an efficient palladium-catalyzed C(sp)-C(sp) cross-coupling reaction using phosphine-olefin ligand: application and mechanistic aspects.

    PubMed

    Shi, Wei; Luo, Yingdong; Luo, Xiancai; Chao, Lei; Zhang, Heng; Wang, Jian; Lei, Aiwen

    2008-11-05

    A pi-acceptor phosphine-electron-deficient olefin ligand was found effective in promoting Pd-catalyzed C(sp)-C(sp) cross-coupling reactions. The new protocol realized the cross-coupling of a broad scope of terminal alkynes and haloalkynes in good to excellent yields with high selectivities. Electron-rich alkynes, which are normally difficult substrates in Glaser couplings, could be employed as either nucleophiles or electrophiles. Alkynes bearing similar substituents, such as n-C5H11CCBr and n-C4H9CCH, which usually suffer from homocoupling side reactions under Cadiot-Chodkiewicz conditions, were successfully cross-coupled in the system. Preliminary kinetic studies revealed that the reaction rate was zero-order in the concentrations of both haloalkynes and terminal alkynes and first order in the loading of Pd(dba)2 and exhibited no obvious dependence on the loading of the copper salt. Control experiments with other phosphines such as PPh3 and DPPF as the ligand were carried out. All the kinetic evidence indicated that the phosphine-olefin ligand facilitated the reductive elimination in the catalytic cycle.

  4. Joint Recovery of f-Elements Using Solvent Based on Carbamoyl-phosphine Oxides Heading Toward ORGA-Process

    SciTech Connect

    Ozawa, M.; Babain, V.; Shadrin, A.; Strelkov, S.; Kiseleva, R.; Murzin, A.

    2007-07-01

    Development of the recovery system which allows realizing joint recovery of all the actinides from the HLW is one of the relevant questions in radiochemistry. Carbamoyl-phosphine oxides (CMPO) were proposed and studied as extractant for rare-earth and transplutonium elements (RE and TPE) recovery from HLW with high acidity, for example TRUEX- and SETFICS-process. Organic system CMPO with TBP in kerosene is usually used as a solvent. However, low solubility of actinide adducts with CMPO results in third phase formation when the actinides concentration in organic phase is high. Application of fluorinated polar diluents increases the solubility of CMPO adducts with actinides in organic phase. It was shown that solvent based on carbamoyl-phosphonate in fluorinated polar diluents allows to recover both uranium and minor actinides concurrently, and there was no precipitation or third phase formation even at high uranium concentration in organic phase. The f-elements joint recovery process based on this solvent was proposed. Solvent containing octyl-phenyl-N,N-di-isobutyl-carbamoyl-methylene-phosphine oxide (O{phi}D[iB]CMPO) in polar diluent meta-nitro-benzo-trifluoride (fluoro-pole-732) was screened out for these studies. And, combined use of them with TBP modifier allows to provide uranium and europium (americium) high recovery characteristics concurrently with an opportunity of attainment of f-elements high concentration in organic phase. As it was indicated, precipitates or third phase was absent even when uranium content in organic phase was 100 g/l. Recovery efficiency to europium remained sufficiently high for its effective recovery. Organic phase saturation about 100% from theoretical attains in europium recovery with this system. Increasing of (O{phi}D[iB]CMPO) concentration in recovery system from 0.2 to 0.8 M results in europium content increasing in organic phase, but no third phase formation is observed. The highest possible europium content in organic phase

  5. Occurrence of matrix-bound phosphine in polar ornithogenic tundra ecosystems: effects of alkaline phosphatase activity and environmental variables.

    PubMed

    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, p<0.01) between MBP and soil/sediment moisture. MBP concentrations showed a significant positive correlation with APA (r=0.668, p<0.0001), total organic carbon (r=0.501, p<0.0001), total hydrogen (r=0.483, p<0.0001) and total sulfur (r=0.398, p<0.001), indicating that the production of MBP is associated with microbially mediated factors rather than the contents of TP, IP and OP in the P-enriched ornithogenic soils/sediments. Our results indicated that MBP is an important gaseous link in the phosphorus biogeochemical cycles of ornithogenic tundra ecosystems in Antarctica and Arctic.

  6. The quaternisation reaction of phosphines and amines in aliphatic alcohols. A similarity analysis using the isokinetic, isosolvent and isoselective relationships.

    PubMed

    Pinheiro, Lidia M V; Calado, António R T; Reis, João Carlos R

    2004-05-07

    Accurate second-order rate constants were measured at 5 K intervals in the temperature range 298.15-328.15 K for the quaternisation reaction of triethylphosphine with iodoethane in methanol, ethanol, propan-1-ol and butan-1-ol. These data are complemented previously reported rate constants for the quaternisation reaction of triethylamine with iodoethane in the same solvents and at similar temperatures. Each of these two reaction series is analysed in terms of the isokinetic relationship (IKR) with respect to solvent variation and of the isosolvent relationship (ISoR) with respect to temperature variation, using in the latter case five different empirical solvent scales. Statistically validated IKR and ISoR have been found for both reaction series. The resulting isokinetic temperatures of 347 K (phosphine series) and of 730 K (amine series) are discussed in terms of Linert's theory of the isokinetic relationship. The best ISoR correlation is obtained using the Dimroth-Reichardt E(T)(N) solvent scale for the phosphine series and the Kamlet-Taft alpha(KT) solvent scale for the amine series. It is demonstrated that no real solvent can be envisaged as having the characteristics of an isokinetic solvent. The selectivity of the nucleophiles triethylphosphine and triethylamine in the attack on iodoethane is examined by treating together both reaction series in terms of the isoselective relationship (ISeR). The isoselective temperature with respect to solvent is found to be 289 K, which is close to the value of 302 K predicted by Exner and Giese's formula on the basis of the individual isokinetic temperatures. A novel ISeR analysis with respect to temperature is performed. It reveals that the alpha(KT) scale is the most appropriate solvent scale for describing this selectivity series, and that it is feasible to find an isoselective solvent. A new equation is developed for predicting the isoselective solvent parameter from individual isosolvent parameters and is shown to

  7. Synthesis and reactivity of rare earth metal alkyl complexes stabilized by anilido phosphinimine and amino phosphine ligands.

    PubMed

    Liu, Bo; Cui, Dongmei; Ma, Jia; Chen, Xuesi; Jing, Xiabin

    2007-01-01

    Anilido phosphinimino ancillary ligand H(2)L(1) reacted with one equivalent of rare earth metal trialkyl [Ln{CH(2)Si(CH(3))(3)}(3)(thf)(2)] (Ln=Y, Lu) to afford rare earth metal monoalkyl complexes [L(1)LnCH(2)Si(CH(3))(3)(THF)] (1 a: Ln=Y; 1 b: Ln=Lu). In this process, deprotonation of H(2)L(1) by one metal alkyl species was followed by intramolecular C--H activation of the phenyl group of the phosphine moiety to generate dianionic species L(1) with release of two equivalnts of tetramethylsilane. Ligand L(1) coordinates to Ln(3+) ions in a rare C,N,N tridentate mode. Complex l a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL(1))LnY(NHC(6)H(3)iPr(2)-2,6)(2)] (2) selectively, that is, the C--H activation of the phenyl group is reversible. When 1 a was exposed to moisture, the hydrolyzed dimeric complex [{(HL(1))Y(OH)}(2)](OH)(2) (3) was isolated. Treatment of [Ln{CH(2)Si(CH(3))(3)}(3)(thf)(2)] with amino phosphine ligands HL(2-R) gave stable rare earth metal bis-alkyl complexes [(L(2-R))Ln{CH(2)Si(CH(3))(3)}(2)(thf)] (4 a: Ln=Y, R=Me; 4 b: Ln=Lu, R=Me; 4 c: Ln=Y, R=iPr; 4 d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4 a and 4 c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L(2-R))Y(NHC(6)H(3)iPr(2)-2,6)(2)(thf)] (5 a: R=Me; 5 b: R=iPr). Complexes 1 a,b and 4 a-d initiated the ring-opening polymerization of d,l-lactide with high activity to give atactic polylactides.

  8. Suppression of spore germination and aflatoxin biosynthesis in Aspergillus parasiticus during and after exposure to high levels of phosphine.

    PubMed

    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.

  9. Phosphine-Free Synthesis of Metal Chalcogenide Quantum Dots by Directly Dissolving Chalcogen Dioxides in Alkylthiol as the Precursor.

    PubMed

    Yao, Dong; Xin, Wei; Liu, Zhaoyu; Wang, Ze; Feng, Jianyou; Dong, Chunwei; Liu, Yi; Yang, Bai; Zhang, Hao

    2017-03-09

    Semiconductor quantum dots (QDs) are competitive emitting materials in developing new-generation light-emitting diodes (LEDs) with high color rendering and broad color gamut. However, the use of highly toxic alkylphosphines cannot be fully avoided in the synthesis of metal selenide and telluride QDs because they are requisite reducing agents and solvents for preparing chalcogen precursors. In this work, we demonstrate the phosphine-free preparation of selenium (Se) and tellurium (Te) precursors by directly dissolving chalcogen dioxides in the alkylthiol under the mild condition. The chalcogen dioxides are reduced to elemental chalcogen clusters, while the alkylthiol is oxidized to disulfides. The chalcogen clusters further combine with the disulfides, generating dispersible chalcogen precursors. The resulting chalcogen precursors are suitable for synthesizing various metal chalcogenide QDs, including CdSe, CdTe, Cu2Te, Ag2Te, PbTe, HgTe, and so forth. In addition, the precursors are of high reactivity, which permits a shorter QD synthesis process at lower temperature. Owing to the high quantum yield (QYs) and easy tunability of the photoluminescence (PL), the as-synthesized QDs are further employed as down-conversion materials to fabricate monochrome and white LEDs.

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

    PubMed Central

    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

  11. Imino-phosphine palladium(II) and platinum(II) complexes: synthesis, molecular structures and evaluation as antitumor agents.

    PubMed

    Motswainyana, William M; Onani, Martin O; Madiehe, Abram M; Saibu, Morounke; Thovhogi, Ntevheleni; Lalancette, Roger A

    2013-12-01

    The imino-phosphine ligands L1 and L2 were prepared via condensation reaction of 2-(diphenylphosphino)benzaldehyde with substituted anilines and obtained in very good yields. An equimolar reaction of L1 and L2 with either PdCl2(cod) or PtCl2(cod) gave new palladium(II) and platinum(II) complexes 1-4. The compounds were characterized by elemental analysis, IR, (1)H and (31)P NMR spectroscopy. The molecular structures of 2, 3 and 4 were confirmed by X-ray crystallography. All the three molecular structures crystallized in monoclinic C2/c space system. The coordination geometry around the palladium and platinum atoms in respective structures exhibited distorted square planar geometry at the metal centers. The complexes were evaluated in vitro for their cytotoxic activity against human breast (MCF-7) and human colon (HT-29) cancer cells, and they exhibited growth inhibitory activities and selectivity that were superior to the standard compound cisplatin.

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

    PubMed

    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.

  13. Probing the Ag, Au, and Cu electrode/pyridine-α-hydroxymethyl biphenyl phosphine oxide isomer interface with SERS

    NASA Astrophysics Data System (ADS)

    Pięta, Ewa; Proniewicz, Edyta; Boduszek, Bogdan; Olszewski, Tomasz K.; Nattich-Rak, Małgorzata; Kim, Younkyoo

    2015-04-01

    The potential-dependent surface enhanced Raman scattering (SERS) and generalized two-dimensional correlation analysis (G2DCA) methods were used to characterize three pyridine-α-hydroxymethyl biphenyl phosphine oxide isomers: (diphenylphosphoryl)(pyridine-2-yl)methanol (α-Py), (diphenylphosphoryl)(pyridine-3-yl)methanol (β-Py), and (diphenylphosphoryl)(pyridine-4-yl)methanol (γ-Py). The aforementioned compounds were deposited onto Ag, Au, and Cu electrode surfaces under different applied electrode potentials in an aqueous solution at physiological pH. On the basis of the enhancement, broadening, and shift in wavenumbers of individual bands, the geometry of the investigated molecules and influence of substituent position on the adsorption mode (in the α-(2-), β-(3-), and γ-(4-) positions), electrode type, and applied electrode potential were examined. It was found that the SERS spectra are dominated by bands assigned to phenyl (Ph) and pyridine (Py) ring vibrations. However, some differences in the arrangement of the aforementioned fragments were observed with changes to the type of the metal surface and the applied electrode potential.

  14. Ruthenium(III)/phosphine/pyridine complexes applied in the hydrogenation reactions of polar and apolar double bonds

    NASA Astrophysics Data System (ADS)

    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.

  15. Fourier transform infrared study on microemulsion system of potassium salt of bis(2-ethylhexyl) phosphinic acid (HA)

    NASA Astrophysics Data System (ADS)

    Zhou, Weijin; Shi, Nai; Wang, Yi; Chang, Zhiyuan; Wu, JinGuang

    1994-01-01

    To study microemulsion formation in a solvent extraction system is to probe into some basic principles of extraction chemistry in the light of combining extraction chemistry with surface chemistry. In our previous investigations, the microemulsions of the salts of HDEHP and PC88A have been studied systematically by FT-IR. In the experiment, we observed the change of peak positions and intensities of P equals O, P-O-C and P-O-H groups during saponification and hydration, and discovered that the peak of P-O-C splits apart into 1045 and 1075 cm-1. The vibration frequency of the P-O-C group in HDEHP and PC88A is quite close to the symmetric stretching frequency of the POO- group, and thus causes difficulties in the study of their peak position and absorbance variation. For this reason we synthesized bis(2-ethylhexyl) phosphinic acid without the P-O-C group. Infrared spectra in the range of 800 - 4000 cm-1 of this microemulsion system was studied.

  16. A facile phosphine-free method for synthesizing PbSe nanocrystals with strong optical limiting effects.

    PubMed

    Wang, Tian-Ming; Gao, Bao; Wang, Qiang; Zhao, Min; Kang, Kai-Bin; Xu, Zhu-Guo; Zhang, Hao-Li

    2013-05-01

    PbSe semiconductor nanocrystals (NCs) have attracted ever-growing interest owing to both their fundamental physics and potential applications in a diverse range of fields such as optoelectronic devices and nonlinear optics. The current fabrication strategy for colloidal PbSe NCs, however, frequently involves acutely toxic reagents and tedious reaction procedures, and is plagued by products with poorly controlled size and morphology. Herein, we report a facile, low-cost, and phosphine-free method for synthesizing PbSe NCs, which provides highly uniform NCs with tunable mid-IR absorption, and they are promising for bio-related applications. These high quality NCs were obtained by the reaction of elemental Se and PbCl2 in oleylamine as both the ligand and reaction medium. The high flexibility and reproducibility of the method reported in this study allows us to synthesize monodispersed PbSe NCs with well-controlled size and morphology. In addition, these products show strong optical limiting effects, and thus hold potential for developing nonlinear optical devices.

  17. Identification of phosphinate dipeptide analog inhibitors directed against the Plasmodium falciparum M17 leucine aminopeptidase as lead antimalarial compounds.

    PubMed

    Skinner-Adams, Tina S; Lowther, Jonathan; Teuscher, Franka; Stack, Colin M; Grembecka, Jolanta; Mucha, Artur; Kafarski, Pawel; Trenholme, Katharine R; Dalton, John P; Gardiner, Donald L

    2007-11-29

    Previous studies have pinpointed the M17 leucyl aminopeptidase of Plasmodium falciparum (PfLAP) as a target for the development of new antimalarials. This metallo-exopeptidase functions in the terminal stages of hemoglobin digestion and is inhibited by bestatin, a natural analog of Phe-Leu. By screening novel phosphinate dipeptide analogues for inhibitory activity against recombinant PfLAP, we have discovered two compounds, 4 (hPheP[CH2]Phe) and 5 (hPheP[CH2]Tyr), with inhibitory constants better than bestatin. These compounds are fast, tight-binding inhibitors that make improved contacts within the active site of PfLAP. Both compounds inhibit the growth of P. falciparum in vitro, exhibiting IC50 values against the chloroquine-resistant clone Dd2 of 20-40 and 12-23 muM, respectively. While bestatin exhibited some in vivo activity against Plasmodium chabaudi chabaudi, compound 4 reduced parasite burden by 92%. These studies establish the PfLAP as a prime target for the development of antimalarial drugs and provide important new lead compounds.

  18. Syntheses, characterization and antifungal activity of heteroleptic nickel(II) complexes with N-alkylsulfonyldithiocarbimates and phosphines

    NASA Astrophysics Data System (ADS)

    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.

  19. Directed Regulation of Multienzyme Complexes of 2-Oxo Acid Dehydrogenases Using Phosphonate and Phosphinate Analogs of 2-Oxo Acids.

    PubMed

    Artiukhov, A V; Graf, A V; Bunik, V I

    2016-12-01

    2-Oxo acid dehydrogenase complexes are important metabolic checkpoints functioning at the intercept of sugar and amino acid degradation. This review presents a short summary of architectural, catalytic, and regulatory principles of the complexes structure and function, based on recent advances in studies of well-characterized family members. Special attention is given to use of synthetic phosphonate and phosphinate analogs of 2-oxo acids as selective and efficient inhibitors of the cognate complexes in biological systems of bacterial, plant, and animal origin. We summarize our own results concerning the application of synthetic analogs of 2-oxo acids in situ and in vivo to reveal functional interactions between 2-oxo acid dehydrogenase complexes and other components of metabolic networks specific to different cells and tissues. Based on our study of glutamate excitotoxicity in cultured neurons, we show how a modulation of metabolism by specific inhibition of its key reaction may be employed to correct pathologies. This approach is further developed in our study on the action of the phosphonate analog of 2-oxoglutarate in animals. The study revealed that upregulation of 2-oxoglutarate dehydrogenase complex is involved in animal stress response and may provide increased resistance to damaging effects, underlying so-called preconditioning. The presented analysis of published data suggests synthetic inhibitors of metabolic checkpoints as promising tools to solve modern challenges of systems biology, metabolic engineering, and medicine.

  20. Addition of Zn during the phosphine-based synthesis of indium phospide quantum dots: doping and surface passivation.

    PubMed

    Mordvinova, Natalia E; Vinokurov, Alexander A; Lebedev, Oleg I; Kuznetsova, Tatiana A; Dorofeev, Sergey G

    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 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.

  1. 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.

    PubMed

    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)<10%. A method comparability study was performed using peptide mapping LC-MS as an orthogonal measurement. For the range of 1-40% trisulfides, the analysis demonstrates that, on average, HILICCAD reads between 0.95 and 1.10 times the 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.

  2. Chlorido(chloro­diphenyl­phosphine-κP)(diphenyl­piperidinophosphine-κP)(η5-penta­methyl­cyclo­penta­dien­yl)ruthenium(II)

    PubMed Central

    Jantscher, Florian; Kirchner, Karl; Mereiter, Kurt

    2009-01-01

    The title compound, [Ru(C10H15)Cl(C12H10ClP)(C17H20NP)], is a half-sandwich complex of RuII with the chloro­diphenyl­phosphine ligand formed from the diphenyl­piperidinophosphine and chlorine of the precursor complex [Ru(η5-C5Me5)(κ1P—Ph2PNC5H10)Cl2] by an unexpected reaction with NaBH4. The complex has a three-legged piano-stool geometry, with Ru—P bond lengths of 2.2598 (5) Å for the chloro­phosphine and 2.3303 (5) Å for the amino­phosphine. PMID:21583392

  3. PROBING THE CARBON–PHOSPHORUS BOND COUPLING IN LOW-TEMPERATURE PHOSPHINE (PH{sub 3})–METHANE (CH{sub 4}) INTERSTELLAR ICE ANALOGUES

    SciTech Connect

    Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I.

    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.

  4. Rotational resonance determination of the structure of an enzyme-inhibitor complex: Phosphorylation of an (aminoalkyl)phosphinate inhibitor of D-alanyl-D-alanine ligase by ATP

    SciTech Connect

    McDermott, A.E.; Creuzet, F.; Griffin, R.G. ); Zawadzke, L.E.; Ye, Qizhuang; Walsh, C.T. )

    1990-06-19

    The authors have used a newly developed solid-state NMR method, rotational resonance, to establish the structure of an inhibited complex formed upon reaction of D-alanyl-D-alanine ligase, ATP, and the aminoalkyl dipeptide analogue (1(S)-aminoethyl)(2-carboxy-2(R)-methyl-1-ethyl)phosphinic acid (Ib). Analogue Ib was determined to be an ATP-dependent, slow-binding inhibitor of the D-Ala-D-Ala ligase from Salmonella typhimurium, with an enzyme-inhibitor half-life of 17 days at 37{degree}C. The inhibited complex shows a {sup 31}P NMR spectrum which is very different from that which would arise from a mixture of the free inhibitor and ATP. Four well-resolved lines were observed. A rotational resonance the spectrum shows evidence for strong dipolar couplings between the phosphinate phosphorus and a phosphate ester species. The dipolar coupling between the phosphorus signals at 53 and {minus}3 ppm was measured at rotational resonance by use of numerical simulations of both the line shape of the signal and the profile of magnetization transfer between the two sites. The measured coupling, 1.0 {plus minus} 0.2 kHz, indicates that the two species are bridged in a P-O-P linkage, with a P-P through-space distance of 2.7 {plus minus} 0.2 {angstrom}. This proves that the mechanism of inactivation involves phosphorylation of the enzyme-bound inhibitor by ATP to form a phosphoryl-phosphinate adduct.

  5. PCN pincer palladium(II) complex catalyzed enantioselective hydrophosphination of enones: synthesis of pyridine-functionalized chiral phosphine oxides as NC(sp(3))O pincer preligands.

    PubMed

    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.).

  6. Structure and Reactivity of [(L•Pd)n•(1,5-cyclooctadiene)] (n=1–2) Complexes Bearing Biaryl Phosphine Ligands

    PubMed Central

    Lee, Hong Geun; Milner, Phillip J.; Colvin, Michael T.; Andreas, Loren; Buchwald, Stephen L.

    2014-01-01

    The structure of the stable Pd(0) precatalyst [(1,5-cyclooctadiene)(L•Pd)2] (L = AdBrettPhos) for the Pd-catalyzed fluorination of aryl triflates has been further studied by solid state NMR and X-ray cystrallography of the analogous N-phenylmaleimide complex. The reactivity of this complex with CDCl3 to form a dearomatized complex is also presented. In addition, studies suggest that related bulky biaryl phosphine ligands form similar complexes, although the smaller ligand BrettPhos forms a monomeric [(1,5-cyclooctadiene)(L•Pd)] species instead. PMID:25346547

  7. Phosphine-mediated cascade reaction of azides with MBH-acetates of acetylenic aldehydes to substituted pyrroles: a facile access to N-fused pyrrolo-heterocycles.

    PubMed

    Reddy, Chada Raji; Reddy, Motatipally Damoder; Srikanth, Boinapally

    2012-06-07

    One-pot synthesis of substituted pyrroles by a cascade reaction of azides with Morita-Baylis-Hillman acetates of acetylenic aldehydes is described and the reaction is efficiently mediated by triphenyl phosphine at room temperature. Sodium azide is successfully used to provide N-unsubstituted pyrroles, while alkyl azides afforded the corresponding N-alkylated pyrroles through a sequence of allylic substitution/azide reduction/cycloisomerization reactions. The obtained products have provided a new entry to indolizino indoles, pyrrolo isoquinolines and 8-oxo-5,6,7,8-tetrahydroindolizine.

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

    PubMed

    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.

  9. Chiral Platinum(II) Complexes Featuring Phosphine and Chloroquine Ligands as Cytotoxic and Monofunctional DNA-Binding Agents.

    PubMed

    Villarreal, Wilmer; Colina-Vegas, Legna; Rodrigues de Oliveira, Clayton; Tenorio, Juan C; Ellena, Javier; Gozzo, Fábio C; Cominetti, Marcia Regina; Ferreira, Antonio G; Ferreira, Marco Antonio Barbosa; Navarro, Maribel; Batista, Alzir A

    2015-12-21

    Chiral molecules in nature are involved in many biological events; their selectivity and specificity make them of great interest for understanding the behavior of bioactive molecules, by providing information about the chiral discrimination. Inspired by these conformational properties, we present the design and synthesis of novel chiral platinum(II) complexes featuring phosphine and chloroquine ligands with the general formula [PtCl(P)2(CQ)]PF6 (where (P)2 = triphenylphosphine (PPh3) (5), 1,3-bis(diphenylphosphine)propane (dppp) (6), 1,4-bis(diphenylphosphine)butane (dppb) (7), 1,1'-bis(diphenylphosphine)ferrocene (dppf) (8), and CQ = chloroquine] and their precursors of the type [PtCl2(P)2] are described. The complexes were characterized by elemental analysis, absorption spectroscopy in the infrared and ultraviolet-visible (UV-vis) regions, multinuclear ((1)H, (13)C, (31)P, (15)N, and (195)Pt) NMR spectroscopy, cyclic voltammetry, and mass spectrometry (in the case of chloroquine complexes). The interactions of the new platinum-chloroquine complexes with both albumin (BSA), using fluorescence spectroscopy, and DNA, by four widely reported methods were also evaluated. These experiments showed that these Pt-CQ complexes interact strongly with DNA and have high affinities for BSA, in contrast to CQ and CQDP (chloroquine diphosphate), which interact weakly with these biomolecules. Additional assays were performed in order to investigate the cytotoxicity of the platinum complexes against two healthy cell lines (mouse fibroblasts (L929) and the Chinese hamster lung (V79-4)) and four tumor cell lines (human breast (MDA-MB-231 and MCF-7), human lung (A549), and human prostate (DU-145)). The results suggest that the Pt-CQ complexes are generally more cytotoxic than the free CQ, showing that they are promising as anticancer drugs.

  10. Bis(phosphinic)diamido yttrium amide, alkoxide, and aryloxide complexes: an evaluation of lactide ring-opening polymerization initiator efficiency.

    PubMed

    Platel, Rachel H; White, Andrew J P; Williams, Charlotte K

    2011-08-15

    The synthesis and characterization of a series of bis(phosphinic)diamido yttrium alkoxide, amide, and aryloxide initiators are reported. The new complexes are characterized using multinuclear nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and, in some cases, X-ray crystallography. The alkoxide complexes are all dimeric in both the solid state and in solution, as are the amide complexes substituted with iso-propyl or phenyl groups on the phosphorus atoms. On the other hand, increasing the steric hindrance of the phosphorus substituents (tert-butyl), enables isolation of mononuclear yttrium amide complexes with either 2,2-dimethylpropylene or ethylene diamido ligand backbones. The complex of 2,6-di-tert-butyl-4-methylphenoxide is also mononuclear. All the new complexes are efficient initiators for rac-lactide ring-opening polymerization. The polymerization kinetics are compared and pseudo first order rate constants, k(obs), determined. The polymerization control is also discussed, by monitoring the number-averaged molecular weight, M(n), and polydispersity index, PDI, obtained using gel permeation chromatography (GPC). The alkoxide complexes are the most efficient initiators, showing very high rates and good polymerization control, behavior consistent with rapid rates of initiation. The phenoxide and amide complexes are less efficient as manifest by nonlinear regions in the kinetic plots, lower values for k(obs), and reduced polymerization control. One of the mononuclear yttrium amide complexes shows heteroselectivity in the polymerization of rac-lactide; however, this effect is reduced on changing the initiating group to phenoxide or on changing the ancillary ligand diamido backbone group.

  11. High-efficiency turquoise-blue electrophosphorescence from a Pt(II)-pyridyltriazolate complex in phosphine oxide host

    SciTech Connect

    Bhansali, Unnat S; Polikarpov, Evgueni; Swensen, James S; Chen, Wei; Jia, Huiping; Gaspar, Daniel J; Gnade, Bruce E; Padmaperuma, Asanga B; Omary, Mohammad A

    2009-12-10

    We have demonstrated high-efficiency turquoise-blue electrophosphorescence from the complex Pt(ptp)2 = bis[3,5–bis(2–pyridyl)–1,2,4–triazolato]platinum(II) doped in the wide band-gap, ambipolar phosphine oxide host HM-A1 = 4-(diphenylphosphoryl)-N,N-diphenylaniline. For devices with 5% Pt(ptp)2 doping in HM-A1, we have achieved a peak external quantum efficiency and power efficiency of (11.8 ± 0.6) % and (61.2 ± 5.9) lm/W with high-pixel values of 13.1 % and 70.6 lm/W, respectively. These parameters maintained (10.6 ± 0.2) % and (40.3 ± 1.2) lm/W at a brightness of 1000 cd/m2 with high-pixel values of 10.8 % and 41.6 lm/W. Examination of several device structures suggests that the high performance is due to improved charge transport and exciton confinement in the emissive region. Devices with 1-10% doping concentration exhibit turquoise-blue emissions (λmax ~ 480 nm) with a monotonic decrease in monomer/excimer intensity ratio upon increasing the doping concentration. Devices with 5% doping exhibit sufficient blue contribution to attain white light upon combination with highly-doped or neat emissive layers of the same phosphor; the work herein represents a significant backdrop toward optimizing such white OLEDs given the performance metrics above, which to our knowledge represent the highest performance for OLEDs that exhibit blue emission maxima.

  12. Structure-Guided, Single-Point Modifications in the Phosphinic Dipeptide Structure Yield Highly Potent and Selective Inhibitors of Neutral Aminopeptidases

    PubMed Central

    2014-01-01

    Seven crystal structures of alanyl aminopeptidase from Neisseria meningitides (the etiological agent of meningitis, NmAPN) complexed with organophosphorus compounds were resolved to determine the optimal inhibitor–enzyme interactions. The enantiomeric phosphonic acid analogs of Leu and hPhe, which correspond to the P1 amino acid residues of well-processed substrates, were used to assess the impact of the absolute configuration and the stereospecific hydrogen bond network formed between the aminophosphonate polar head and the active site residues on the binding affinity. For the hPhe analog, an imperfect stereochemical complementarity could be overcome by incorporating an appropriate P1 side chain. The constitution of P1′-extended structures was rationally designed and the lead, phosphinic dipeptide hPhePψ[CH2]Phe, was modified in a single position. Introducing a heteroatom/heteroatom-based fragment to either the P1 or P1′ residue required new synthetic pathways. The compounds in the refined structure were low nanomolar and subnanomolar inhibitors of N. meningitides, porcine and human APNs, and the reference leucine aminopeptidase (LAP). The unnatural phosphinic dipeptide analogs exhibited a high affinity for monozinc APNs associated with a reasonable selectivity versus dizinc LAP. Another set of crystal structures containing the NmAPN dipeptide ligand were used to verify and to confirm the predicted binding modes; furthermore, novel contacts, which were promising for inhibitor development, were identified, including a π–π stacking interaction between a pyridine ring and Tyr372. PMID:25192493

  13. Genetic linkage analysis of the lesser grain borer Rhyzopertha dominica identifies two loci that confer high-level resistance to the fumigant phosphine.

    PubMed Central

    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

  14. Metabolism of aspirin and procaine in mice pretreated with O-4-nitrophenyl methyl(phenyl)phosphinate or O-4-nitrophenyl diphenylphosphinate

    SciTech Connect

    Joly, J.M.; Brown, T.M.

    1986-07-01

    Concentrations of (carboxyl-/sup 14/C)procaine in blood of mice were increased threefold for 27 min by exposure to O-4-nitrophenyl diphenylphosphinate 2 hr prior to (carboxyl-/sup 14/C)procaine injection ip, while there was no effect of O-4-nitrophenyl methyl(phenyl)phosphinate pretreatment. There was no effect of either organophosphinate on the primary hydrolysis of (acetyl-l-/sup 14/C)aspirin when assessed by the expiration of (/sup 14/C)carbon dioxide; however, O-4-nitrophenyl diphenylphosphinate pretreatment produced transient increases in blood concentrations of both (carboxyl-/sup 14/C)aspirin and (carboxyl-/sup 14/C)salicylic acid following administration of (carboxyl-/sup 14/C)aspirin. Liver carboxylesterase activity in O-4-nitrophenyl diphenylphosphinate pretreated mice was 11% of control activity. These results indicate the potential for drug interaction with O-4-nitrophenyl diphenylphosphinate but not with O-4-nitrophenyl methyl(phenyl)phosphinate. It appears that liver carboxylesterase activity has a minor role in hydrolysis of aspirin in vivo, but may be more important in procaine metabolism.

  15. 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.

    PubMed

    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.

  16. The Role of Tris(2-carboxyethyl)phosphine Reducing Agent in the Controlled Formation of α,ω-Alkanedithiols Monolayers on Au(111) with Monocoordinated and Bicoordinated Configurations.

    PubMed

    Euti, Esteban M; Vélez-Romero, Patricio; Leiva, Ezequiel P M; Macagno, Vicente A; Paredes-Olivera, Patricia A; Patrito, E Martín; Cometto, Fernando P

    2016-09-20

    The addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density functional theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the -SH groups of the dithiol to the phosphorus atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers.

  17. Structure-guided, single-point modifications in the phosphinic dipeptide structure yield highly potent and selective inhibitors of neutral aminopeptidases.

    PubMed

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

    2014-10-09

    Seven crystal structures of alanyl aminopeptidase from Neisseria meningitides (the etiological agent of meningitis, NmAPN) complexed with organophosphorus compounds were resolved to determine the optimal inhibitor-enzyme interactions. The enantiomeric phosphonic acid analogs of Leu and hPhe, which correspond to the P1 amino acid residues of well-processed substrates, were used to assess the impact of the absolute configuration and the stereospecific hydrogen bond network formed between the aminophosphonate polar head and the active site residues on the binding affinity. For the hPhe analog, an imperfect stereochemical complementarity could be overcome by incorporating an appropriate P1 side chain. The constitution of P1'-extended structures was rationally designed and the lead, phosphinic dipeptide hPhePψ[CH2]Phe, was modified in a single position. Introducing a heteroatom/heteroatom-based fragment to either the P1 or P1' residue required new synthetic pathways. The compounds in the refined structure were low nanomolar and subnanomolar inhibitors of N. meningitides, porcine and human APNs, and the reference leucine aminopeptidase (LAP). The unnatural phosphinic dipeptide analogs exhibited a high affinity for monozinc APNs associated with a reasonable selectivity versus dizinc LAP. Another set of crystal structures containing the NmAPN dipeptide ligand were used to verify and to confirm the predicted binding modes; furthermore, novel contacts, which were promising for inhibitor development, were identified, including a π-π stacking interaction between a pyridine ring and Tyr372.

  18. Structure-Guided, Single-Point Modifications in the Phosphinic Dipeptide Structure Yield Highly Potent and Selective Inhibitors of Neutral Aminopeptidases

    SciTech Connect

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

    2014-10-09

    Seven crystal structures of alanyl aminopeptidase from Neisseria meningitides (the etiological agent of meningitis, NmAPN) complexed with organophosphorus compounds were resolved to determine the optimal inhibitor–enzyme interactions. The enantiomeric phosphonic acid analogs of Leu and hPhe, which correspond to the P1 amino acid residues of well-processed substrates, were used to assess the impact of the absolute configuration and the stereospecific hydrogen bond network formed between the aminophosphonate polar head and the active site residues on the binding affinity. For the hPhe analog, an imperfect stereochemical complementarity could be overcome by incorporating an appropriate P1 side chain. The constitution of P1'-extended structures was rationally designed and the lead, phosphinic dipeptide hPhePψ[CH2]Phe, was modified in a single position. Introducing a heteroatom/heteroatom-based fragment to either the P1 or P1' residue required new synthetic pathways. The compounds in the refined structure were low nanomolar and subnanomolar inhibitors of N. meningitides, porcine and human APNs, and the reference leucine aminopeptidase (LAP). The unnatural phosphinic dipeptide analogs exhibited a high affinity for monozinc APNs associated with a reasonable selectivity versus dizinc LAP. In conclusion, another set of crystal structures containing the NmAPN dipeptide ligand were used to verify and to confirm the predicted binding modes; furthermore, novel contacts, which were promising for inhibitor development, were identified, including a π–π stacking interaction between a pyridine ring and Tyr372.

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

    PubMed

    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.

  20. Effect of the Phosphine Steric and Electronic Profile on the Rh-Promoted Dehydrocoupling of Phosphine–Boranes

    PubMed Central

    2014-01-01

    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)(η6-FC6H5)][BArF4] [L = Ph2P(CH2)3PPh2, ArF = 3,5-(CF3)2C6H3] with 2 equiv of H3B·PR2H affords [Rh(L)(H)(σ,η-PR2BH3)(η1-H3B·PR2H)][BArF4]. These complexes undergo dehydrocoupling to give the diboraphosphine complexes [Rh(L)(H)(σ,η2-PR2·BH2PR2·BH3)][BArF4]. With electron-withdrawing groups on the phosphine–borane there is the parallel formation of the products of B–P cleavage, [Rh(L)(PR2H)2][BArF4], 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){η2-H3B·P(Ad)2H}][BArF4], that undergoes B–P bond cleavage to give [Rh(L){η1-H3B·P(Ad)2H}{P(Ad)2H}][BArF4]. 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. PMID:24617924

  1. Alkylthiol-enabled Se powder dissolution in oleylamine at room temperature for the phosphine-free synthesis of copper-based quaternary selenide nanocrystals.

    PubMed

    Liu, Yi; Yao, Dong; Shen, Liang; Zhang, Hao; Zhang, Xindong; Yang, Bai

    2012-05-02

    Enhancement of Se solubility in organic solvents without the use of alkylphosphine ligands is the key for phosphine-free synthesis of selenide semiconductor nanocrystals (NCs). In this communication, we demonstrate the dissolution of elemental Se in oleylamine by alkylthiol reduction at room temperature, which generates soluble alkylammonium selenide. This Se precursor is highly reactive for hot-injection synthesis of selenide semiconductor NCs, such as Cu(2)ZnSnSe(4), Cu(InGa)Se(2), and CdSe. In the case of Cu(2)ZnSnSe(4), for example, the as-synthesized NCs possessed small size, high size monodispersity, strong absorbance in the visible region, and in particular a promising increase in photocurrent under AM1.5 illumination. The current preparation of the Se precursor is simple and convenient, which will promote the synthesis and practical applications of selenide NCs.

  2. Third phase formation in the extraction of Nd(III) by octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphine oxide (O{Phi}CMPO)

    SciTech Connect

    Suresh, A.; Brahmmananda Rao, C.V.S.; Sabharwal, K.N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    1999-01-01

    Third phase formation in the extraction of Nd(III) by 0.2 M Octyl(Phenyl)-N,N-Diisobutyl Carbamoyl methyl phosphine oxide (O{Phi}CMPO) in n-dodecane has been studied with tri-n-butyl phosphate (TBP) and tri-n-amyl phosphate (TAP) as modifiers to provide a comparison between these two modifier systems. The effect of concentration of TAP as modifier for the extraction of Nd(III) by 0.2 M O{Phi}CMPO has been studied. The extraction of Nd(III) by TAP/n-dodecane in the absence of O{Phi}CMPO has also been studied and the results are reported here.

  3. Extraction of Am(III), Eu(III) and U(VI) from perchloric acid and mixtures of acids by dialkyl-(diaryl) [diethylcarbamoylmethyl] phosphine oxides

    SciTech Connect

    Chmutova, M.K.; Litvina, M.N.; Nesterova, N.P.; Myasoedov, B.F.; Kabachnik, M.I.

    1992-07-01

    Extraction of Am(III), and Eu(III) and U(VI) from perchloric acid solutions by dialkyl(diaryl) [diethyl-carbamoylmethyl] phosphine oxides (CMPO) has been investigated. It has been shown that elements are extracted more effectively from perchloric acid solutions than from nitric acid. An `anomalous aryl effect` increases sufficiently in perchloric media as compared with nitric media. Solvate numbers of elements also increase in perchloric acid, they being extremely high for aryl-substituted reagents and not so high for alkyl-substituted compounds. It has been shown that in HNO{sub 3} and HClO{sub 4} solutions the value of `anomalous aryl effect` directly depends on the difference in values of element solvate numbers in complexes with aryl- and alkyl-substituted CMPO. Am(III), Eu(III) and U(VI) are not practically extracted from phosphoric and sulphuric acids by CMPO solutions. 16 refs., 7 figs., 3 tabs.

  4. Structure-Guided, Single-Point Modifications in the Phosphinic Dipeptide Structure Yield Highly Potent and Selective Inhibitors of Neutral Aminopeptidases

    DOE PAGES

    Vassiliou, Stamatia; Węglarz-Tomczak, Ewelina; Berlicki, Łukasz; ...

    2014-10-09

    Seven crystal structures of alanyl aminopeptidase from Neisseria meningitides (the etiological agent of meningitis, NmAPN) complexed with organophosphorus compounds were resolved to determine the optimal inhibitor–enzyme interactions. The enantiomeric phosphonic acid analogs of Leu and hPhe, which correspond to the P1 amino acid residues of well-processed substrates, were used to assess the impact of the absolute configuration and the stereospecific hydrogen bond network formed between the aminophosphonate polar head and the active site residues on the binding affinity. For the hPhe analog, an imperfect stereochemical complementarity could be overcome by incorporating an appropriate P1 side chain. The constitution of P1'-extendedmore » structures was rationally designed and the lead, phosphinic dipeptide hPhePψ[CH2]Phe, was modified in a single position. Introducing a heteroatom/heteroatom-based fragment to either the P1 or P1' residue required new synthetic pathways. The compounds in the refined structure were low nanomolar and subnanomolar inhibitors of N. meningitides, porcine and human APNs, and the reference leucine aminopeptidase (LAP). The unnatural phosphinic dipeptide analogs exhibited a high affinity for monozinc APNs associated with a reasonable selectivity versus dizinc LAP. In conclusion, another set of crystal structures containing the NmAPN dipeptide ligand were used to verify and to confirm the predicted binding modes; furthermore, novel contacts, which were promising for inhibitor development, were identified, including a π–π stacking interaction between a pyridine ring and Tyr372.« less

  5. Novel gold(I) complexes with 5-phenyl-1,3,4-oxadiazole-2-thione and phosphine as potential anticancer and antileishmanial agents.

    PubMed

    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 <0.10 to 1.66 μM against cancer cell lines and from 0.9 to 4.2 μM for Leishmania infantum intracellular amastigotes. Compound (6-A) was very selective against murine melanoma B16F10, colon cancer CT26.WT cell lines and L. infantum intracellular amastigotes. Compound (7-B) presented the highest anticancer activity against both cancer cell lines while the promising antileishmanial lead was compound (6-A). Tiethylphosphine 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.

  6. Carbon­yl[4-(2,3-dimethyl­phenyl­amino)pent-3-en-2-onato-κ2 N,O](triphenyl­phosphine-κP)rhodium(I)

    PubMed Central

    Venter, Gertruida J. S.; Steyl, Gideon; Roodt, Andreas

    2009-01-01

    In the title compound, [Rh(C13H16NO)(C18H15P)(CO)], the coordination geometry of the RhI atom is square-planar, formed by the coordinating N and O atoms of the bidentate enaminoketonate ligand, one C atom from the carbonyl group and a P atom from triphenyl­phosphine. The complex displays a 0.591 (3):0.409 (3) ratio disorder of the phenyl unit of the monoanionic N,O-bidentate ligand. Intra­molecular hydrogen bonding is observed between a C—H group of the triphenyl­phosphine unit and the O atom of the enamino­ketonate ligand. PMID:21578084

  7. Extraction mechanism of Sc(III) and separation from Th(IV), Fe(III) and Lu(III) with bis(2,4,4-trimethylpentyl)phosphinic acid in n-hexane from sulphuric acid solutions

    SciTech Connect

    Wang, Chun; Li, Deqian )

    1994-06-01

    The extraction equilibrium data of sulphuric acid and scandium(III) with bis(2,4,4-trimethylpentyl)phosphinic acid (H[BTMPP]) from sulphuric acid solutions have been obtained. There are two extraction mechanisms of scandium(III) with H[BTMPP] at different ranges of aqueous acidity. The extraction of Sc(III) proceeds according to a cation exchange reaction at lower aqueous acidity and to a solvating reaction at higher acidity. The practicability of separating Sc(III) from Th(IV),Fe(III) and Lu(III) by controlling the aqueous acidity was discussed. The effect of temperature on extraction of Sc(III) was observed and thermodynamic functions were calculated. IR and NMR spectra were made for organic extracts. The extraction characteristics of H[BTMPP] and di(2-ethylhexyl)phosphinic acid (H[DEHP]) were contrasted to obtain more information about extraction with H[BTMPP]. 12 refs., 6 figs., 1 tab.

  8. Phosphoryl group as a strong σ-donor anionic phosphine-type ligand: a combined experimental and theoretical study on long-lived room temperature luminescence of the [Ru(tpy)(bpy)(Ph2PO)]+ complex.

    PubMed

    Lebon, Emilie; Sylvain, Rémy; Piau, Rémi E; Lanthony, Cloé; Pilmé, Julien; Sutra, Pierre; Boggio-Pasqua, Martial; Heully, Jean-Louis; Alary, Fabienne; Juris, Alberto; Igau, Alain

    2014-02-17

    A phosphoryl Ru(II) polypyridyl complex was prepared in a one-pot process. Theoretical analysis suggests that the phosphoryl ligand may be viewed as a strong σ-donor anionic phosphine L-type ligand. State-of-the-art free-energy profile calculations on the excited states demonstrate that both favorable thermodynamic and kinetic factors are responsible for the remarkable room temperature luminescence properties of the phosphoryl complex.

  9. Carbonyl[4-(2,6-dimethyl­phenyl­amino)pent-3-en-2-onato-κ2 N,O](triphenyl­phosphine-κP)rhodium(I) acetone hemi­solvate

    PubMed Central

    Venter, Gertruida J. S.; Steyl, Gideon; Roodt, Andreas

    2009-01-01

    In the title compound, [Rh(C13H16NO)(C18H15P)(CO)]·0.5C3H6O, the Rh atom exhibits a square-planar coordination geometry, being coordinated by the N and O atoms of the bidentate β-diketonato ligand, a P atom from the triphenyl­phosphine unit and a C atom from the carbonyl group. The asymmetric unit also contains a disordered half-mol­ecule, lying about an inversion center, of the acetone solvate. Inter­molecular C—H⋯O hydrogen bonds are observed between a C—H group of the triphenyl­phosphine unit and a carbonyl O atom and between the methyl group of the enamino­ketonato backbone and the solvent O atom. In addition, an intra­molecular inter­action is observed between a C—H group of the triphenyl­phosphine unit and the O atom of the enamino­ketonato ligand. PMID:21578632

  10. Aluminum dialkyl phosphinate flame retardants and their hydrolysates: analytical method and occurrence in soil and sediment samples from a manufacturing site.

    PubMed

    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

  11. Mn2+ complexes of 1-oxa-4,7-diazacyclononane based ligands with acetic, phosphonic and phosphinic acid pendant arms: stability and relaxation studies.

    PubMed

    Drahoš, Bohuslav; Pniok, Miroslav; Havlíčková, Jana; Kotek, Jan; Císařová, Ivana; Hermann, Petr; Lukeš, Ivan; Tóth, Eva

    2011-10-21

    A new class of macrocyclic ligands based on 1-oxa-4,7-diazacyclononane was synthesized and their Mn(2+) complexes were investigated with respect to stability and relaxation properties. Each ligand has two pendant arms involving carboxylic (H(2)L(1)--1-oxa-4,7-diazacyclononane-4,7-diacetic acid), phosphonic (H(4)L(2)--1-oxa-4,7-diazacyclononane-4,7-bis(methylenephosphonic acid)), phosphinic (H(2)L(3)--1-oxa-4,7-diazacyclononane-4,7-bis(methylenephosphinic acid)) or phenylphosphinic (H(2)L(4)--1-oxa-4,7-diazacyclononane-4,7-bis[methylene(phenyl)phosphinic acid]) acid moieties. H(2)L(3) and H(2)L(4) were synthesized for the first time. The crystal structure of the Mn(2+) complex with H(2)L(4) confirmed a coordination number of 6 for Mn(2+). The protonation constants of all ligands and the stability constants of their complexes with Mn(2+) and some biologically or biomedically relevant metal ions were determined by potentiometry. The protonation sequence of H(2)L(3) was followed by (1)H and (31)P NMR titration and the second protonation step was attributed to the second macrocyclic nitrogen atom. The potentiometric data revealed a relatively low thermodynamic stability of the Mn(2+) complexes with all ligands investigated. For H(2)L(3) and H(2)L(4), full Mn(2+) complexation cannot be achieved even with 100% ligand excess. The transmetallation of MnL(1) and MnL(2) with Zn(2+) was too fast to be followed at pH 6. Variable temperature (1)H NMRD and (17)O NMR measurements have been performed on MnL(1) and MnL(2) to provide information on water exchange and rotational dynamics. The (17)O chemical shifts indicate hydration equilibrium between mono- and bishydrated species for MnL(1), while MnL(2) is monohydrated. The water exchange is considerably faster on MnL(1) (k(ex)(298) = 1.2 × 10(9) s(-1)) than on MnL(2) (k(ex)(298) = 1.2 × 10(7) s(-1)). Small endogenous anions (phosphate, carbonate, citrate) do not replace the coordinated water in either of the complexes, but they

  12. Halloysite-nanotubes supported FeNi alloy nanoparticles for catalytic decomposition of toxic phosphine gas into yellow phosphorus and hydrogen.

    PubMed

    Tang, Xuejiao; Li, Lili; Shen, Boxiong; Wang, Chengjun

    2013-05-01

    The FeNi alloy nanoparticles (FeNi and BFeNi) supported on natural halloysite nanotubes (HNTs) were prepared for catalytic decomposition of toxic phosphine (PH₃) to yellow phosphorus and hydrogen. The Fourier transform infrared spectroscopy, X-ray diffraction, inductively coupled plasma, scanning electron microscope, and hydrogen temperature-programmed reduction tests were carried out to characterize the physicochemical properties of HNTs and the prepared nano-catalysts. Nearly 100% PH₃ was decomposed into yellow phosphorus and hydrogen at 420 °C with prepared FeNi/HNTs catalysts. Metallic Ni and Fe₃O₄ could be the catalytic active sites in FeNi/HNTs for PH₃ decomposition under the low temperature. The boron (B) additives decrease the catalytic activity of FeNi/HNTs for PH₃ decomposition due to the formation of the spinal NiFe₂O₄ and Fe₂B which replace the active Fe₃O₄ and metallic Ni in catalysts. The developed FeNi/HNTs are low-cost and effective catalysts for air-pollution control and recycle of the hazardous waste PH₃ gas in industry.

  13. Broad HOMO-LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core.

    PubMed

    Dixon, Isabelle M; Lebon, Emilie; Loustau, Gilles; Sutra, Pierre; Vendier, Laure; Igau, Alain; Juris, Alberto

    2008-11-07

    The synthesis of new ruthenium(II) terpyridine bipyridine complexes bearing a phosphorus(III) ligand is presented. The steric and electronic properties of the phosphorus ligand were varied using aminophosphines, alkyl and aryl phosphites and the bulky tri(isopropyl)phosphine. All complexes were characterized by multi-nuclear NMR spectroscopy, mass spectrometry and X-ray diffraction analysis. The electronic properties of the complexes were probed by cyclic voltammetry, absorption and luminescence spectroscopy. The complexes do not show luminescence at room temperature, whereas at 77 K in an alcoholic matrix, emission is observed in the range 600-650 nm with lifetimes of 3.5-5.5 micros, originating from 3MLCT states. The MLCT transition spans over 65 nm, which corresponds to a variation of 0.4 eV in the HOMO-LUMO gap. The oxidation potential of the ruthenium varies over a broad range of 290 mV, from +1.32 V vs. SCE with L = PiPr3 to +1.61 V vs. SCE with L = P(OPh)3. This range is unprecedented upon the variation of a single monodentate ligand coordinated by the same heteroatom in the same oxidation and charge states. This work underlines the specific capacity of phosphorus in bringing up a large variety of electronic properties by changing its substituents.

  14. Synthesis, structure and reactivity of Pd and Ir complexes based on new lutidine-derived NHC/phosphine mixed pincer ligands.

    PubMed

    Sánchez, Práxedes; Hernández-Juárez, Martín; Álvarez, Eleuterio; Paneque, Margarita; Rendón, Nuria; Suárez, Andrés

    2016-11-14

    Coordination studies of new lutidine-derived hybrid NHC/phosphine ligands (CNP) to Pd and Ir have been performed. Treatment of the square-planar [Pd(CNP)Cl](AgCl2) complex 2a with KHMDS produces the selective deprotonation at the CH2P arm of the pincer to yield the pyridine-dearomatised complex 3a. A series of cationic [Ir(CNP)(cod)](+) complexes 4 has been prepared by reaction of the imidazolium salts 1 with Ir(acac)(cod). These derivatives exhibit in the solid state, and in solution, a distorted trigonal bipyramidal structure in which the CNP ligands adopt an unusual C(axial)-N(equatorial)-P(equatorial) coordination mode. Reactions of complexes 4 with CO and H2 yield the carbonyl species 5a(Cl) and 6a(Cl), and the dihydrido derivatives 7, respectively. Furthermore, upon reaction of complex 4b(Br) with base, selective deprotonation at the methylene CH2P arms is observed. The, thus formed, deprotonated Ir complex 8b reacts with H2 in a ligand-assisted process leading to the trihydrido complex 9b, which can also be obtained by reaction of 7b(Cl) with H2 in the presence of KO(t)Bu. Finally, the catalytic activity of Ir-CNP complexes in the hydrogenation of ketones has been briefly assessed.

  15. Exponential Sum Absorption Coefficients of Phosphine from 2750 to 3550/cm for Application to Radiative Transfer Analyses on Jupiter and Saturn

    NASA Technical Reports Server (NTRS)

    Temma, T.; Baines, K. H.; Butler, R. A. H.; Brown, L. R.; Sagui, L.; Kleiner, I.

    2006-01-01

    PH3 exponential sum k coefficients were computed between 2750 and 3550/cm (2.82-3.64 (microns), in view of future application to radiative transfer analyses of Jupiter and Saturn in a phosphine absorption band near 3 microns. The temperature and pressure of this data set cover the ranges from 80 to 350 K and from 10 (exp -3)to 10(exp 1) bars, respectively. Transmission uncertainty incurred by the use of the k coefficients is smaller than a few percent as long as the radiation is confined above an altitude of a few bars in the giant planets. In spectral regions of weak absorption at high pressures close to 10 bars, contributions from far wings of strong absorption lines must be carefully taken into account. Our data set helps map the three-dimensional distribution of PH3 on the giant planets, revealing their global atmospheric dynamics extending down to the deep interior. The complete k coefficient data set of this work is available at the Web site of the NASA Planetary Data System Atmospheres Node.

  16. Frustrated Lewis pair modification by 1,1-carboboration: disclosure of a phosphine oxide triggered nitrogen monoxide addition to an intramolecular P/B frustrated Lewis pair.

    PubMed

    Liedtke, René; Scheidt, Felix; Ren, Jinjun; Schirmer, Birgitta; Cardenas, Allan Jay P; Daniliuc, Constantin G; Eckert, Hellmut; Warren, Timothy H; Grimme, Stefan; Kehr, Gerald; Erker, Gerhard

    2014-06-25

    The vicinal frustrated Lewis pair (FLP) mes2P-CH2CH2-B(C6F5)2 (3) reacts with phenyl(trimethylsilyl)acetylene by 1,1-carboboration to give the extended C3-bridged FLP 6 featuring a substituted vinylborane subunit. The FLP 6 actively cleaves dihydrogen. The FLP 3 also undergoes a 1,1-carboboration reaction with diphenylphosphino(trimethylsilyl)acetylene to give the P/B/P FLP 11 that features a central unsaturated four-membered heterocyclic P/B FLP and a pendant CH2CH2-Pmes2 functional group. Compound 11 reacts with nitric oxide (NO) by oxidation of the pendant Pmes2 unit to the P(O)mes2 phosphine oxide and N,N-addition of the P/B FLP unit to NO to yield the persistent P/B/PO FLPNO aminoxyl radical 14. This reaction is initiated by P(O)mes2 formation and opening of the central Ph2P···B(C6F5)2 linkage triggered by the pendant CH2CH2-P(O)mes2 group.

  17. Production of Galactooligosaccharides Using β-Galactosidase Immobilized on Chitosan-Coated Magnetic Nanoparticles with Tris(hydroxymethyl)phosphine as an Optional Coupling Agent

    PubMed Central

    Chen, Su-Ching; Duan, Kow-Jen

    2015-01-01

    β-Galactosidase was immobilized on chitosan-coated magnetic Fe3O4 nanoparticles and was used to produce galactooligosaccharides (GOS) from lactose. Immobilized enzyme was prepared with or without the coupling agent, tris(hydroxymethyl)phosphine (THP). The two immobilized systems and the free enzyme achieved their maximum activity at pH 6.0 with an optimal temperature of 50 °C. The immobilized enzymes showed higher activities at a wider range of temperatures and pH. Furthermore, the immobilized enzyme coupled with THP showed higher thermal stability than that without THP. However, activity retention of batchwise reactions was similar for both immobilized systems. All the three enzyme systems produced GOS compound with similar concentration profiles, with a maximum GOS yield of 50.5% from 36% (w·v−1) lactose on a dry weight basis. The chitosan-coated magnetic Fe3O4 nanoparticles can be regenerated using a desorption/re-adsorption process described in this study. PMID:26047337

  18. Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

    PubMed

    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.

  19. Random Mating Between Two Widely Divergent Mitochondrial Lineages of Cryptolestes ferrugineus (Coleoptera: Laemophloeidae): A Test of Species Limits in a Phosphine-Resistant Stored Product Pest.

    PubMed

    Toon, A; Daglish, G J; Ridley, A W; Emery, R N; Holloway, J C; Walter, G H

    2016-10-01

    Effective pest management relies on accurate delimitation of species and, beyond this, on accurate species identification. Mitochondrial COI sequences are useful for providing initial indications in delimiting species but, despite acknowledged limitations in the method, many studies involving COI sequences and species problems remain unresolved. Here we illustrate how such impasses can be resolved with microsatellite and nuclear sequence data, to assess more directly the amount of gene flow between divergent lineages. We use a population genetics approach to test for random mating between two 8 ± 2% divergent COI lineages of the rusty grain beetle, Cryptolestes ferrugineus (Stephens). This species has become strongly resistant to phosphine, a fumigant used worldwide for disinfesting grain. The possibility of cryptic species would have significant consequences for resistance management, especially if resistance was confined to one mitochondrial lineage. We find no evidence of restricted gene flow or nonrandom mating across the two COI lineages of these beetles, rather we hypothesize that historic population structure associated with early Pleistocene climate changes likely contributed to divergent lineages within this species.

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

    SciTech Connect

    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.

  1. 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.

    PubMed

    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.

  2. Phospha-Michael addition reaction of maleimides employing N-heterocyclic phosphine-thiourea as a phosphonylation reagent: synthesis of 1-aryl-2,5-dioxopyrrolidine-3-yl-phosphonate derivatives.

    PubMed

    Molleti, Nagaraju; Bjornberg, Chad; Kang, Jun Yong

    2016-12-07

    N-Heterocyclic phosphine (NHP)-thiourea as a novel phosphonylation reagent has been successfully applied for the phospha-Michael reaction of maleimides under catalyst and additive free reaction conditions. This methodology enables desymmetrization of a variety of maleimide derivatives to provide 1-aryl-2,5-dioxopyrrolidine-3-yl-phosphonates in up to 92% yield. Synthetic manipulation of this Michael adduct afforded an ethylphosphonate and a phosphino lactam. Furthermore, a scale-up experiment for its practical usage as a versatile precursor in organic synthesis was readily demonstrated.

  3. Oligo-nuclear silver thiocyanate complexes with monodentate tertiary phosphine ligands, including novel 'cubane' and 'step' tetramer forms of AgSCN : PR3 (1:1)4.

    PubMed

    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.

  4. A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.

    1982-01-01

    The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

  5. Synthesis, structure, catalytic and calculated non-linear optical properties of cis- and trans-, mer-chlorobis(triphenyl phosphine/triphenyl arsine)-dipicolinato ruthenium III complexes

    NASA Astrophysics Data System (ADS)

    Trivedi, Manoj; Nagarajan, R.; Kumar, Abhinav; Singh, Narendra K.; Rath, Nigam P.

    2011-05-01

    The new mononuclear Ru III complexes cis-, mer-[Ru( k3-dipic)(EPh 3) 2Cl]·2H 2O (E = P ( 1), As ( 2)), (L = 2,6-pyridyldicarboxylate; dipic) have been synthesized and characterized. The X-ray crystal structure of 1 reveals that the coordination geometry around the Ru III center is distorted octahedral in which three sites are occupied by tridentate dipic ligand and remaining three sites are occupied by two mutually cis triphenyl phosphine ligands and one chloride ions. In chloroform solvent, cis-, mer-[Ru( k3-dipic)(EPh 3) 2Cl]·2H 2O (E = P ( 1), As ( 2)) complexes undergoes thermal rearrangement to more stable trans-, mer-[Ru( k3-dipic)(EPh 3) 2Cl] (E = P( 3), As( 4)) complexes. Complexes 1 and 2 show rhombic EPR spectral features, while complex 3 and 4 show tetragonal distortion. The new Ru III complexes 1 and 2 display both Ru III-Ru II reduction and Ru III-Ru IV oxidation processes. These geometric isomers exhibit textbook differences both in spectroscopic as well as structural properties in the solid state. The new complexes 1 and 2 were found to catalyze the oxidation of alcohols to carbonyl derivatives using N-methyl morpholine- N-oxide as co-oxidant. The first static hyperpolarizability ( β) for all of the complexes have been investigated by density functional theory (DFT) which suggests β value increases from trans to cis form. Also, the solvent-induced effects on the non-linear optical properties (NLO) were studied by using self-consistent reaction field (SCRF) method. As the solvent polarity increases, the β value increases monotonically. The electronic absorption bands of 1 have been assigned by time dependent density functional theory (TD-DFT).

  6. Effect of a novel selective and potent phosphinic peptide inhibitor of endopeptidase 3.4.24.16 on neurotensin-induced analgesia and neuronal inactivation.

    PubMed

    Vincent, B; Jiracek, J; Noble, F; Loog, M; Roques, B; Dive, V; Vincent, J P; Checler, F

    1997-06-01

    1. We have examined a series of novel phosphinic peptides as putative potent and selective inhibitors of endopeptidase 3.4.24.16. 2. The most selective inhibitor, Pro-Phe-psi(PO2CH2)-Leu-Pro-NH2 displayed a Ki value of 12 nM towards endopeptidase 3.4.24.16 and was 5540 fold less potent on its related peptidase endopeptidase 3.4.24.15. Furthermore, this inhibitor was 12.5 less potent on angiotensin-converting enzyme and was unable to block endopeptidase 3.4.24.11, aminopeptidases B and M, dipeptidylaminopeptidase IV and proline endopeptidase. 3. The effect of Pro-Phe-psi(PO2CH2)-Leu-Pro-NH2, in vitro and in vivo, on neurotensin metabolism in the central nervous system was examined. 4. Pro-Phe-psi(PO2CHH2)-Leu-Pro-NH2 dose-dependently inhibited the formation of neurotensin 1-10 and concomittantly protected neurotensin from degradation by primary cultured neurones from mouse embryos. 5. Intracerebroventricular administration of Pro-Phe-psi(PO2CH2)-Leu-Pro-NH2 significantly potentiated the neurotensin-induced antinociception of mice in the hot plate test. 6. Altogether, our study has established Pro-Phe-psi(PO2CH2)-Leu-Pro-NH2 as a fully selective and highly potent inhibitor of endopeptidase 3.4.24.16 and demonstrates, for the first time, the contribution of this enzyme in the central metabolism of neurotensin.

  7. Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes.

    PubMed

    Liu, Bo; Cui, Dongmei

    2009-01-21

    Stoichiometric reactions between mesityl azide (MesN3, Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3)2(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)2; Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-C6H3iPr2))2(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN3)]Ln[(MesN3)(CH2SiMe3)]2 (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)]Lu[NH(2,6-C6H3iPr2)]2 (4), and bis(alkynyl) complex (5) (L(MesN3)Lu (C[triple bond, length as m-dash]CPh)2)2, respectively. The triazenyl group in coordinates to the metal ion in a rare eta2-mode via N(beta) and N(gamma) atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN3), in , and chelates to the metal ion in a eta3-mode via N(alpha) and N(gamma) atoms. In the presence of excess phenylacetylene, complex isomerized to , where the triazenyl group coordinates to the metal ion in a eta3 mode via N(alpha) and N(gamma) atoms. Complexes , , and have shown an unprecedented catalytic activity towards the cycloaddition of organic azides and aromatic alkynes to afford 1,5-disubstituted 1,2,3-triazoles selectively.

  8. Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect.

    PubMed

    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.

  9. Phosphine-stabilised Au{sub 9} clusters interacting with titania and silica surfaces: The first evidence for the density of states signature of the support-immobilised cluster

    SciTech Connect

    Andersson, Gunther G. E-mail: vladimir.golovko@canterbury.ac.nz Al Qahtani, Hassan S.; Golovko, Vladimir B. E-mail: vladimir.golovko@canterbury.ac.nz; Alvino, Jason F.; Bennett, Trystan; Wrede, Oliver; Mejia, Sol M.; Metha, Gregory F. E-mail: vladimir.golovko@canterbury.ac.nz; Adnan, Rohul; Gunby, Nathaniel; Anderson, David P.

    2014-07-07

    Chemically made, atomically precise phosphine-stabilized clusters Au{sub 9}(PPh{sub 3}){sub 8}(NO{sub 3}){sub 3} were deposited on titania and silica from solutions at various concentrations and the samples heated under vacuum to remove the ligands. Metastable induced electron spectroscopy was used to determine the density of states at the surface, and X-ray photoelectron spectroscopy for analysing the composition of the surface. It was found for the Au{sub 9} cluster deposited on titania that the ligands react with the titania substrate. Based on analysis using the singular value decomposition algorithm, the series of MIE spectra can be described as a linear combination of 3 base spectra that are assigned to the spectra of the substrate, the phosphine ligands on the substrate, and the Au clusters anchored to titania after removal of the ligands. On silica, the Au clusters show significant agglomeration after heat treatment and no interaction of the ligands with the substrate can be identified.

  10. Disulfides of manganese carbonyl. Synthesis of Mn(2)(CO)(7)(mu-S2) and its reactions with tertiary phosphines and arsines.

    PubMed

    Adams, Richard D; Kwon, O-Sung; Smith, Mark D

    2002-12-02

    The reaction of Mn(2)(CO)(9)(NCMe) with thiirane yielded the sulfidomanganese carbonyl compounds Mn(2)(CO)(7)(mu-S(2)), 2, Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)), 3, and Mn(4)(CO)(14)(NCMe)(mu(3)-S(2))(mu(4)-S(2)), 4, by transfer of sulfur from the thiirane to the manganese complex. Compound 3 was obtained in better yield from the reaction of 2 with CO, and compound 4 is obtained from the reaction of 2 with NCMe. The reaction of 2 with PMe(2)Ph yielded the tetramanganese disulfide Mn(4)(CO)(15)(PMe(2)Ph)(2)(mu(3)-S)(2), 5, and S=PMe(2)Ph. The reaction of 5 with PMe(2)Ph yielded Mn(4)(CO)(14)(PMe(2)Ph)(3)(mu(3)-S)(2), 6, by ligand substitution. The reaction of 2 with AsMe(2)Ph yielded the new complexes Mn(4)(CO)(14)(AsMe(2)Ph)(2)(mu(3)-S(2))(2), 7, Mn(4)(CO)(14)(AsMe(2)Ph)(mu(3)-S(2))(mu(4)-S(2)), 8, Mn(6)(CO)(20)(AsMe(2)Ph)(2)(mu(4)-S(2))(3), 9, and Mn(2)(CO)(6)(AsMe(2)Ph)(mu-S(2)), 10. Reaction of 2 with AsPh(3) yielded the monosubstitution derivative Mn(2)(CO)(6)(AsPh(3))(mu-S(2)), 11. Reaction of 7 with PMe(2)Ph yielded Mn(4)(CO)(15)(AsMe(2)Ph)(2)(mu(3)-S)(2), 12. The phosphine analogue of 7, Mn(4)(CO)(14)(PMe(2)Ph)(2)(mu(3)-S(2))(2), 13, was prepared from the reaction of Mn(2)(CO)(9)(PMe(2)Ph) with Me(3)NO and thiirane. Compounds 2-9 and 11-13 were characterized by single-crystal X-ray diffraction. Compound 2 contains a disulfido ligand that bridges two Mn(CO)(3) groups that are joined by a Mn-Mn single bond, 2.6745(5) A in length. A carbonyl ligand bridges the Mn-Mn bond. Compounds 3 and 4 contain four manganese atoms with one triply bridging and one quadruply bridging disulfido ligand. Compounds 5 and 6 contain four manganese atoms with two triply bridging sulfido ligands. Compound 9 contains three quadruply bridging disulfido ligands imbedded in a cluster of six manganese atoms.

  11. Mixed-metal supramolecular complexes coupling phosphine-containing Ru(II) light absorbers to a reactive Pt(II) through polyazine bridging ligands.

    PubMed

    Swavey, Shawn; Fang, Zhenglai; Brewer, Karen J

    2002-05-06

    Supramolecular bimetallic Ru(II)/Pt(II) complexes [(tpy)Ru(PEt(2)Ph)(BL)PtCl(2)](2+) and their synthons [(tpy)Ru(L)(BL)](n)()(+) (where L = Cl(-), CH(3)CN, or PEt(2)Ph; tpy = 2,2':6',2''-terpyridine; and BL = 2,2'-bipyrimidine (bpm) or 2,3-bis(2-pyridyl)pyrazine (dpp)) have been synthesized and studied by cyclic voltammetry, electronic absorption spectroscopy, mass spectral analysis, and (31)P NMR. The mixed-metal bimetallic complexes couple phosphine-containing Ru chromophores to a reactive Pt site. These complexes show how substitution of the monodentate ligand on the [(tpy)RuCl(BL)](+) synthons can tune the properties of these light absorbers (LA) and incorporate a (31)P NMR tag by addition of the PEt(2)Ph ligand. The redox potentials for the Ru(III/II) couples occur at values greater than 1.00 V versus the Ag/AgCl reference electrode and can be tuned to more positive potentials on going from Cl(-) to CH(3)CN or PEt(2)Ph (E(1/2) = 1.01, 1.55, and 1.56 V, respectively, for BL = bpm). The BL(0/-) couple at -1.03 (bpm) and -1.05 V (dpp) for [(tpy)Ru(PEt(2)Ph)(BL)](2+) shifts dramatically to more positive potentials upon the addition of the PtCl(2) moiety to -0.34 (bpm) and -0.50 V (dpp) for the [(tpy)Ru(PEt(2)Ph)(BL)PtCl(2)](2+) bridged complex. The lowest energy electronic absorption for these complexes is assigned as the Ru(d pi) --> BL(pi*) metal-to-ligand charge transfer (MLCT) transition. These MLCT transitions are tuned to higher energy in the monometallic synthons when Cl(-) is replaced by CH(3)CN or PEt(2)Ph (516, 452, and 450 nm, for BL = bpm, respectively) and to lower energy when Pt(II)Cl(2) is coordinated to the bridging ligand (560 and 506 nm for BL = bpm or dpp). This MLCT state displays a broad emission at room temperature for all the dpp systems with the [(tpy)Ru(PEt(2)Ph)(dpp)PtCl(2)](2+) system exhibiting an emission centered at 750 nm with a lifetime of 56 ns. These supramolecular complexes [(tpy)Ru(PEt(2)Ph)(BL)PtCl(2)](2+) represent the

  12. A very peculiar family of N-heterocyclic phosphines: unusual structures and the unique reactivity of 1,3,2-diazaphospholenes.

    PubMed

    Gudat, D

    2016-04-14

    This Perspective gives an account of the peculiar electronic and molecular structures of N-heterocyclic phosphines featuring either a single 1,3,2-diazaphospholene (DAP) ring with an exocyclic P-substituent X or two DAP rings linked by a P-P bond (bis-diazaphospholenyls), respectively, and their impact on the chemical properties of these molecules. The bonding situation in simple DAPs is epitomized by strong hyperconjugation between endocyclic π-type electrons and the exocyclic P-X bond. This interaction may induce a perceptible ionic polarization of the P-X bond which can persist even in the limit of a vanishing electronegativity gradient between P and X, and becomes visible in unusual geometric distortions of molecular structures and a unique chemical behaviour. Structural distortions are particularly evident in bond lengthening effects in P-halogen and P-phosphino derivatives R2P-DAP (with R2P ≠ DAP) which span the whole range from covalent molecules to contact ion pairs with a close relation to frustrated Lewis-pairs. The most significant impact on the chemical properties is found for P-phosphino- and P-hydrogen derivatives where reactions at substantially accelerated rates or totally new reaction modes can be observed, and new stoichiometric and first catalytic processes exploiting these features are currently emerging. The recently discovered bis-diazaphospholenyls differ from the simple derivatives as their central bond remains unpolarised as a consequence of the symmetric molecular structure. The occurrence of low-energy P-P bond homolysis that was nonetheless observed in one case is according to the results of thermochemical studies of P-P bond fission reactions attributable to the effects of steric congestion and induces chemical reactivity that can be considered complementary to that of the simple R2P-DAPs. Some concluding remarks will pay attention to a facet of DAP reactivity that has so far been widely neglected but is currently receiving

  13. Structural Properties, Cytotoxicity, and Anti-Inflammatory Activity of Silver(I) Complexes with tris(p-tolyl)Phosphine and 5-Chloro-2-Mercaptobenzothiazole

    PubMed Central

    Kyros, L.; Kourkoumelis, N.; Kubicki, M.; Male, L.; Hursthouse, M. B.; Verginadis, I. I.; Gouma, E.; Karkabounas, S.; Charalabopoulos, K.; Hadjikakou, S. K.

    2010-01-01

    The synthesis and characterization of the silver(I) chloride complex of formula {[AgCI(CMBZT)(TPTP)2] · (MeOH)} (1) (CMBZT = 5-chloro-2-mercaptobenzothiazole, TPTP = tris(p-tolyl)phosphine) is described. Also the structure of the hydrate derivative {[AgCI(TPTP)3] · (0.5 · H2O)} (2) of the corresponding known anhydrous silver complex (Zartilas et al., 2009), and the polymorph 3 of the known [AgI(TPTP)3] complex (Zartilas et al., 2009) were determined and compared with the known ones. In addition, the structure of the known one silver(I) cluster {[AgI(TPTP)]4} (4) (Meijboom et al., 2009) was re-determined at 120(2) K and possible Ag-Ag interactions were analyzed. The compounds 1–4 were characterized by X-ray crystallography at r.t (1) and 120 K (2–4). All these complexes and {[(Et3NH)+]2 · [Ag6(μ3-Hmna)4(μ3-mna)2]2− · (DMSO)2 · (H2O)} (5) (Hmna = 2-mercaptonicotinic acid) were evaluated for cytotoxic and anti-inflammatory activity. The in vitro testing of cytotoxic activity of 1–5 against leiomyosarcoma cancer cells (LMS), were evaluated with Trypan Blue and Thiazolyl Blue Tetrazolium Bromide or 3-(4.5-dimethylthiazol-2-yl)-2.5-diphenyltetrazolium bromide (MTT) assays. The flow cytometry assay for complex 1 and showed that at 15 μM of 1, 62.38% of LMS cells undergo apoptosis, while 7% of LMS cells undergo cell necrosis. The antitumor activity of 3 is comparable with that of its reported polymorph (Zartilas et al., 2009). The anti-inflammatory, activity of complexes 1–3 and 5 was also studied. The activity towards cell viability was 2 > 3 > 5 > 1 > 4, while the order of the inhibitory activity in cell growth proliferation follows the order, 2 > 3 > 1 > 4 > 5. The anti-inflammatory activity on the other hand is 1 > 2 > 5 > ⋯ >3. PMID:20379345

  14. Metal- and ligand-assisted CO2 insertion into Ru-C, Ru-N, and Ru-O bonds of ruthenium(II) phosphine complexes: a density functional theory study.

    PubMed

    Vadivelu, Prabha; Suresh, Cherumuttathu H

    2015-01-20

    The CO2 insertion reactions of [L4Ru(η(2)-CH2C6H4)] (1), [L4Ru(η(2)-OC6H3Me)] (2), and [L4Ru(η(2)-NHC6H4)] (3), where L = PH3 and PMe3, are modeled using density functional theory methods. In 1 and 2, the metal-assisted CO2 insertion occurs because of the favorable initial axial phosphine dissociation mechanism, whereas in 3, the ligand (NHC6H4)-assisted mechanism operates (ΔG(⧧) = +19.0 kcal/mol), wherein the nucleophilic affinity of the -NHC6H4 moiety aids the CO2 insertion process. The modeled mechanisms are consistent with the experimental findings by Hartwig et al. (J. Am. Chem. Soc, 1991, 113, 6499), in which the rate of the reactions of 1 and 2 depends on the added phosphine concentration, whereas the rate of the reaction of 3 is independent of the added phosphine concentration. In 1 and 2, CO2 is preferably inserted into the Ru-Caryl bond rather than the competitive Ru-CH2 and Ru-O bonds, respectively. In 1, the π-type orbital interaction of the aryl ring with the metal center is found to stabilize the transition state for Ru-Caryl bond insertion (ΔG(⧧) = +25.7 kcal/mol). In 2, the Ru-Caryl insertion (ΔG(⧧) = +23.0 kcal/mol) is thermodynamically preferred, while the kinetically preferred Ru-O bond insertion (ΔG(⧧) = +17.4 kcal/mol) is highly reversible. The more electron-donating and sterically bulky PMe3 facilitates the CO2 insertion of 1 and 2 because the initial dissociation of axial PMe3 is easier than that of PH3 by ca. +11.0 kcal/mol, whereas in the case of 3, the effect of PMe3 slightly increases the ΔG(⧧) value of 3. The increase in the nucleophilic affinity of amido nitrogen in 3 and the increase in the polarity of the solvent decrease the ΔG(⧧) value of 3 by 48%. The inclusion of the chelating dimethylphosphinoethane ligand in 3 along with the electron-donating substituent at the -NHC6H4 moiety and the polar solvent further reduces the ΔG(⧧) value of 3 by 62%, which demonstrates the role of the chelating ligand, electron

  15. [2-(Diphenyl­phosphan­yl)benzene­thiol­ato-κ2 P,S](pyridine-2-thiol­ato-κS)(triphenyl­phosphine-κP)palladium(II)

    PubMed Central

    Ríos-Sanchez, Raúl; Hernández-Ortega, Simón; Morales-Morales, David; Avila-Sorrosa, Alcives

    2010-01-01

    In the title compound, [Pd(C5H4NS)(C18H14PS)(C18H15P)], the PdII atom has a slightly distorted square-planar environment. Two coordination sites are occupied by a P,S-chelating 2-(diphenyl­phosphan­yl)benzene­thiol­ate ligand and the other two by a P atom from a triphenyl­phosphine ligand and an S atom from a pyridine-2-thiol­ate ligand, exhibiting a trans arrangement of the two P-donor atoms. In the crystal structure, weak intra- and inter­molecular C—H⋯π and π–π inter­actions are observed. The pyridyl ring is equally disordered over two positions. PMID:21588560

  16. Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

    PubMed

    Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

    2001-10-22

    The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

  17. Quantum dynamics on a three-sheeted six-dimensional ab initio potential-energy surface of the phosphine cation: Simulation of the photoelectron spectrum and the ultrafast radiationless decay dynamics

    SciTech Connect

    Bhattacharyya, Swarnendu Domcke, Wolfgang; Dai, Zuyang

    2015-11-21

    A diabatic three-sheeted six-dimensional potential-energy surface has been constructed for the ground state and the lowest excited state of the PH{sub 3}{sup +} cation. Coupling terms of Jahn-Teller and pseudo-Jahn-Teller origin up to eighth order had to be included to describe the pronounced anharmonicity of the surface due to multiple conical intersections. The parameters of the diabatic Hamiltonian have been optimized by fitting the eigenvalues of the potential-energy matrix to ab initio data calculated at the CASSCF/MRCI level employing the correlation-consistent triple-ζ basis. The theoretical photoelectron spectrum of phosphine and the non-adiabatic nuclear dynamics of the phosphine cation have been computed by propagating nuclear wave packets with the multiconfiguration time-dependent Hartree method. The theoretical photoelectron bands obtained by Fourier transformation of the autocorrelation function agree well with the experimental results. It is shown that the ultrafast non-radiative decay dynamics of the first excited state of PH{sub 3}{sup +} is dominated by the exceptionally strong Jahn-Teller coupling of the asymmetric bending vibrational mode together with a hyperline of conical intersections with the electronic ground state induced by the umbrella mode. Time-dependent population probabilities have been computed for the three adiabatic electronic states. The non-adiabatic Jahn-Teller dynamics within the excited state takes place within ≈5 fs. Almost 80% of the excited-state population decay to the ground state within about 10 fs. The wave packets become highly complex and delocalized after 20 fs and no further significant transfer of electronic population seems to occur up to 100 fs propagation time.

  18. Highly improved electroluminescence from a series of novel Eu(III) complexes with functional single-coordinate phosphine oxide ligands: tuning the intramolecular energy transfer, morphology, and carrier injection ability of the complexes.

    PubMed

    Xu, Hui; Yin, Kun; Huang, Wei

    2007-01-01

    The functional single-coordinate phosphine oxide ligands (4-diphenylaminophenyl)diphenylphosphine oxide (TAPO), (4-naphthalen-1-yl-phenylaminophenyl)diphenylphosphine oxide (NaDAPO), and 9-[4-(diphenylphosphinoyl)phenyl]-9H-carbazole (CPPO), as the direct combinations of hole-transporting moieties, and electron-transporting triphenylphosphine oxide (TPPO) were designed and synthesized (amines or carbazole), together with their Eu(III) complexes [Eu(tapo)(2)(tta)(3)] (1), [Eu(nadapo)(2)(tta)(3)] (2), and [Eu(cppo)(2)(tta)(3)] (3; TTA: 2-thenoyltrifluoroacetonate). The investigation indicated that by taking advantage of the modification inertia of the phosphine oxide ligands, the direct introduction of the hole-transport groups as chromophore made TAPO, NaDAPO, and CPPO obtain the most compact structure and mezzo S(1) and T(1) energy levels, which improved the intramolecular energy transfer in their Eu(III) complexes. The amorphous phase of 1-3 proved the weak intermolecular interaction, which resulted in extraordinarily low self-quenching of the complexes. The excellent double-carrier transport ability of the ligands was studied with Gaussian calculations, and the bipolar structure of TAPO and CPPO was proved. The great improvement of the double-carrier transport ability of 1-3 was shown by cyclic voltammetry. Their HOMO and LUMO energy levels of around 5.3 and 3.0 eV, respectively, are the best results for Eu(III) complexes reported so far. A single-layer organic light-emitting diode of 2 had the impressive brightness of 59 cd m(-2) which, to the best of our knowledge, is the highest reported so far. Both of the four-layer devices based on pure 1 and 2 had a maximum brightness of more than 1000 cd m(-2), turn-on voltages lower than 5 V, maximum external quantum yields of more than 3 % and excellent spectral stability.

  19. Half-sandwich o-N,N-dimethylaminobenzyl complexes over the full size range of group 3 and lanthanide metals. synthesis, structural characterization, and catalysis of phosphine P--H bond addition to carbodiimides.

    PubMed

    Zhang, Wen-Xiong; Nishiura, Masayoshi; Mashiko, Tomohiro; Hou, Zhaomin

    2008-01-01

    The acid-base reactions between the rare-earth metal (Ln) tris(ortho-N,N-dimethylaminobenzyl) complexes [Ln(CH2C(H4NMe2-o)3] with one equivalent of the silylene-linked cyclopentadiene-amine ligand (C5Me4H)SiMe2NH(C6H2Me3-2,4,6) afforded the corresponding half-sandwich aminobenzyl complexes [{Me2Si(C5Me4)(NC6H2Me3-2,4,6)}Ln(CH2C6H4NMe2-o)(thf)] (2-Ln) (Ln=Y, La, Pr, Nd, Sm, Gd, Lu) in 60-87 % isolated yields. The one-pot reaction between ScCl(3) and [Me2Si(C5Me4)(NC6H2Me3-2,4,6)]Li2 followed by reaction with LiCH2C6H4NMe2-o in THF gave the scandium analogue [{Me2Si(C5Me4)(NC6H2Me3-2,4,6)}Sc(CH2C6H4NMe2-o)] (2-Sc) in 67 % isolated yield. 2-Sc could not be prepared by the acid-base reaction between [Sc(CH2C6H4NMe2-o)3] and (C5Me4H)SiMe2NH(C6H2Me3-2,4,6). These half-sandwich rare-earth metal aminobenzyl complexes can serve as efficient catalyst precursors for the catalytic addition of various phosphine P--H bonds to carbodiimides to form a series of phosphaguanidine derivatives with excellent tolerability to aromatic carbon-halogen bonds. A significant increase in the catalytic activity was observed, as a result of an increase in the metal size with a general trend of La>Pr, Nd>Sm>Gd>Lu>Sc. The reaction of 2-La with 1 equiv of Ph2PH yielded the corresponding phosphide complex [{Me2Si(C5Me4)(NC6H2Me3-2,4,6)}La(PPh2)(thf)2] (4), which, on recrystallization from benzene, gave the dimeric analogue [{Me2Si(C5Me4)(NC6H2Me3-2,4,6)}La(PPh2)]2 (5). Addition of 4 or 5 to iPrN=C=NiPr in THF yielded the phosphaguanidinate complex [{Me2Si(C5Me4)(NC6H2Me3-2,4,6)}La{iPrNC(PPh2)NiPr}(thf)] (6), which, on recrystallization from ether, afforded the ether-coordinated structurally characterizable analogue [{Me2Si(C5Me4)(NC6H2Me3-2,4,6)}La{iPrNC(PPh2)NiPr}(OEt2)] (7). The reaction of 6 or 7 with Ph2PH in THF yielded 4 and the phosphaguanidine iPrN=C(PPh2)NHiPr (3a). These results suggest that the catalytic formation of a phosphaguanidine compound proceeds through the nucleophilic addition

  20. Cu(I) complexes bearing the new sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate ligand and the water-soluble phosphine 1,3,5-triaza-7-phosphaadamantane or related ligands.

    PubMed

    Wanke, Riccardo; Smoleński, Piotr; da Silva, M Fátima C Guedes; Martins, Luísa M D R S; Pombeiro, Armando J L

    2008-11-03

    The new sterically hindered scorpionate tris(3-phenylpyrazolyl)methanesulfonate (Tpms(Ph))(-) has been synthesized and its coordination behavior toward a Cu(I) center, in the presence of 1,3,5-triaza-7-phosphaadamantane (PTA), N-methyl-1,3,5-triaza-7-phosphaadamantane tetraphenylborate ((mPTA)[BPh4]) or hexamethylenetetramine (HMT) has been studied. The reaction between Li(Tpms(Ph)) (1) and [Cu(MeCN)4][PF6] yields [Cu(Tpms(Ph))(MeCN)] (2) which, upon further acetonitrile displacement on reaction with PTA, HMT, or (mPTA)[BPh4], gives the corresponding complexes [Cu(Tpms(Ph))(PTA)] (3), [Cu(Tpms(Ph))(HMT)] (4), and [Cu(Tpms(Ph))(mPTA)][PF6] (5). All the compounds have been characterized by (1)H, (31)P, (13)C, COSY or HMQC-NMR, IR, elemental analysis, and single crystal X-ray diffraction. In the complexes (3) and (5), which bear a phosphine ligand (i.e., PTA and mPTA, respectively), the new scorpionate ligand shows the typical N, N, N-coordination mode, whereas in (2) and (4), bearing a N-donor ligand (i.e., MeCN and HMT, respectively), it binds the metal via the N,N,O chelating mode, involving the sulfonate moiety.

  1. Unraveling the formation of HCPH(X2A') molecules in extraterrestrial environments: crossed molecular beam study of the reaction of carbon atoms, C(3Pj), with phosphine, PH3(X1A1).

    PubMed

    Guo, Y; Gu, X; Zhang, F; Sun, B J; Tsai, M F; Chang, A H H; Kaiser, R I

    2007-05-03

    The reaction between ground state carbon atoms, C(3P(j)), and phosphine, PH3(X(1)A1), was investigated at two collision energies of 21.1 and 42.5 kJ mol(-1) using the crossed molecular beam technique. The chemical dynamics extracted from the time-of-flight spectra and laboratory angular distributions combined with ab initio calculations propose that the reaction proceeds on the triplet surface via an addition of atomic carbon to the phosphorus atom. This leads to a triplet CPH3 complex. A successive hydrogen shift forms an HCPH2 intermediate. The latter was found to decompose through atomic hydrogen emission leading to the cis/trans-HCPH(X(2)A') reaction products. The identification of cis/trans-HCPH(X(2)A') molecules under single collision conditions presents a potential pathway to form the very first carbon-phosphorus bond in extraterrestrial environments like molecular clouds and circumstellar envelopes, and even in the postplume chemistry of the collision of comet Shoemaker-Levy 9 with Jupiter.

  2. Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β'-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine.

    PubMed

    Gu, Yiting; Hu, Pengfei; Ni, Chunjie; Tong, Xiaofeng

    2015-05-20

    Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of β'-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the β'-addition/[4 + 4] cycloaddition domino sequence. In this sequence, β'C of allenoate 1 is an electrophilic center, and its β'C and γC serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a γ-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of γC and 1,3-dipole chemical behavior of βC and β'C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.

  3. Vibrational study of new Pt(II) and Pd(II) complexes with functionalized nitrogen-containing tertiary phosphine oxides. Ab initio study of ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline.

    PubMed

    Trendafilova, N; Bauer, G; Georgieva, I; Tosheva, T; Varbanov, S

    2003-01-01

    Vibrational study of new Pt(II) and Pd(II) complexes of functionalized nitrogen-containing tertiary phosphine oxides, namely ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline (o-, m- and p-dpmoa), (CH3)2P(O)CH2OC6H4NH2, have been presented. Geometry optimization of the ligands was performed at HF/6-31G* and B3LYP/6-31G* levels of the theory. Harmonic frequencies were calculated at HF/6-31G* optimized geometries. Relative gas-phase and solution-phase (H2O and CH3CN) basicities of o-, m- and p-dpmoa ligands have been determined by ab initio calculations at STO-3G level with the Onsager reaction field model. On the basis of the vibrational study, physical and analytical data it was suggested that the ligands in the complexes studied coordinate through the amino group and form square-planar platinum and palladium complexes of the general formula ML2Cl2 (M = Pt, Pd, L = o-, m- and p-dpmoa).

  4. Vibrational study of new Pt(II) and Pd(II) complexes with functionalized nitrogen-containing tertiary phosphine oxides. Ab initio study of ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Bauer, G.; Georgieva, I.; Tosheva, T.; Varbanov, S.

    2003-01-01

    Vibrational study of new Pt(II) and Pd(II) complexes of functionalized nitrogen-containing tertiary phosphine oxides, namely ortho-, meta- and para-dimethylphosphinylmethyleneoxyaniline ( o-, m- and p-dpmoa), (CH 3) 2P(O)CH 2OC 6H 4NH 2, have been presented. Geometry optimization of the ligands was performed at HF/6-31G* and B3LYP/6-31G* levels of the theory. Harmonic frequencies were calculated at HF/6-31G* optimized geometries. Relative gas-phase and solution-phase (H 2O and CH 3CN) basicities of o-, m- and p-dpmoa ligands have been determined by ab initio calculations at STO-3G level with the Onsager reaction field model. On the basis of the vibrational study, physical and analytical data it was suggested that the ligands in the complexes studied coordinate through the amino group and form square-planar platinum and palladium complexes of the general formula ML 2Cl 2 (M=Pt, Pd, L= o-, m- and p-dpmoa).

  5. Bioinspired Hydrogenase Models: The Mixed-Valence Triiron Complex [Fe3(CO)7(μ-edt)2] and Phosphine Derivatives [Fe3(CO)7-x (PPh3) x (μ-edt)2] (x = 1, 2) and [Fe3(CO)5(κ(2)-diphosphine)(μ-edt)2] as Proton Reduction Catalysts.

    PubMed

    Rahaman, Ahibur; Ghosh, Shishir; Unwin, David G; Basak-Modi, Sucharita; Holt, Katherine B; Kabir, Shariff E; Nordlander, Ebbe; Richmond, Michael G; Hogarth, Graeme

    2014-03-24

    The mixed-valence triiron complexes [Fe3(CO)7-x (PPh3) x (μ-edt)2] (x = 0-2; edt = SCH2CH2S) and [Fe3(CO)5(κ(2)-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist only in the dibasal form in both the solid state and solution. The carbonyl on the central iron atom is semibridging, and this leads to a rotated structure between the bridged diiron center. IR studies reveal that all complexes are inert to protonation by HBF4·Et2O, but addition of acid to the pentacarbonyl complexes results in one-electron oxidation to yield the moderately stable cations [Fe3(CO)5(PPh3)2(μ-edt)2](+) and [Fe3(CO)5(κ(2)-diphosphine)(μ-edt)2](+), species which also result upon oxidation by [Cp2Fe][PF6]. The electrochemistry of the formally Fe(I)-Fe(II)-Fe(I) complexes has been investigated. Each undergoes a quasi-reversible oxidation, the potential of which is sensitive to phosphine substitution, generally occurring between 0.15 and 0.50 V, although [Fe3(CO)5(PPh3)2(μ-edt)2] is oxidized at -0.05 V. Reduction of all complexes is irreversible and is again sensitive to phosphine substitution, varying between -1.47 V for [Fe3(CO)7(μ-edt)2] and around -1.7 V for phosphine-substituted complexes. In their one-electron-reduced states, all complexes are catalysts for the reduction of protons to hydrogen, the catalytic overpotential being increased upon successive phosphine substitution. In comparison to the diiron complex [Fe2(CO)6(μ-edt)], [Fe3(CO)7(μ-edt)2] catalyzes proton reduction at 0.36 V less negative potentials. Electronic structure calculations have been carried out in order to fully elucidate the nature of the oxidation and reduction processes. In all complexes, the HOMO comprises an iron-iron bonding orbital localized between the two iron atoms

  6. Isomer dependence in the assembly and lability of silver(I) trifluoromethanesulfonate complexes of the heteroditopic ligands, 2-, 3-, and 4-[di(1H-pyrazolyl)methyl]phenyl(di-p-tolyl)phosphine.

    PubMed

    Gardinier, James R; Hewage, Jeewantha S; Lindeman, Sergey V

    2014-11-17

    Three isomers of a new heteroditopic ligand that contains a di(1H-pyrazolyl)methyl (-CHpz2) moiety connected to a di(p-tolyl)phosphine group via a para-, meta-, or ortho-phenylene spacer (pL, mL, and oL, respectively) have been synthesized by using a palladium(0)-catalyzed coupling reaction between HP(p-tolyl)2 and the appropriate isomer of (IC6H4)CHpz2. The 1:1 complexes of silver(I) trifluoromethanesulfonate, Ag(OTf), were prepared to examine the nature of ligand coordination and the type of supramolecular isomer (monomeric, cyclic oligomeric, or polymeric) that would be obtained. The single crystal X-ray diffraction studies showed that [Ag(pL)](OTf), 1, and [Ag(mL)](OTf), 2, possessed cyclic dimeric dications, whereas [Ag(oL)](OTf), 3, was a coordination polymer. The polymeric chain in 3 could be disrupted by reaction with triphenylphosphine, and the resulting complex, [Ag(oL)(PPh3)](OTf), 4, possessed a monometallic cation where the ligand was bound to silver in a chelating κ(2)P,N- coordination mode. The solution structures of 1-4 were probed via a combination of IR, variable-temperature multinuclear ((1)H, (13)C, (31)P) NMR spectroscopy, as well as by electron spray ionization (ESI)(+) mass spectrometry. A related complex [Ag(m-IC6H4CHpz2)2](OTf), 5, was also prepared, and its solid-state and solution spectroscopic properties were studied for comparison purposes. These studies suggest that the cyclic structures of 1 and 2 are likely preserved but are dynamic in solution at room temperature. Moreover, both 3 and 4 have dynamic solution structures where 3 is likely extensively dissociated in CH3CN or acetone rather than being polymeric as in the solid state.

  7. Oxygen atom transfer reactions from dioxygen to phosphines via a bridging sulfur dioxide in a trinuclear cluster complex of rhenium, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)].

    PubMed

    Saito, Taro; Sunaga, Tomoaki; Sakai, Nobuaki; Nakamura, Yoichi; Yamamoto, Saori; Iriuchijima, Daisuke; Yoza, Kenji

    2005-06-13

    A trinuclear rhenium sulfide cluster complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(3)Cl(6)(PMe(2)Ph)(3)], synthesized from Re(3)S(7)Cl(7), dimethylphenylphosphine, and [(Ph(3)P)(2)N]Cl is readily converted to a bridging SO(2) complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)], by reaction with O(2). The oxygen atoms on the SO(2) ligand react with phosphines or phosphites to form phosphine oxides or phosphates, and the original cluster complex is recovered. The reaction course has been monitored by (31)P NMR as well as by UV-vis spectroscopy. The catalytic oxygenation of PMePh(2) in the presence of the SO(2) complex shows that turnovers are 8 per hour at 23 degrees C in CDCl(3). The X-ray structures of the cluster complexes are described.

  8. Insertion, coupling and elimination processes in the reactions of the unsaturated alkyl-bridged complexes [Mo₂(η⁵-C₅H₅)₂(μ-CH₂R)(μ-PCy₂)(CO)₂] (R = H, Ph) with isocyanides and secondary phosphines.

    PubMed

    Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Martínez, M Eugenia; Ramos, Alberto; Ruiz, Miguel A

    2014-06-07

    The methyl-bridged complex [Mo2Cp2(μ-Me)(μ-PCy2)(CO)2] (Cp = η(5)-C5H5) reacted with stoichiometric amounts of CN(t)Bu at 243 K to give the C,O:C,O-bridged acyl complex [Mo2Cp2{μ-C,O:C,O-C(O)Me}(μ-PCy2)(CN(t)Bu)(CO)], which at room temperature slowly rearranges into its iminoacyl-bridged isomer [Mo2Cp2(μ-C,N:C,N-MeCN(t)Bu)(μ-PCy2)(CO)2]. In contrast, the C:O-bridged acyl complex [Mo2Cp2{μ-C:O-C(O)Me}(μ-PCy2)(CN(t)Bu)(CO)] was the major product obtained when the above reaction was carried out at room temperature. Density Functional Theory (DFT) was used to find the most likely structures of all these isomers, of which the iminoacyl complex was the absolute minimum. In contrast to the above reactions, up to three molecules of the ligand added rapidly to the methyl complex when using the aryl isocyanides CNR (R = o-C6H4Me, p-C6H4OMe), triggering the coupling between the methyl ligand and one of the cyclopentadienyl groups to give the corresponding methylcyclopentadiene derivatives [Mo2Cp(η(4)-C5H5Me)(μ-PCy2)(CNR)3(CO)]. Carbonylation of the latter complex (R = o-C6H4Me) induced the displacement of the η(4)-bound ligand, but also gave small yields of the hydride derivative [Mo2Cp(η(5)-C5H4Me)(μ-H)(μ-PCy2){CN(o-C6H4Me)}(CO)3] (Mo-Mo = 3.2467(5) Å), the latter resulting from a C-H cleavage in the methylcyclopentadiene ligand. The reaction of the title complexes with phosphines HPR (R' = Et, Ph) gave two major products: the corresponding aldehyde complexes [Mo2Cp2(μ-PCy2)(μ-PR){η(2)-C(O)HR}(CO)] (Mo-Mo = 2.8288(5) Å when R = CH2Ph and R' = Et) and the dicarbonyl complexes [Mo2Cp2(μ-PCy2)(μ-PR)(CO)2], these following from alternative reductive elimination processes, from hydrogen and either acyl or alkyl ligands, respectively.

  9. [4′-(2-Bromo-5-pyrid­yl)-2,2′:6′,2′′-terpyridine-κ3 N,N′,N′′]bis(triphenyl­phosphine-κP)­copper(I) tetra­fluorido­borate dichloro­methane hemisolvate

    PubMed Central

    Polson, Matthew I. J.; Hanan, Garry S.; Taylor, Nicholas J.

    2008-01-01

    In the title complex, [Cu(C20H13BrN4)(C18H15P)2]BF4·0.5CH2Cl2, the copper(I) cation adopts a distorted tetra­hedral arrangement, coordinated by two triphenyl­phosphine ligands and two N atoms of the potentially tridentate terpyridine ligand. One half-mol­ecule of dichloro­methane crystallizes with the complex. The chlorine atoms are disordered over two sites with occupancies fixed at 0.30 and 0.20 respectively. The N donor atom of the central pyridine inter­acts weakly with the copper centre at a distance of 3.071 Å. PMID:21200553

  10. Superatomic S(2) silver clusters stabilized by a thiolate-phosphine monolayer: insight into electronic and optical properties of Ag14(SC6H3F2)12(PPh3)8 and Ag16(SC6H3F2)14(DPPE)4.

    PubMed

    Gell, Lars; Lehtovaara, Lauri; Häkkinen, Hannu

    2014-09-18

    The electronic structure of two recently crystallographically solved, thiolate-phosphine protected silver clusters Ag14 and Ag16 are analyzed via density functional theory (DFT) and their optical excitations are analyzed from time-dependent DFT perturbation theory. Both clusters can be characterized as having the S(2) free-electron configuration in the metal core, which is the first time such a configuration is confirmed for structurally known ligand-protected noble metal clusters. However, their different core shapes and ligand layer induce significantly different optical spectra. Performance of gradient-corrected DFT functionals is discussed and it is shown that the asymptotically correct Leeuwen-Baerends LB94 functional reproduces the optical spectrum of Ag14 in a good agreement with experiment. Choice of the functional becomes important for clusters where the optical transitions are dominated by the electron-rich ligand layer.

  11. Phosphine photochemistry in the atmosphere of Saturn

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

    The photochemistry of PH3 in the atmosphere of Saturn is studied, including the effects of coupling with the photochemistries of NH3 and hydrocarbons. The vertical concentration of PH3 is found to be extremely sensitive to the eddy diffusion coefficient (K) profile used. If K is roughly 10,000 sq cm/sec in the upper troposphere, PH3 should be depleted there with a scale height of about 3.5 km. An upper limit of 100,000 sq cm/sec is estimated for K. If the gas phase concentration of P2H4 can be neglected, production of molecular phophorus is very unlikely unless the spin-forbidden recombination reaction PH+H2+M - PH3+M occurs with an exceptionally low rate. Coupling of PH3 and hydrocarbon photochemistries is very important. Possible observable amounts of the organophosphorus molecules CH3PH2 and HCP are tentatively predicted.

  12. Cyanidotetra-kis-(trimethyl-phosphine)cobalt(I).

    PubMed

    Xu, Xiaofeng; Feng, Lei; Li, Xiaoyan

    2011-04-01

    The title compound, [Co(CN)(C(3)H(9)P)(4)], was obtained as a product of the reaction of [Co(PMe(3))(4)] with a molar equivalent of 2,6-difluoro-benzonitrile in diethyl ether. This compound is stable in the air for several hours, but rapidly decomposes at room temperature in solution. The cobalt(I) atom has s trigonal-bipyramidal coordination enviroment in which the cyano group and one of the PMe(3) groups are in the axial positions.

  13. Phosphine photochemistry in the atmosphere of Saturn

    NASA Astrophysics Data System (ADS)

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

    1984-09-01

    The photochemistry of PH3 in the atmosphere of Saturn is studied, including the effects of coupling with the photochemistries of NH3 and hydrocarbons. The vertical concentration of PH3 is found to be extremely sensitive to the eddy diffusion coefficient (K) profile used. If K is roughly 10,000 sq cm/sec in the upper troposphere, PH3 should be depleted there with a scale height of about 3.5 km. An upper limit of 100,000 sq cm/sec is estimated for K. If the gas phase concentration of P2H4 can be neglected, production of molecular phophorus is very unlikely unless the spin-forbidden recombination reaction PH+H2+M - PH3+M occurs with an exceptionally low rate. Coupling of PH3 and hydrocarbon photochemistries is very important. Possible observable amounts of the organophosphorus molecules CH3PH2 and HCP are tentatively predicted.

  14. Phosphine-free synthesis of high-quality reverse type-I ZnSe/CdSe core with CdS/CdxZn1 - xS/ZnS multishell nanocrystals and their application for detection of human hepatitis B surface antigen

    NASA Astrophysics Data System (ADS)

    Shen, Huaibin; Yuan, Hang; Niu, Jin Zhong; Xu, Shasha; Zhou, Changhua; Ma, Lan; Li, Lin Song

    2011-09-01

    Highly photoluminescent (PL) reverse type-I ZnSe/CdSe nanocrystals (NCs) and ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS core/multishell NCs were successfully synthesized by a phosphine-free method. By this low-cost, 'green' synthesis route, more than 10 g of high-quality ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS NCs were synthesized in a large scale synthesis. After the overgrowth of a CdS/CdxZn1 - xS/ZnS multishell on ZnSe/CdSe cores, the PL quantum yields (QYs) increased from 28% to 75% along with the stability improvement. An amphiphilic oligomer was used as a surface coating agent to conduct a phase transfer experiment, core/multishell NCs were dissolved in water by such surface modification and the QYs were still kept above 70%. The as-prepared water dispersible ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS core/multishell NCs not only have high fluorescence QYs but also are extremely stable in various physiological conditions. Furthermore, a biosensor system (lateral flow immunoassay system, LFIA) for the detection of human hepatitis B surface antigen (HBsAg) was developed by using this water-soluble core/multishell NCs as a fluorescent label and a nitrocellulose filter membrane for lateral flow. The result showed that such ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS core/multishell NCs were excellent fluorescent labels to detect HBsAg. The sensitivity of HBsAg detection could reach as high as 0.05 ng ml - 1.

  15. 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.

    PubMed

    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 < 2%. The accuracy of the developed method has been checked by determining uranium using standard addition method and was found to be accurate with a 98-105% recovery rate. The developed method has been applied for the analysis of a number of uranium samples generated from uranium 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.

  16. The Mutagenic Potential of: 4-fluorophenyl methyl (phenyl) phosphinate, 4-nitrophenyl 4-trifluoromethylphenyl (methyl) phosphinate, 4-nitrophenyl 3-trifluoromethylphenyl (methyl) phosphinate, 4-methylsulfinylphenyl methyl (phenyl) phospinate.

    DTIC Science & Technology

    1981-09-01

    OF INOV 6S IS OBSOLETE SE C, 3 UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When Data Entered) ABSTRACT The mutagenic potential of 4 fluorophenyl...valid. The study was conducted to comply to the best of our ability with the Good Laboratory Practice Regulations outlined by the Food and Drug

  17. Tris(4-methyl­phen­yl)phosphine selenide

    PubMed Central

    Muller, Alfred

    2011-01-01

    In the title mol­ecule, C21H21PSe or PSe(C7H7)3, the P atom has a distorted PSeC3 tetra­hedral environment, formed by the Se atom [P=Se = 2.1119 (5) Å] and three aryl rings. Two short intra­molecular C—H⋯Se contacts occur. In the crystal, weak inter­molecular C—H⋯Se inter­actions link the mol­ecules into zigzag double chains propagating in [100]. The previous report of this structure [Zhdanov et al. (1953 ▶). Dokl. Akad. Nauk SSSR (Russ.) (Proc. Nat. Acad. Sci. USSR), 92, 983–985] contained no geometrical data. PMID:21522754

  18. Tris(4-methyl-phen-yl)phosphine selenide.

    PubMed

    Muller, Alfred

    2010-12-08

    In the title mol-ecule, C(21)H(21)PSe or PSe(C(7)H(7))(3), the P atom has a distorted PSeC(3) tetra-hedral environment, formed by the Se atom [P=Se = 2.1119 (5) Å] and three aryl rings. Two short intra-molecular C-H⋯Se contacts occur. In the crystal, weak inter-molecular C-H⋯Se inter-actions link the mol-ecules into zigzag double chains propagating in [100]. The previous report of this structure [Zhdanov et al. (1953 ▶). Dokl. Akad. Nauk SSSR (Russ.) (Proc. Nat. Acad. Sci. USSR), 92, 983-985] contained no geometrical data.

  19. [4-(Dimethyl-amino)-phen-yl]diphenyl-phosphine selenide.

    PubMed

    Davis, Wade L; Muller, Alfred

    2012-11-01

    In the title compound, C(20)H(20)NPSe, the P atom lies in a distorted tetra-hedral environment. The Tolman cone angle is 157° indicating steric crowding at this atom. In the crystal, weak C-H⋯Se inter-actions create linked dimeric units and C-H⋯π inter-actions are also observed.

  20. 40 CFR 180.225 - Phosphine; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Soybean, seed 0.1 Sunflower, seed 0.1 Sweet potato, roots 0.01 Tangelo 0.01 Tangerine 0.01 Tomato 0.01... Orange, sweet 0.01 Papaya 0.01 Peanut 0.1 Pecan 0.1 Pepper 0.01 Persimmon 0.01 Pistachio 0.1 Rice,...

  1. 40 CFR 180.225 - Phosphine; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Soybean, seed 0.1 Sunflower, seed 0.1 Sweet potato, roots 0.01 Tangelo 0.01 Tangerine 0.01 Tomato 0.01... Orange, sweet 0.01 Papaya 0.01 Peanut 0.1 Pecan 0.1 Pepper 0.01 Persimmon 0.01 Pistachio 0.1 Rice,...

  2. 40 CFR 180.225 - Phosphine; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Soybean, seed 0.1 Sunflower, seed 0.1 Sweet potato, roots 0.01 Tangelo 0.01 Tangerine 0.01 Tomato 0.01... Orange, sweet 0.01 Papaya 0.01 Peanut 0.1 Pecan 0.1 Pepper 0.01 Persimmon 0.01 Pistachio 0.1 Rice,...

  3. 40 CFR 180.225 - Phosphine; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Soybean, seed 0.1 Sunflower, seed 0.1 Sweet potato, roots 0.01 Tangelo 0.01 Tangerine 0.01 Tomato 0.01... Orange, sweet 0.01 Papaya 0.01 Peanut 0.1 Pecan 0.1 Pepper 0.01 Persimmon 0.01 Pistachio 0.1 Rice,...

  4. 40 CFR 180.225 - Phosphine; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Soybean, seed 0.1 Sunflower, seed 0.1 Sweet potato, roots 0.01 Tangelo 0.01 Tangerine 0.01 Tomato 0.01... Orange, sweet 0.01 Papaya 0.01 Peanut 0.1 Pecan 0.1 Pepper 0.01 Persimmon 0.01 Pistachio 0.1 Rice,...

  5. Latitudinal variability of arsine, germane and phosphine in Jupiter's troposphere

    NASA Astrophysics Data System (ADS)

    Giles, Rohini Sara; Fletcher, Leigh N.; Irwin, Patrick Gerard Joseph

    2016-10-01

    High-resolution 5-μm observations of Jupiter from the CRIRES instrument at the Very Large Telescope are used to measure latitudinal variability in AsH3, GeH4 and PH3. The 5-micron region is a spectral window allowing us to probe down to Jupiter's middle troposphere (4-8 bar). CRIRES observations in 2012 and 2013 provide high-resolution (R=96,000) latitudinally-resolved spectra in the 4.7-5.2 μm region. In the middle troposphere, AsH3, GeH4and PH3 are disequilibrium species that are only present because of rapid upwelling from deeper regions of the planet. Their observed abundances depend on the chemical lifetimes, the strength of the vertical mixing and the rate of photolytic destruction, and are therefore likely to vary with latitude. We analyse the CRIRES observations using the NEMESIS radiative transfer code and retrieval algorithm in order to search for any latitudinal variability in the disequilibrium species. We find that there is a significant degeneracy between the retrieved gaseous abundances and the cloud structure - specifically, the scattering properties of the main tropospheric cloud deck, and the presence/absence of an additional deep cloud. Because of these degeneracies, there is no clear evidence for any variability in GeH4. However, for AsH3 and PH3, there are significant latitudinal differences in the observed lineshape that cannot be accounted for by clouds. We conclude that both of these gases show an enhancement at high latitudes. In the case of AsH3, the retrieved abundance varies from subsolar in the equatorial regions (as seen in previous studies) to supersolar in the polar regions. Our findings are in contrast with the theoretical simulations of Wang et al. (2016, doi:10.1016/j.icarus.2016.04.027), which predict that AsH3 and PH3 should not vary with latitude, and that GeH4 should decrease in abundance at high latitudes.

  6. Computer-aided optimization of phosphinic inhibitors of bacterial ureases.

    PubMed

    Vassiliou, Stamatia; Kosikowska, Paulina; Grabowiecka, Agnieszka; Yiotakis, Athanasios; Kafarski, Paweł; Berlicki, Lukasz

    2010-08-12

    Urease inhibitors can be considered as a tool to control the damaging effect of ureolytic bacteria infections in humans which occur commonly in the developed countries. Computer-aided optimization of the aminomethylphosphinate structures by modifying both their N- and P-termini led to the invention of a novel group of inhibitors of bacterial ureases. Introduction of P-hydroxymethyl group into the molecule resulted in considerable increase of the inhibitory activity against enzymes purified from Bacillus pasteurii and Proteus vulgaris as compared with their P-methyl counterparts described previously. The designed compounds represent a competitive reversible class of urease inhibitors. The most potent, N-methyl-aminomethyl-P-hydroxymethylphosphinic acid, displayed K(i) = 360 nM against P. vulgaris enzyme.

  7. Diorganostyrylzinndiorganophosphine und Ihre Tricarbonylnickelkomplexe (Diorganostyryltin Phosphines and its Tricarbonylnickel Complexes).

    DTIC Science & Technology

    1979-12-03

    Umkristallisieren aus Pentan/Benzol/Toluol gereinigt werden konnen; IVb zeigt bereits ab 0°C Polym erisationserschei- nungen. Vb und VIb werden als heligelbe...einem Rar.ger Engeneering M6ssbauer Spectrometer benutzt wurde. in C 6 D 6c) die Ha lbwertsbreiten wurden als glei~h vorausgesetzt , um dos Si gnal als

  8. 7 CFR 305.7 - Phosphine treatment schedules.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...-4 NAP1 50 or above 2.1 grams/cubic meter 120 T203-g-3 NAP 50 or above 2.1 grams/cubic meter 120 T301-a-6 NAP 50 or above 60 grams/1000 ft3 120 T301-d-1-2 NAP 50 or above 36 grams/1000 ft3 72 T311...

  9. Phosphine Chemistry on Mo(110) and Oxidized Mo(110)

    DTIC Science & Technology

    1993-01-01

    temperature the O(KLL) peak of MoOx (0(520 eV)/Mo(187 eV) ratioy = shoulder (85 K) developed; it originates from multilayer phys- 0.3). It was found...400 TEMPERATURE (K) MOOx (o/Mo-4.0J Figure 6. Comparison of PH3 TPD spectra from PH3/Mo(I 10) and from PH3/D2/Mo(l 10). so 150 250 350 450 550

  10. Response of light brown apple moth to oxygenated phosphine fumigation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The light brown apple moth (LBAM), Epiphyas postvittana (Walker), poses a serious threat to California agriculture and is currently quarantined by several major trading partners. Fumigation is the only tool to assure pest-free postharvest vegetable and fruit products. However, current fumigants for ...

  11. Diamagnetic molybdenum nitride complexes supported by diligating tripodal triamido-phosphine ligands as precursors to paramagnetic phosphine donors.

    PubMed

    Hatnean, Jillian A; Johnson, Samuel A

    2015-09-07

    The reaction of the ligand precursors P[CH2NHAr(R)]3 () with (Me2N)3Mo[triple bond, length as m-dash]N generated the complexes P(CH2NAr(R))3Mo[triple bond, length as m-dash]N (), where Ar(R) = 3,5-(CH3)2C6H3 (), Ph (), and 3,5-(CF3)2C6H3 (), with (Me2N)3Mo[triple bond, length as m-dash]N generated the complexes P(CH2NAr(R))3Mo[triple bond, length as m-dash]N (). Complex was obtained in poor yield, due to the formation of P(CH2N-3,5-(CF3)2C6H3)2(CH2NH-3,5-(CF3)2C6H3)(NMe2H)(NMe2)Mo[triple bond, length as m-dash]N () as the major product. Reaction of with VMes3THF generated the paramagnetic complexes P(CH2NAr(R))3Mo(μ-N)V(Mes)3 (). The reaction of with Ni(acac)2 generated the Ni(0) complexes Ni[P(CH2NAr(R))3Mo[triple bond, length as m-dash]N]4 () in poor yield. These complexes were synthesized in higher yields from the reaction of with Ni(COD)2, where COD = 1,5-cyclooctadiene. Reaction of either with V(Mes)3THF or with Ni(COD)2 generated the paramagnetic nonanuclear complex Ni[P(CH2NAr(R))3Mo(μ-N)VMes3]4 ().

  12. The Reduction of a Nitrile (CN) Group by Sodium Borohydride. The Preparation of Phosphine--Amine and Phosphine--Iimidate Complesex of Tungsten Carbonyl.

    ERIC Educational Resources Information Center

    Faust, Kristen E.; Storhoff, Bruce N.

    1989-01-01

    Describes an experiment for advanced-level undergraduate students for extending student experiences involving recording and interpreting infrared (IR) and nuclear magnetic resonance (NMR) spectra from reactions of organometallic compounds. Experimental procedures, analyses and structural assignments, and suggestions for extension and modification…

  13. Coriolis Interactions in the nu2, nu4a, nu4b, and nu3a States of Phosphine-d1

    PubMed

    Kshirsagar; Job

    1997-10-01

    Spectra of the nu4a (HPH bend) and nu4b (HPD bend) bands of the PH2D molecule have been recorded and analyzed. The Coriolis interactions between the two states as well as the various Coriolis interactions of the nu4a and nu4b states with the nu2 state have been included in the analysis. Several new assignments of transitions which occur with enhanced intensity in the nu2 band also have been made. The parameters of the nu4a and nu4b states, improved parameters of the nu2 state, and the interaction parameters have been determined. The data on the nu3a band of PH2D have been reanalyzed by taking into account the b-axis Coriolis interaction of the nu3a state with the 2nu2 state. Copyright 1997 Academic Press. Copyright 1997Academic Press

  14. Nucleophilic Substitution Reactions Using Phosphine Nucleophiles: An Introduction to Phosphorus-31 NMR

    ERIC Educational Resources Information Center

    Sibbald, Paul A.

    2015-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is commonly used in modern synthetic chemistry to monitor the conversion of reactants to products. Since instruction in the use of NMR spectroscopy typically does not occur until after the introduction of nucleophilic substitution reactions, organic chemistry students are not able to take advantage of…

  15. Privileged phosphine-based metal-organic frameworks for broad-scope asymmetric catalysis.

    PubMed

    Falkowski, Joseph M; Sawano, Takahiro; Zhang, Teng; Tsun, Galen; Chen, Yuan; Lockard, Jenny V; Lin, Wenbin

    2014-04-09

    A robust and porous Zr metal-organic framework (MOF) based on a BINAP-derived dicarboxylate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantioselective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantioselective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP precatalysts with the same coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to α,β-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.

  16. Structural motifs in (t-butoxy) zirconium phosphinates, arsinates, and phosphates.

    PubMed

    Kumara Swamy, K C; Veith, Michael; Huch, Volker; Mathur, Sanjay

    2003-09-22

    Reaction of zirconium tetrakis(tert-butoxide) (1) with dicylohexylphosphinic acid in toluene leads to the dinuclear compound [Zr(mu,mu'-O(2)P(cycl-C(6)H(11))(2))(O-t-Bu)(3)](2) (2) in which the zirconium is pentacoordinated. An analogous reaction using diphenylphosphinic acid in tetrahydrofuran also leads to a dinuclear complex [Zr(mu,mu'-O(2)PPh(2))(THF)((O-t-Bu)(3)](2).C(6)H(5)CH(3) (3.C(6)H(5)CH(3)), in which zirconium is hexacoordinated. A novel exchange of tert-butoxy and phenoxy groups occurs when 1 is treated with diphenyl phosphate [(PhO)(2)PO(2)H] leading to the isolation of the exchange product [Zr(mu,mu'-O(2)P(O-t-Bu)(OPh))(mu-OPh)(O-t-Bu)(2)](2) (4). In contrast to the above, trinuclear zirconium compounds Zr(3(mu,mu'-O(2)AsMe(2))(2)(mu2,mu'-O(2)AsMe(2))(O-t-Bu)(7)(mu-O-t-Bu)(2) (5) and Zr(3(mu,mu'-O(2)P(O-t-Bu)(2))(5)(O-t-Bu)(7).(1)/(2)C(6)H(5)CH(3) (6.(1)/(2)C(6)H(5)CH(3)) have been isolated from the reaction of 1 with cacodylic acid and di-tert-butyl phosphate, respectively. The X-ray structures of 2, 3, 5, and 6 have been determined; although the X-ray structural analysis of 4 could not be satisfactorily finished, it reveals the disposition of the substituents. The solution state NMR data suggest that these compounds undergo structural changes in solution. Possible relationships among the various structures are discussed.

  17. INVESTIGATING THE DEAROMATIVE REARRANGEMENT OF BIARYL PHOSPHINE-LIGATED PD(II) COMPLEXES

    PubMed Central

    Milner, Phillip J.; Maimone, Thomas J.; Su, Mingjuan; Chen, Jiahao; Müller, Peter; Buchwald, Stephen L.

    2012-01-01

    A series of monoligated L•PdII(Ar)X complexes (L = dialkyl biarylphosphine) have been prepared and studied in an effort to better understand an unusual dearomative rearrangement previously documented in these systems. Experimental and theoretical evidence suggest a concerted process involving the unprecedented PdII-mediated insertion of an aryl group into an unactivated arene. PMID:23153301

  18. Teratogenic Potential of 4-Nitrophenyl Methyl Phenyl Phosphinate (MPP) in Rats.

    DTIC Science & Technology

    1987-10-01

    examination or alIizarin red stain for skeletal examination. MPP did not produce dose-related teratogenic or embryotoxic effects in Spraguetbawley rats. o0 OR...examination. MPP did not produce dose-related teratogenic or embryotoxic effects in Sprague-Dawley rats. KEY WORDS: Developmental Toxicology, Teratology...INCLUSIVE STUDY DATES: 31 Aug 82- 15 March 83 OBJECTIVES: The purpose of this study was to determine the teratogenic and embryotoxic potential of MPP

  19. CHIRAL-AT-METAL OSMIUM(VI) PHOSPHINE COMPLEXES. (R829553)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  20. rac-[2-(Dicyclohexylphosphanyl)phenyl](phenyl)phosphinic diisopropyl-amide-borane hemihydrate.

    PubMed

    Evans, Stephen J; Renison, C Alicia; Williams, D Bradley G; Muller, Alfred

    2013-02-01

    In the title compound, C(30)H(48)BNOP(2)·0.5H(2)O, the water molecule is disordered about an inversion centre. Both phospho-rus atoms shows distortions in their tetra-hedral environments with the cyclo-hexyl substituents disordered over two orientations in a 0.851 (3):0.149 (3) occupancy ratio. The crystal structure is assembled via O-H⋯O inter-actions between pairs of phosphininc amide mol-ecules and water molecules, creating hydrogen-bonded dimers with graph-set R(2) (4)(8) along [001]. Weak C-H⋯O inter-actions are also observed.

  1. Generation of Phosphorus Ester, Phosphorus Amide, and Phosphine Derivatives of Low Coordination Number

    DTIC Science & Technology

    1989-12-12

    Thionation causes downfield shifts, and the product contained strong doublets (J = 75.6 Hz) at +89.3 and +114.5. These signals constituted about 50% of the...the thionation on the phosphole oxide dimer ., followed by oxygen insertion with a peracid. The thionation gave a crystalline product 9 in good yield...Me P P-" 8 t I 8 Et 9 CEt When the thionation of the bridged phosphonate 6 was attempted at 1100 with Lawesson’s reagent, the reaction mixture was

  2. Complexes between hypohalous acids and phosphine derivatives. Pnicogen bond versus halogen bond versus hydrogen bond

    NASA Astrophysics Data System (ADS)

    Li, Qingzhong; Zhu, Hongjie; Zhuo, Hongying; Yang, Xin; Li, Wenzuo; Cheng, Jianbo

    2014-11-01

    The complexes of HOBr:PH2Y (Y = H, F, Cl, Br, CH3, NH2, OH, and NO2), HOCl:PH2F, and HOI:PH2F have been investigated with ab initio calculations at the MP2/aug-cc-pVTZ level. Four types of structures (1, 2, 3a, and 3b) were observed for these complexes. 1 is stabilized by an O⋯P pnicogen bond, 2 by a P⋯X halogen bond, 3a by a H⋯P hydrogen bond and a P⋯X pnicogen bond, and 3b by H⋯P and H⋯Br hydrogen bonds. Their relative stability is related to the halogen X of HOX and the substituent Y of PH2Y. These structures can compete with interaction energy of -10.22 ∼ -29.40 kJ/mol. The Hsbnd O stretch vibration shows a small red shift in 1, a small irregular shift in 2, but a prominent red shift in 3a and 3b. The Xsbnd O stretch vibration exhibits a smaller red shift in 1, a larger red shift in 2, but an insignificant blue shift in 3a and 3b. The Psbnd Y stretch vibration displays a red shift in 1 but a blue shift in 2, 3a, and 3b. The formation mechanism, stability, and properties of these structures have been analyzed with molecular electrostatic potentials, orbital interactions, and non-covalent interaction index.

  3. Factors influencing the purity of electronic grade phosphine delivered to MOCVD tools

    NASA Astrophysics Data System (ADS)

    Feng, Jun; Owens, Mitch; Raynor, Mark W.

    2010-04-01

    Increasing mobility of InP films with usage time of one PH 3 cylinder prompted an investigation into factors influencing the purity of delivered PH 3. The presence of hygroscopic H xPO y residues in a delivery system greatly increases the dry-down time compared to that of a clean system. Static delivery system tests show increasing H 2O concentration with time and twice the increase in PH 3 versus N 2 over 48 h indicating reaction of metal oxides in components with PH 3 to generate H 2O. Gas purity may also vary during cylinder usage. Depletion of a high-purity PH 3 cylinder shows consistently low gas phase H 2O levels before phase-break but increasing levels after phase-break, as the cylinder depressurizes. The results highlight the importance of using pure PH 3, employing rigorous cycle-purging procedures to prevent H xPO y contamination, switching out cylinders in good time and using purification technology to control H 2O.

  4. Solid Molecular Phosphine Catalysts for Formic Acid Decomposition in the Biorefinery.

    PubMed

    Hausoul, Peter J C; Broicher, Cornelia; Vegliante, Roberta; Göb, Christian; Palkovits, Regina

    2016-04-25

    The co-production of formic acid during the conversion of cellulose to levulinic acid offers the possibility for on-site hydrogen production and reductive transformations. Phosphorus-based porous polymers loaded with Ru complexes exhibit high activity and selectivity in the base-free decomposition of formic acid to CO2 and H2 . A polymeric analogue of 1,2-bis(diphenylphosphino)ethane (DPPE) gave the best results in terms of performance and stability. Recycling tests revealed low levels of leaching and only a gradual decrease in the activity over seven runs. An applicability study revealed that these catalysts even facilitate selective removal of formic acid from crude product mixtures arising from the synthesis of levulinic acid.

  5. Phosphinogold(I) Dithiocarbamate Complexes: Effect of the Nature of Phosphine Ligand on Anticancer Properties

    PubMed Central

    2015-01-01

    The reactions of potassium salts of the dithiocarbamates L {where L = pyrazolyldithiocarbamate (L1), 3,5-dimethylpyrazolyldithiocarbamate (L2), or indazolyldithiocarbamate (L3)} with the gold precursors [AuCl(PPh3)], [Au2Cl2(dppe)], [Au2Cl2(dppp)], or [Au2Cl2(dpph)] lead to the new gold(I) complexes [AuL(PPh3)] (1–3), [Au2L2(dppe)] (4–6), [(Au2L2)(dppp)] (7–9), and [Au2(L)2(dpph)] (10–12) {where dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane, and dpph = 1,6-bis(diphenylphosphino)hexane}. These gold compounds were characterized by a combination of NMR and infrared spectroscopy, microanalysis, and mass spectrometry; and in selected cases by single-crystal X-ray crystallography. Compounds 4–6, which have dppe ligands, are unstable in solution for prolonged periods, with 4 readily transforming to the Au18 cluster [Au18S8(dppe)6]Cl2 (4a) in dichloromethane. Compounds 1–3 and 7–12 are all active against human cervical epithelioid carcinoma (HeLa) cells, but the most active compounds are 10 and 11, with IC50 values of 0.51 μM and 0.14 μM, respectively. Compounds 10 and 11 are more selective toward HeLa cells than they are toward normal cells, with selectivities of 25.0 and 70.5, respectively. Further tests, utilizing the 60-cell-line Developmental Therapeutics Program at the National Cancer Institute (U.S.A.), showed 10 and 11 to be active against nine other types of cancers. PMID:24476103

  6. Solar cells made by laser-induced diffusion directly from phosphine gas

    NASA Astrophysics Data System (ADS)

    Turner, G. B.; Tarrant, D.; Pollock, G.; Pressley, R.; Press, R.

    1981-12-01

    A method for making p-n junctions is presented, which is based on immersion in a transparent dopant gas followed by irradiation with a pulsed laser. An alexandrite laser operating at 0.73 micron is used where photolysis of the dopant gas PH3 does not occur, and multiple pulses of 2.2-2.7 J/sq cm are used to make Si solar cells with a total area efficiency up to 8.6% without benefit of anti-reflection coatings. Use of other gases should allow p-type doping, and the spatial localization inherent in the process could make the method applicable to structures such as interdigitated solar cells, transistors, and integrated circuits.

  7. Preparation of methylenediphosphine oxides and carbamoylmethyl-phosphines oxides from trimethylsilyl phosphinites

    SciTech Connect

    Chauzov, V.A.; Studnev, Yu.N.; Iznoskova, M.G.; Fokin, A.V.

    1987-06-20

    The conversion of diorganophosphonous acids to trimethylsilyl esters by the action of trimethylchlorosilane and trimethylamine and subsequent alkylation of the esters obtained by chloromethyldiorganophosphine oxides or N,N-dialkylamides of chloroacetic acid is shown to be a simple and effective method for the preparation of tetraorganomethylenediphosphine oxides and N,N-dialkylcarbamoylmethylphosphine oxides from diorganophosphinous acids. A full analysis of hydrogen 1 and phosphorus 31 NMR spectral data, performed in a number of deuterated solvents, is included.

  8. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    PubMed

    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.

  9. (2-{[2-(diphenyl-phosphino)phen-yl]thio}-phen-yl)diphenyl-phosphine sulfide.

    PubMed

    Alvarez-Larena, Angel; Martinez-Cuevas, Francisco J; Flor, Teresa; Real, Juli

    2012-11-01

    In the title compound, C(36)H(28)P(2)S(2), the dihedral angle between the central benzene rings is 66.95 (13)°. In the crystal, molecules are linked via C(ar)-H⋯π and π-π inter-actions [shortest centroid-centroid distance between benzene rings = 3.897 (2) Å].

  10. Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts.

    PubMed

    Weber, Katharina; Weyhermüller, Thomas; Bill, Eckhard; Erdem, Özlen F; Lubitz, Wolfgang

    2015-07-20

    Diamagnetic iron chloro compounds [(P(Ph)2N(Ph)2)FeCp*Cl] [1Cl] and [(P(Cy)2N(Ph)2)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [(P(Ph)2N(Ph)2)FeCp*H] [1H] and [(P(Cy)2N(Ph)2)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and (57)Fe Mössbauer spectroscopy (P(Ph)2N(Ph)2 = 1,3,5,7-tetraphenyl-1,5-diphospha-3,7-diazacyclooctane, P(Cy)2N(Ph)2 = 1,5-dicyclohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacyclooctane, Cp* = pentamethylcyclopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the P(R)2N(Ph)2 ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong acid trifluoromethanesulfonimide [NHTf2] (pKa(MeCN) = 1.0). In contrast to the related complex [(P(tBu)N(Bn))2FeCp(C6F5)H], which was reported by Liu et al. (Nat. Chem. 2013, 5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.

  11. Solar cells made by laser-induced diffusion directly from phosphine gas

    SciTech Connect

    Turner, G.B.; Tarrant, D.; Pollock, G.; Pressley, R.; Press, R.

    1981-12-15

    A new method for making p-n junctions based on immersion in a transparent dopant gas followed by irradiation with a pulsed laser is presented. An alexandrite laser was used, operating at 0.73 ..mu..m where photolysis of the dopant gas PH/sub 3/ does not occur. Multiple pulses of 2.2--2.7 J/cm/sup 2/ were used to make Si solar cells with total area efficiencies up to 8.6% without benefit of antireflection coatings.

  12. A second monoclinic modification of triphenyl­phosphine oxide hemihydrate

    PubMed Central

    Ng, Seik Weng

    2009-01-01

    In the crystal of the title compound, C18H15OP·0.5H2O, a water molecule links to two adjacent triphenylphosphine molecules by way of O—H⋯O hydrogen bonds. The crystal is twinned, the minor twin component being 36%. PMID:21583272

  13. Tris(4-tert-butyl­phen­yl)phosphine oxide

    PubMed Central

    Hao, Yin-Ge; Yao, Jin-Cai; Li, Jun-Xian; He, Yu-Xin; Zhang, Yu-Qing

    2010-01-01

    In the title compound, C30H39OP, the P=O bond length is 1.4866 (12) Å and the P—C bond lengths range from 1.804 (2) to 1.808 (13) Å. The molecle is located on a crystallographic mirror plane. The methyl groups of one tert-butyl group are disordered over two sites in a 0.776 (4):0.224 (4) ratio. PMID:21580096

  14. The Mechanochemical Reaction of Palladium(II) Chloride with a Bidentate Phosphine

    ERIC Educational Resources Information Center

    Berry, David E.; Carrie, Philippa; Fawkes, Kelli L.; Rebner, Bruce; Xing, Yao

    2010-01-01

    This experiment describes the reaction of palladium(II) chloride with 1,5-bis(diphenylphosphino)pentane by grinding the two powders together in the solid state. The product is the precursor for the metalation reaction at one of the methylene carbon atoms of the ligand's backbone. The final product is known to be a catalyst for Suzuki-Miyaura…

  15. EVALUATION OF PHOSPHINE-OXYGEN DIFFUSION SYSTEM AS A PROCESS FOR SILICON INTEGRATED CIRCUIT FABRICATION.

    DTIC Science & Technology

    Experimental conditions for the attainment of sheet resistance with high reproducibility at emitter doping levels have been obtained using the...gaseous PH3-O2 process. Under these conditions, the deposition sheet resistance follows an activation energy relationship with temperature (with E = 2.9 eV...1000C. The two-step process shows that the final diffused sheet resistance and junction depth can be predicted from the deposition sheet resistance . The

  16. Reactions of (CF3)3BCO with amines and phosphines.

    PubMed

    Finze, Maik; Bernhardt, Eduard; Willner, Helge; Lehmann, Christian W

    2006-01-23

    Reactions of tris(trifluoromethyl)borane carbonyl, (CF(3))(3)BCO, with ammonia yielded either a mixture of [NH(4)][(CF(3))(3)BC(O)NH(2)], [NH(4)][(CF(3))(3)BCN], and [NH(4)](2)[{(CF(3))(3)BC(O)}(2)NH] or neat [NH(4)](2)[{(CF(3))(3)BC(O)}(2)NH] depending on the reaction conditions. The salt K[(CF(3))(3)BC(O)NH(2)] was obtained as the sole product from the reaction of NH(3) with K[(CF(3))(3)BC(O)F]. A simple synthesis for cyanotris(trifluoromethyl)borates, M[(CF(3))(3)BCN], was developed by dehydration of M[(CF(3))(3)BC(O)NH(2)] (M = [NH(4)], K) using phosgene. In addition, syntheses of the tris(trifluoromethyl)boron species [(CF(3))(3)BC(O)NH(n)()Pr](-), [(CF(3))(3)BC(O)NMe(2)](-), and (CF(3))(3)BC(O)NMe(3), as well as of (CF(3))(3)BC(O)PMe(3), were performed. All species were characterized by multinuclear NMR spectroscopy. As far as neat substances resulted, IR and Raman spectra were recorded and their thermal behaviors were studied by differential scanning calorimetry. The interpretation of reaction pathways, structures, and vibrational spectra are supported by DFT calculations. The solid-state structure of K(2)[{(CF(3))(3)BC(O)}(2)NH].2MeCN was determined by single-crystal X-ray diffraction.

  17. Contact doping of silicon wafers and nanostructures with phosphine oxide monolayers.

    PubMed

    Hazut, Ori; Agarwala, Arunava; Amit, Iddo; Subramani, Thangavel; Zaidiner, Seva; Rosenwaks, Yossi; Yerushalmi, Roie

    2012-11-27

    Contact doping method for the controlled surface doping of silicon wafers and nanometer scale structures is presented. The method, monolayer contact doping (MLCD), utilizes the formation of a dopant-containing monolayer on a donor substrate that is brought to contact and annealed with the interface or structure intended for doping. A unique feature of the MLCD method is that the monolayer used for doping is formed on a separate substrate (termed donor substrate), which is distinct from the interface intended for doping (termed acceptor substrate). The doping process is controlled by anneal conditions, details of the interface, and molecular precursor used for the formation of the dopant-containing monolayer. The MLCD process does not involve formation and removal of SiO(2) capping layer, allowing utilization of surface chemistry details for tuning and simplifying the doping process. Surface contact doping of intrinsic Si wafers (i-Si) and intrinsic silicon nanowires (i-SiNWs) is demonstrated and characterized. Nanowire devices were formed using the i-SiNW channel and contact doped using the MLCD process, yielding highly doped SiNWs. Kelvin probe force microscopy (KPFM) was used to measure the longitudinal dopant distribution of the SiNWs and demonstrated highly uniform distribution in comparison with in situ doped wires. The MLCD process was studied for i-Si substrates with native oxide and H-terminated surface for three types of phosphorus-containing molecules. Sheet resistance measurements reveal the dependency of the doping process on the details of the surface chemistry used and relation to the different chemical environments of the P═O group. Characterization of the thermal decomposition of several monolayer types formed on SiO(2) nanoparticles (NPs) using TGA and XPS provides insight regarding the role of phosphorus surface chemistry at the SiO(2) interface in the overall MLCD process. The new MLCD process presented here for controlled surface doping provides a simple yet highly versatile means for achieving postgrowth doping of nanometer scale structures and interfaces.

  18. Synthesis and characterization of functional thienyl-phosphine microporous polymers for carbon dioxide capture.

    PubMed

    Chen, Xianghui; Qiao, Shanlin; Du, Zhengkun; Zhou, Yuanhang; Yang, Renqiang

    2013-07-25

    A novel kind of functional organic microporous polymer is designed by introducing polar organic groups (P=O and P=S) and electron-rich heterocyclic into the framework to obtain high carbon dioxide capture capacity. The estimated Brunauer-Emmett-Teller (BET) surface areas of these polymers are about 600 m(2) g(-1) and the highest CO2 uptake is 2.26 mmol g(-1) (1.0 bar/273 K). Interestingly, the polymer containing P=O groups shows greater CO2 capture capacity than that containing P=S groups at the same temperature. In addition, these polymers show high isosteric heats of CO2 adsorption (28.6 kJ mol(-1) ), which can be competitive with some nitrogen-rich networks. Therefore, these microporous polymers are promising candidates for carbon dioxide capture.

  19. Electron and Hole Transport in a Wide Bandgap Organic Phosphine Oxide for Blue Electrophosphorecsence

    SciTech Connect

    Cai, Xiuyu; Padmaperuma, Asanga B.; Sapochak, Linda S.; Vecchi, Paul A.; Burrows, Paul E.

    2008-02-28

    We report blue phosphorescent organic light-emitting devices (OLEDs) using an ambipolar host, N-(4-diphenylphosphoryl phenyl) carbazole (MPO12), doped with iridium (III) bis[4,6-difluorophenyl)-pyridinato-N,C2´]picolinate (FIrpic). The external quantum efficiency and operating voltage is 9.1±0.1% and 4.8 V, respectively, measured at a brightness of 800 cd/m2 with no outcoupling enhancement. By varying the layer structure of the OLEDs, we show that MPO12 is capable of transporting both electrons and holes, in contrast to previous demonstrations using diphosphine oxides, which only transported electrons. The improved hole transport results in improved device efficiency.

  20. p-Tolyl bis­(o-tolyl­amido)­phosphinate

    PubMed Central

    Sabbaghi, Fahimeh; Mancilla Percino, Teresa; Pourayoubi, Mehrdad; Leyva, Marco A.

    2010-01-01

    In the title compound, C21H23N2O2P, the P atom has a distorted tetra­hedral configuration. The O atom of the OC6H4-4-CH3 group and the N atoms show sp 2 character. In the crystal, adjacent mol­ecules are linked by N—H⋯O hydrogen bonds into helical chains parallel to the b axis. PMID:21587971

  1. Adsorption of low concentration phosphine in yellow phosphorus off-gas by impregnated activated carbon.

    PubMed

    Wang, Xueqian; Ning, Ping; Shi, Yan; Jiang, Ming

    2009-11-15

    In order to utilize high concentration CO comprehensively, impregnated activated carbon sorbent and the catalytic oxidation reaction for PH(3) were investigated in this study. Carbon was impregnated with HCl, KNO(3), or hexanediol. The activated carbon modified by 7% (mass fraction) HCl could enhance the adsorption purification ability significantly. Raising the reaction temperature or increasing the oxygen content of the gas can improve the purification efficiency. The structure of the materials after modification was determined using nitrogen adsorption. The modification decreased the volume of pores smaller than 2 nm in diameter with the most noticeable change occurring in the micropores ranging from 0.3 nm to 1.5 nm in diameter. Decreases in micropore volume accounted for 87% of the total pore volume change. After the adsorption, the surface areas decreased 28%, 29% of which was due to decreased micropore surface. HCl significantly increased the performance of carbon as a PH(3) adsorbent when HCl impregnation was applied whereas the effects of other materials used in this study were much less pronounced. HCl present in the small pores probably acted as a catalyst for oxygen activation that caused PH(3) oxidation. As a result of this process, H(3)PO(4) and P(4)O(10) were formed, strongly adsorbed, and present in the small pores ranging from 0.3 nm to 1.5 nm. In conclusion, this study provides evidence that CO from industrial off-gas can be purified and used as the raw material for a broader range of products.

  2. Synthesis and structure of tridentate bis(phosphinic amide)-phosphine oxide complexes of yttrium nitrate. Applications of 31P,89Y NMR methods in structural elucidation in solution.

    PubMed

    Popovici, Cristinel; Fernández, Ignacio; Oña-Burgos, Pascual; Roces, Laura; García-Granda, Santiago; Ortiz, Fernando López

    2011-07-07

    The synthesis and characterisation of a tridentate ligand containing two diphenylphosphinic amide side-arms connected through the ortho position to a phenylphosphine oxide moiety and the 1:1 and 2:1 complexes formed with yttrium nitrate are reported for the first time. The free ligand (R(P1)*,S(P3)*)-11 is obtained diastereoselectively by reaction of ortho-lithiated N,N-diisopropyl-P,P-diphenylphosphinic amide with phenylphosphonic dichloride. Complexes [Y((R(P1)*,S(P3)*)-11)(NO(3))(3)] and [Y((R(P1)*,S(P3)*)-11)(2)(NO(3))](NO(3))(2) were isolated by mixing ligand 11 with Y(NO(3))(3)·6H(2)O in acetonitrile at room temperature in a ligand to metal molar ratio of 1:1 and 2:1, respectively. The 1:1 derivative is the product of thermodynamic control when a molar ratio of ligand to yttrium salt of 1:1 is used. The new compounds have been characterised both as the solid (X-ray diffraction) and in solution (multinuclear magnetic resonance). In both yttrium complexes the ligand acts as a tridentate chelate. The arrangement of the two ligands in the 2:1 complex affords a pseudo-meso structure. Tridentate chelation of yttrium(III) in both complexes is retained in solution as evidenced by (89)Y NMR data obtained via(31)P,(89)Y-HMQC, and (89)Y,(31)P-DEPT experiments. The investigation of the solution behaviour of the Y(III) complexes through PGSE NMR diffusion measurements showed that average structures in agreement with the 1:1 and 1:2 stoichiometries are retained in acetonitrile.

  3. Taking TiF4 complexes to extremes--the first examples with phosphine co-ligands.

    PubMed

    Jura, Marek; Levason, William; Petts, Edmund; Reid, Gillian; Webster, Michael; Zhang, Wenjian

    2010-11-14

    The first soft donor adducts of TiF(4), [TiF(4)(diphosphine)] (diphosphine = o-C(6)H(4)(PMe(2))(2), R(2)P(CH(2))(2)PR(2), R = Me or Et) have been prepared from [TiF(4)(MeCN)(2)] and the diphosphines in rigorously anhydrous CH(2)Cl(2), as extremely moisture sensitive yellow solids, and characterised by multinuclear NMR ((1)H, (31)P, (19)F), IR and UV/vis spectroscopy. The crystal structure of [TiF(4){Et(2)P(CH(2))(2)PEt(2)}] has been determined and shows a distorted six-coordinate geometry with disparate Ti-F(transF) and Ti-F(transP) distances and long Ti-P bonds. Weaker soft donor ligands including Ph(3)P, Ph(2)P(CH(2))(2)PPh(2), o-C(6)H(4)(PPh(2))(2), Ph(2)As(CH(2))(2)AsPh(2), o-C(6)H(4)(AsMe(2))(2) and (i)PrS(CH(2))(2)S(i)Pr do not form stable complexes with TiF(4), although surprisingly, fluorotitanate(IV) salts of the previously unknown doubly protonated ligand cations [LH(2)][Ti(4)F(18)] (L = o-C(6)H(4)(PPh(2))(2), o-C(6)H(4)(AsMe(2))(2) and (i)PrS(CH(2))(2)S(i)Pr) are formed in some cases as minor by-products. The structure of [o-C(6)H(4)(PPh(2)H)(2)][Ti(4)F(18)] shows the first authenticated example of a diprotonated o-phenylene-diphosphine. The synthesis and full spectroscopic characterisation are reported for a range of TiF(4) adducts with hard N- or O-donor ligands for comparison purposes, along with crystal structures of [TiF(4)(thf)(2)], [TiF(4)(Ph(3)EO)(2)]·2CH(2)Cl(2) (E = P or As), and [TiF(4)(bipy)].

  4. Graphitic carbon nitride/phosphorus-rich aluminum phosphinates hybrids as smoke suppressants and flame retardants for polystyrene.

    PubMed

    Shi, Yongqian; Yu, Bin; Duan, Lijin; Gui, Zhou; Wang, Bibo; Hu, Yuan; Yuen, Richard K K

    2017-03-06

    Graphitic carbon nitride/organic aluminum hypophosphites (g-C3N4/OAHPi) hybrids, i.e., CPDCPAHPi and CBPODAHPi, were synthesized by esterification and salification reactions, and then incorporated into polystyrene (PS) to prepare composites through a melt blending method. Structure and morphology characterizations demonstrated the successful synthesis of PDCPAHPi, BPODAHPi and their hybrids. The g-C3N4 protected OAHPi from external heat and thus improved the thermal stability of OAHPi. Combining g-C3N4 with OAHPi contributed to reduction in peak of heat release rate, total heat release and smoke production rate of PS matrix. Reduced smoke released has also been demonstrated by smoke density chamber testing. Additionally, introduction of the hybrids led to decreased release of flammable aromatic compounds. These properties improvement could be attributed to gas phase action and physical barrier effect in condensed phase: phosphorus-containing low-energy radicals generated from OAHPi effectively captured high-energy free-radicals evolved from PS; g-C3N4 nanosheets retarded the permeation of heat and the escape of volatile degradation products. Therefore, g-C3N4/OAHPi hybrids will provide a potential strategy to reduce the fire hazards of PS.

  5. (η6-p-Cymene)bis­(trichlorido­stannyl)(triethoxy­phosphine-κP)ruthenium(II)

    PubMed Central

    Shapovalov, Sergey S.; Therrien, Bruno

    2009-01-01

    In the title complex, [RuSn2(C10H14)Cl6(C6H15O3P)], the Ru—Sn bond lengths [2.5619 (3) and 2.5669 (3) Å] are about 0.3 Å shorter than the sum of the covalent Ru and Sn radii (1.46 + 1.39 = 2.85 Å), in line with other structurally characterized arene ruthenium trichlorido­stannyl derivatives. The Ru(II) atom is surrounded by a para-cymene, a triethylphosphite and two trichloridostannyl ligands in a typical piano-stool coordination. PMID:21578155

  6. cis-cis-trans-Bis(acetonitrile-κN)dichloridobis(triphenyl­phosphine-κP)ruthenium(II) acetonitrile disolvate

    PubMed Central

    Al-Far, Ahmad M.; Slaughter, LeGrande M.

    2008-01-01

    The title compound, [RuCl2(C2H3N)2(C18H15P)2]·2C2H3N, was obtained upon stirring an acetonitrile/ethanol solution of [RuCl2(PPh3)3]. In the crystal structure, each RuII ion is coordinated by two Cl [Ru—Cl = 2.4308 (7) and 2.4139 (7) Å], two N [Ru—N = 2.016 (2) and 2.003 (2) Å], and two P [Ru—P = 2.3688 (7) and 2.3887 (7) Å] atoms in a distorted octa­hedral geometry. Packing inter­actions include typical C—H⋯π contacts involving phenyl groups as well as weak hydrogen bonds between CH3CN methyl H atoms and Cl or solvent CH3CN N atoms. PMID:21200532

  7. P,P-Bis[4-(dimethyl-amino)-phen-yl]-N,N-bis-(propan-2-yl)phosphinic amide.

    PubMed

    Evans, Stephen J; Renison, C Alicia; Williams, D Bradley G; Muller, Alfred

    2013-02-01

    The mol-ecular structure of the title compound, C(22)H(34)N(3)OP, adopts a distorted tetra-hedral geometry at the P atom, with the most noticeable distortion being for the O-P-N angle [117.53 (10)°]. An effective cone angle of 187° was calculated for the compound. In the crystal, weak C-H⋯O inter-actions create infinite chains along [100], whereas C-H⋯π inter-actions propagating in [001] generate a herringbone motif.

  8. Line positions and intensities of the phosphine (PH3) Pentad near 4.5μm

    SciTech Connect

    Malathy Devi, V.; Kleiner, Isabelle; Sams, Robert L.; Brown, Linda R.; Benner, D. Chris; Fletcher, Leigh N.

    2014-04-01

    In order to improve the spectroscopic database for remote sensing of the giant planets, line positions and intensities are determined for the five bands (2ν2, ν2 + ν4, 2ν4, ν1 and ν3) that comprise the Pentad of PH3 between 1950 and 2450 cm-1. Knowledge of PH3 spectral line parameters in this region is important for the exploration of dynamics and chemistry on Saturn, (using existing Cassini/VIMS observations) and future near-IR data of Jupiter from Juno and ESA’s Jupiter Icy Moons Explorer (JUICE). For this study, spectra of pure PH3 from two Fourier transform spectrometers were obtained: (a) five high-resolution (0.00223 cm-1), high signal-to-noise (~1800) spectra recorded at room temperature (298.2 K) with the Bruker IFS 125HR Fourier transform spectrometer (FTS) at the Pacific Northwest National Laboratory (PNNL), Richland, Washington and (b) four high-resolution (at 0.0115 cm-1 resolution), high signal-to-noise (~700) spectra recorded at room temperature in the region 1800–5200 cm-1 using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory (NSO) on Kitt Peak. Individual line parameters above 2150 cm-1 were retrieved by simultaneous multispectrum fittings of all five Bruker spectra, while retrievals with the four Kitt Peak spectra were done in the 1938–2168 cm-1 range spectrum by spectrum and averaged. In all, positions and intensities were obtained for more than 4400 lines. These included 53 A+A- split pairs of transitions (arising due to vibration–rotation interactions (Coriolis-type interaction) between the ν3 and ν1 fundamental bands) for K" = 3, 6, and 9. Over 3400 positions and 1750 intensities of these lines were ultimately identified as relatively unblended and modeled up to J = 14 and K = 12 with rms values of 0.00133 cm-1 and 7.7%, respectively. The PH3 line parameters (observed positions and measured intensities with known quantum assignments) and Hamiltonian constants are reported. Finally, comparisons with other recent studies are discussed.

  9. cis-Bis(nitrato-κ2 O,O′)bis­(triethyl­phosphine oxide-κO)nickel(II)

    PubMed Central

    Seidel, Rüdiger W.

    2009-01-01

    In the title compound, [Ni(NO3)2(C6H15OP)2], the NiII ion, lying on a crystallographic twofold axis, adopts a distorted octa­hedral coordination, consisting of O-donor atoms of two symmetry-related triethyl­phospine oxide and two bidentate nitrate ligands. PMID:21582983

  10. Allenes in Asymmetric Catalysis. Asymmetric Ring-Opening of Meso-Epoxides Catalyzed by Allene-Containing Phosphine Oxides

    PubMed Central

    Pu, Xiaotao; Qi, Xiangbing; Ready, Joseph M.

    2009-01-01

    Unsymmetrically substituted allenes (1,2 dienes) are inherently chiral and can be prepared in optically pure form. Nonetheless, to date the allene framework has not been incorporated into ligands for asymmetric catalysis. Since allenes project functionality differently than either tetrahedral carbon or chiral biaryls, they may create complementary chiral environments. This study demonstrates that optically active C2 symmetric allene-containing bisphosphine oxides can catalyze the addition of SiCl4 to meso epoxides with high enantioselectivity. The epoxide-opening likely involves generation of a Lewis acidic, cationic (bisphosphine oxide)SiCl3 complex. The fact that high asymmetric induction is observed suggests that allenes may represent a new platform for the development of ligands and catalysts for asymmetric synthesis. PMID:19722613

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

    DTIC Science & Technology

    1982-09-01

    tD8100909 removed from study due to severe urinary tract infection which was discovered at neoropsy. APPENDIX D (Cont) Lewis--27 TABLE 3 ’stimates of the...sacrifice from the study due to a severe urinary tract infection . The infection was judged not to be compound related, consequently, the results for this

  12. (2-{[2-(diphenyl­phosphino)phen­yl]thio}­phen­yl)diphenyl­phosphine sulfide

    PubMed Central

    Alvarez-Larena, Angel; Martinez-Cuevas, Francisco J.; Flor, Teresa; Real, Juli

    2012-01-01

    In the title compound, C36H28P2S2, the dihedral angle between the central benzene rings is 66.95 (13)°. In the crystal, molecules are linked via Car—H⋯π and π–π inter­actions [shortest centroid–centroid distance between benzene rings = 3.897 (2) Å]. PMID:23284423

  13. Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions.

    PubMed

    Lu, Xiao-Xia; Tang, Hau-San; Ko, Chi-Chiu; Wong, Jenny Ka-Yan; Zhu, Nianyong; Yam, Vivian Wing-Wah

    2005-03-28

    The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.

  14. VizieR Online Data Catalog: ExoMol line lists for phosphine (PH3) (Sousa-Silva+,

    NASA Astrophysics Data System (ADS)

    Sousa-Silva, C.; Al-Refaie, A. F.; Tennyson, J.; Yurchenko, S. N.

    2014-11-01

    The data are in two parts. The first, ph3_0-46.dat contains a list of 9,787,832 rovibrational states. Each state is labelled with: 6 normal mode vibrational quantum numbers, 1 multiplexed L quantum number and the vibrational symmetry; three rotational quantum numbers including the total angular momentum J, the projection of J in the z-axis K,rotational symmetry and the total symmetry quantum number Gamma In addition there are nine local mode vibrational numbers and the largest coefficient used to assign the state in question. Each rovibrational state has a unique number, which is the number of the row in which it appears in the file. This number is the means by which the state is related to the second part of the data system, the transitions files. The total degeneracy is also given to facilitate the intensity calculations. Because of their size, the transitions are listed in 100 separate files, each containing all the transitions in a 100cm-1 frequency range. These and their contents are ordered by increasing frequency. The name of the file includes the lowest frequency in the range; thus the a-00500.dat file contains all the transitions in the frequency range 500-600cm-1. The transition files contain three columns: the reference number in the energy file of the upper state; that of the lower state; and the Einstein A coefficient of the transition. The energy file and the transitions files are zipped, and need to be extracted before use. There is a Fortran 90 programme, s_SAlTY.f90 which may be used to generate synthetic spectra (see s_SAlTY.txt for details). Using this, it is possible to generate absorption or emission spectra in either 'stick' form or else cross-sections convoluted with a gaussian with the half-width at half maximum being specified by the user, or with a the temperature-dependent doppler half-width. Sample input files s*.inp for use with sSAlTY.f90 are supplied. (10 data files).

  15. Phosphine-free Stille-Migita chemistry for the mild and orthogonal modification of DNA and RNA.

    PubMed

    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.

  16. The importance of the Lewis base in lithium mediated metallation and bond cleavage reaction of allyl amines and allyl phosphines.

    PubMed

    Blair, V L; Stevens, M A; Thompson, C D

    2016-06-21

    Metallation of two analogous N- and P-allyl molecules Ph2NCH2CHCH2 and Ph2PCH2CHCH2 with nBuLi have shown contrasting reactivities based on the choice of Lewis donor. With metallation of the alpha carbon atom was achieved regardless of the Lewis donor used while in comparison metallation of showed an unexpected donor denticity dependence with P-C bond clevage induced with the tri-dentate PMDETA. Complementary DFT and solution studies rationalise this outcome.

  17. Tris[3,5-bis­(trifluoro­meth­yl)phen­yl]phosphine oxide

    PubMed Central

    Shawkataly, Omar bin; Pankhi, Mohd. Aslam A.; Mohamed-Ibrahim, Mohamed Ismail; Hamdan, M. Razak; Fun, Hoong-Kun

    2009-01-01

    In the title compound, C24H9F18OP, an intra­molecular C—H⋯O short contact generates a five-membered ring, producing an S(5) ring motif. The dihedral angles between the benzene rings are 57.68 (10), 77.80 (11) and 79.48 (10)°. Each of the six trifluoro­methyl substituents shows rotational disorder over two positions with refined site-occupany ratios of 0.64 (3)/0.36 (3), 0.649 (14)/0.351 (14), 0.52 (2)/0.48 (2), 0.545 (16)/0.455 (16), 0.774 (9)/0.226 (9) and 0.63 (5)/0.37 (5). The crystal structure is stabilized by inter­molecular C—H⋯O and C—H⋯F inter­actions. PMID:21583895

  18. Synthesis and evaluation of glycopolymeric decorated gold nanoparticles functionalized with gold-triphenyl phosphine as anti-cancer agents.

    PubMed

    Adokoh, Christian K; Quan, Stephen; Hitt, Mary; Darkwa, James; Kumar, Piyush; Narain, Ravin

    2014-10-13

    In this study, statistical glyco-dithiocarbamate (DTC) copolymers were synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequently used to prepare glyconanoparticles and conjugated glyconanoparticles with the anticancer drug, gold(I) triphenylphosphine. These glyconanoparticles and the corresponding conjugates were then tested for their in vitro cytotoxicity in both normal and cancer cell lines using Neutral Red assay. The glyconanoparticles and their Au(I)PPh3 conjugates were all active against MCF7 and HepG2 cells, but galactose-functionalized glyconanoparticles {P(GMA-EDAdtc(AuPPh3)-st-LAEMA)AuNP} were found to be the most cytotoxic to HepG2 cells (IC50 ∼ 4.13 ± 0.73 μg/mL). The p(GMA-EDAdtc(AuPPh3)-st-LAEMA)AuNP was found to be a 4-fold more potent antitumor agent in HepG2 cells, and the overexpressed asialoglycoprotein (ASGPR) receptors revealed to play an important role in the cytotoxicity, presumably by the enhanced uptake. In addition, the glyconanoparticles Au(I) conjugates are found to be significantly more toxic as compared to the standard chemotherapeutic reagents such as cisplatin and cytarabine.

  19. Line positions and intensities of the phosphine (PH3) Pentad near 4.5 μm

    NASA Astrophysics Data System (ADS)

    Malathy Devi, V.; Kleiner, Isabelle; Sams, Robert L.; Brown, Linda R.; Benner, D. Chris; Fletcher, Leigh N.

    2014-04-01

    In order to improve the spectroscopic database for remote sensing of the giant planets, line positions and intensities are determined for the five bands (2ν2, ν2 + ν4, 2ν4, ν1 and ν3) that comprise the Pentad of PH3 between 1950 and 2450 cm-1. Knowledge of PH3 spectral line parameters in this region is important for the exploration of dynamics and chemistry on Saturn, (using existing Cassini/VIMS observations) and future near-IR data of Jupiter from Juno and ESA's Jupiter Icy Moons Explorer (JUICE). For this study, spectra of pure PH3 from two Fourier transform spectrometers were obtained: (a) five high-resolution (0.00223 cm-1), high signal-to-noise (∼1800) spectra recorded at room temperature (298.2 K) with the Bruker IFS 125HR Fourier transform spectrometer (FTS) at the Pacific Northwest National Laboratory (PNNL), Richland, Washington and (b) four high-resolution (at 0.0115 cm-1 resolution), high signal-to-noise (∼700) spectra recorded at room temperature in the region 1800-5200 cm-1 using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory (NSO) on Kitt Peak. Individual line parameters above 2150 cm-1 were retrieved by simultaneous multispectrum fittings of all five Bruker spectra, while retrievals with the four Kitt Peak spectra were done in the 1938-2168 cm-1 range spectrum by spectrum and averaged. In all, positions and intensities were obtained for more than 4400 lines. These included 53 A+A- split pairs of transitions (arising due to vibration-rotation interactions (Coriolis-type interaction) between the ν3 and ν1 fundamental bands) for K″ = 3, 6, and 9. Over 3400 positions and 1750 intensities of these lines were ultimately identified as relatively unblended and modeled up to J = 14 and K = 12 with rms values of 0.00133 cm-1 and 7.7%, respectively. The PH3 line parameters (observed positions and measured intensities with known quantum assignments) and Hamiltonian constants are reported. Comparisons with other recent studies are discussed.

  20. New Ru complexes containing the N-tridentate bpea and phosphine ligands: consequences of meridional vs facial geometry.

    PubMed

    Mola, Joaquim; Rodríguez, Montserrat; Romero, Isabel; Llobet, Antoni; Parella, Teodor; Poater, Albert; Duran, Miquel; Solà, Miquel; Benet-Buchholz, Jordi

    2006-12-25

    The synthesis and isolation of the complex cis,fac-[RuIICl2(bpea)(PPh3)][3; bpea = N,N-bis(2-pyridylmethyl)ethylamine] and three geometrical isomers of the complex [RuIICl(bpea)(dppe)](BF4) [4; dppe = (1,2-diphenylphosphino)ethane], trans,fac (4a), cis,fac (4b), and mer(down) (4c), have been described (see Chart 1 for a drawing of their structures). These complexes have been characterized through analytical, spectroscopic (IR, UV/vis, and 1D and 2D NMR), and electrochemical (cyclic voltammetry) techniques. In addition, complexes 3, 4a, and 4b have been further characterized in the solid state through monocrystal X-ray diffraction analysis. The molecular and electronic structures of isomers 4a, 4b, 4c, and 4d (the mer(up) isomer) have also been studied by means of density functional theory (DFT) calculations. Furthermore, their low-energy electronic transitions have been simulated using time-dependent DFT approaches, which have allowed unraveling of their metal-to-ligand charge-transfer nature. Complexes 3 and 4a-c are capable of catalyzing H-transfer types of reactions between alcohols and aromatic ketones such as acetophenone and 2,2-dimethylpropiophenone (DP). A strong influence of the facial versus meridional geometry in the bpea ligand coordination mode is observed for these catalytic reactions, with the meridional isomer being much more active than the facial one. The meridional isomer is even capable of carrying out the H-transfer reaction of bulky substrates such as DP at room temperature.

  1. Synthesis, characterization and structural determination of some nickel(II) complexes containing imido Schiff bases and substituted phosphine ligands.

    PubMed

    Kianfar, Ali Hossein; Ebrahimi, Mostafa

    2013-11-01

    Some new tridentate ONN Schiff base complexes of [NiL(PR3)] (where L=Salicylidene2-amino4-nitrobenzene (L(1)), 5-BrSalicylidene2-amino4-nitrobenzene (L(2)), 5-NO2Salicylidene2-amino4-nitrobenzene (L(3)), 5-MeOSalicylidene2-amino4-nitrobenzene (L(4)) and 3-MeOSalicylidene2-amino4-nitrobenzene (L(5)), R=Bu and Ph (with L(1))) were synthesised and characterized by IR, UV-Vis, (1)H NMR spectroscopy and elemental analysis. The geometry of [NiL(1)(PPh3)] was determined by X-ray crystallography. It indicated that the complex had a planar structure and four coordinates in the solid state. The thermogravimetry (TG) and differential thermoanalysis (DTA) of the synthesized complexes were carried out in the range of 20-600°C, leading to the decomposition of L(1)-L(3) type in three stages and of L(4)-L(5) and [NiL(1)(PPh3)] type in four stages. Thermal decomposition of the complexes was closely the dependent upon the nature of the Schiff base ligands and proceeded via the first order kinetics.

  2. Characterizing traditional and chlorine-shared halogen bonds in complexes of phosphine derivatives with ClF and Cl2.

    PubMed

    Alkorta, Ibon; Elguero, José; Del Bene, Janet E

    2014-06-12

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out on the halogen-bonded complexes H2XP:ClF and H2XP:Cl2, with X = F, Cl, OH, NC, CN, CCH, CH3, and H. H2XP:ClF complexes are stabilized by chlorine-shared halogen bonds with short P-Cl and significantly elongated Cl-F distances. H2XP:Cl2 complexes with X = OH and CH3 form only chlorine-shared halogen bonds, while those with X = H, NC, and CN form only traditional halogen bonds. On the H2FP:Cl2, H2(CCH)P:Cl2, and H2ClP:Cl2 potential surfaces small barriers separate two equilibrium structures, one with a traditional halogen bond and the other with a chlorine-shared bond. The binding energies of H2XP:ClF and H2XP:Cl2 complexes are influenced by the electron-donating ability of H2XP and the electron accepting ability of ClF and ClCl, the nature of the halogen bond, other secondary interactions, and charge-transfer interactions. Changes in electron populations on P, F, and Cl upon complex formation do not correlate with changes in the chemical shieldings of these atoms. EOM-CCSD spin-spin coupling constants for complexes with chlorine-shared halogen bonds do not exhibit the usual dependencies on distance. (2X)J(P-F) and (2X)J(P-Cl) for complexes with chlorine-shared halogen bonds do not correlate with P-F and P-Cl distances, respectively. (1X)J(P-Cl) values for H2XP:ClF correlate best with the Cl-F distance, and approach the values of (1)J(P-Cl) for the corresponding cations H2XPCl(+). Values of (1X)J(P-Cl) for complexes H2XP:ClCl with chlorine-shared halogen bonds correlate with the binding energies of these complexes. (1)J(F-Cl) and (1)J(Cl-Cl) for complexes with chlorine-shared halogen bonds correlate linearly with the distance between P and the proximal Cl atom. In contrast, (2X)J(P-Cl) and (1X)J(P-Cl) for complexes with traditional halogen bonds exhibit more normal distance dependencies.

  3. High-efficiency turquoise-blue electrophosphorescence from a Pt(II)-pyridyltriazolate complex in a phosphine oxide host

    NASA Astrophysics Data System (ADS)

    Bhansali, Unnat S.; Polikarpov, Evgueni; Swensen, James S.; Chen, Wei-Hsuan; Jia, Huiping; Gaspar, Daniel J.; Gnade, Bruce E.; Padmaperuma, Asanga B.; Omary, Mohammad A.

    2009-12-01

    We demonstrate high-efficiency turquoise-blue electrophosphorescence from bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) [Pt(ptp)2] doped in 4-(diphenylphosphoryl)-N ,N-diphenylaniline(HM-A1). Organic light-emitting diodes (OLEDs) with 5% Pt(ptp)2:HM-A1 attain peak power efficiency of 61.2 lm/W, versus 40.8 lm/W for analogous devices employing the standard turquoise-blue phosphor bis[(4,6-difluorophenyl)-pyridinato-N,C2'](picolinato)iridium(III) (FIrpic). Devices with x% Pt(ptp)2:HM-A1 exhibit blue emission maxima (λmax˜480 nm) with monotonic increase in excimer/monomer intensity ratio at higher doping levels within 1%-10%, causing color shift toward green and less charge balance. This work represents a significant step toward optimizing future white OLEDs from the same phosphor via combination of low-doped and higher-doped or neat films.

  4. Mutagenic Potential of: 4-Nitrophenyl Dimethyl Phosphinate (TA007) using the Sex-Linked Recessive Lethal Test in Drosophila melanogaster.

    DTIC Science & Technology

    1984-10-01

    XXXXII-67 LAIR Code: TAO07 Chemical Abstract Service Registry Number: 13344-08-6 Molecular structure: HCH C3 Empirical formula: C H No P8 10 4...Molecular structure: H3C I- cH3 Chemical Abstract Service Registry Number: 13344-08-6 Empirical formula: C8 H 10NO 4P Molecular weight: 215.15 pH: N/A non

  5. The Mutagenic Potential of: 4-Nitrophenyl Diphenyl Phosphinate Using the Drosophila melanogaster Sex-Linked Recessive Lethal Test.

    DTIC Science & Technology

    1983-03-01

    an aqueous system, a mixture of Tween 80 , ethanol (100%), citrate buffer, (5.0 mM) and distilled water were prepared to stabilize the test Powers-4...chemical fromulated with TWeen 80 , ethanol (100%), citrate buffer (5.0 mM), distilled water, and 1% fructose. These males formed the test Tgroups...Concurrent exposure, 250 ul of a mixture of Tween 80 , ethanol (100%), citrate buffer (5.0 mM), distilled water, and 1% fructose for CS males to feed upon

  6. Mutagenic Potential of 4-Nitrophenyl Monochloromethyl (Phenyl) Phosphinate Using the Drosophila melanogaster Sex-Linked Recessive Lethal Test.

    DTIC Science & Technology

    1983-08-01

    11CiNO P 0 !12-C1 Molecular Weight: 311.67 Vehicle Due to the instability o ,TAO09 when prepared in an aqueous system, a mixture of Tween 80 , ethanol...variousToncentrations of the test chemical formulated with Tween 80 , ethanol (100%), citrate buffer (5.0 mM), water and 1% fructose. These males Im...a mixture of Tween 80 , ethanol (100%), citrate buffer (5.0 .M), and 1% fructose for CS males to feed upon (250 ul) were designated as negative

  7. Mutagenic Potential of 4-Nitrophenyl Methyl (Phenyl) Phosphinate Using the Drosophila melanogaster Sex-Linked Recessive Lethal Test.

    DTIC Science & Technology

    1983-04-01

    inst ability of (TWq I) when prepared in an aqueous system, a mixture of Tween 80 R, ethanol, citrate buffer and water were prepared to stabilize the...concentrations of the test chemical formulated with Tween 80 , ethanol, citrate buffer, water and 1% fructose. These m0es formed the test groups. Concurrent...exposure of the Tween 80 , ethanol, citrate buffer, water and 1% fructose (250 ul) for CS males to feed upon were designated as negative control

  8. Size-dependent stability toward dissociation and ligand binding energies of phosphine-ligated gold cluster ions

    SciTech Connect

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2014-01-01

    The stability of sub-nanometer size gold clusters ligated with organic molecules is of paramount importance to the scalable synthesis of monodisperse size-selected metal clusters with highly tunable chemical and physical properties. For the first time, a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS) equipped with surface induced dissociation (SID) has been employed to investigate the time and collision energy resolved fragmentation behavior of cationic doubly charged gold clusters containing 7-9 gold atoms and 6-7 triphenylphosphine (TPP) ligands prepared by reduction synthesis in solution. The TPP ligated gold clusters are demonstrated to fragment through three primary dissociation pathways: (1) Loss of a neutral TPP ligand from the precursor gold cluster, (2) asymmetric fission and (3) symmetric fission and charge separation of the gold core resulting in formation of complementary pairs of singly charged fragment ions. Threshold energies and activation entropies of these fragmentation pathways have been determined employing Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental SID data. It is demonstrated that the doubly charged cluster ion containing eight gold atoms and six TPP ligands, (8,6)2+, exhibits exceptional stability compared to the other cationic gold clusters examined in this study due to its large ligand binding energy of 1.76 eV. Our findings demonstrate the dramatic effect of the size and extent of ligation on the gas-phase stability and preferred fragmentation pathways of small TPP-ligated gold clusters.

  9. Side Effects of Smallpox Vaccination

    MedlinePlus

    ... Vesicant/Blister Agent Poisoning Phosphine Case Definition: Phosphine Phosphorus, elemental, white or yellow Case Definition: Phosphorus Potassium cyanide (KCN) Pulmonary/choking/lung agents Ricin ...

  10. Someone You Are Close to May Get the Smallpox Vaccine: What You Should Know and Do

    MedlinePlus

    ... Vesicant/Blister Agent Poisoning Phosphine Case Definition: Phosphine Phosphorus, elemental, white or yellow Case Definition: Phosphorus Potassium cyanide (KCN) Pulmonary/choking/lung agents Ricin ...

  11. What to Do After You've Gotten the Smallpox Vaccine

    MedlinePlus

    ... Vesicant/Blister Agent Poisoning Phosphine Case Definition: Phosphine Phosphorus, elemental, white or yellow Case Definition: Phosphorus Potassium cyanide (KCN) Pulmonary/choking/lung agents Ricin ...

  12. Selective extraction of metal ions with polymeric extractants by ion exchange/redox

    DOEpatents

    Alexandratos, Spiro D.

    1987-01-01

    The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

  13. Heteroleptic Copper(I) Complexes of “Scorpionate” Bis-pyrazolyl Carboxylate Ligand with Auxiliary Phosphine as Potential Anticancer Agents: An Insight into Cytotoxic Mode

    NASA Astrophysics Data System (ADS)

    Khan, Rais Ahmad; Usman, Mohammad; Dhivya, Rajakumar; Balaji, Perumalsamy; Alsalme, Ali; Allohedan, Hamad; Arjmand, Farukh; Alfarhan, Khalid; Akbarsha, Mohammad Abdulkader; Marchetti, Fabio; Pettinari, Claudio; Tabassum, Sartaj

    2017-03-01

    New copper(I) complexes [CuCl(PPh3)(L)] (1: L = LA = 4-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane (2: L = LB = 3-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane) were prepared and characterised by elemental analysis and various spectroscopic techniques such as FT-IR, NMR, UV–Vis, and ESI-MS. The molecular structures of complexes 1 and 2 were analyzed by theoretical B3LYP/DFT method. Furthermore, in vitro DNA binding studies were carried out to check the ability of complexes 1 and 2 to interact with native calf thymus DNA (CT-DNA) using absorption titration, fluorescence quenching and circular dichroism, which is indicative of more avid binding of the complex 1. Moreover, DNA mobility assay was also conducted to study the concentration-dependent cleavage pattern of pBR322 DNA by complex 1, and the role of ROS species to have a mechanistic insight on the cleavage pattern, which ascertained substantial roles by both hydrolytic and oxidative pathways. Additionally, we analyzed the potential of the interaction of complex 1 with DNA and enzyme (Topo I and II) with the aid of molecular modeling. Furthermore, cytotoxic activity of complex 1 was tested against HepG2 cancer cell lines. Thus, the potential of the complex 1 is promising though further in vivo investigations may be required before subjecting it to clinical trials.

  14. Molecular and biochemical evidence on the protection of cardiomyocytes from phosphine-induced oxidative stress, mitochondrial dysfunction and apoptosis by acetyl-L-carnitine.

    PubMed

    Baghaei, Amir; Solgi, Reza; Jafari, Abbas; Abdolghaffari, Amir Hossein; Golaghaei, Alireza; Asghari, Mohammad Hossein; Baeeri, Maryam; Ostad, Seyed Nasser; Sharifzadeh, Mohammad; Abdollahi, Mohammad

    2016-03-01

    The aim of the present study was to investigate the efficacy of acetyl-L-carnitine (ALCAR) on pathologic changes of mitochondrial respiratory chain activity, ATP production, oxidative stress, and cellular apoptosis/necrosis induced by aluminum phosphide (AlP) poisoning. The study groups included: the Sham that received almond oil only; the AlP that received oral LD50 dose of aluminum; the AC-100, AC-200, and AC-300 which received concurrent oral LD50 dose of AlP and single 100, 200, and 300 mg/kg of ALCAR by intraperitoneal injection. After 24 h, the rats were sacrificed; the heart and blood sample were taken for measurement of biochemical and mitochondrial factors. The results specified that ALCAR significantly attenuated the oxidative stress (elevated ROS and plasma iron levels) caused by AlP poisoning. ALCAR also increased the activity of cytochrome oxidase, which in turn amplified ATP production. Furthermore, flow cytometric assays and caspase activity indicated that ALCAR prohibited AlP-induced apoptosis in cardiomyocytes.

  15. Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

    NASA Astrophysics Data System (ADS)

    Jenkins, Darkus E.; Assefa, Zerihun

    2017-04-01

    The synthesis and structural characterization of the bridging ligand, 1-methyl benzimidazole diphenylphosphine (MBDP) and its coordination with Au(I) and Ag(I) metal ions is reported. Two ligands coordinate to the metal ions in head to tail fashion forming a metallacycle coordination consisting of strong M-M bonding interaction with Ausbnd Au = 2.808 and Agsbnd Ag = 3.017 Å. Linear coordination is observed for the gold, while the silver shows distorted tetrahedral arrangement. X-ray crystal data of [(MBDP)2Au2](CH3CN)(BF4)2 (2) crystallizes in the monoclinic system with the space group of P21/n with cell constants of a = 8.9993 (8) Å, b = 19.6166 (18) Å, c = 13.4484 (12) Å, β = 100.966 (2)°, R = 0.026, and Rw = 0.064. The structure of [(MBDP)2(CH3CN)4Ag2](BF4)2, (3) crystallizes in the P (-)1 space group and the unit cell is a = 10.5423 (10) Å, b = 10.7638 (10) Å, c = 12.3530 (12) Å; α = 88.592 (3)°, β = 73.097 (3)°, γ = 84.422 (3)°, V = 1334.8 (2) Å3 with Z = 1, R = 0.034 and Rw = 0.093. The coordinating ligand as well as both dinuclear compounds reported here are luminescent in the near UV region. As supported by the DFT theoretical work, the emission is suggested to be primarily ligand based π- π* transition.

  16. P-[N-(Diphenyl­phospho­rothio­yl)iso­propyl­amino]-N-isopropyl-P-phenyl­thio­phosphinic amide

    PubMed Central

    Peulecke, Normen; Aluri, Bhaskar R.; Wöhl, Anina; Spannenberg, Anke; Al-Hazmi, Mohammed H.

    2009-01-01

    The title compound, C24H30N2P2S2, was obtained by the reaction of Ph2PN(iPr)P(Ph)N(iPr)H with elemental sulfur in tetra­hydro­furan. In the solid state, intra­molecular N—H⋯S hydrogen bonding influences the mol­ecular conformation; a P—N—P—N torsion angle of 2.28 (9)° is observed. The two phenyl rings attached to one P atom form a dihedral angle of 74.02 (4)°. PMID:21583899

  17. rac-Carbon­yl{1-[(diphenyl­phosphino)meth­yl]ethanethiol­ato}(triphenyl­phosphine)rhodium(I)

    PubMed Central

    Hernández-Ortega, Simón; Morales-Morales, David

    2008-01-01

    The title compound, [Rh(C15H16PS)(C18H15P)(CO)], was synthesized from the reaction of the ligand rac-[Ph2PCH2CH(CH3)SH] with trans-[Rh(F)(CO)(PPh3)2] in a 1:1 molar ratio in toluene. The Rh atom is four-coordinated in a distorted square-planar geometry with the P—S ligand [Ph2PCH2CH(CH3)S] acting as a chelate and the PPh3 and disordered CO [site occupation factors of 0.61 (5) and 0.39 (5)] ligands completing the coordination. PMID:21580902

  18. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes.

    PubMed

    Matveeva, Anna G; Vologzhanina, Anna V; Goryunov, Evgenii I; Aysin, Rinat R; Pasechnik, Margarita P; Matveev, Sergey V; Godovikov, Ivan A; Safiulina, Alfiya M; Brel, Valery K

    2016-03-28

    Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.

  19. Synthesis, structure, and optical-limiting properties of heterobimetallic [M(3)CuS(4)] cuboidal clusters (M = Mo or W) with terminal phosphine ligands.

    PubMed

    Feliz, M; Garriga, J M; Llusar, R; Uriel, S; Humphrey, M G; Lucas, N T; Samoc, M; Luther-Davies, B

    2001-11-19

    Cubane-type clusters of formula [Mo(3)CuS(4)Cl(4)(dmpe)(3)](PF(6)) (4), [Mo(3)CuS(4)Br(4)(dmpe)(3)](PF(6)) (5), and [W(3)CuS(4)Br(4)(dmpe)(3)](PF(6)) (6) have been prepared by reacting the incomplete cuboidal trimers [Mo(3)S(4)Cl(3)(dmpe)(3)](PF(6)) (1), [Mo(3)S(4)Br(3)(dmpe)(3)](PF(6)) (2), and [W(3)S(4)Br(3)(dmpe)(3)](PF(6)) (3), respectively, with CuX (X = Cl or Br) or the mononuclear copper complex [Cu(CH(3)CN)(4)](+) in THF. The reaction takes place without global changes in the metal oxidation states, and compounds 4-6 with a [M(3)CuS(4)](5+) core possess 16 e(-) for metal-metal bonding. X-ray structural analysis of 4-6 revealed an effective C(3v) symmetry for the M(3)Cu unit with the M-M distances being statistically the same for M = Mo or W. However, the M-Cu distance is 0.04 and 0.1 A longer than the M-M bond length for Mo and W, respectively. There is no significant structural rearrangement of the ligand-metal bonding in proceeding from [M(3)S(4)X(3)(dmpe)(3)](+) to [M(3)CuS(4)X(4)(dmpe)(3)](+). The cyclic voltammograms of the [Mo(3)CuS(4)] cubane clusters show one quasi-reversible reduction process at E(1/2) = -0.31 V for 4 and at E(1/2) = -0.23 V for 5 and one irreversible reduction at -0.69 and -0.58 V for 4 and 5, respectively. The tungsten cluster 6 shows a unique quasi-reversible reduction wave at E(1/2) = -0.71 V. The incorporation of copper into the incomplete [M(3)S(4)] cuboidal complexes produces a decrease of the reduction potential for both molybdenum and tungsten. Absorption spectra of 1-6 are broadly similar; replacing Mo by W in proceeding from 2 to 3 or from 5 to 6 and replacing Br by Cl in proceeding from 2 to 1 or from 5 to 4 results in a blue shift of the three UV-visible absorption bands. All six clusters exhibit optical limiting, as measured by the Z-scan technique at 523 nm using 40 ns pulses. The power-limiting mechanism remains obscure, but under the conditions employed, threshold-limiting fluence decreases on replacing W by Mo on proceeding from 3 to 2 or 6 to 5 and on proceeding from tetranuclear cluster (4-6) to trinuclear precursor (1-3, respectively). For all six clusters, values of the excited-state cross section sigma(eff) are larger than those of the corresponding ground-state cross section sigma(0); i.e., all clusters are efficient optical limiters.

  20. Heteroleptic Copper(I) Complexes of “Scorpionate” Bis-pyrazolyl Carboxylate Ligand with Auxiliary Phosphine as Potential Anticancer Agents: An Insight into Cytotoxic Mode

    PubMed Central

    Khan, Rais Ahmad; Usman, Mohammad; Dhivya, Rajakumar; Balaji, Perumalsamy; Alsalme, Ali; AlLohedan, Hamad; Arjmand, Farukh; AlFarhan, Khalid; Akbarsha, Mohammad Abdulkader; Marchetti, Fabio; Pettinari, Claudio; Tabassum, Sartaj

    2017-01-01

    New copper(I) complexes [CuCl(PPh3)(L)] (1: L = LA = 4-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane; (2: L = LB = 3-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane) were prepared and characterised by elemental analysis and various spectroscopic techniques such as FT-IR, NMR, UV–Vis, and ESI-MS. The molecular structures of complexes 1 and 2 were analyzed by theoretical B3LYP/DFT method. Furthermore, in vitro DNA binding studies were carried out to check the ability of complexes 1 and 2 to interact with native calf thymus DNA (CT-DNA) using absorption titration, fluorescence quenching and circular dichroism, which is indicative of more avid binding of the complex 1. Moreover, DNA mobility assay was also conducted to study the concentration-dependent cleavage pattern of pBR322 DNA by complex 1, and the role of ROS species to have a mechanistic insight on the cleavage pattern, which ascertained substantial roles by both hydrolytic and oxidative pathways. Additionally, we analyzed the potential of the interaction of complex 1 with DNA and enzyme (Topo I and II) with the aid of molecular modeling. Furthermore, cytotoxic activity of complex 1 was tested against HepG2 cancer cell lines. Thus, the potential of the complex 1 is promising though further in vivo investigations may be required before subjecting it to clinical trials. PMID:28338061

  1. Synthesis of chiral 2,2{prime}-bis(diphenylphosphino)-1,1{prime}-binaphthyl (BINAP) via a novel nickel-catalyzed phosphine insertion

    SciTech Connect

    Cai, D.; Payack, J.F.; Bender, D.R.

    1994-11-18

    2,2{prime}-Bis(diphenylphosphino)-1,1{prime}binaphthyl (BINAP), introduced in the early 1980`s, has become one of the most successful chiral ligands for catalytic asymmetric induction. Its wide application has been somewhat limited due to the scarce supply and expense of BINAP and up to now, there has been only one reported practical synthesis of chiral BINAP.

  2. Computational study of the double C-Cl bond activation of dichloromethane and phosphine alkylation at [CoCl(PR3)3].

    PubMed

    Algarra, Andrés G; Braunstein, Pierre; Macgregor, Stuart A

    2013-03-28

    Density functional theory calculations have been employed to model the double C-Cl bond activation of CH(2)Cl(2) at [CoCl(PR(3))(3)] to give [CoCl(3)(CH(2)PR(3))(PR(3))(2)]. Calculations incorporating dichloromethane solution (PCM approach) on a [CoCl(PMe(3))(3)] model system showed the two C-Cl cleavage steps to involve different mechanisms. The first C-Cl cleavage step occurs on the triplet surface and proceeds via Cl abstraction with a barrier of 19.1 kcal mol(-1). Radical recombination would then give singlet mer,trans-[CoCl(2)(CH(2)Cl)(PMe(3))(3)] with an overall free energy change of +1.8 kcal mol(-1). Alternative C-Cl activation processes based on nucleophilic attack by the Co centre at dichloromethane with loss of Cl(-) have significantly higher barriers. The second C-Cl cleavage occurs via nucleophilic attack of PMe(3) at the CH(2)Cl ligand with formation of a new P-C bond and displacement of Cl(-). This may either occur in an intermolecular fashion (after prior PMe(3) dissociation) or intramolecularly. Both processes have similar barriers of ca. 12 kcal mol(-1). The comproportionation of [CoCl(3)(CH(2)PMe(3))(PMe(3))(2)] with [CoCl(PMe(3))(3)] to give [CoCl(2)(CH(2)PMe(3))(PMe(3))], [CoCl(2)(PMe(3))(2)] and 2 PMe(3) is computed to be strongly exergonic, consistent with the observation of this process in analogous experimental systems.

  3. Scanning tunneling microscopy study of low temperature silicon epitaxy on hydrogen/silicon(001) and phosphine adsorption on silicon(111)-7x7

    NASA Astrophysics Data System (ADS)

    Ji, Jeong-Young

    A three-chamber ultra-high-vacuum (UHV) system with preparation, scanning tunneling microscopy (STM), and chemical vapor deposition (CVD) chambers was designed and built. Here, one can perform surface preparation, STM e-beam lithography, precursor gas dosing, ion sputtering, silicon epitaxy, and various measurements such as reflection high energy electron diffraction (RHEED), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES). Processes performed in the ultra-clean preparation and gas-filled CVD chambers can be monitored by transferring the samples back to the STM chamber to take topographical images. Si deposition on H-terminated Si(001)-2x1 surfaces at temperatures 300--530 K was studied by scanning tunneling microscopy. Hydrogen apparently hinders Si adatom diffusion and enhances surface roughening. Post-growth annealing transfers the top layer atoms downward to fill in vacancies in the lower layer, restoring the crystallinity of the thin film. Hydrogen is shown to remain on the growth front up to at least 10 ML. Si deposition onto the H/Si(001)-3x1 surface at 530 K suggests that dihydride units further suppress Si adatom diffusion and increase surface roughness. PH3 adsorption on Si(111)-7x7 was studied for various exposures between 0.3--60 L at room temperature by means of the scanning-tunneling-microscopy (STM). PH3-, PH2-, H-reacted, and unreacted adatoms can be identified by analyzing STM images at different sample biases. Most of PH3 adsorbs dissociatively on the surface at initial exposure, generating H and PH2 adsorption sites, followed by molecular adsorption of PH3. Rest atoms are more reactive than the adatoms and PH 2-reacted rest atom sites are also observed in STM images. Statistical analysis shows that center adatoms are more reactive than corner adatoms and the saturation P coverage is ˜0.22 ML. Finally, 900 K annealing of a PH 3 dosed surface results in a disordered, partially P-covered surface and PH3 dosing at 900 K forms the same surface reconstruction as a P2-adsorbed surface at similar temperature.

  4. Dibenzothiophene Sulfone-Based Phosphine Oxide Electron Transporters with Unique Asymmetry for High-Efficiency Blue Thermally Activated Delayed Fluorescence Diodes.

    PubMed

    Fan, Chaochao; Duan, Chunbo; Han, Chunmiao; Han, Bin; Xu, Hui

    2016-10-12

    Three asymmetrical electron transporters as dibenzothiophene sulfone (DBSO)-diphenylphosphine oxide (DPPO) hybrids, collectively named mnDBSODPO, were designed and prepared. All of these materials achieve the high triplet energy of ∼3.0 eV to restrain the exciton linkage from emissive layers. The dependence of inductive and steric effects for DPPO groups on the substitution position, the intermolecular interaction suppression, the encapsulations of high-polar DBSO cores, and the favorable electrical performance are successfully integrated on 36DBSODPO, which can simultaneously suppress the exciton quenching by formation of an interfacial dipole and enhancing the charge flux balance. As a result, 36DBSODPO endowed its tetralayer blue thermally activated delayed fluorescence (TADF) devices with impressive performance, including the maximum external quantum efficiency around 19%, and reduced efficiency roll-offs, which verifies the great potential of asymmetrical electron transporting materials for highly efficient TADF devices.

  5. Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

    SciTech Connect

    Ghosh, Prasenjit; Fagan, Paul J.; Marshall, William J.; Hauptman, Elisabeth; Bullock, R. Morris

    2009-07-20

    A ruthenium hydride with a bulky substituted Cp ligand, (CpiPr4)Ru(CO)2H (CpiPr4 = C5(i-C3H7)4H) was prepared from the reaction of Ru3(CO)12 with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (CpiPr4)Ru(CO)2H was determined by x-ray crystallography. The ruthenium hydride complex (C5Bz5)Ru(CO)2H (Bz = CH2Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)2]2, was produced from the reaction of 1,2,3-trimethylindene with Ru3(CO)12, and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)2]2(μ H)}+OTf –. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)3, PCy3, PMe3, P(p C6H4F)3] were prepared by reaction of Cp(CO)2RuH with added L. Protonation of (CpiPr4)Ru(CO)2H, Cp*Ru(CO)2H or CpRu(CO)[P(OPh)3]H by HOTf 80 °C led to equilibria with the cationic dihydrogen complexes, but H2 was released at higher temperatures. Protonation of CpRu[P(OPh)3]2H with HOTf gave an observable dihydrogen complex, {CpRu[P(OPh)3]2(η2 H2)}+OTf – that was converted at -20 °C to the dihydride complex {CpRu[P(OPh)3]2(H)2}+OTf –. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H2 (750 psi) at 110 °C. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.

  6. Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

    SciTech Connect

    Bullock, R.M.; Ghosh, P.; Fagan, P.J.; Marshall, W.J.; Hauptman, E.

    2009-07-20

    A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H (Cp{sup iPr{sub 4}} = C{sub 5}(i-C{sub 3}H{sub 7}){sub 4}H) was prepared from the reaction of Ru{sub 3}(CO){sub 12} with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H was determined by X-ray crystallography. The ruthenium hydride complex (C{sub 5}Bz{sub 5})Ru(CO){sub 2}H (Bz = CH{sub 2}Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}, was produced from the reaction of 1,2,3-trimethylindene with Ru{sub 3}(CO){sub 12}, and protonation of this dimer with HOTf gives {l_brace}[(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}-({mu}-H){r_brace}{sup +}OTf{sup -}. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh){sub 3}, PCy{sub 3}, PMe{sub 3}, P(p-C{sub 6}H{sub 4}F){sub 3}] were prepared by reaction of Cp(CO){sub 2}RuH with added L. Protonation of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H, Cp*Ru(CO){sub 2}H, or CpRu(CO)[P-(OPh){sub 3}]H by HOTf at -80 C led to equilibria with the cationic dihydrogen complexes, but H{sub 2} was released at higher temperatures. Protonation of CpRu[P(OPh){sub 3}]{sub 2}H with HOTf gave an observable dihydrogen complex, {l_brace}CpRu[P-(OPh){sub 3}]{sub 2}({eta}{sup 2}-H{sub 2}){r_brace}+OTf{sup -} that was converted at -20 C to the dihydride complex {l_brace}CpRu[P(OPh){sub 3}]{sub 2}(H){sub 2}{r_brace}{sup +}OTf{sup -}. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H{sub 2} (750 psi) at 110 C.

  7. A new approach for the preparation of well-defined Rh and Pt nanoparticles stabilized by phosphine-functionalized silica for selective hydrogenation reactions.

    PubMed

    Llop Castelbou, J; Szeto, K C; Barakat, W; Merle, N; Godard, C; Taoufik, M; Claver, C

    2017-03-18

    In this work, a new methodology for the synthesis of well-defined metallic nanoparticles supported on silica is described. This methodology is based on the surface control provided by SOMC. The nanoparticles are formed via the organometallic approach and are catalytically active in the hydrogenation of p-xylene, 3-hexyne, 4-phenyl-2 butanone, benzaldehyde, and furfural.

  8. FUNDAMENTAL STUDIES IN ELECTROCHEMISTRY.

    DTIC Science & Technology

    ORGANIC PHOSPHORUS COMPOUNDS), (*ELECTROCHEMISTRY, OXIDATION, REDUCTION, SULFIDES, PHOSPHINE OXIDES, CATALYSTS , FLUORINE COMPOUNDS, BENZENE, POLAROGRAPHIC ANALYSIS, ADSORPTION, ELECTROLYSIS, ELECTRODES.

  9. Photooxidation of mixed aryl and biarylphosphines.

    PubMed

    Zhang, Dong; Celaje, Jeff A; Agua, Alon; Doan, Chad; Stewart, Timothy; Bau, Robert; Selke, Matthias

    2010-07-02

    Arylphosphines and dialkylbiarylphosphines react with singlet oxygen to form phosphine oxides and phosphinate esters. For mixed arylphosphines, the most electron-rich aryl group migrates to form the phosphinate, while for dialkylbiarylphosphines migration of the alkyl group occurs. Dialkylbiarylphosphines also yield arene epoxides, especially in electron-rich systems. Phosphinate ester formation is increased at high temperature, while protic solvents increase the yield of epoxide. The product distribution provides evidence for Buchwald's recent conformational model for the aerobic oxidation of dialkylbiarylphosphines.

  10. Advances in developing alternative treatments for postharvest pest control

    Technology Transfer Automated Retrieval System (TEKTRAN)

    USDA-ARS made two significant advances in the last 10 years in the development of alternative treatments for postharvest pest control: oxygenated phosphine fumigation and nitric oxide fumigation. Oxygenated phosphine is phosphine fumigation in an oxygen enriched atmosphere. It is significantly more...

  11. Thermodynamic properties of molecular borane phosphines, alane amines, and phosphine alanes and the [BH(4)(-)][PH(4)(+)], [AlH(4)(-)][NH(4)(+)], and [AlH(4)(-)][PH(4)(+)] salts for chemical hydrogen storage systems from ab initio electronic structure theory.

    PubMed

    Grant, Daniel J; Dixon, David A

    2005-11-10

    The heats of formation for the molecules BH(3)PH(3), BH(2)PH(2), HBPH, AlH(3)NH(3), AlH(2)NH(2), HAlNH, AlH(3)PH(3), AlH(2)PH(2), HAlPH, AlH(4)(-), PH(3), PH(4), and PH(4)(+), as well as the diatomics BP, AlN, and AlP, have been calculated by using ab initio molecular orbital theory. The coupled cluster with single and double excitations and perturbative triples method (CCSD(T)) was employed for the total valence electronic energies. Correlation consistent basis sets were used, up through the augmented quadruple-zeta, to extrapolate to the complete basis set limit. Additional d core functions were used for Al and P. Core/valence, scalar relativistic, and spin-orbit corrections were included in an additive fashion to predict the atomization energies. Geometries were calculated at the CCSD(T) level up through at least aug-cc-pVTZ and frequencies were calculated at the CCSD(T)/aug-cc-pVDZ level. The heats of formation of the salts [BH(4)(-)][PH(4)(+)](s), [AlH(4)(-)][NH(4)(+)](s), and [AlH(4)(-)][PH(4)(+)](s) have been estimated by using an empirical expression for the lattice energy and the calculated heats of formation of the two component ions. The calculations show that both AlH(3)NH(3)(g) and [AlH(4)(-)][NH(4)(+)](s) can serve as good hydrogen storage systems that release H(2) in a slightly exothermic process. In addition, AlH(3)PH(3) and the salts [AlH(4)(-)][PH(4)(+)] and [BH(4)(-)][PH(4)(+)] have the potential to serve as H(2) storage systems. The hydride affinity of AlH(3) is calculated to be -70.4 kcal/mol at 298 K. The proton affinity of PH(3) is calculated to be 187.8 kcal/mol at 298 K in excellent agreement with the experimental value of 188 kcal/mol. PH(4) is calculated to be barely stable with respect to loss of a hydrogen to form PH(3).

  12. Solid-state synthesis and characterization of σ-alkane complexes, [Rh(L2)(η(2),η(2)-C7H12)][BAr(F)4] (L2 = bidentate chelating phosphine).

    PubMed

    Pike, Sebastian D; Chadwick, F Mark; Rees, Nicholas H; Scott, Mark P; Weller, Andrew S; Krämer, Tobias; Macgregor, Stuart A

    2015-01-21

    The use of solid/gas and single-crystal to single-crystal synthetic routes is reported for the synthesis and characterization of a number of σ-alkane complexes: [Rh(R2P(CH2)nPR2)(η(2),η(2)-C7H12)][BAr(F)4]; R = Cy, n = 2; R = (i)Pr, n = 2,3; Ar = 3,5-C6H3(CF3)2. These norbornane adducts are formed by simple hydrogenation of the corresponding norbornadiene precursor in the solid state. For R = Cy (n = 2), the resulting complex is remarkably stable (months at 298 K), allowing for full characterization using single-crystal X-ray diffraction. The solid-state structure shows no disorder, and the structural metrics can be accurately determined, while the (1)H chemical shifts of the Rh···H-C motif can be determined using solid-state NMR spectroscopy. DFT calculations show that the bonding between the metal fragment and the alkane can be best characterized as a three-center, two-electron interaction, of which σCH → Rh donation is the major component. The other alkane complexes exhibit solid-state (31)P NMR data consistent with their formation, but they are now much less persistent at 298 K and ultimately give the corresponding zwitterions in which [BAr(F)4](-) coordinates and NBA is lost. The solid-state structures, as determined by X-ray crystallography, for all these [BAr(F)4](-) adducts are reported. DFT calculations suggest that the molecular zwitterions within these structures are all significantly more stable than their corresponding σ-alkane cations, suggesting that the solid-state motif has a strong influence on their observed relative stabilities.

  13. trans-Chlorido[6-chloro-4-(4-methoxy­benz­yl)-3-oxo-3,4-dihydro­pyrazin-2-yl]­bis­(triphenyl­phosphine)palladium(II)

    PubMed Central

    Robeyns, Koen; Alen, Jo; De Borggraeve, Wim M.; Compernolle, Frans; Van Meervelt, Luc

    2008-01-01

    The title compound, [Pd(C12H10ClN2O2)Cl(C18H15P)2], is the inter­mediate of the reduction of a 3,5-dichloro­pyrazinone [Loosen, Tutonda, Khorasani, Compernolle & Hoornaert (1991 ▶). Tetra­hedron, 47, 9259–9268]. This species is formed by oxidative addition of coordinatively unsaturated Pd0 to the reactive 3-position of the heterocycle. The coordination around the Pd atom is square planar, with two trans PPh3 ligands. π–π inter­actions are observed between the centroid of the pyrazinone ring and planes of two adjacent phenyl rings, one from each PPh3 group (3.25 and 3.078 Å), stabilizing the inter­mediate structure. This could explain the reduced reactivity towards substitution of the Cl atom by the formate anion, resulting in poor yield of the reduced compound. 3-Substituted pyrazinones are important precursors in the synthesis of 5-amino­piperidinone-2-carboxyl­ate (APC) systems. PMID:21200660

  14. Phosphine-catalyzed reactions of activated olefins tethered to cycloalkanones. substrate- and solvent-controlled synthesis of bicyclo[3.2.1]octanones, mixed acetals, and Morita-Baylis-Hillman products.

    PubMed

    Wang, Yanhui; Jaunet, Alexis; Geoffroy, Philippe; Miesch, Michel

    2013-12-20

    The n-Bu3P organocatalyzed reaction of cycloalkanones, i.e., cyclopentanones or 1,3-cyclopentanediones tethered to actived olefins, afforded selectively and in high yields three different types of products: bicyclo[3.2.1]octanones, mixed acetals, and Morita-Baylis-Hillman products. The progress of the reaction was closely related to the reaction medium and to the length of the tether located between the cyclopentanone (-dione) and the activated olefin.

  15. Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

    2015-06-15

    We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.

  16. Mixed chloride/phosphine complexes of the dirhenium core. 10. Redox reactions of an edge-sharing dirhenium(III) non-metal-metal-bonded complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4).

    PubMed

    Cotton, F A; Dikarev, E V; Petrukhina, M A

    2001-12-17

    Reduction and oxidation reactions of the dirhenium(III) non-metal-metal-bonded edge-sharing complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4) (1), have been studied. Several new mono- and dinuclear rhenium compounds have been isolated and structurally characterized in the course of this study. Reductions of 1 with 1 and 2 equiv of KC(8) result in an unusual face-sharing complex having an Re(2)(5+) core, Re(2)(mu-Cl)(3)Cl(2)(PMe(3))(4) (2), and a triply bonded Re(II) compound, 1,2,7,8-Re(2)Cl(4)(PMe(3))(4) (3), respectively. Two-electron reduction of 1 in the presence of tetrabutylammonium chloride affords a new triply bonded complex of the Re(2)(4+) core, [Bu(n)()(4)N][1,2,7-Re(2)Cl(5)(PMe(3))(3)] (4). Oxidation of 1 with NOBF(4) yields a Re(IV) mononuclear compound, trans-ReCl(4)(PMe(3))(2) (5). Two isomers of the monomeric Re(III) anion, [ReCl(4)(PMe(3))(2)](-) (6, 7), have been isolated as side products. The crystal structures of compounds 2 and 4-7 have been determined by X-ray crystallography. The Re-Re distance in the face-sharing complex 2 of 2.686(1) A is relatively short. The metal-metal bond length in anion 4 of 2.2354(7) A is consistent with the usual values for the triply bonded Re(2)(4+) core compounds. In addition, a cis arrangement of trimethylphosphine ligands in the starting material 1 is retained upon reduction in the dinuclear products 2-4.

  17. Electrocatalytic reduction of organohalides mediated by the dihalo-molybdenum phosphinic complexes trans-[MoX(2)(Ph(2)PCH(2)CH(2)PPh(2))(2)] (X = I, Br)-A mechanistic study by cyclic voltammetry digital simulation.

    PubMed

    Martins, Natércia C T; Guedes da Silva, M Fátima C; Wanke, Riccardo; Pombeiro, Armando J L

    2009-06-28

    trans-[MoX(2)(dppe)(2)] (X = I, Br) act as inner-sphere electron-transfer mediators for the electrocatalytic reduction of organohalides RX to R + X(-), at both Mo(II)--> Mo(I) and Mo(I)--> Mo(0) reduction processes, each of them involving a cathodically induced heterolytic metal-halide bond cleavage with liberation of X(-) that is followed by addition of RX to the metal. Digital simulation of cyclic voltammetry at a wide range of scan rates allowed to estimate the rate constants of the various chemical steps for both electrocatalytic cycles, which were compared in terms of Mo-X bond dissociation energies, electronic and stereochemical effects.

  18. A study of the reaction of perfluoroalkyl Grignard reagents with phosphoryl chloride and phenylphosphonic dichloride.

    PubMed

    Hosein, Adil I; Caffyn, Andrew J M

    2012-11-21

    Perfluoroalkyl Grignard reagents react with phosphoryl halides at -78 °C to room temperature to selectively produce bis(perfluoroalkyl)phosphonyl halides, which after aqueous work up, give bis(perfluoroalkyl)phosphinic acids in high overall yields. Reaction of perfluoroalkyl Grignards with phenylphosphonic dichloride gives high yields of bis(perfluoroalkyl)phenyl phosphine oxides which are readily hydrolysed to perfluoroalkyl(phenyl)phosphinic acids.

  19. Recent Developments in the Addition of Phosphinylidene-Containing Compounds to Unactivated Unsaturated Hydrocarbons: Phosphorus-Carbon Bond-Formation via Hydrophosphinylation and Related Processes

    PubMed Central

    Coudray, Laëtitia

    2012-01-01

    Summary The reactions of phosphinylidene-containing compounds with unactivated unsaturated hydrocarbons are reviewed. The review is organized by phosphorus-containing functional group types. Free-radical and metal-catalyzed additions of R1R2P(O)H to alkenes, alkynes, and related compounds, deliver functionalized organophosphorus compounds RP(O)R1R2, including H-phosphinates, phosphinates, tertiary phosphine oxides, and phosphonates. The review covers the literature up to February 2008. PMID:23308039

  20. Gene disruption technologies have the potential to transform stored product insect pest control

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stored product insects feed on grains and processed commodities manufactured from grain post-harvest, reducing the nutritional value and contaminating food. Currently, the main defense against stored product insect pests is the pesticide fumigant phosphine. Phosphine is highly toxic to all animals, ...

  1. Hydroformylation: An Old Yet New Industrial Route to Alcohols.

    ERIC Educational Resources Information Center

    Pruett, Roy L.

    1986-01-01

    Discusses trends in hydroformylation chemistry, considering these catalysis and ligands: (1) cobalt, (2) cobalt-phosphine, and (3) rhodium-phosphine. Indicates that rhodium technology will grow in domination of hydroformylation practice. In addition, processes adapted to special cases of functional olefins and to higher olefins can be expected.…

  2. Palladium-catalyzed phosphonylation: synthesis of C3-, C4-, and C5-phosphonylated pyrazoles.

    PubMed

    Tran, Gaël; Gomez Pardo, Domingo; Tsuchiya, Tomoki; Hillebrand, Stefan; Vors, Jean-Pierre; Cossy, Janine

    2013-11-01

    A palladium-catalyzed cross-coupling between 3-, 4-, and 5-halo-pyrazoles and H-phosphonates, H-phosphinates, and secondary phosphine oxides has been developed. This coupling reaction constitutes the first general method allowing the introduction of a great diversity of phosphorus substituents on the different carbons of the pyrazole ring in a one-step process.

  3. Conjugate and method for forming aminomethyl phosphorus conjugates

    DOEpatents

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

    1999-01-01

    A method of forming phosphine-amine conjugates includes reacting a hydroxymethyl phosphine group of an amine-free first molecule with at least one free amine group of a second molecule to covalently bond the first molecule with the second molecule through an aminomethyl phosphorus linkage and the conjugates formed thereby.

  4. Conjugate and method for forming aminomethyl phosphorus conjugates

    SciTech Connect

    Katti, K.V.; Berning, D.E.; Volkert, W.A.; Ketring, A.R.; Churchill, R.

    1999-09-07

    A method of forming phosphine-amine conjugates includes reacting a hydroxymethyl phosphine group of an amine-free first molecule with at least one free amine group of a second molecule to covalently bond the first molecule with the second molecule through an aminomethyl phosphorus linkage and the conjugates formed thereby.

  5. Poly(arylene ether)s That Resist Atomic Oxygen

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul; Smith, Joseph G., Jr.

    1994-01-01

    Novel poly(arylene ether)s containing phosphine oxide (PAEPO's) made via aromatic nucleophilic displacement reactions of activated aromatic dihalides (or, in some cases, activated aromatic dinitro compounds) with new bisphenol monomers containing phosphine oxide. Exhibited favorable combination of physical and mechanical properties and resistance to monatomic oxygen in oxygen plasma environment. Useful as adhesives, coatings, films, membranes, moldings, and composite matrices.

  6. Structure and Optical Properties of Noble Metal Nanoparticles

    DTIC Science & Technology

    2012-08-29

    bare and passivated (thiolate-, phosphine-, or carboxylate-stabilized) gold and silver nanoparticles. The location of the ligands is responsible for...lowering. Nanoparticles, Nanowires, Gold, Silver , Thiolate, Phosphine, Carboxylate, Density Functional Theory, Time-Dependent Density Functional Theory...conditions under which gold and silver nanoparticles display broad/molecular or sharp surface plasmon resonance (SPR) optical absorption behavior. The

  7. Systems and strippable coatings for decontaminating structures that include porous material

    DOEpatents

    Fox, Robert V [Idaho Falls, ID; Avci, Recep [Bozeman, MT; Groenewold, Gary S [Idaho Falls, ID

    2011-12-06

    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  8. Polyphosphazine-based polymer materials

    DOEpatents

    Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

    2010-05-25

    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  9. Methods for removing contaminant matter from a porous material

    DOEpatents

    Fox, Robert V [Idaho Falls, ID; Avci, Recep [Bozeman, MT; Groenewold, Gary S [Idaho Falls, ID

    2010-11-16

    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  10. Phospha-Michael Addition as a New Click Reaction for Protein Functionalization.

    PubMed

    Lee, Yan-Jiun; Kurra, Yadagiri; Liu, Wenshe R

    2016-03-15

    A new type of click reaction between an alkyl phosphine and acrylamide was developed and applied for site-specific protein labeling in vitro and in live cells. Acrylamide is a small electrophilic olefin that readily undergoes phospha-Michael addition with an alkyl phosphine. Our kinetic study indicated a second-order rate constant of 0.07 m(-1)  s(-1) for the reaction between tris(2-carboxyethyl)phosphine and acrylamide at pH 7.4. To demonstrate its application in protein functionalization, we used a dansyl-phosphine conjugate to successfully label proteins that were site-specifically installed with N(ɛ) -acryloyl-l-lysine and employed a biotin-phosphine conjugate to selectively probe human proteins that were metabolically labeled with N-acryloyl-galactosamine.

  11. Interaction of some extreme-pressure type lubricating compounds with an iron surface

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1973-01-01

    An iron surface was exposed to the extreme-pressure type lubricant benzyl chloride, dichlorophenyl phosphine, dichlorophenyl phosphine sulfide, ophenyl phosphine oxide. Iron, in the sputter-cleaned state, was exposed to these materials statically and during dynamic friction experiments. With benzyl chloride only chlorine adsorbed to the surface, and with dichlorophenyl phosphine no adsorption occurred, while the addition of sulfur to that same molecular structure resulted in the promotion of carbon and chlorine adsorption. substitution of oxygen for sulfur in the dichlorobenzyl phosphine molecule resulted in carbon, chlorine, and oxygen adsorption. With none of the phosphorus containing molecules was phosphorus detected on the surface. Sliding in an atmosphere of benzyl chloride promoted adsorption of chlorine to the iron surface. Increases in load resulted in a decrease in the surface concentration of iron chloride.

  12. Mechanistic Investigations of Reactions of the Frustrated Lewis Pairs (Triarylphosphines/B(C6F5)3) with Michael Acceptors.

    PubMed

    Dupré, Jonathan; Gaumont, Annie-Claude; Lakhdar, Sami

    2017-02-03

    Frustrated Lewis pair (FLP)-catalyzed reduction of Michael acceptors is a challenging reaction that proceeds with specific FLP structures. Kinetics and equilibrium of the reactions of two phosphines (Ar3P), namely tri(1-naphthyl)phosphine and tri(o-tolyl)phosphine, are reported with reference electrophiles. The reason for the failure of the FLPs (Ar3P/B(C6F5)3) to reduce activated alkenes under H2 pressure is shown to be a hydrophosphination process that inhibits the reduction reaction. Kinetic and thermodynamic factors controlling both pathways are discussed in light of Mayr's free linear energy relationships.

  13. Catalytic Wittig and aza-Wittig reactions

    PubMed Central

    Lao, Zhiqi

    2016-01-01

    This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines. PMID:28144327

  14. Synthesis and Characterization of Mixed Substituent P-n-Propyl-N-trimethylphosphoranimines

    SciTech Connect

    Klaehn, John Ray; Luther, Thomas Alan; Harrup, Mason Kurt; Stewart, Frederick Forrest

    2003-07-01

    One approach to the synthesis of polyphosphazenes is the condensation polymerization of phosphoranimines. In this work, several novel P-n-propyl-N-trimethylsilylphosphoranimines have been synthesized and characterized. Modifications to the literature synthetic routes were required to obtain the precursor phosphines. The N-trimethylsilylphosphoranimines were obtained though oxidation of the phosphine with bromine and then subsequent nucleophilic displacement using lithium phenoxide. These phosphoranimines were stable for long periods of time under dry inert conditions. NMR analyses revealed complex splitting patterns beyond typical coupling due to the stereocenter at phosphorus. We report several approaches to the n-propyl containing phosphines

  15. Ruthenium-catalyzed stereoselective anti-Markovnikov-addition of thioamides to alkynes.

    PubMed

    Goossen, Lukas J; Blanchot, Mathieu; Salih, Kifah S M; Karch, Ralf; Rivas-Nass, Andreas

    2008-10-16

    A catalyst system generated in situ from bis(2-methallyl)-cycloocta-1,5-diene-ruthenium(II) and a phosphine was found to efficiently catalyze the addition of thioamides to terminal alkynes with exclusive formation of the anti-Markovnikov thioenamide products. The stereoselectivity of the addition is usually high and controlled by the choice of the phosphine ligand, whereas the (E)-isomers are predominantly formed in the presence of tri(n-octyl)phosphine, the use of bis(dicyclohexylphosphino)methane preferentially leads to the formation of the (Z)-configured thioenamides.

  16. Unexpected hydrodeiodo Sonogashira-Heck-Casser coupling reaction of 2,2'-diiodobiphenyls with acetylenes.

    PubMed

    Chou, Meng-Yen; Mandal, Ashis Baran; Leung, Man-kit

    2002-03-08

    2,2'-Diiodobiphenyl-4,4'-dicarboxylic acid dimethyl ester (3) undergoes either a ring-closure reaction with phenylacetylene to give 4 or hydrodeiodo phenylethynylation to give 5 under the catalytic conditions of Pd(OAc)(2)/CuI/phosphine in amines. In these reactions, the amine and the phosphine ligands play important roles in controlling the reactivity. Among the ligands we used, tris(o-tolyl)phosphine is the best ligand for hydrodeiodo phenylethynylation, while the bidentate phosphine ligand retards both of the reactions. On the basis of our results, we propose that 5 is formed through a fast hydrodeiodination, followed by a Sonogashira phenylethynylation. The results of the deuterium labeling experiments show that proton exchange between the acetylenic proton and the alkyl protons of amine occurs effectively under the reaction conditions. In addition, the hydrogen that replaces the iodide in the hydrodeiodination process arises mainly from the acetylenic proton.

  17. Functional Si and CdSe quantum dots: synthesis, conjugate formation, and photoluminescence quenching by surface interactions.

    PubMed

    Sudeep, P K; Emrick, Todd

    2009-12-22

    Silicon quantum dots (QDs) were prepared with a corona of di-n-octyl phosphine oxides, by performing hydrosilylation chemistry on the surface of hydrogen-terminated Si QDs. These novel Si QDs proved well-suited to serve as "ligands" for other semiconductor QDs, such as CdSe, by interaction of the phosphine oxide corona with the CdSe surface. A pronounced photoluminescence quenching of CdSe quantum dots was observed upon introduction of the phosphine oxide functionalized Si QDs to a CdSe QD solution. Surface functionalization of the Si QDs proved critically important to observing these effects, as conventional (alkane-covered) Si QD samples gave no evidence of electronic interactions with TOPO-covered CdSe. In a comparative system, phosphine oxide terminated oligo(phenylene vinylene) molecules acting as CdSe QD ligands provide a similar fluorescence quenching, with exciton decay kinetics supporting the formation of an electronically interacting hybrid materials system.

  18. Elastomer-modified phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1983-01-01

    Phosphine oxide-containing polyimide resins modified by elastomers, are disclosed which have improved mechanical properties. These products are particularly useful in the production of fiber or fabric-reinforced composites or laminates.

  19. New approach to phosphinoalkynes based on Pd- and Ni-catalyzed cross-coupling of terminal alkynes with chlorophosphanes.

    PubMed

    Beletskaya, Irina P; Afanasiev, Vladimir V; Kazankova, Marina A; Efimova, Irina V

    2003-11-13

    [reaction: see text] The first example of direct phosphination of terminal alkynes with chlorophosphanes catalyzed by Ni or Pd complexes is described. Both aromatic and aliphatic terminal acetylenes undergo the coupling reaction to give corresponding coupling product in high yield.

  20. 46 CFR 148.415 - Toxic gas analyzers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... calibrated according to the instructions of its manufacturer. The atmosphere in the cargo hold and adjacent... section must be met are: (a) Arsine; (b) Carbon monoxide; (c) Hydrogen cyanide; (d) Hydrogen sulfide; (e) Phosphine; and (f) Sulfur dioxide....

  1. 46 CFR 148.415 - Toxic gas analyzers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... calibrated according to the instructions of its manufacturer. The atmosphere in the cargo hold and adjacent... section must be met are: (a) Arsine; (b) Carbon monoxide; (c) Hydrogen cyanide; (d) Hydrogen sulfide; (e) Phosphine; and (f) Sulfur dioxide....

  2. 46 CFR 148.415 - Toxic gas analyzers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... calibrated according to the instructions of its manufacturer. The atmosphere in the cargo hold and adjacent... section must be met are: (a) Arsine; (b) Carbon monoxide; (c) Hydrogen cyanide; (d) Hydrogen sulfide; (e) Phosphine; and (f) Sulfur dioxide....

  3. 46 CFR 148.415 - Toxic gas analyzers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... calibrated according to the instructions of its manufacturer. The atmosphere in the cargo hold and adjacent... section must be met are: (a) Arsine; (b) Carbon monoxide; (c) Hydrogen cyanide; (d) Hydrogen sulfide; (e) Phosphine; and (f) Sulfur dioxide....

  4. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn Ruth

    2011-12-13

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  5. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn

    2006-10-17

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  6. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn Ruth

    2010-11-23

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  7. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn

    2003-05-27

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  8. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn R.

    2010-02-23

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g. on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  9. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn R.

    2011-04-12

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  10. Chemoselective ligation

    DOEpatents

    Saxon, Eliana; Bertozzi, Carolyn R.

    2011-05-10

    The present invention features a chemoselective ligation reaction that can be carried out under physiological conditions. In general, the invention involves condensation of a specifically engineered phosphine, which can provide for formation of an amide bond between the two reactive partners resulting in a final product comprising a phosphine moiety, or which can be engineered to comprise a cleavable linker so that a substituent of the phosphine is transferred to the azide, releasing an oxidized phosphine byproduct and producing a native amide bond in the final product. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

  11. Prophylactic and Treatment Drugs for Organophosphorus Poisoning

    DTIC Science & Technology

    1991-01-01

    with 4- nitrophenol and dicyclohexylcarbodiimide in 62% yield. 25 CHART NO. 7 4- NITROPHENYL METHYL (1-NAPHTHYL) PHOSPHINATE 0 MgBr CH3 ..- P--OH + CH 3...dicyclohexylcarbodiimide gave the title compound A in 69% yield. 2.22 4- Nitrophenyl chloromethyl(4-methoxvphenvl)phosphinate 0 CH3 P- N0 The synthesis route...Chem 1983, 2, 104. 28. "The Synthesis of Neurotropic and Musculotropic Stimula- i tors and Inhibitors. Part V. Derivatives of Aminophenyl Phosphates as

  12. SOLVENT EXTRACTION PROCESS FOR URANIUM FROM CHLORIDE SOLUTIONS

    DOEpatents

    Blake, C.A. Jr.; Brown, K.B.; Horner, D.E.

    1960-05-24

    An improvement was made in a uranium extraction process wherein the organic extractant is a phosphine oxide. An aqueous solution containing phosphate ions or sulfate ions together with uranium is provided with a source of chloride ions during the extraction step. The presence of the chloride ions enables a phosphine oxide to extract uranium in the presence of strong uranium- complexing ions such as phosphate or sulfate ions.

  13. Ru-catalyzed stereoselective addition of imides to alkynes.

    PubMed

    Goossen, Lukas J; Blanchot, Mathieu; Brinkmann, Claus; Goossen, Käthe; Karch, Ralph; Rivas-Nass, Andreas

    2006-12-08

    A catalyst system formed in situ from bis(2-methylallyl)cycloocta-1,5-dieneruthenium(II) ((cod)Ru[met]2), a phosphine, and scandium(III) trifluoromethanesulfonate (Sc(OTf)3) was found to efficiently catalyze the anti-Markovnikov addition of imides to terminal alkynes, allowing mild and atom-economic synthesis of enimides. Depending on the phosphine employed, both the (E)- and the (Z)-isomer can be accessed stereoselectively.

  14. Methods for suppressing isomerization of olefin metathesis products

    DOEpatents

    Firth, Bruce E.; Kirk, Sharon E.; Gavaskar, Vasudeo S.

    2015-09-22

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent is phosphorous acid, a phosphorous acid ester, phosphinic acid, a phosphinic acid ester or combinations thereof. Methods of refining natural oils are described.

  15. Inhibition of Xenobiotic-Degrading Hydrolases by Organophosphinates

    DTIC Science & Technology

    1985-07-01

    which were not substrates. Bovline pancreatic trypsin and P-chymotrypsin were stereo- selective in reactions with 4-nitrophenyl isopropyl(phenyl...dinitrobenzoylphenylglycine. Trypsin, but not’Z-chymotrypsin, exhibited a similar stereoselective reaction wiih 4-nitrophenyl ethyl(phenyl)phosphinate...stereo- selective in reactions with 4-nitrophenyl isopropyl(phenyl)phosphinate, with more rapid loss of the longer retained enantiomer in high performance

  16. Reductive Elimination of H-H, H-CH3, and CH3-CH3 from Bis(Phosphine)Platinum(II), - Palladium(II), and -Nickel(II) Complexes: A Theoretical Study Using the SCF-X alpha-SW Method.

    DTIC Science & Technology

    1981-03-04

    3071-3080. Cook, M., Ph.D., Harvard University , unpublished. 17. The RptP and PPtP angle used were taken from (Ph3P)2Pt(PhC’CPH) (Glanville, J. 0...facilitate comparison 2 3 2’ t aiiaecmaio L L R R M - M\\I LL / R R 0.0 MU-NI M Nt dps-Cs 4, c 2v 03h d 90 -6 :z HMO ,:-4.0 -600 4b2 0 W Soo z EU -10000... HMO Model and Its Application" Wiley Interscience, New York, 1976. 27. Hine, J., "Structural Effects on Equilibria in Organic Chemistry" Wiley

  17. Synthesis of low color, atomic oxygen resistant polyimides

    NASA Technical Reports Server (NTRS)

    MacInnes, Dave

    1995-01-01

    The purpose of this project was to develop low color, atomic oxygen resistant polyimides for potential applications on spacecraft in low earth orbit. The material is needed in order to protect satellites and spacecraft from the gases and radiation found at those altitudes. Phosphorous containing polyimides have been shown to be especially resistant to corrosion and weight loss under oxygen plasma. Unfortunately the color of these phosphorous containing polyimides is still too high for them to be good heat insulators. While they are not as effective as teflon, the current material of choice. polyimides are much less dense than teflon and would be especially valuable if they could be made with low color. The approach taken was to synthesize a monomer which would contain the elements needed for giving the final polyimide its desired properties. In particular the monomer should incorporate phosphine or phosphine oxides and have bulky side groups to block any color forming charge transfer structures. The target molecule, 3,5-di-(trifluoromethylphenyl)-bis(3-aminophenyl) phosphine oxide, (containing both a phosphine oxide group and a bulky ditrifluoromethylphenyl group) was synthesized via three reactions in overall yield of 21 percent. In addition, a model compound, bis(3-phenylamine) phenyl phosphine oxide, was synthesized two different ways in order to establish the conditions for the nitration of phosphine oxides and their reduction to the amine. Finally, a trisubstituted phosphine oxide was synthesized. In all, seven phosphorus containing organic compounds were synthesized, purified and characterized. The model compound was reacted with oxydiphthalic anhydride to form a polyamic acid with inherent viscosity of 0.34. This material was cast into a film and heated, forming a normally colored fairly strong polyimide with a Tg of 240 C. The target compound was reacted with 6-fluorodiphthalic anhydride to give a polyamic acid with inherent viscosity of 0.19 and cast to

  18. Diagnosis of aluminum phosphide poisoning using a new analytical approach: forensic application to a lethal intoxication.

    PubMed

    Yan, Hui; Xiang, Ping; Zhang, Sujing; Shen, Baohua; Shen, Min

    2017-02-27

    Aluminum phosphide (AlP) is an effective and cheap pesticide that is commonly used worldwide, but it is also a common cause of human poisoning and carries a high mortality rate. AlP reacts with moisture in air, water, and hydrochloric acid in the stomach to produce phosphine (PH3) gas. Two routes of exposure are ingestion of AlP and inhalation of phosphine generated by the action of moisture on AlP. Absorbed phosphine is rapidly metabolized into phosphite and hypophosphite. A method is described for the analysis of the phosphine metabolites in various biological matrices. The method involves reacting the sample with zinc and aqueous H2SO4 in a volatile organic analysis vial. The metabolites were transformed into phosphine gas and then analyzed by headspace gas chromatography coupled with mass spectrometry (HS-GC-MS). This method is capable of detecting quantities of PH3 as low as 0.2 μg/mL in a sample. After validation, the method was applied to animal experiments and a real case of human AlP intoxication. This approach has the advantage of detecting metabolites of PH3, in case the PH3 was converted, and can be considered a useful additional tool for the diagnosis of AlP poisoning in forensic science.

  19. High Efficiency InP Solar Cells from Low Toxicity Tertiarybutylphosphine

    NASA Technical Reports Server (NTRS)

    Hoffman, Richard W., Jr.; Fatemi, Navid S.; Wilt, David M.; Jenkins, Phillip P.; Brinker, David J.; Scheiman, David A.

    1994-01-01

    Large scale manufacture of phosphide based semiconductor devices by organo-metallic vapor phase epitaxy (OMVPE) typically requires the use of highly toxic phosphine. Advancements in phosphine substitutes have identified tertiarybutylphosphine (TBP) as an excellent precursor for OMVPE of InP. High quality undoped and doped InP films were grown using TBP and trimethylindium. Impurity doped InP films were achieved utilizing diethylzinc and silane for p and n type respectively. 16 percent efficient solar cells under air mass zero, one sun intensity were demonstrated with Voc of 871 mV and fill factor of 82.6 percent. It was shown that TBP could replace phosphine, without adversely affecting device quality, in OMVPE deposition of InP thus significantly reducing toxic gas exposure risk.

  20. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOEpatents

    Ramprasad, Dorai; Waller, Francis Joseph

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  1. Evolution of hydroformylation chemistry

    SciTech Connect

    Slaugh, L.H.

    1995-12-01

    A new generation of hydroformylation catalysts was discovered in 1960 at Shell Development Company which dramatically altered the chemistry of producing industrially important alcohols from synthesis gas (CO/H{sub 2}) and olefins. These new homogeneous catalysts were obtained via the use of auxiliary tertiary phosphine ligands with the conventional OXO cobalt carbonyl catalyst. This is believed to have been the first historical example illustrating the utility of phosphine ligands to modify the catalytic properties of homogenous catalysts. In contradistinction to the conventional OXO reaction, highly linear alcohols were obtained in a single-step operation with ease of catalyst recycle. Based on this discovery, an industrial process was developed to produce large volume, environmentally friendly detergent alcohols. The chemistry of this process and a comparison with other hydroformylation catalyst systems will be made. Recent results obtained with phosphine-modified cobalt catalysts for the hydroformylation of substrates other than olefins will be presented.

  2. Determination of equilibrium constants and computational interaction energies for adducts of [Rh2(RCO2)(4-n)(PC)n] (n = 0-2) with Lewis bases.

    PubMed

    Hirva, Pipsa; Esteban, Julio; Lloret, Julio; Lahuerta, Pascual; Pérez-Prieto, Julia

    2007-04-02

    Properties of dirhodium catalysts with cyclometalated aryl phosphine ligands have been studied. We report here the study of the acid-base reaction of Rh2(RCO2)2(PC)2(H2O)2 catalysts (PC = cyclometalated aryl phosphine) with different Lewis bases. The determination of the equilibrium constants of these reactions can be used to study to which extent the properties of the axial coordination site of the catalyst, considered the active site, are affected by modification of the metalated phosphines, the carboxylate ligands, or the incoming axial ligand. The trends in the computational density functional theory interaction energies show good agreement with the major trends in the equilibrium constants, thus enabling a further study of the influence of the modification of the ligand core.

  3. Catalyst- and solvent-dependent stereodivergence in the intramolecular Et(2)Zn/Pd(0) -promoted carbonyl propargylation: mechanistic implications.

    PubMed

    Arrate, Mónica; Durana, Aritz; Lorenzo, Paula; de Lera, Ángel R; Álvarez, Rosana; Aurrecoechea, José M

    2013-10-04

    Carbonyl-tethered propargylic benzoates undergo intramolecular carbonylpropargylation upon treatment with Et2 Zn in the presence of a catalytic amount of Pd(0) with the formation of 2-alkynylcyclopentanol products. A ligand/solvent effect on the cis/trans selectivity (referring to the relative positions of alkynyl and OH groups) of ring-closure has been found. In a non-coordinating solvent (benzene), increasing the electron-donating ability of the phosphine ligand (while decreasing its dissociation ability) leads to an increased tendency towards the trans product. On the other hand, the combination of a coordinating solvent (THF) and PPh3 , an easily dissociated phosphine, results in the exclusive formation of cis products. Experimental and computational results are compatible with a divergent behavior of an allenylethylpalladium intermediate that partitions between competitive carbonyl-addition and transmetalation pathways, each leading to a different diastereoisomer. These results also suggest that the dissociating ability of the phosphine regulates that behavior.

  4. Selective Synthesis of 5- or 6-Aryl Octahydrocyclopenta[b]pyrroles from a Common Precursor Through Control of Competing Pathways in a Pd-Catalyzed Reaction

    PubMed Central

    Ney, Joshua E.; Wolfe, John P.

    2009-01-01

    The Pd/phosphine-catalyzed reaction of 1 with aryl bromides leads to the selective synthesis of either 6-aryl octahydrocyclopenta[b]pyrroles (3), the corresponding 5-aryl isomers 5, diarylamine 2, or hexahydrocyclopenta[b]pyrrole 4 depending on the structure of the phosphine ligand. These transformations are effective with a variety of different aryl bromides, and provide 3-5 with excellent levels of diastereoselectivity (dr ≥ 20:1). The changes in product distribution are believed to derive from the influence of Pd-catalyst structure on the relative rates of reductive elimination, β-hydride elimination, alkene insertion, and alkene dissociation processes in a mechanistically complex reaction. The effect of phosphine ligand structure on product distribution is described in detail, along with analysis of a proposed mechanism for these transformations. PMID:15954769

  5. Basic Reactivity Pattern of a Cyclic Disilylated Germylene

    PubMed Central

    2016-01-01

    In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene. Reaction via the silagermene was also observed in the reaction with benzophenone. Reaction of a germylene phosphine adduct with GeCl2·(dioxane) provided insertion of the silylated germylene into a Ge–Cl bond, leading to a germylated chlorogermylene phosphine adduct. PMID:27570360

  6. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOEpatents

    Ramprasad, D.; Waller, F.J.

    1999-04-06

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  7. A comparison of the relative activities of a number of GABAB antagonists in the isolated vas deferens of the rat.

    PubMed Central

    Hills, J. M.; Larkin, M. M.; Howson, W.

    1991-01-01

    1. A series of GABAB receptor antagonists were tested against (+/-)-baclofen for activity on the presynaptic GABAB receptor in the rat vas deferens. 2. All the antagonists tested caused a rightward shift in the concentration-response curve to (+/-)-baclofen. 3. pA2 values calculated from full Schild analysis were as follows: phaclofen, pA2 = 4.3; delta-amino valeric acid, pA2 = 4.4; 3-aminopropyl(diethoxymethyl)phosphinic acid (CGP 35348), pA2 = 5.0; 3-amino-propyl(n-hexyl)phosphinic acid (3-APHPA), pA2 = 4.5. 4. These results show that none of the above compounds possess potent antagonist activity at the GABAB receptor (i.e. pA2 > 6) in this peripheral tissue. In addition, the more recently available phosphinic acid antagonists, appear to offer no great advance over the GABAB antagonists previously available. PMID:1364830

  8. Method for separating metal chelates from other materials based on solubilities in supercritical fluids

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

    2001-01-01

    A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

  9. Zinc Phosphide Poisoning

    PubMed Central

    Doğan, Erdal; Güzel, Abdulmenap; Çiftçi, Taner; Aycan, İlker; Çetin, Bedri; Kavak, Gönül Ölmez

    2014-01-01

    Zinc phosphide has been used widely as a rodenticide. Upon ingestion, it gets converted to phosphine gas in the body, which is subsequently absorbed into the bloodstream through the stomach and the intestines and gets captured by the liver and the lungs. Phosphine gas produces various metabolic and nonmetabolic toxic effects. Clinical symptoms are circulatory collapse, hypotension, shock symptoms, myocarditis, pericarditis, acute pulmonary edema, and congestive heart failure. In this case presentation, we aim to present the intensive care process and treatment resistance of a patient who ingested zinc phosphide for suicide purposes. PMID:25101186

  10. Aluminium phosphide-induced leukopenia

    PubMed Central

    Ntelios, Dimitrios; Mandros, Charalampos; Potolidis, Evangelos; Fanourgiakis, Panagiotis

    2013-01-01

    Acute intoxication from the pesticide aluminium phosphide is a relatively rare, life-threatening condition in which cardiovascular decompensation is the most feared problem. We report the case of a patient exposed to aluminium phosphide-liberated phosphine gas. It resulted in the development of a gastroenteritis-like syndrome accompanied by severe reduction in white blood cell numbers as an early and prominent manifestation. By affecting important physiological processes such as mitochondrial function and reactive oxygen species homeostasis, phosphine could cause severe toxicity. After presenting the characteristics of certain leucocyte subpopulations we provide the current molecular understanding of the observed leukopenia which in part seems paradoxical. PMID:24172776

  11. Unusual complication of aluminum phosphide poisoning: Development of hemolysis and methemoglobinemia and its successful treatment

    PubMed Central

    Soltaninejad, Kambiz; Nelson, Leiws S.; Khodakarim, Nastaran; Dadvar, Zohreh; Shadnia, Shahin

    2011-01-01

    Methemoglobinemia and hemolysis are rare findings following phosphine poisoning. In this paper, a case of aluminum phosphide (AlP) poisoning complicated by methemoglobinemia and hemolysis with a successful treatment is reported. A 28-year-old male patient presented following intentional ingestion of an AlP tablet. In this case, hematuria, hemolysis and methemoglobinemia were significant events. A methemoglobin level of 46% was detected by CO-oximetry. The patient was treated with ascorbic acid and methylene blue and he also received supportive care. Two weeks after admission, the patient was discharged from the hospital. Hemolysis and methemoglobinemia may complicate the course of phosphine poisoning. PMID:21814377

  12. Unusual complication of aluminum phosphide poisoning: Development of hemolysis and methemoglobinemia and its successful treatment.

    PubMed

    Soltaninejad, Kambiz; Nelson, Leiws S; Khodakarim, Nastaran; Dadvar, Zohreh; Shadnia, Shahin

    2011-04-01

    Methemoglobinemia and hemolysis are rare findings following phosphine poisoning. In this paper, a case of aluminum phosphide (AlP) poisoning complicated by methemoglobinemia and hemolysis with a successful treatment is reported. A 28-year-old male patient presented following intentional ingestion of an AlP tablet. In this case, hematuria, hemolysis and methemoglobinemia were significant events. A methemoglobin level of 46% was detected by CO-oximetry. The patient was treated with ascorbic acid and methylene blue and he also received supportive care. Two weeks after admission, the patient was discharged from the hospital. Hemolysis and methemoglobinemia may complicate the course of phosphine poisoning.

  13. Reversible Silylene Insertion Reactions into Si-H and P-H σ-Bonds at Room Temperature.

    PubMed

    Rodriguez, Ricardo; Contie, Yohan; Nougué, Raphael; Baceiredo, Antoine; Saffon-Merceron, Nathalie; Sotiropoulos, Jean-Marc; Kato, Tsuyoshi

    2016-11-07

    Phosphine-stabilized silylenes react with silanes and a phosphine by silylene insertion into E-H σ-bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step.

  14. Highly regioselective palladium-catalyzed direct arylation of oxazole at C-2 or C-5 with aryl bromides, chlorides, and triflates.

    PubMed

    Strotman, Neil A; Chobanian, Harry R; Guo, Yan; He, Jiafang; Wilson, Jonathan E

    2010-08-20

    Complementary palladium-catalyzed methods for direct arylation of oxazole with high regioselectivity (>100:1) at both C-5 and C-2 have been developed for a wide range of aryl and heteroaryl bromides, chlorides, iodides, and triflates. C-5 arylation is preferred in polar solvents with phosphines 5 or 6, whereas C-2 arylation is preferred by nonpolar solvents and phosphine 3. This represents the first general method for C-5 selective arylation of oxazole and should see broad applicability in the synthesis of biologically active molecules. Additionally, potential mechanisms for these two competing arylation processes are proposed on the basis of mechanistic observations.

  15. New ruthenium nitrosyl pincer complexes bearing an O2 ligand. Mono-oxygen transfer.

    PubMed

    Fogler, Eran; Efremenko, Irena; Gargir, Moti; Leitus, Gregory; Diskin-Posner, Yael; Ben-David, Yehoshoa; Martin, Jan M L; Milstein, David

    2015-03-02

    We report on Ru((II))(μ(2)-O2) nitrosyl pincer complexes that can return to their original Ru(0) state by reaction with mono-oxygen scavengers. Potential intermediates were calculated by density functional theory (DFT) and a mechanism is proposed, revealing a new type of metal-ligand cooperation consisting of activation of the O2 moiety by both the metal center and the NO ligand. Reaction of the Ru(0) nitrosyl complex 1 with O2 quantitatively yielded the crystallographically characterized Ru((II)) (μ(2)-O2) nitrosyl complex 2. Reaction of 2 with the mono-oxygen scavengers phosphines or CO gave the Ru(0) complex 1 and phosphine oxides, or the carbonyl complex 3 (1 trapped by CO) and CO2, respectively. Reaction of 2 with 1 equiv of phosphine at room temperature or -40 °C resulted in immediate formation of half an equivalent of 1 and 1 equiv of phosphine oxide, while half an equivalent of 2 remained unchanged. Overnight reaction at room temperature of 2 with excess CO (≥3 equiv) resulted in 3 and CO2 gas as the only products. Reaction of 1 with 1 equiv of mono-oxygen source (dioxirane) at -78 °C yielded the Ru((II))(μ(2)-O2) complex 2. Similarly, reaction of the Ru(0) dearomatized complex 4 with O2 led to the crystallographicaly characterized Ru((II))(μ(2)-O2) complex 5. Further reaction of 5 with mono-oxygen scavengers (phosphines or CO) led to the Ru(0) complex 4 and phosphine oxides or complex 6 (4 trapped by CO) and CO2. When instead only 1 equiv of 5 was reacted with 1 equiv of phosphine at room temperature, immediate formation of half an equivalent of 4 and 1 equiv of phosphine oxide took place, while half an equivalent of 5 remained unchanged. When 5 reacted with an excess of CO (≥3 equiv), complex 6 and CO2 gas were the only products obtained. DFT studies indicate a new mode of metal-ligand cooperation involving the nitrosyl ligand in the oxygen transfer process.

  16. Coordination Chemistry of Cyclic Disilylated Germylenes and Stannylenes with Group 11 Metals

    PubMed Central

    2014-01-01

    Reactions of Et3P adducts of bissilylated germylenes and stannylenes with gold, silver, and copper cyanides led to cyanogermyl or -stannyl complexes of the respective metals. In the course of the reaction the phosphine moved to the metal, while the cyanide migrated to the low-coordinate group 14 element. The respective gold complexes were found to be monomeric, whereas the silver and copper complexes exhibited a tendency to dimerize in the solid state. Attempts to abstract the phosphine ligand with B(C6F5)3 led only to the formation of adducts with the borane coordinating to the cyanide nitrogen atom. PMID:25550678

  17. Design and Synthesis of Candidate Prophylactic and Therapeutic Compounds for Use in the Management of Organophosphorus Poisoning.

    DTIC Science & Technology

    1985-01-01

    followed a general literature procedure (ref. 42). Thus compound 1 was treated with hydrogen peroxide in the presence of sodium tungstate and tetrasodium...ethylenediaminetetraacetate (1.0 g, 0.002 mol) and sodium tungstate dihydrate (1.0 g, 0.003 mol) in water (10 mL) was added to a solution of 4-bromo-2,2,6,6...was employed as shown in Chart No. 3. Diphenyl(ethyl)phosphine oxide was treated with powdered sodium hydroxide at 250C to give phosphinic acid 1 in 69

  18. On the Mechanism of Pd(0)-Catalyzed, Cu(I) Carboxylate-Mediated Thioorganic-Boronic Acid Desulfitative Coupling. A Non-innocent Role for Carboxylate Ligand

    PubMed Central

    Musaev, Djamaladdin G.; Liebeskind, Lanny S.

    2009-01-01

    Computational studies of the mechanism of the Pd-catalyzed, Cu(I)-carboxylate-mediated desulfitative coupling of thioorganics with boronic acids have determined that the requisite Cu(I)-carboxylate plays multiple important roles. The Cu(I)-carboxylate enhances both the transmetalation and the C-C reductive elimination steps: it acts as a reactive transmetalation center and it provides a vital carboxylate ligand. The carboxylate ligand functions not only as an activator for the boronic acid, but it also displaces a phosphine ligand at the palladium center generating a catalytically competent mono-phosphine-palladium intermediate. PMID:20161122

  19. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1983-01-01

    Bis- and tris-imides derived from tris (m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride. Such monomers or their oligomes may be used to impregnate fibers and fabrics which when cured, are flame resistant. Also an improved method of producing tris (m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst is described.

  20. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1985-01-01

    Cured polymers of bis and tris-imides derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a monoimide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride prior to curing are disclosed and claimed. Such polymers are flame resistant. Also disclosed are an improved method of producing tris(m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst and fiber reinforced cured resin composites.

  1. Quasi-two-dimensional metallic hydrogen inside di-phosphide at high pressure

    NASA Astrophysics Data System (ADS)

    Degtyarenko, N. N.; Mazur, E. A.

    2016-09-01

    The method of mathematical modelling was used for the calculation of the structural, electronic, phononic, and other characteristics of various normal phases of phosphorus hydrides with stoichiometry PHk. It was shown that the di-phosphine may form 2D lattice of the metallic hydrogen in it, stabilized by phosphorus atoms under high hydrostatic pressure. The resulting structure with the elements of H-P-H has a locally stable (or metastable) phonon spectrum. The properties of di-phosphine were compared with the properties of similar structures such as the sulphur hydrides.

  2. The Synthesis of Novel Oxazolinylphosphinic Esters and Amides and Application to the Cyanosilylation of Aldehydes

    PubMed Central

    Luo, Mei

    2015-01-01

    A new class of modular functionalized oxazolines are synthesized using a simple, novel one-pot method under inert moisture-free conditions. Then the oxazolines can be further elaborated to phosphine-containing oxazolines. The first step is to synthesize intermediates via the reaction of 2 - hydroxybenzonitrile or 2-aminobenzonitrile with chiral amino alcohols, subsequent reactions with phosphine chlorides, providing products in moderate yields. Product structures are fully characterized by NMR, IR, MS and X-Ray analyses. These compounds are found to be highly active catalysts for the cyanosilylation of prochiral benzaldehyde (20-96% yield).

  3. Partial pressures and nature of products. Application to the photolysis of PH3 and NH3 in the atmosphere of Jupiter and Saturn.

    PubMed

    Guillemin, J C; El Chaouch, S; Bouayad, A; Janati, T

    2001-01-01

    The photolysis of mixtures of gases containing NH3 or PH3 presents important differences mainly due to the strength of the X-H bond. On some examples, these differences are evidenced and the consequences for mixtures of gases containing these two compounds are shown: the photolysis of ammonia and ethylene mainly gives ethyl-, butyl- and hexylamine whereas the photolysis of phosphine and ethylene leads to ethyl- and vinylphosphine. When gaseous mixtures of NH3, PH3 and ethylene are photolyzed together, the presence of phosphine dramatically decreases the formation of nitrogen derivatives. The relevance of such lab studies to the atmospheres of Jupiter and Saturn is discussed.

  4. Investigations on low-temperature MOVPE growth of InGaAs/InP using alternative sources (TBAs, TBP)

    SciTech Connect

    Czub, M.; Strupinski, W.; Weber, J.; Gyuro, I.

    1996-12-31

    Growth of high quality InP and InGaAs using the less hazardous liquid group V precursors, TBAs and TBP has been achieved. A systematic study compares the quality of InP and InGaAs epitaxial layers grown by low-pressure organometallic vapor phase epitaxy (MOVPE) using TMG and TEG trimethylindium (TMIn), phosphine (PH{sub 3}), arsino (AsH{sub 3}) and tetriarybutylophosphine (TBP) and tertriarybutylarsin (TBAs) sources. High quality InP Layers are obtained with both phosphorus sources for growth at high V/III ratio and at low temperatures with the TBP, TBAs sources than with the phosphine and arsine sources.

  5. Another side of the oxazaphospholidine oxide chiral ortho-directing group.

    PubMed

    Martins, Nelson; Mateus, Nuno; Vinci, Daniele; Saidi, Ourida; Brigas, Amadeu; Bacsa, John; Xiao, Jianliang

    2012-05-28

    A new ferrocenyl oxazaphospholidine oxide 3 was synthesized together with its P-epimer 2 in the reaction of ferrocene lithium with phosphoramidite chloride 1. 3 was successfully derivatized into planar chiral 1,2-ferrocenes, including phosphine ligands, via highly diastereoselective ortho-lithiation and subsequent functionalization; these compounds display opposite planar chirality to those obtained from 2. Some of these 1,2-ferrocenes were further lithiated, allowing for the introduction of a free phosphine group at the oxazaphospholidine ring. The X-ray structures of the compounds 2 and 3 as well as those of the new 1,2-ferrocenes 4 and 7 have been determined.

  6. Polyurea-encapsulated palladium(II) acetate: a robust and recyclable catalyst for use in conventional and supercritical media.

    PubMed

    Ley, Steven V; Ramarao, Chandrashekar; Gordon, Richard S; Holmes, Andrew B; Morrison, Angus J; McConvey, Ian F; Shirley, Ian M; Smith, Stephen C; Smith, Martin D

    2002-05-21

    Palladium(II) acetate microencapsulated in polyurea (MC-[Pd]) is an economical and versatile heterogeneous catalyst for a range of phosphine-free cross-coupling reactions in both conventional solvents and supercritical carbon dioxide (scCO2); the catalyst can be recovered by a simple filtration and recycled up to four times.

  7. Synthesis and Migratory-Insertion Reactivity of CpMo(CO)[subscript3](CH[subscript3]): Small-Scale Organometallic Preparations Utilizing Modern Glovebox Techniques

    ERIC Educational Resources Information Center

    Whited, Matthew T.; Hofmeister, Gretchen E.

    2014-01-01

    Experiments are described for the reliable small-scale glovebox preparation of CpMo(CO)[subscript 3](CH[subscript 3]) and acetyl derivatives thereof through phosphine-induced migratory insertion. The robust syntheses introduce students to a variety of organometallic reaction mechanisms and glovebox techniques, and they are easily carried out…

  8. Merging gold and organocatalysis: a facile asymmetric synthesis of annulated pyrroles.

    PubMed

    Hack, Daniel; Loh, Charles C J; Hartmann, Jan M; Raabe, Gerhard; Enders, Dieter

    2014-04-01

    The combination of cinchona-alkaloid-derived primary amine and Au(I) -phosphine catalysts allowed the selective C-H functionalization of two adjacent carbon atoms of pyrroles under mild reaction conditions. This sequential dual activation provides seven-membered-ring-annulated pyrrole derivatives in excellent yields and enantioselectivities.

  9. Controlled-Stress Large-Area Pulsed Laser Deposition of Yttria Stabilized Zirconia

    DTIC Science & Technology

    2006-05-31

    2-36 2.5.3 Transmission Electron Microscopy ............................................................. 2-36 2.5.4 Energy -Dispersive X...2-37 2.5.6 Auger Electron Spectroscopy ...organometallic compounds and hydrides, such as dimethyl cadmium (DMCd), trimethyl gallium (TMGa), AsH3, phosphine (PH3), hydrogen selenide (H2Se

  10. A Convenient Synthetic Protocol to 1,2-Bis(dialkylphosphino)ethanes

    PubMed Central

    Doyle, Laurence R; Heath, Alex; Low, Choon Heng; Ashley, Andrew E

    2014-01-01

    1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step. PMID:26190960

  11. Bifunctional Organo/Metal Cooperatively Catalyzed [3 + 2] Annulation of para-Quinone Methides with Vinylcyclopropanes: Approach to Spiro[4.5]deca-6,9-diene-8-ones.

    PubMed

    Yuan, Zhenbo; Wei, Weiwei; Lin, Aijun; Yao, Hequan

    2016-07-15

    A novel [3 + 2] annulation between para-quinone methides and vinylcyclopropanes for the synthesis of spiro[4.5]deca-6,9-diene-8-ones has been described. The palladium and phosphine-thiourea cooperative catalysis system played an important role in high yields and diastereoselectivities. The reaction exhibited good functional group tolerance and scalability.

  12. Global Analysis of Transcript and Protein Levels Across the Plasmodium falciparum Life Cycle

    DTIC Science & Technology

    2004-01-01

    presence of 500 ng·mL1 pyrimethamine and gametocytogenesis was induced (Ifediba and Vanderberg 1981). N-acetyl-D- glucosamine (50 mM) was added to the...in 5 mM Tris(2-Carboxyethyl)phosphine hydrochloride (TCEP, Roche); (3) alkylated by 20 mM iodoacetamide (IAM); and (4) digested with proteinase K

  13. Multiporphyrin coordination arrays based on complexation of magnesium(II) porphyrins with porphyrinylphosphine oxides.

    PubMed

    Atefi, Farzad; McMurtrie, John C; Arnold, Dennis P

    2007-06-07

    Di- and triporphyrin arrays consisting of 5,15-diphenylporphyrinatomagnesium(II) (MgDPP) coordinated to free-base and Ni(II) porphyrinyl mono- and bis-phosphine oxides, as well as the self-coordinating diphenyl[10,20-diphenylporphyrinatomagnesium(II)-5-yl]phosphine oxide [MgDPP(Ph(2)PO)], were synthesised in excellent yields and characterised by various spectroscopic techniques. Phosphine oxides stabilise Mg(II) coordination to porphyrins and the resulting complexes have convenient solubilities, while the Ni(II) complexes exhibit interesting intramolecular fluorescence quenching behaviour. The binding constant of MgDPP to triphenylphosphine oxide (5.3 +/- 0.1 x 10(5) M(-1)) and the very high self-association constant of [MgDPP(Ph(2)PO)] (5.5 +/- 0.5 x 10(8) M(-1)) demonstrate the strong affinity of phosphine oxides towards Mg(II) porphyrins. These complexes are the first strongly bound synthetic Mg(II) multiporphyrin complexes and could potentially mimic the "special pair" in the photosynthetic reaction centre.

  14. Plasma deposition of amorphous metal alloys

    DOEpatents

    Hays, Auda K.

    1986-01-01

    Amorphous metal alloy coatings are plasma-deposited by dissociation of vapors of organometallic compounds and metalloid hydrides in the presence of a reducing gas, using a glow discharge. Tetracarbonylnickel, phosphine, and hydrogen constitute a typical reaction mixture of the invention, yielding a NiPC alloy.

  15. Aluminum hypophosphite microencapsulated to improve its safety and application to flame retardant polyamide 6.

    PubMed

    Ge, Hua; Tang, Gang; Hu, Wei-Zhao; Wang, Bi-Bo; Pan, Ying; Song, Lei; Hu, Yuan

    2015-08-30

    Aluminum hypophosphite (AHP) is an effective phosphorus-containing flame retardant. But AHP also has fire risk that it will decompose and release phosphine which is spontaneously flammable in air and even can form explosive mixtures with air in extreme cases. In this paper, AHP has been microencapsulated by melamine cyanurate (MCA) to prepare microencapsulated aluminum hypophosphite (MCAHP) with the aim of enhancing the fire safety in the procedure of production, storage and use. Meanwhile, MCA was a nitrogen-containing flame retardant that can work with AHP via the nitrogen-phosphorus synergistic effect to show improved flame-retardant property than other capsule materials. After microencapsulation, MCA presented as a protection layer inhibit the degradation of AHP and postpone the generation of phosphine. Furthermore, the phosphine concentration could be effectively diluted by inert decomposition products of MCA. These nonflammable decomposition products of MCA could separate phosphine from air delay the oxidizing reaction with oxygen and decrease the heat release rate, which imply that the fire safety of AHP has been improved. Furthermore, MCAHP was added into polyamide 6 to prepare flame retardant polyamide 6 composites (FR-PA6) which show good flame retardancy.

  16. Rhenium and technetium bi- and tricarbonyl complexes in a new strategy for biomolecule incorporation using click chemistry.

    PubMed

    Hayes, Thomas R; Kasten, Benjamin B; Barnes, Charles L; Benny, Paul D

    2014-05-21

    A versatile strategy to prepare fac-[M(I)(CO)3](+) and cis-[M(I)(CO)2](+) (M = Re, (99m)Tc) complexes was developed using Huisgen click chemistry and monodentate phosphine ligands to readily incorporate biomolecules and tailor the chemical properties.

  17. Red-luminescent biphosphine stabilized 'Cu₁₂S₆' cluster molecules.

    PubMed

    Yang, Xiao-Xun; Issac, Ibrahim; Lebedkin, Sergej; Kühn, Michael; Weigend, Florian; Fenske, Dieter; Fuhr, Olaf; Eichhöfer, Andreas

    2014-09-28

    The synthesis, molecular structures and luminescence properties of two 'Cu12S6' cluster molecules with stabilizing bidentate phosphine ligands are described. Both display in the solid state at ambient temperature high photoluminescence quantum yields (≥48%) and good stability towards oxygen.

  18. 40 CFR 721.10370 - Phosphonic acid, p-octyl-, lanthanum (3+) salt (2:1).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Phosphonic acid, p-octyl-, lanthanum... New Uses for Specific Chemical Substances § 721.10370 Phosphonic acid, p-octyl-, lanthanum (3+) salt... substance identified as phosphinic acid, p-octyl-, lanthanum (3+) salt (2:1) (PMN P-10-99; CAS No....

  19. 40 CFR 721.10370 - Phosphonic acid, p-octyl-, lanthanum (3+) salt (2:1).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phosphonic acid, p-octyl-, lanthanum... New Uses for Specific Chemical Substances § 721.10370 Phosphonic acid, p-octyl-, lanthanum (3+) salt... substance identified as phosphinic acid, p-octyl-, lanthanum (3+) salt (2:1) (PMN P-10-99; CAS No....

  20. 40 CFR 721.10370 - Phosphonic acid, p-octyl-, lanthanum (3+) salt (2:1).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phosphonic acid, p-octyl-, lanthanum... New Uses for Specific Chemical Substances § 721.10370 Phosphonic acid, p-octyl-, lanthanum (3+) salt... substance identified as phosphinic acid, p-octyl-, lanthanum (3+) salt (2:1) (PMN P-10-99; CAS No....