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Sample records for metal catalysed partial

  1. Axial Changes of Catalyst Structure and Temperature in a Fixed-Bed Microreactor During Noble Metal Catalysed Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Hannemann, S.; Grunwaldt, Jan-Dierk; Kimmerle, B.

    2009-01-01

    The catalytic partial oxidation of methane (CPO) over flame-made 2.5%Rh-2.5%Pt/Al2O3 and 2.5%Rh/Al2O3 in 6%CH4/3%O-2/He shows the potential of in situ studies using miniaturized fixed-bed reactors, the importance of spatially resolved studies and its combination with infrared thermography and on......-line mass spectrometry. This experimental strategy allowed collecting data on the structure of the noble metal (oxidation state) and the temperature along the catalyst bed. The reaction was investigated in a fixed-bed quartz microreactor (1-1.5 mm diameter) following the catalytic performance by on-line gas...... mass spectrometry (MS). Above the ignition temperature of the catalytic partial oxidation of methane (310-330 A degrees C), a zone with oxidized noble metals was observed in the inlet region of the catalyst bed, accompanied by a characteristic hot spot (over-temperature up to 150 A degrees C), while...

  2. Lewis acidic metal catalysed organic transformations by designed ...

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Journal of Chemical Sciences; Volume 122; Issue 3. Lewis acidic metal catalysed organic transformations by designed multi-component structures and assemblies. Afsar Ali Amit P Singh Rajeev Gupta. Perspective Articles Volume 122 Issue 3 May 2010 pp ...

  3. Catalysed electrolytic metal oxide dissolution processes

    International Nuclear Information System (INIS)

    Machuron-Mandard, X.

    1994-01-01

    The hydrometallurgical processes designed for recovering valuable metals from mineral ores as well as industrial wastes usually require preliminary dissolution of inorganic compounds in aqueous media before extraction and purification steps. Unfortunately, most of the minerals concerned hardly or slowly dissolve in acidic or basic solutions. Metallic oxides, sulfides and silicates are among the materials most difficult to dissolve in aqueous solutions. They are also among the main minerals containing valuable metals. The redox properties of such materials sometimes permit to improve their dissolution by adding oxidizing or reducing species to the leaching solution, which leads to an increase in the dissolution rate. Moreover, limited amounts of redox promoters are required if the redox agent is regenerated continuously thanks to an electrochemical device. Nuclear applications of such concepts have been suggested since the dissolution of many actinide compounds (e.g., UO 2 , AmO 2 , PuC, PuN,...) is mainly based on redox reactions. In the 1980s, improvements of the plutonium dioxide dissolution process have been proposed on the basis of oxidation-reduction principles, which led a few years later to the design of industrial facilities (e.g., at Marcoule or at the french reprocessing plant of La Hague). General concepts and well-established results obtained in France at the Atomic Energy Commission (''Commissariat a l'Energie Atomique'') will be presented and will illustrate applications to industrial as well as analytical problems. (author)

  4. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  5. Lewis acidic metal catalysed organic transformations by designed ...

    Indian Academy of Sciences (India)

    Administrator

    ing metal–organic frameworks containing Lewis acidic metal ions. The emphasis has been given to un- derstand the ... frameworks (MOFs) and metal–organic coordination networks (MOCNs) offer unique opportunities.5 .... of square-grid complex 1 was postulated to be more cationic than that of Cd(NO3)2⋅4H2O and thus.

  6. Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

    Science.gov (United States)

    Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M

    2012-12-01

    Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.

  7. Characterisation of hydrocarbonaceous overlayers important in metal-catalysed selective hydrogenation reactions

    Science.gov (United States)

    Lennon, David; Warringham, Robbie; Guidi, Tatiana; Parker, Stewart F.

    2013-12-01

    The hydrogenation of alkynes to alkenes over supported metal catalysts is an important industrial process and it has been shown that hydrocarbonaceous overlayers are important in controlling selectivity profiles of metal-catalysed hydrogenation reactions. As a model system, we have selected propyne hydrogenation over a commercial Pd(5%)/Al2O3 catalyst. Inelastic neutron scattering studies show that the C-H stretching mode ranges from 2850 to 3063 cm-1, indicating the mostly aliphatic nature of the overlayer and this is supported by the quantification of the carbon and hydrogen on the surface. There is also a population of strongly hydrogen-bonded hydroxyls, their presence would indicate that the overlayer probably contains some oxygen functionality. There is little evidence for any olefinic or aromatic species. This is distinctly different from the hydrogen-poor overlayers that are deposited on Ni/Al2O3 catalysts during methane reforming.

  8. Heavy Metal Pollution Assessment by Partial Geochemical ...

    African Journals Online (AJOL)

    Bheema

    Key words: Partial and total extraction, Amorphous phase, Scavenging, Heavy metal pollutants. 1. .... dissolving Mn and Fe mineral phases and assess heavy metals pollution in the mineral phases. These techniques are used to ..... Selective extraction techniques for the recognition of buried mineralization,. Curara Well ...

  9. [Designing metal frame removable partial dentures

    NARCIS (Netherlands)

    Witter, D.J.; Barel, J.C.; Keltjens, H.M.A.M.; Creugers, N.H.J.

    2011-01-01

    Oral health care providers have the full responsibility for designing metal frame removable partial dentures and making all of the necessary preparations. Important principles of design are that the denture should hamper natural cleaning and daily oral hygiene as little as possible and that it

  10. Metal-catalysed steam reforming of ethanol in the production of hydrogen for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Breen, J.P.; Burch, R.; Coleman, H.M. [School of Chemistry, Queen' s University Belfast, David Keir Building, Stranmillis Road, Belfast, BT9 5AG N. Ireland (United Kingdom)

    2002-11-08

    A range of oxide-supported metal catalysts have been investigated for the steam reforming of ethanol/water mixtures for the production of hydrogen. Alumina-supported catalysts are very active at lower temperatures for the dehydration of ethanol to ethene which, at higher temperatures, is converted into H{sub 2}, CO, and CO{sub 2} as the major products and CH{sub 4} as a minor product. The order of activity of the metals is Rh>Pd>Ni=Pt. With ceria/zirconia-supported catalysts, the formation of ethene is not observed and the order of activity at higher temperatures is Pt{>=}Rh>Pd. By using combinations of a ceria/zirconia-supported metal catalyst with the alumina support it is shown that the formation of ethene does not inhibit the steam reforming reaction at higher temperatures. It is concluded that the support plays a significant role in the steam reforming of ethanol.

  11. Access to the meta position of arenes through transition metal catalysed C-H bond functionalisation: a focus on metals other than palladium.

    Science.gov (United States)

    Mihai, Madalina T; Genov, Georgi R; Phipps, Robert J

    2018-01-02

    The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play in all manner of important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis in the range of methodologies that are available to elaborate arene C-H bonds. Regioselectivity is an important consideration when selecting a method and, of all those available, it is arguably those that target the meta position that are fewest in number. The rapid development of transition metal-catalysed C-H bond functionalisation over the last few decades has opened new possibilities for meta-selective C-H functionalisation through the diverse reactivity of transition metals and their compatibility with a wide range of directing groups. The pace of discovery of such processes has grown rapidly in the last five years in particular and it is the purpose of this review to examine these but in doing so to place the focus on metals other than palladium, the specific contributions of which have been very recently reviewed elsewhere. It is hoped this will serve to highlight to the reader the breadth of current strategies and mechanisms that have been used to tackle this challenge, which may inspire further progress in the field.

  12. The central chirality of the metal atom and configurational relations in asymmetric reactions catalysed by metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Pavlov, Valerii A [N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)

    2004-12-31

    The recently published data on the dependence of the configuration of the reaction product on the structure of a catalytic metal complex (or an intermediate determining the asymmetric induction) in asymmetric catalytic reactions of hydrogen-transfer hydrogenation of acetophenone, hydroformylation of styrene, allylic alkylation of 1,3-diphenylprop-2-enyl acetate and alkylation of benzaldehyde with dialkylzinc are systematised. The applicabilities of octant and quadrant projections of the complexes are compared in order to establish the relationships between their structures and the enantioselectivities of the reactions. The known mechanisms of asymmetric induction in these reactions are discussed with regard to the C{sub 1} or C{sub 2} symmetry of the catalytic complex. The reasons for a decrease in the enantioselectivities of hydrogen-transfer hydrogenation, hydroformylation and alkylation by dialkylzinc [in the absence of Ti(OPr{sup i}){sub 4}] when performed with complexes with chiral C{sub 2}-symmetric ligands (as compared with complexes with asymmetric ligands) are considered.

  13. Investigation of Partially Crystalline Zr77Ni23 Metallic Glass

    Directory of Open Access Journals (Sweden)

    Amra Salčinović Fetić

    2016-08-01

    Full Text Available This paper presents the results of an extensive research of partially crystalline Zr77Ni23 metallic glass (indicated numbers refer to atomic percentages. The partially crystalline Zr77Ni23 samples were prepared by melt-spinning using a device constructed in the Metal Physics Laboratory, Faculty of Science in Sarajevo. XRD pattern shows crystalline peaks which correspond to an orthorhombic structure of Zr3Ni superimposed on an amorphous pattern. Homogeneity and chemical composition were investigated using scanning electron microscopy (SEM and energy-dispersive X-ray spectroscopy (EDX. Crystallization was studied by differential scanning calorimetry (DSC. DSC analysis indicated a simple thermally activated process. Overall activation energy of the crystallization was calculated using Kissinger's model for nonisothermal process and compared with those given by the Augis-Bennett model. By monitoring of the electrical resistance in the temperature range 80 – 270 K a small and negative thermal coefficient of electrical resistance was observed. This means that electrical resistance varies slightly with temperature and it makes this metallic glass suitable for application in electronic circuits for which this property is an important requirement.

  14. Titanium-catalysed dehydrocoupling of chiral carbosilanes

    Indian Academy of Sciences (India)

    Administrator

    Transition metal-catalysed dehydrocoupling of organosilanes containing primary, secondary and tertiary SiH groups has been developed as an effective route to short chain oligosilanes 1. Studies have been extended using NMR spectroscopy 2 to understand the underlying stereochemistry of these oligomers.

  15. Oxygen partial pressure: a key to alloying and discovery in metal oxide--metal eutectic systems

    International Nuclear Information System (INIS)

    Holder, J.D.; Clark, G.W.; Oliver, B.F.

    1978-01-01

    Control of oxygen partial pressure is essential in the directional solidification of oxide--metal eutectic composites by techniques involving gas-solid and gas-liquid interactions. The existence of end components in the eutectic composite is Po 2 sensitive as are melt stoichiometry, solid phase compositions, and vapor losses due to oxidation-volatilization. Simple criteria are postulated which can aid the experimentalist in selecting the proper gas mixture for oxide--metal eutectic composite growth. The Cr 2 O 3 --Mo--Cr systems was used to verify certain aspects of the proposed criteria

  16. Evaluation of metal-polymeric fixed partial prosthesis using optical coherence tomography

    Science.gov (United States)

    Sinescu, C.; Negrutiu, M. L.; Duma, V. F.; Marcauteanu, C.; Topala, F. I.; Rominu, M.; Bradu, A.; Podoleanu, A. Gh.

    2013-11-01

    Metal-Polymeric fixed partial prosthesis is the usual prosthetic treatment for many dental patients. However, during the mastication the polymeric component of the prosthesis is fractured and will be lost. This fracture is caused by the material defects or by the fracture lines trapped inside the esthetic components of the prosthesis. This will finally lead to the failure of the prosthetic treatment. Nowadays, there is no method of identification and forecast for the materials defects of the polymeric materials. The aim of this paper is to demonstrate the capability of Optical Coherence Tomography (OCT) as a non-invasive clinical method that can be used for the evaluation of metal-polymeric fixed partial prostheses. Twenty metal-polymeric fixed partial prostheses were used for this study. The esthetic component of the prostheses has been Adoro (Ivoclar). Optical investigations of the metal prostheses have revealed no material defects or fracture lines. All the prostheses were temporary cemented in the oral cavities of the patients for six month. The non-invasive method used for the investigations was OCT working in Time Domain mode at 1300 nm. The evaluations of the prostheses were performed before and after their cementation in the patient mouths. All the imagistic results were performed in 2D and than in 3D, after the reconstruction. The results obtained after the OCT evaluation allowed for the identification of 4 metal-polymeric fixed partial prostheses with material defects immediately after finishing the technological procedures. After 6 month in the oral environment other 3 fixed partial prostheses revealed fracture lines. In conclusion, OCT proved to be a valuable tool for the noninvasive evaluation of the metal-polymeric fixed partial prostheses.

  17. Catalysed hydrogen isotope exchange

    International Nuclear Information System (INIS)

    1973-01-01

    A method is described for enhancing the rate of exchange of hydrogen atoms in organic compounds or moieties with deuterium or tritium atoms. It comprises reacting the organic compound or moiety and a compound which is the source of deuterium or tritium in the presence of a catalyst consisting of a non-metallic, metallic or organometallic halide of Lewis acid character and which is reactive towards water, hydrogen halides or similar protonic acids. The catalyst is a halide or organometallic halide of: (i) zinc or another element of Group IIb; (ii) boron, aluminium or another element of Group III; (iii) tin, lead, antimony or another element of Groups IV to VI; or (iv) a transition metal, lanthanide or stable actinide; or a halohalide. (author)

  18. Performance evaluation of a biodiesel fuelled transportation engine retrofitted with a non-noble metal catalysed diesel oxidation catalyst for controlling unregulated emissions.

    Science.gov (United States)

    Shukla, Pravesh Chandra; Gupta, Tarun; Agarwal, Avinash Kumar

    2018-02-15

    In present study, engine exhaust was sampled for measurement and analysis of unregulated emissions from a four cylinder transportation diesel engine using a state-of-the-art FTIR (Fourier transform infrared spectroscopy) emission analyzer. Test fuels used were Karanja biodiesel blend (B20) and baseline mineral diesel. Real-time emission measurements were performed for raw exhaust as well as exhaust sampled downstream of the two in-house prepared non-noble metal based diesel oxidation catalysts (DOCs) and a baseline commercial DOC based on noble metals. Two prepared non-noble metal based DOCs were based on Co-Ce mixed oxide and Lanthanum based perovskite catalysts. Perovskite based DOC performed superior compared to Co-Ce mixed oxide catalyst based DOC. Commercial noble metal based DOC was found to be the most effective in reducing unregulated hydrocarbon emissions in the engine exhaust, followed by the two in-house prepared non-noble metal based DOCs. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Impression Procedures for Metal Frame Removable Partial Dentures as Applied by General Dental Practitioners.

    NARCIS (Netherlands)

    Fokkinga, W.A.; Uchelen, J. van; Witter, D.J.; Mulder, J.; Creugers, N.H.J.

    2016-01-01

    This pilot study analyzed impression procedures for conventional metal frame removable partial dentures (RPDs). Heads of RPD departments of three dental laboratories were asked to record features of all incoming impressions for RPDs during a 2-month period. Records included: (1) impression

  20. Comparison Of Different Noble Metal Catalysts For The Low Temperature Catalytic Partial Oxidation Of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, S.; Truong, T.-B.; Vogel, F.

    2005-03-01

    The generation of synthesis gas at low temperatures can contribute to a more economic production of clean transportation fuels (Fischer-Tropsch liquids) from natural gas. In this report, the performance of different noble metal catalysts in a low temperature catalytic partial oxidation process is presented. (author)

  1. Methyltrioctylammonium chloride catalysed sonochemical synthesis ...

    Indian Academy of Sciences (India)

    Methyltrioctylammonium chloride catalysed sonochemical synthesis of acridine diones. BHUPINDER KAUR and HARISH KUMAR. ∗. Department of Chemistry, Sant Longowal Institute of Engineering and Technology, Longowal 148 106, India e-mail: choprahk67@gmail.com. MS received 21 May 2012; revised 30 January ...

  2. Palladium-Catalysed Coupling Reactions

    NARCIS (Netherlands)

    de Vries, Johannes G.; Beller, M; Blaser, HU

    2012-01-01

    Palladium-catalysed coupling reactions have gained importance as a tool for the production of pharmaceutical intermediates and to a lesser extent also for the production of agrochemicals, flavours and fragrances, and monomers for polymers. In this review only these cases are discussed where it seems

  3. Methyltrioctylammonium chloride catalysed sonochemical synthesis ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. Methyltrioctylammonium chloride catalysed sonochemical synthesis of acridine diones ... The greener, clean and efficient protocol for the synthesis of acridine diones derivatives has been achieved by reacting aromatic aldehyde, dimedone and amines ...

  4. Co-metal-organic-frameworks with pure uniform crystal morphology prepared via Co2 + exchange-mediated transformation from Zn-metallogels for luminol catalysed chemiluminescence

    Science.gov (United States)

    Tang, Xue Qian; Xiao, Bo Wen; Li, Chun Mei; Wang, Dong Mei; Huang, Cheng Zhi; Li, Yuan Fang

    2017-03-01

    Cation exchange-mediated transformation from Zn-metallogels (MOGs), which was a mild facile strategy relative to the demanding hydrothermal method, was employed to develop Co2 + metal-organic frameworks (Co-MOFs) at room temperature. The obtained Co-MOFs was of uniform octahedral morphology and possessed high activity to catalyze luminol chemiluminescence without extra oxidants. By adding cysteine, the CL emission of luminol-Co-MOFs system was further enhanced. Based on this phenomenon, Co-MOFs was utilized to build a practical sensing platform for cysteine determination. Under the optimized conditions, the relative CL intensity (ΔI) was proportional to the concentration of cysteine in the range of 2-10 μM, and the detection limit was 0.49 μM (3S/N). Moreover, the established method was applied to the determination of cysteine in commercially available pharmaceutical injections.

  5. Partial dynamic structure factors in Ni62Nb38 metallic glass

    International Nuclear Information System (INIS)

    Syrykh, G.F.; Khlopkin, M.N.; Zemlyanov, M.G.; Ivanov, A.S.; Schober, H.

    2002-01-01

    The total dynamic structure factors S(Q,E) in three Ni 62 Nb 38 samples with different isotope content were investigated by inelastic neutron scattering, over a range of momentum and energy transfer: Q=0.5-5 A -1 and E=1-40 meV at the IN6 spectrometer (ILL, Grenoble, France). According to the Ashcroft-Langreth formalism, the partial dynamic structure factors S NiNi (Q,E), S NbNb (Q,E) and S NiNb (Q,E) were reconstructed. It is the first experimental observation showing the existence of collective vibrational excitations in the Ni 62 Nb 38 metallic glass system at a partial dynamic structure factor level. (orig.)

  6. Dynamics of Radical-Mediated Enzyme Catalyses

    Science.gov (United States)

    Warncke, Kurt

    1997-11-01

    An emergent class of enzymes harnesses the extreme reactivity of electron-deficient free radical species to perform some of the most difficult reactions in biology. The regio- and stereo-selectivity achieved by these enzymes defies long-held ideas that radical reactions are non-specific. The common primary step in these catalyses is metal- or metallocenter-assisted generation of an electron-deficient organic "initiator radical". The initiator radical abstracts a hydrogen atom from the substrate, opening a new reaction channel for rearrangement to the product. Our aim is to elucidate the detailed molecular mechanisms of the radical pair separation and radical rearrangement steps. Radical pair separation and substrate radical rearrangement are tracked by using time-resolved (10-7 to 10-3 s) techniques of pulsed-electron paramagnetic resonance spectroscopy (FT-EPR, ESEEM). Synchronous time-evolution of the reactions is attained by triggering with a visible laser pulse. Transient non-Boltzmann population of the states of the spin-coupled systems, and resultant electron spin polarization, facilitates study at or near room temperature under conditions where the enzymes are operative. The systems examined include ethanolamine deaminase, a vitamin B12 coenzyme-dependent enzyme, ribonucleotide reductase and photosynthetic reaction centers. The electronic and nuclear structural and kinetic information obtained from the pulsed-EPR studies is used to address how the initiator radicals are stabilized against deleterious recombination with the metal, and to distinguish the participation of concerted versus sequential rearrangement pathways.

  7. Partial Discharge Monitoring on Metal-Enclosed Switchgear with Distributed Non-Contact Sensors

    Directory of Open Access Journals (Sweden)

    Chongxing Zhang

    2018-02-01

    Full Text Available Metal-enclosed switchgear, which are widely used in the distribution of electrical energy, play an important role in power distribution networks. Their safe operation is directly related to the reliability of power system as well as the power quality on the consumer side. Partial discharge detection is an effective way to identify potential faults and can be utilized for insulation diagnosis of metal-enclosed switchgear. The transient earth voltage method, an effective non-intrusive method, has substantial engineering application value for estimating the insulation condition of switchgear. However, the practical application effectiveness of TEV detection is not satisfactory because of the lack of a TEV detection application method, i.e., a method with sufficient technical cognition and analysis. This paper proposes an innovative online PD detection system and a corresponding application strategy based on an intelligent feedback distributed TEV wireless sensor network, consisting of sensing, communication, and diagnosis layers. In the proposed system, the TEV signal or status data are wirelessly transmitted to the terminal following low-energy signal preprocessing and acquisition by TEV sensors. Then, a central server analyzes the correlation of the uploaded data and gives a fault warning level according to the quantity, trend, parallel analysis, and phase resolved partial discharge pattern recognition. In this way, a TEV detection system and strategy with distributed acquisition, unitized fault warning, and centralized diagnosis is realized. The proposed system has positive significance for reducing the fault rate of medium voltage switchgear and improving its operation and maintenance level.

  8. Proline-catalysed Mannich reactions of acetaldehyde.

    Science.gov (United States)

    Yang, Jung Woon; Chandler, Carley; Stadler, Michael; Kampen, Daniela; List, Benjamin

    2008-03-27

    Small organic molecules recently emerged as a third class of broadly useful asymmetric catalysts that direct reactions to yield predominantly one chiral product, complementing enzymes and metal complexes. For instance, the amino acid proline and its derivatives are useful for the catalytic activation of carbonyl compounds via nucleophilic enamine intermediates. Several important carbon-carbon bond-forming reactions, including the Mannich reaction, have been developed using this approach, all of which are useful for making chiral, biologically relevant compounds. Remarkably, despite attempts, the simplest of all nucleophiles, acetaldehyde, could not be used in this way. Here we show that acetaldehyde is a powerful nucleophile in asymmetric, proline-catalysed Mannich reactions with N-tert-butoxycarbonyl (N-Boc)-imines, yielding beta-amino aldehydes with extremely high enantioselectivities-desirable products as drug intermediates and in the synthesis of other biologically active molecules. Although acetaldehyde has been used as a nucleophile in reactions with biological catalysts such as aldolases and thiamine-dependent enzymes, and has also been employed indirectly, its use as an inexpensive and versatile two-carbon nucleophile in asymmetric, small-molecule catalysis will find many practical applications.

  9. Resolution of Metallic Biliary Stent Allergic Reaction After Partial Stent Removal in a Patient with Nickel Sensitivity.

    Science.gov (United States)

    Esparaz, Anthony M; Ahmed, Muneeb

    2017-07-01

    Local and systemic reactions to implanted metallic devices, particularly to those containing nickel, are well documented. Metal ions are released due to exposure of the metal to blood, proteins, other body fluids, and sheer mechanical stress. Metal ions then complex with native proteins and become antigens, which can elicit hypersensitivity reactions. Another case report depicts a specific allergic complication (early stent occlusion) related to metallic biliary stent implantation. We present a case of allergic symptoms, associated with eating, in a patient who developed nickel sensitivity after biliary metal stent placement confirmed by allergic skin testing to the same metallic biliary stent placed one year earlier. Symptoms resolved following partial removal of the non-epithelialized portion of the biliary stent.

  10. Impression Procedures for Metal Frame Removable Partial Dentures as Applied by General Dental Practitioners.

    Science.gov (United States)

    Fokkinga, Wietske A; van Uchelen, Judith; Witter, Dick J; Mulder, Jan; Creugers, Nico H J

    2016-01-01

    This pilot study analyzed impression procedures for conventional metal frame removable partial dentures (RPDs). Heads of RPD departments of three dental laboratories were asked to record features of all incoming impressions for RPDs during a 2-month period. Records included: (1) impression procedure, tray type (stock/custom), impression material (elastomer/alginate), use of border-molding material (yes/no); and (2) RPD type requested (distal-extension/tooth-bounded/combination). Of the 132 total RPD impressions, 111 (84%) involved custom trays, of which 73 (55%) were combined with an elastomer. Impression border-molding material was used in 4% of the cases. Associations between impression procedure and RPD type or dentists' year/university of graduation were not found.

  11. Partially Hydrogenated Graphene Materials Exhibit High Electrocatalytic Activities Related to Unintentional Doping with Metallic Impurities.

    Science.gov (United States)

    Jankovský, Ondřej; Libánská, Alena; Bouša, Daniel; Sedmidubský, David; Matějková, Stanislava; Sofer, Zdeněk

    2016-06-13

    Partially hydrogenated graphene materials, synthesized by the chemical reduction/hydrogenation of two different graphene oxides using zinc powder in acidic environment or aluminum powder in alkaline environment, exhibit high electrocatalytic activities, as well as electrochemical sensing properties. The starting graphene oxides and the resultant hydrogenated graphenes were characterized in detail. Their electrocatalytic activity was examined in the oxygen reduction reaction, whereas sensing properties towards explosives were tested by using picric acid as a redox probe. Findings indicate that the high electrocatalytic performance originates not only from the hydrogenation of graphene, but also from unintentional contamination of graphene with manganese and other metals during synthesis. A careful evaluation of the obtained data and a detailed chemical analysis are necessary to identify the origin of this anomalous electrocatalytic activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Longevity of resin-bonded fixed partial dental prostheses made with metal alloys.

    Science.gov (United States)

    Tanoue, Naomi

    2016-07-01

    The purpose of this study was to evaluate the clinical performance of resin-bonded fixed partial dental prostheses (RBFPDPs) made with metal alloys. The retention of 311 RBFPDPs from 226 patients fabricated from 1983 to 2013 using an adhesive resin was clinically evaluated. Partial or complete debonding of the RBFPDP or framework fracture was considered a treatment failure. All data were obtained from clinical examinations, and missing data were censored at the date of the last available information. The effect of the following factors on survival rate were investigated: patient gender, location (maxilla/mandible and anterior/posterior), number of missing teeth, number of abutment teeth, framework structure, type of metal alloy, patient age at the point of cementation, cement type, and distinction of the treating dentist. Data were analyzed with the Kaplan-Meier survival tests, log-rank tests, and Cox regression analyses (α = 0.05). The Kaplan-Meier survival rate was 41.2 % ± 6.5 % (standard error) at 28.8 years (last outcome event). Significant differences were found for patient age and treating dentist (p < 0.05). The risk of failure in younger patients was 1.7 times greater than that in older patients and that of inexperienced dentists was 2.0 times greater than that of dentist experienced and specialized in adhesive dentistry. When fabricating RBFPDPs for younger patients, mechanical preparation for bonding may be necessary in consideration of the risk for debonding. Experienced dentists may achieve better results. Mastery of skills is necessary to ensure excellent prognoses for RBFPDPs.

  13. Direct evidence for a coordination-insertion mechanism of ethylene oligomerization catalysed by neutral 2,6-bisiminopyridine iron monoalkyl complexes

    OpenAIRE

    Cartes, M. Ángeles; Rodríguez-Delgado, Antonio; Palma, Pilar; Sánchez, Luis J.; Cámpora, Juan; CSIC - Unidad de Recursos de Información Científica para la Investigación (URICI)

    2014-01-01

    1H NMR studies on ethylene oligomerization catalysed by the neutral monoalkyl complex [Fe(Me)(iPrBIP)] allow direct observation of alkyl iron intermediates as well as reversible ethylene coordination to the metal center, providing for the first time experimental evidence for a coordination-insertion mechanism of iron-catalysed ethylene upgrade reactions. © 2014 the Partner Organisations.

  14. [Developing a plan of treatment with a cast metal frame removable partial denture].

    Science.gov (United States)

    Witter, D J; Barèl, J C; Keltjens, H M A M; de Baat, C; Creugers, N H J

    2011-02-01

    When considering prosthetic replacement of absent teeth, a treatment plan is necessary. In evaluating whether replacement of teeth is sensible, the causes and consequences of tooth loss must be considered. This concerns information about problems having to do with the patient, potential complications, purely prosthodontic problems, and specific problems. The patient-related problems require collecting data through patient history as well as a clinical and radiologic examination. Complications are risk-factors which negatively influence the prognosis of general health or of a treatment. Potential complications should be eliminated as much as possible through a preliminary treatment. Purely prosthodontic problems are conditions in the area of absence of several teeth or parts of them, and in the area of occlusal and mandibular stability and articulation. Specific problems may be related to inadequate interocclusal space and the quality of the abutment teeth. A cast metal frame removable partial denture may be a relatively inexpensive and minimally treatment alternative for an expensive and complicated treatment with 1 or more fixed partial dentures.

  15. New synthesis ways of supported metallic catalysts and structure-reactivity relations in catalysis by metals; Nouvelles voies de syntheses de catalyseurs metalliques supportes et relations structure-reactivite en catalyse par les metaux

    Energy Technology Data Exchange (ETDEWEB)

    Uzio, D.

    2006-01-15

    This work deals with some research studies in the field of supported metallic catalysts. In all these works have been studied the characteristics bound to the active sites and the relations between these characteristics and the catalytic performances. The genesis of colloidal suspensions of transition metallic oxide has been used for the preparation of selective hydrogenation catalysts. At first studied in the case of palladium, this new synthesis way has been used for other metals such as Pt, Ni or Co. These studies have then been developed for preparing bimetallic catalysts (PdSn) with as supplementary aim the control of the homogeneity of the bimetallic character at the scale of nano-metric particles. These works have particularly allowed to specify the chemistry of the solutions of some metallic complexes and to rationalize the chemical processes carried out in the usual fabrication processes. Studies on size effects and the study of the reactivity of the nano and sub nano-metric particle have then been developed. Indeed, the clusters containing some atoms can see their intrinsic properties varied very strongly under the influence of several parameters as the number of atoms, the nature of the support, the reactional atmosphere. Using the knowledge acquired during the preceding works (chemistry of palladium aqueous solutions), the study of new methods of preparation of particles containing very few atoms has brought new data on the properties of hyper dispersed particles as well as on the principle of sensitivity to structure. The contribution of the support to the catalytic process for the hydrogenation of different substrates has been studied too. (O.M.)

  16. Group 4 metallocene catalysed full dehydrogenation of hydrazine borane.

    Science.gov (United States)

    Thomas, Johannes; Klahn, Marcus; Spannenberg, Anke; Beweries, Torsten

    2013-10-01

    A study of the full dehydrogenation of hydrazine borane (H2N-NH2·BH3) to give H2 and N2 as gaseous products catalysed by a variety of group 4 metallocene alkyne complexes of the type CpM(L)(η(2)-Me3SiC2SiMe3) (Cp' = substituted or unsubstituted η(5)-cyclopentadienyl; M = Ti, no L; M = Zr, L = pyridine) and group 4 metallocene hydrides is presented. Volumetric data show that the amount of hydrogen released is strongly dependent on both, the metal and the cyclopentadienyl ligand.

  17. Chlorodifluoromethane-triggered formation of difluoromethylated arenes catalysed by palladium

    Science.gov (United States)

    Feng, Zhang; Min, Qiao-Qiao; Fu, Xia-Ping; An, Lun; Zhang, Xingang

    2017-09-01

    Difluoromethylated aromatic compounds are of increasing importance in pharmaceuticals, agrochemicals and materials. Chlorodifluoromethane (ClCF2H), an inexpensive, abundant and widely used industrial raw material, represents the ideal and most straightforward difluoromethylating reagent, but introduction of the difluoromethyl group (CF2H) from ClCF2H into aromatics has not been reported. Here, we describe a direct palladium-catalysed difluoromethylation method for coupling ClCF2H with arylboronic acids and esters to generate difluoromethylated arenes with high efficiency. The reaction exhibits a remarkably broad substrate scope, including heteroarylboronic acids, and was used for difluoromethylation of a range of pharmaceuticals and biologically active compounds. Preliminary mechanistic studies revealed that a palladium difluorocarbene intermediate is involved in the reaction. Although numerous metal-difluorocarbene complexes have been prepared, the catalytic synthesis of difluoromethylated or difluoromethylenated compounds involving metal-difluorocarbene complexes has not received much attention. This new reaction therefore also opens the door to understand metal-difluorocarbene complex catalysed reactions.

  18. Brønsted acid-surfactant (BAS catalysed cyclotrimerization of aryl methyl ketone

    Directory of Open Access Journals (Sweden)

    Kiran Phatangare

    2012-07-01

    Full Text Available A brønsted acid-surfactant catalysed and simple, mild, metal catalyst free and chemo-selective method has been developed for synthesis of 1, 3, 5-triaryl benzenes from aryl methyl ketones. The advantages of this protocol subsume green and sustainable reaction medium, mild reaction conditions, easy product recovery and its good yields.

  19. Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

    Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

  20. Palladium-catalysed ortho arylation of acetanilides

    Indian Academy of Sciences (India)

    Administrator

    State Key Laboratory of Applied Organic Chemistry, Lanzhou 73000, P.R. China e-mail: hgs2368@163.com. MS received 12 January 2009; revised 20 July 2009; accepted 14 September 2009. Abstract. The palladium-catalysed direct arylation of acetanilides by using C–H activation methodo- logy has been demonstrated.

  1. Deconjugation of glucuronides catalysed by UDPglucuronyltransferase

    NARCIS (Netherlands)

    Peters, W. H.; Jansen, P. L.; Cuypers, H. T.; de Abreu, R. A.; Nauta, H.

    1986-01-01

    Evidence was found for UDPglucuronyltransferase-catalysed deconjugation of p-nitrophenol-, 4-methylumbelliferone- and phenolphthalein-glucuronides. The evidence is based on the following observations: 1, deconjugation is UDP-dependent and the reactions show Michaels-Menten kinetics with respect to

  2. Investigating the influence of heavy metals on macro-invertebrate assemblages using Partial Cononical Correspondence Analysis (pCCA

    Directory of Open Access Journals (Sweden)

    G. Beasley

    2003-01-01

    Full Text Available This paper defines the spectrum of impairment to stream macroinvertebrates arising from urban runoff. Field sampling of stream sediments at 62 sites across Yorkshire, UK was used to investigate the influence of heavy metals and habitat on macroinvertebrate family distribution using partial Canonical Correspondence Analysis (pCCA. Increasing urbanization and trafficking was associated with increasing levels of metal pollution but, even when traffic is light, family numbers can be reduced by 50%. Industrial areas and motorway runoff depress macroinvertebrate numbers but drainage from streets with no off-road parking in residential areas can have similar impacts. The heavy metals in the sediment accounted for approximately 24% of the variation in macroinvertebrate community composition while the physical habitat variables used in RIVPACS (River InVertebrate Prediction And Classification System (Wright, 2000 accounted for an additional 30%. Zinc and nickel were the main metal influences regardless of the time of sampling; at these sites copper is less than critical. Results agree with those reported in other studies in which families mainly from the orders Ephemeroptera (mayfly, Plecoptera (stonefly and Tricoptera (caddisfly displayed metal sensitivity in that they were absent from metal polluted streams. However, within each of these orders, a continuum of sensitivity is evident: this highlights the risks of generalising on orders rather than using family or indeed species data. Keywords: macroinvertebrates, heavy metals, urban streams, tolerance, sensitivity

  3. Control of Partial Coalescence of Self-Assembled Metal Nano-Particles across Lyotropic Liquid Crystals Templates towards Long Range Meso-Porous Metal Frameworks Design

    Directory of Open Access Journals (Sweden)

    Ludovic F. Dumée

    2015-10-01

    Full Text Available The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation.

  4. Control of Partial Coalescence of Self-Assembled Metal Nano-Particles across Lyotropic Liquid Crystals Templates towards Long Range Meso-Porous Metal Frameworks Design.

    Science.gov (United States)

    Dumée, Ludovic F; Lemoine, Jean-Baptiste; Ancel, Alice; Hameed, Nishar; He, Li; Kong, Lingxue

    2015-10-26

    The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation.

  5. Peptide catalysed prebiotic polymerization of RNA

    DEFF Research Database (Denmark)

    Wieczorek, Rafal; Luisi, Pier Luigi; Monnard, Pierre-Alain

    A short peptide composed of only two amino acid residues, serine and histidine, is here reported to enable oligomerization of RNA monomers. SerHis dipeptide was previously reported to catalyse formation of peptide bonds (Gorlero et al. 2009) as well as possessing broad hydrolytic activities...... – in such environment hydrolysis is thermodynamically favoured over condensation. However, the thermodynamic equilibrium towards condensation can be shifted even in this environment. In this poster we describe a prebiotically plausible system in which the SerHis dipeptide acts as catalyst for the formation of RNA...... these conditions, most of the water is in the form of ice crystals and the other reactants are upconcentrated in the remaining liquid micro-inclusions, hence creating an environment with low water activity in which condensation reactions can occur. The ability of simple peptides to catalyse RNA synthesis could...

  6. Palladium-catalysed ortho arylation of acetanilides

    Indian Academy of Sciences (India)

    Full Papers Volume 122 Issue 2 March 2010 pp 149-155 ... Abstract. The palladium-catalysed direct arylation of acetanilides by using C-H activation methodology has been demonstrated. Several acetanilides were coupled with aryl iodides in the presence of 10 mol% of Pd(OAc)2, 1.0 equiv of Cu(OTf)2, and 0.6 equiv of ...

  7. Remarkably enhanced gas separation by partial self-conversion of a laminated membrane to metal-organic frameworks.

    Science.gov (United States)

    Liu, Yi; Pan, Jia Hong; Wang, Nanyi; Steinbach, Frank; Liu, Xinlei; Caro, Jürgen

    2015-03-02

    Separation methods based on 2D interlayer galleries are currently gaining widespread attention. The potential of such galleries as high-performance gas-separation membranes is however still rarely explored. Besides, it is well recognized that gas permeance and separation factor are often inversely correlated in membrane-based gas separation. Therefore, breaking this trade-off becomes highly desirable. Here, the gas-separation performance of a 2D laminated membrane was improved by its partial self-conversion to metal-organic frameworks. A ZIF-8-ZnAl-NO3 layered double hydroxide (LDH) composite membrane was thus successfully prepared in one step by partial conversion of the ZnAl-NO3 LDH membrane, ultimately leading to a remarkably enhanced H2 /CH4 separation factor and H2 permeance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Gold film-catalysed benzannulation by Microwave-Assisted, Continuous Flow Organic Synthesis (MACOS

    Directory of Open Access Journals (Sweden)

    Gjergji Shore

    2009-07-01

    Full Text Available Methodology has been developed for laying down a thin gold-on-silver film on the inner surface of glass capillaries for the purpose of catalysing benzannulation reactions. The cycloaddition precursors are flowed through these capillaries while the metal film is being heated to high temperatures using microwave irradiation. The transformation can be optimized rapidly, tolerates a wide number of functional groups, is highly regioselective, and proceeds in good to excellent conversion.

  9. Selective observation of the Cu(I)-amicyanin metal site by paramagnetic NMR on partially oxidised samples

    International Nuclear Information System (INIS)

    Salgado, Jesus; Kalverda, Arnout P.; Canters, Gerard W.

    1997-01-01

    The relaxation enhancement caused by paramagnetic copper(II) is used to observe selectively the metal site of copper(I)-amicyanin by one- and two-dimensional NMR spectroscopy. The paramagnetic effect is communicated to the diamagnetic protein through the electron self-exchange reaction in partially oxidised samples, and can be used for the selective detection of protons around the metal. Relaxation-selective NMR pulse sequences, like super-WEFT and WEFT-NOESY, are used to achieve the desired selection of the signals. The spectra obtained show well-resolved signals corresponding to protons within a radius of∼7 A from the metal, including almost all protons from the coordinated residues. A significant increase in resolution as well as selection of the most relevant part of the protein (close to the active centre) are the principal advantages of this technique, which can be used to obtain specific information about the metal site in blue copper proteins, to assist in the assignment of their NMR spectra and to determine functional properties like the electron self-exchange rate

  10. Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

    Energy Technology Data Exchange (ETDEWEB)

    Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

    2015-03-24

    Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

  11. Relationships between the distribution of O atoms on partially oxidized metal (Al, Ag, Cu, Ti, Zr, Hf) surfaces and the adsorption energy: A density-functional theory study

    Science.gov (United States)

    Houska, J.; Kozak, T.

    2017-06-01

    We investigate the oxidation of selected metal (Al, Ag, Cu, Ti, Zr, and Hf) surfaces by the density functional theory. We go through a wide range of (233 per metal) distributions of O atoms on a partially oxidized metal surface. First, we focus on the qualitative information whether the preferred distribution of O atoms is heterogeneous (stoichiometric oxide + metal) or homogeneous (substoichiometric oxide). We find that the former is energetically preferred, e.g., for Al, while the latter is energetically preferred, e.g., for Ti, Zr, and Hf. Second, we provide the quantitative values of adsorption energies corresponding to the energetically preferred O atom distributions for various partial coverages of various metals by O. Third, we discuss and show an example of implications of the aforementioned findings for the understanding and simulations of sputtering.

  12. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

    NARCIS (Netherlands)

    Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang

    2010-01-01

    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to

  13. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)

    Unknown

    ted enantioselective aldol addition reactions of ace- tone and substituted acetones with aldehydes catalysed by proline. Conflicting kinetic evidence has been obtained by Agami et al9 for the participa- tion of two molecules of proline in the transition states of proline-catalysed intramolecular cycliza- tions and by Houk et al10 ...

  14. A Novel Partially Covered Self-Expandable Metallic Stent with Proximal Flare in Patients with Malignant Gastric Outlet Obstruction.

    Science.gov (United States)

    Takahara, Naminatsu; Isayama, Hiroyuki; Nakai, Yousuke; Yoshida, Shuntaro; Saito, Tomotaka; Mizuno, Suguru; Yagioka, Hiroshi; Kogure, Hirofumi; Togawa, Osamu; Matsubara, Saburo; Ito, Yukiko; Yamamoto, Natsuyo; Tada, Minoru; Koike, Kazuhiko

    2017-07-15

    Endoscopic placement of self-expandable metal stents (SEMSs) has emerged as a palliative treatment for malignant gastric outlet obstruction (GOO). Although covered SEMSs can prevent tumor ingrowth, frequent migration of covered SEMSs may offset their advantages in preventing tumor ingrowth. We conducted this multicenter, single-arm, retrospective study at six tertiary referral centers to evaluate the safety and efficacy of a partially covered SEMS with an uncovered large-bore flare at the proximal end as an antimigration system in 41 patients with symptomatic malignant GOO. The primary outcome was clinical success, and the secondary outcomes were technical success, stent dysfunction, adverse events, and survival after stent placement. The technical and clinical success rates were 100% and 95%, respectively. Stent dysfunctions occurred in 17 patients (41%), including stent migration in nine (23%), tumor ingrowth in one (2%), and tumor overgrowth in four (10%). Two patients (5%) developed adverse events: one pancreatitis and one perforation. No procedure-related death was observed. A novel partially covered SEMS with a large-bore flare proximal end was safe and effective for malignant GOO but failed to prevent stent migration. Further research is warranted to develop a covered SEMS with an optimal antimigration system.

  15. Dipeptide catalysed prebiotic polymerization of RNA

    DEFF Research Database (Denmark)

    Wieczorek, Rafal; Luisi, Pier Luigi; Monnard, Pierre-Alain

    2011-01-01

    toward more peptide synthesis. In the present work we describe a prebiotically plausible system in which the SerHis dipeptide acts as catalyst for the formation of RNA oligomers from imidazole derivatives of mononucleotides. The thermodynamic shift towards condensation was achieved using water......-concentrated in the remaining liquid microinclusions, thus creating an environment with low water activity in which condensation reactions can occur. Successful oligomerization of RNA monomers catalysed by the SerHis dipeptide was observed in a broad range of pH, and with all four natural nucleobases. The isomeric dipeptide...... HisSer did not exhibit any catalytic properties thus indicating that the specific, spatial arrangement of amino acid residues in the SerHis structure is responsible for its catalytic activity. Establishing novel synthetic pathways to RNA polymerization is important, as to date no convincing prebiotic...

  16. L'alkylidénolyse des oléfines catalysée par les complexes des métaux de transition Alkylidenolysis of Olefins Catalysed by Transition-Metal Complexes

    Directory of Open Access Journals (Sweden)

    Chauvin Y.

    2006-11-01

    Full Text Available Une grande variété de complexes de métaux de transition, homogènes ou hétérogènes, sont susceptibles de provoquer la scission des doubles et triples liaisons carbone-carbone. Les caractéristiques générales de la réaction de disproportion (x métathèse » des oléfines acycliques et de la polymérisation des oléfines cycliques impliquent l'existence d'intermédiaires de réaction dont les analogues stables sont connus. Les applications de la réaction sont variées : interconversion des oléfines et synthèse de polymères de structures nouvelles. A great variety of homogeneous or heterogeneous transition metal complexes may induce the splitting of the double and triple carbon-carbon bonds. The general characteristics of the disproportionation reaction (x metathesis » of acyclic olefins and cyclic-olefin polymerization imply the existence of reaction intermediates whose stable analogs are known. This reaction has various applications such as olefin interconversion and synthesizing polymers with new structures.

  17. Palladium-catalysed electrophilic aromatic C-H fluorination

    Science.gov (United States)

    Yamamoto, Kumiko; Li, Jiakun; Garber, Jeffrey A. O.; Rolfes, Julian D.; Boursalian, Gregory B.; Borghs, Jannik C.; Genicot, Christophe; Jacq, Jérôme; van Gastel, Maurice; Neese, Frank; Ritter, Tobias

    2018-02-01

    Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.

  18. A partially substituted calix[4]resorcarene receptor and its selective recognition for soft metal cations (silver and mercury).

    Science.gov (United States)

    Danil de Namor, Angela F; Chaaban, Jinane K

    2008-02-21

    A partially substituted calix[4]resorcarene receptor, namely, 5,17-ethylthiomethylated calix[4]resorcarene, 1, has been synthesized and characterized by 1H NMR in CD3OD, CDCl3, and CD3CN and 13C NMR in CD3OD, as well as by 2D NMR. Partition data in the methanol-hexane and acetonitrile-hexane solvent systems show that the monomeric species are predominant in these solvents. The solubility of 1 in various solvents was determined at 298.15 K. These data were used to calculate the standard solution Gibbs energy of 1 in these solvents. Taking hexane as the reference solvent, the standard transfer Gibbs energy of 1 to various solvents was calculated. Good agreement is found between the DeltatG(o) values in the hexane-methanol and hexane-acetonitrile and the DeltapG(o) values of this ligand in these solvent systems. The higher partition constant of 1 in the hexane-methanol relative to the hexane-acetonitrile solvent system contrasts with corresponding data for the fully functionalized receptor, 2. This is explained in terms of the solvation differences of these receptors in these solvents as reflected in the DeltatG(o) values. The cation complexing properties of this receptor were investigated through 1H NMR, conductance, calorimetric, and potentiometric methods. Among the metal cations (alkali, alkaline earth, heavy, and transition), 1 interacts only with Ag+ in methanol and Hg2+ in propylene carbonate, acetonitrile, methanol, and N,N-dimethylformamide. While 1 forms a 1:1 complex with Ag+ in methanol, the hosting ability of the receptor for the mercury cation is enhanced in methanol, acetonitrile, and N,N-diethylformamide. Thus, Hg2+ complexes of 1:2 (ligand:metal cation) stoichiometry are found in these solvents. In moving to propylene carbonate, the composition of the mercury complex is altered from 1:2 to 1:1. The results are compared with corresponding data for 2 and these metal cations in the appropriate solvents. The lack of stability observed for 2 and Hg2+ in

  19. The dissolution of organic ion exchange resins using iron-catalysed hydrogen peroxide

    International Nuclear Information System (INIS)

    Hawkings, N.; Horton, K.D.; Snelling, K.W.

    1980-10-01

    Feasibility studies have been made of the dissolution/partial decomposition of radioactive waste resins by means of iron-catalysed hydrogen peroxide. They have shown that the procedure is limited in its application and successfully treats only polystyrene/divinylbenzene-based resins. Evaporation of the final solution produces a solid residue which is difficult to handle and results in only a relatively small reduction in volume. It is concluded that the method could be used to dissolve specific waste resins for easier handling and disposal, but is not of general applicability. (author)

  20. Clinical application of removable partial dentures using thermoplastic resin-part I: definition and indication of non-metal clasp dentures.

    Science.gov (United States)

    Fueki, Kenji; Ohkubo, Chikahiro; Yatabe, Masaru; Arakawa, Ichiro; Arita, Masahiro; Ino, Satoshi; Kanamori, Toshikazu; Kawai, Yasuhiko; Kawara, Misao; Komiyama, Osamu; Suzuki, Tetsuya; Nagata, Kazuhiro; Hosoki, Maki; Masumi, Shin-Ichi; Yamauchi, Mutsuo; Aita, Hideki; Ono, Takahiro; Kondo, Hisatomo; Tamaki, Katsushi; Matsuka, Yoshizo; Tsukasaki, Hiroaki; Fujisawa, Masanori; Baba, Kazuyoshi; Koyano, Kiyoshi; Yatani, Hirofumi

    2014-01-01

    This position paper proposes a definition and naming standard for removable partial dentures (RPDs) using thermoplastic resin, and presents a guideline for clinical application. A panel of 14 experts having broad experience with clinical application of RPDs using thermoplastic resin was selected from members of the Japan Prosthodontic Society. At a meeting of the panel, "non-metal clasp denture" was referred as the generic name of RPDs with retentive elements (resin clasps) made of thermoplastic resin. The panel classified non-metal clasp dentures into two types: one with a flexible structure that lacks a metal framework and the other having a rigid structure that includes a metal framework. According to current prosthetic principles, flexible non-metal clasp dentures are not recommended as definitive dentures, except for limited cases such as patients with a metal allergy. Rigid non-metal clasp dentures are recommended in cases where patients will not accept metal clasps for esthetic reasons. Non-metal clasp dentures should follow the same design principles as conventional RPDs using metal clasps. Copyright © 2013 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  1. Feasibility of estimating heavy metal concentrations in water column using hyperspectral data and partial least squares regression

    Science.gov (United States)

    Chen, Yiyun; Liu, Yaolin; Wang, Dun; Kong, XueSong; Zeng, Chen

    2009-10-01

    Mining and smelting often produce acidic wastes that can cause severe biogeochemical changes downstream from these mines. Dexing copper mine, as the largest open cast mine in China, is connected to Poyang Lake by Le An river. Water and spectra samples were taken from Le An River and two of its branches, and afterward the concentrations of Cd, Cu, Pb and Zn were measured in the lab. Different spectral pre-processing methods were applied to the spectra, including Savitzky-Golay spectral smoothing, SNV, first derivative, second derivative spectral transforming. On the purpose of estimating metal concentrations from differently pre-processed spectra, partial least squares regression was then used in model calibrations. For deciding the optimal number of PLS factors included in the PLS model, the model with the lowest root mean square error of validation is chosen. The coefficient of determination (R2v) between the predicted and the reference values from the test set are used as an evaluation mean. For estimating Pb concentration, R2v = 0.915, which is acceptable. For Cd concentration, R2v = 0.697 and 0.683 for Zn. PLS model seems to failed in estimating Cu concentration, for the best R2v for PLS model of Cu is lower than 0.5. From the aspects of spectral pre-processing methods, first derivative after Savitzky-Golay smoothing performs superior to others. In conclusion, PLS models based on carefully pre-processed hyperspectral data turn out to be a promising solution for detecting certain heavy metals concentrations in river.

  2. Zn (OTf) 2-catalysed indolylation and pyrrolylation of isatins: Efficient ...

    Indian Academy of Sciences (India)

    catalysed indolylation and pyrrolylation of isatins: Efficient synthesis and biochemical assay of 3,3-di(heteroaryl)oxindoles. C Praveen S Narendiran P Dheenkumar P T Perumal. Regular Articles Volume 125 Issue 6 November 2013 pp 1543- ...

  3. Zeolite H-BEA catalysed multicomponent reaction: One-pot ...

    Indian Academy of Sciences (India)

    BEA catalysed multicomponent reaction: One-pot synthesis of amidoalkyl naphthols - Biologically active drug-like molecules. Sunil R Mistry Rikesh S Joshi Kalpana C Maheria. Volume 123 Issue 4 July 2011 pp 427-432 ...

  4. Iron-catalysed tritiation of pharmaceuticals

    Science.gov (United States)

    Pony Yu, Renyuan; Hesk, David; Rivera, Nelo; Pelczer, István; Chirik, Paul J.

    2016-01-01

    A thorough understanding of the pharmacokinetic and pharmacodynamic properties of a drug in animal models is a critical component of drug discovery and development. Such studies are performed in vivo and in vitro at various stages of the development process—ranging from preclinical absorption, distribution, metabolism and excretion (ADME) studies to late-stage human clinical trials—to elucidate a drug molecule’s metabolic profile and to assess its toxicity. Radiolabelled compounds, typically those that contain 14C or 3H isotopes, are one of the most powerful and widely deployed diagnostics for these studies. The introduction of radiolabels using synthetic chemistry enables the direct tracing of the drug molecule without substantially altering its structure or function. The ubiquity of C-H bonds in drugs and the relative ease and low cost associated with tritium (3H) make it an ideal radioisotope with which to conduct ADME studies early in the drug development process. Here we describe an iron-catalysed method for the direct 3H labelling of pharmaceuticals by hydrogen isotope exchange, using tritium gas as the source of the radioisotope. The site selectivity of the iron catalyst is orthogonal to currently used iridium catalysts and allows isotopic labelling of complementary positions in drug molecules, providing a new diagnostic tool in drug development.

  5. Iron-catalysed tritiation of pharmaceuticals.

    Science.gov (United States)

    Yu, Renyuan Pony; Hesk, David; Rivera, Nelo; Pelczer, István; Chirik, Paul J

    2016-01-14

    A thorough understanding of the pharmacokinetic and pharmacodynamic properties of a drug in animal models is a critical component of drug discovery and development. Such studies are performed in vivo and in vitro at various stages of the development process--ranging from preclinical absorption, distribution, metabolism and excretion (ADME) studies to late-stage human clinical trials--to elucidate a drug molecule's metabolic profile and to assess its toxicity. Radiolabelled compounds, typically those that contain (14)C or (3)H isotopes, are one of the most powerful and widely deployed diagnostics for these studies. The introduction of radiolabels using synthetic chemistry enables the direct tracing of the drug molecule without substantially altering its structure or function. The ubiquity of C-H bonds in drugs and the relative ease and low cost associated with tritium ((3)H) make it an ideal radioisotope with which to conduct ADME studies early in the drug development process. Here we describe an iron-catalysed method for the direct (3)H labelling of pharmaceuticals by hydrogen isotope exchange, using tritium gas as the source of the radioisotope. The site selectivity of the iron catalyst is orthogonal to currently used iridium catalysts and allows isotopic labelling of complementary positions in drug molecules, providing a new diagnostic tool in drug development.

  6. Transition metal catalysed Grignard-like allylic activation across ...

    Indian Academy of Sciences (India)

    Unknown

    The reaction chosen for the present study is the Barbier variation of the Grignard reaction, wherein the organic halide and a carbonyl compound react to provide the corresponding homoallylic alcohol5. With specific reference to carbonyl allylation via tin(II) salts, it was previously shown that allyltrihalostannane is formed as a ...

  7. Transition metal catalysed Grignard-like allylic activation across ...

    Indian Academy of Sciences (India)

    Unknown

    Contemporary chemistry is characterized by the number and variety of topics, which cut across traditional divides. The interest in combining transition and main group elements to generate new structural motifs, often clusters, provides distinct opportunities in the field of catalysis. In this direction, ligand-assisted ...

  8. Lewis acidic metal catalysed organic transformations by designed ...

    Indian Academy of Sciences (India)

    Administrator

    exclusive use of SiO4/AlO4 building blocks. Second, the desirable chemical modification within the inte- rior of the material has limitations. Such chemical modifications are important for expanding and enhancing the catalytic performance of the resultant material. Third, the catalytic applications of zeolites are restricted to ...

  9. Using SF6 Decomposed Component Analysis for the Diagnosis of Partial Discharge Severity Initiated by Free Metal Particle Defect

    Directory of Open Access Journals (Sweden)

    Ju Tang

    2017-08-01

    Full Text Available The decomposition characteristics of a SF6 gas-insulated medium were used to diagnose the partial discharge (PD severity in DC gas-insulated equipment (DC-GIE. First, the PD characteristics of the whole process were studied from the initial PD to the breakdown initiated by a free metal particle defect. The average discharge magnitude in a second was used to characterize the PD severity and the PD was divided into three levels: mild PD, medium PD, and dangerous PD. Second, two kinds of voltage in each of the above PD levels were selected for the decomposition experiments of SF6. Results show that the negative DC-PD in these six experiments decomposes the SF6 gas and generates five stable decomposed components, namely, CF4, CO2, SO2F2, SOF2, and SO2. The concentrations and concentration ratios of the SF6 decomposed components can be associated with the PD severity. A minimum-redundancy-maximum-relevance (mRMR-based feature selection algorithm was used to sort the concentrations and concentration ratios of the SF6 decomposed components. Back propagation neural network (BPNN and support vector machine (SVM algorithms were used to diagnose the PD severity. The use of C(CO2/CT1, C(CF4/C(SO2, C(CO2/C(SOF2, and C(CF4/C(CO2 shows good performance in diagnosing PD severity. This finding serves as a foundation in using the SF6 decomposed component analysis (DCA method to diagnose the insulation faults in DC-GIE and assess its insulation status.

  10. Extension of the Single-Event Methodology to Metal Catalysis: Application to Fischer-Tropsch Synthesis Extension de la méthodologie des événements constitutifs à la catalyse métallique : Application à la synthèse Fischer-Tropsch

    Directory of Open Access Journals (Sweden)

    Lozano-Blanco G.

    2010-10-01

    Full Text Available The single-event methodology has been extended to metal catalysis using Fischer-Tropsch synthesis on an iron-based catalyst as case study. The reaction mechanism has been assessed in terms of elementary steps that could be categorized in reaction families such as reductive elimination, β-hydride elimination and methylene insertion. A computer code has been developed for the generation of the reaction network containing these elementary steps. The representation of reacting and intermediate species explicitly takes into account metal-carbon bonds as well as the presence of oxygen. The model has been validated using iron-based catalytic data at 623 K, 0.6 to 2.1 MPa, inlet molar H2/CO ratio between 2 and 6. 14 parameters, among which 10 activation energies and 4 atomic chemisorption enthalpies have been adjusted to the experimental data. Experimentally observed trends in alkane and 1-alkene product yields with the carbon number were adequately reproduced as well as the individual molar yields of the non-hydrocarbon products. La méthodologie par événements constitutifs a été étendue à la catalyse métallique en utilisant la synthèse Fischer-Tropsch sur un catalyseur au fer comme cas d'étude. Le mécanisme réactionnel a été décomposé en étapes élémentaires qui peuvent être classées par type de réactions, telles que l'élimination réductrice, l'élimination d'hydrure en β, et l'insertion de groupe méthylène. Un code de calcul a été développé pour générer le réseau réactionnel impliquant ces étapes élémentaires. La représentation des réactifs et des espèces intermédiaires prend en compte explicitement les liaisons carbone-métal et inclut la présence d'atomes d'oxygène. Le modèle a été validé sur une base de données obtenues sur un catalyseur à base de fer à 623 K, sur une plage de 0,6 à 2,1 MPa, un ratio H2/CO en entrée variant de 2 à 6. Quatorze paramètres, dont 10 énergies d'activation et 4

  11. Carbon dioxide hydrogenation catalysed by well-defined Mn(i) PNP pincer hydride complexes.

    Science.gov (United States)

    Bertini, Federica; Glatz, Mathias; Gorgas, Nikolaus; Stöger, Berthold; Peruzzini, Maurizio; Veiros, Luis F; Kirchner, Karl; Gonsalvi, Luca

    2017-07-01

    The catalytic reduction of carbon dioxide is of great interest for its potential as a hydrogen storage method and to use carbon dioxide as C-1 feedstock. In an effort to replace expensive noble metal-based catalysts with efficient and cheap earth-abundant counterparts, we report the first example of Mn(i)-catalysed hydrogenation of CO 2 to HCOOH. The hydride Mn(i) catalyst [Mn(PNP NH - i Pr)(H)(CO) 2 ] showed higher stability and activity than its Fe(ii) analogue. TONs up to 10 000 and quantitative yields were obtained after 24 h using DBU as the base at 80 °C and 80 bar total pressure. At catalyst loadings as low as 0.002 mol%, TONs greater than 30 000 could be achieved in the presence of LiOTf as the co-catalyst, which are among the highest activities reported for base-metal catalysed CO 2 hydrogenations to date.

  12. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    Science.gov (United States)

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-01-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C–N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions. PMID:27708259

  13. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    Science.gov (United States)

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-10-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C-N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions.

  14. Taille des particules et catalyse Particle Size and Catalysis

    Directory of Open Access Journals (Sweden)

    Boitiaux J. P.

    2006-11-01

    hydrogène pouvaient tout à fait rendre compte des phénomènes observés. En plus de cela un métal déposé sur silice et un métal déposé sur alumine peuvent se comporter de façon tout à fait différente. Tout ceci montre que certaines interprétations sont trop simplistes et que faire varier la taille des particules par n'importe quel moyen et étudier les conséquences sur l'acte catalytique n'est pas suffisant. Les deux approches complémentaires, celle du cristallographe qui tente de décrire les petites particules à partir des paramètres du métal massique et celle du chimiste qui tente de déduire la structure du comportement du catalyseur observé dans la réaction étudiée, n'arrivent pas vraiment à se rejoindre pour aboutir à une description en tout point acceptable de la structure de la particule. D'un côté le physico-chimiste utilise des simplifications outrancières lorsqu'il tente de décrire ses structures grâce à l'usage de fonctions d'état qui n'ont pas toujours des solutions évidentes. D'un autre le chimiste manipule des objets réels mais arrive difficilement à isoler le paramètre qu'il veut étudier. Ses conclusions ne sont jamais à l'abri des artefacts apportés par les conditions opératoires ou les effets de support. Ce dilemme existe aussi pour le physicien qui tente de synthétiser des agrégats bien définis dans un flux gazeux mais loin de la réalité de la catalyse. De même pour le chimiste qui veut ramener les effets de structure à de simples comparaisons entre les faces exposées par les monocristaux. Néanmoins l'apport des deux est indispensable car ils donnent des idées directrices indispensables pour l'homme de catalyse qui tente de maîtriser l'ensemble des paramètres. While heterogeneous catalysis, and especially catalysis by metals, is concerned with the size of the particles and hence with the developed surface area, this is not only to prepare an effective product at minimum cost. The study of the

  15. STRUCTURAL INTERACTIONS OF HYDROGEN WITH BULK AMORPHOUS MICROSTRUCTURES IN METALLIC SYSTEMS UNDERSTANDING THE ROLE OF PARTIAL CRYSTALLINITY ON PERMEATION AND EMBRITTLEMENT

    Energy Technology Data Exchange (ETDEWEB)

    Brinkman, Kyle; Fox, Elise; Korinko, Paul; Adams, Thad

    2010-05-10

    The development of metallic glasses in bulk form has led to a resurgence of interest into the utilization of these materials for a variety of applications. A potentially exciting application for these bulk metallic glass (BMG) materials is their use as composite membranes to replace high cost Pd/Pd-alloy membranes for enhanced gas separation processes. One of the major drawbacks to the industrial use of Pd/Pd-alloy membranes is that during cycling above and below a critical temperature an irreversible change takes place in the palladium lattice structure which can result in significant damage to the membrane. Furthermore, the cost associated with Pd-based membranes is a potential detractor for their continued use and BMG alloys offer a potentially attractive alternative. Several BMG alloys have been shown to possess high permeation rates, comparable to those measured for pure Pd metal. In addition, high strength and toughness when either in-situ or ex-situ second phase dispersoids are present. Both of these properties, high permeation and high strength/toughness, potentially make these materials attractive for gas separation membranes that could resist hydrogen 'embrittlement'. However, a fundamental understanding of the relationship between partially crystalline 'structure'/devitrification and permeation/embrittlement in these BMG materials is required in order to determine the operating window for separation membranes and provide additional input to the material synthesis community for improved alloy design. This project aims to fill the knowledge gap regarding the impact of crystallization on the permeation properties of metallic glass materials. The objectives of this study are to (i) determine the crystallization behavior in different gas environments of Fe and Zr based commercially available bulk metallic glass and (ii) quantify the effects of partial crystallinity on the hydrogen permeation properties of these metallic glass membranes.

  16. A hydrogen fuel cell for rapid, enzyme-catalysed organic synthesis with continuous monitoring.

    Science.gov (United States)

    Wan, Lei; Megarity, Clare F; Siritanaratkul, Bhavin; Armstrong, Fraser A

    2018-01-23

    A one-pot fuel cell for specific, enzyme-catalysed organic synthesis, with continuous monitoring of rate and reaction progress, combines an electrode catalysing rapid, reversible and diffusion-controlled interconversion of NADP + and NADPH with a Pt electrode catalysing 2H + /H 2 interconversion. This Communication demonstrates its performance and characteristics using the reductive amination of 2-oxoglutarate as a test system.

  17. Co-TUD-1 catalysed aerobic oxidation of cyclohexane

    NARCIS (Netherlands)

    Ramanathan, A.; Hamdy Mohamed Saad, M.S.; Parton, R.; Maschmeyer, T.; Jansen, J.C.; Hanefeld, U.

    2009-01-01

    Co-TUD-1, an amorphous sponge-like mesoporous cobalt-containing silicate, was shown to be a very active and selective catalyst for the aerobic oxidation of cyclohexane. In addition, the decomposition of cyclohexyl hydroperoxide (CHHP) was carried out over Co-TUD-1 and it catalysed complete

  18. Selenium dioxide catalysed oxidation of acetic acid hydrazide by ...

    Indian Academy of Sciences (India)

    Abstract. Selenium dioxide catalysed acetic acid hydrazide oxidation by bromate was studied in hydrochloric acid medium. The order in oxidant concentration, substrate and catalyst were found to be unity. Increasing hydrogen ion concentration increases the rate of the reaction due to protonation equilibria of the oxidant.

  19. Palladium-Catalysed Dimerisation of Furfural | Taljaard | South ...

    African Journals Online (AJOL)

    5,5'-Diformyl-2,2'-difuran has been synthesized in 60% yield by the palladium acetate-catalysed aryl coupling of furfural in acetonitrile in the presence of dioxygen under pressure. Various reaction conditions have been exploited, and mechanistic aspects of the reaction are discussed. South African Journal of Chemistry ...

  20. Synthesis of sugars catalysed by microgel conjugated rabbit muscle ...

    African Journals Online (AJOL)

    Microgel has been prepared and covalently conjugated to rabbit muscle aldolase and employed to catalyse reactions between dihydroxyacetone phosphate, DHAP natural and non-natural acceptors aldehydes in aqueous, aqueous – organic solvents at ambient temperature. The microgel conjugated enzyme was found to ...

  1. Phenylboronic acid catalysed synthesis of 1,5-benzodiazepines via ...

    Indian Academy of Sciences (India)

    J. Chem. Sci. Vol. 125, No. 4, July 2013, pp. 745–749. c Indian Academy of Sciences. Phenylboronic acid catalysed synthesis of 1,5-benzodiazepines via cyclocondensation of ... active compounds and gaining great consideration in the field of .... thesis of this heterocycles was accomplished by con- densation reaction of ...

  2. Selenium dioxide catalysed oxidation of acetic acid hydrazide by ...

    Indian Academy of Sciences (India)

    Selenium dioxide catalysed acetic acid hydrazide oxidation by bromate was studied in hydrochloric acid medium. The order in oxidant concentration, substrate and catalyst were found to be unity. Increasing hydrogen ion concentration increases the rate of the reaction due to protonation equilibria of the oxidant.

  3. L-proline-catalysed synthesis of functionalized unsymmetrical ...

    Indian Academy of Sciences (India)

    J. Chem. Sci. Vol. 125, No. 3, May 2013, pp. 623–626. c Indian Academy of Sciences. L-proline-catalysed synthesis of functionalized unsymmetrical ... Abstract. Aromatic aldehydes have been employed in a one-pot four-component reaction with ethyl acetoace- tate, 1,3-indandione ... from a 'green chemistry' point of view.

  4. pH-optima in lipase-catalysed esterification

    NARCIS (Netherlands)

    Buthe, Andreas; Recker, Tobias; Heinemann, Matthias; Hartmeier, Winfried; Büchs, Jochen; Ansorge-Schumacher, Marion B.

    2005-01-01

    Though lipases are frequently applied in ester synthesis, fundamental information on optimal pH or substrate concentration, can almost only be found for the reverse reaction - hydrolysis. This study demonstrates that the pH-optima of lipase-catalysed esterifications differ significantly from the

  5. Activity, stability and kinetic parameters for α-chymotrypsin catalysed ...

    Indian Academy of Sciences (India)

    under the effect of nonionic and zwitterionic surfactants to obtain an in depth knowledge of enzymatic reaction in micellar media. We propose the advances in catalytic activity of α-CT with various degrees of hydration to varying AOT concentration and its stability in RM medium. The hydrolysis of PNPA catalysed by α-CT.

  6. Recyclable hydrotalcite clay catalysed Baylis-Hillman reaction

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. Recyclable hydrotalcite clay catalysed Baylis-Hillman reaction ... The Baylis-Hillman reaction using ionic liquid/hydrotalcite clay catalytic system has been observed to be more reactive in terms of yield and reaction rate than DABCO/acetonitrile system.

  7. Schiff base complex-catalysed enantioselective epoxidation of ...

    Indian Academy of Sciences (India)

    Administrator

    Chiral Ru(II) Schiff base complex-catalysed enantioselective epoxidation of styrene derivatives. R I KURESHY, N H KHAN, S H R ABDI, S T PATEL, P IYER and. R V JASRA. Silicates and Catalysis Discipline, Central Salt and Marine Chemicals. Research Institute, Bhavnagar 364 002, India. Ruthenium(II) chiral Schiff base ...

  8. Hybrid diphosphorus ligands in rhodium catalysed asymmetric hydroformylation

    NARCIS (Netherlands)

    Chikkali, S.H.; van der Vlugt, J.I.; Reek, J.N.H.

    2014-01-01

    This review aims to illustrate recent advances in the application of hybrid diphosphorus ligands for the Rh catalysed hydroformylation of alkenes, discussing the most prevalent classes of hybrid systems, i.e. phosphine-phosphinite, phosphine-phosphonite, phosphine-phosphite,

  9. catalysed indolylation and pyrrolylation of isatins: Efficient synthesis ...

    Indian Academy of Sciences (India)

    Abstract. An efficient and cheap synthetic approach to 3,3-di(indolyl)oxindoles and 3,3-di(pyrrolyl) oxindoles has been developed via Zn(OTf)2 catalysed indolylation and pyrrolylation of isatins. A preliminary biochemical assay of the synthesized molecules in rodent models were performed to estimate the serum glutamate ...

  10. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2S,3S-ketols. 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme– substrate ...

  11. Theoretical studies on the mechanism of palladium (II)-catalysed ...

    Indian Academy of Sciences (India)

    The mechanism of palladium(II)-catalysed carboxylation of acetanilide with CO has been investigated using density functional theory calculation done at the B3LYP/6-31G(d, p)(SDD for Pd) level of theory. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model ...

  12. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)

    A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2, 3-ketols 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme-substrate interactions.

  13. Using Intraoral Scanning Technology for Three-Dimensional Printing of Kennedy Class I Removable Partial Denture Metal Framework: A Clinical Report.

    Science.gov (United States)

    Hu, Feng; Pei, Zhenhua; Wen, Ying

    2017-11-16

    Removable partial dentures (RPDs) are used to restore missing teeth and are traditionally fabricated using the lost-wax casting technique. The casting process is arduous, time-consuming, and requires a skilled technician. The development of intraoral scanning and 3D printing technology has made rapid prototyping of the RPD more achievable. This article reports a completed case of direct fabrication of a maxillary RPD metal framework (Kennedy Class I) using intraoral scanning and 3D printing techniques. Acceptable fit and satisfactory clinical outcome were demonstrated. Intraoral scanning and 3D printing for fabrication of the RPD metal framework is a useful alternative to conventional impression and casting techniques, especially for patients suffering from nasal obstruction or intolerance. © 2017 by the American College of Prosthodontists.

  14. Partial oxidation of methane to synthesis gas in a dual catalyst bed system combining irreducible oxide and metallic catalysts

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    Operation of partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia (YSZ) at very high temperatures (¿900°C) slightly improves the selectivity to synthesis gas, which is caused by some activity of YSZ for steam and dry reforming of methane. LaCoO3 perovskite is not active in

  15. A palladium-catalysed multicomponent coupling approach to conjugated poly(1,3-dipoles) and polyheterocycles

    Science.gov (United States)

    Leitch, David C.; Kayser, Laure V.; Han, Zhi-Yong; Siamaki, Ali R.; Keyzer, Evan N.; Gefen, Ashley; Arndtsen, Bruce A.

    2015-06-01

    Conjugated polymers have emerged over the past several decades as key components for a range of applications, including semiconductors, molecular wires, sensors, light switchable transistors and OLEDs. Nevertheless, the construction of many such polymers, especially highly substituted variants, typically involves a multistep synthesis. This can limit the ability to both access and tune polymer structures for desired properties. Here we show an alternative approach to synthesize conjugated materials: a metal-catalysed multicomponent polymerization. This reaction assembles multiple monomer units into a new polymer containing reactive 1,3-dipoles, which can be modified using cycloaddition reactions. In addition to the synthetic ease of this approach, its modularity allows easy adaptation to incorporate a range of desired substituents, all via one-pot reactions.

  16. Asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with a new trifluoromethoxylation reagent

    Science.gov (United States)

    Guo, Shuo; Cong, Fei; Guo, Rui; Wang, Liang; Tang, Pingping

    2017-06-01

    Fluorinated organic compounds are becoming increasingly important in pharmaceuticals, agrochemicals and materials science. The introduction of trifluoromethoxy groups into new drugs and agrochemicals has attracted much attention due to their strongly electron-withdrawing nature and high lipophilicity. However, synthesis of trifluoromethoxylated organic molecules is difficult owing to the decomposition of trifluoromethoxide anion and β-fluoride elimination from transition-metal-trifluoromethoxide complexes, and no catalytic enantioselective trifluoromethoxylation reaction has been reported until now. Here, we present an example of an asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with trifluoromethyl arylsulfonate (TFMS) as a new trifluoromethoxylation reagent. Compared to other trifluoromethoxylation reagents, TFMS is easily prepared and thermally stable with good reactivity. In addition, this reaction is operationally simple, scalable and proceeds under mild reaction conditions. Furthermore, broad scope and good functional group compatibility has been demonstrated by application of the method to the bromotrifluoromethoxylation of double bonds in natural products and natural product derivatives.

  17. Ultrasonic enhancement of lipase-catalysed transesterification for biodiesel synthesis.

    Science.gov (United States)

    Bhangu, Sukhvir Kaur; Gupta, Shweta; Ashokkumar, Muthupandian

    2017-01-01

    The production of biodiesel was carried out from canola oil and methanol catalysed by lipase from Candida rugosa under different ultrasonic experimental conditions using horn (20kHz) and plate (22, 44, 98 and 300kHz) transducers. The effects of experimental conditions such as horn tip diameter, ultrasonic power, ultrasonic frequency and enzyme concentrations on biodiesel yield were investigated. The results showed that the application of ultrasound decreased the reaction time from 22-24h to 1.5h with the use of 3.5cm ultrasonic horn, an applied power of 40W, methanol to oil molar ratio of 5:1 and enzyme concentration of 0.23wt/wt% of oil. Low intensity ultrasound is efficient and a promising tool for the enzyme catalysed biodiesel synthesis as higher intensities tend to inactivate the enzyme and reduce its efficiency. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Hydrogenase-catalysed deposition of vivianite on mild steel

    Energy Technology Data Exchange (ETDEWEB)

    Silva, S. da; Basseguy, R.; Bergel, A

    2004-05-30

    A simple device was designed with two mild steel electrodes placed face to face in the same phosphate solution and coupled through an external electrical circuit. A dialysis membrane retained hydrogenase from Ralstonia eutropha in contact with one electrode only. The simultaneous measurements of the electron flux in the electrical circuit and of nicotinamide adenine dinucleotide (NADH) production catalysed by hydrogenase proved that the enzyme induced the occurrence of cathodic and anodic micro-sites on the same electrode surface. A clear galvanic current was observed, which stopped after a few hours, because of the formation of a protective film of vivianite on the electrode that was in contact with hydrogenase. Hydrogenase in phosphate solution proved to be an effective trigger of mild steel corrosion. These results may be the basis of a new and easy-to-handle hydrogenase-catalysed phosphating process, which operates under mild conditions, avoids using toxic compounds, and is quite rapid.

  19. Zeolite and zeotype-catalysed transformations of biofuranic compounds

    DEFF Research Database (Denmark)

    Li, Hu; Yang, Song; Riisager, Anders

    2016-01-01

    ,5-furandicarboxylic acid can be obtained from hexoses and pentoses via selective dehydration and subsequent etherification, hydrogenation, oxidation reactions, which show great potential for industrial applications to replace petroleum-based chemicals and fuels. Zeolite and zeotype micro- and mesoporous materials...... introducing zeolite-catalysed hydrolysis of di-, oligo- and polysaccharides and isomerization reactions of monomeric sugars. Subsequently, the catalytic dehydration reactions of hexoses and pentoses to obtain HMF and furfural are reported. Particularly, a variety of reaction pathways towards upgrading...

  20. Protease-catalysed Direct Asymmetric Mannich Reaction in Organic Solvent

    Science.gov (United States)

    Xue, Yang; Li, Ling-Po; He, Yan-Hong; Guan, Zhi

    2012-10-01

    We reported the first enzyme-catalysed, direct, three-component asymmetric Mannich reaction using protease type XIV from Streptomyces griseus (SGP) in acetonitrile. Yields of up to 92% with enantioselectivities of up to 88% e.e. and diastereoselectivities of up to 92:8 (syn:anti) were achieved under the optimised conditions. This enzyme's catalytic promiscuity expands the application of this biocatalyst and provides a potential alternative method for asymmetric Mannich reactions.

  1. Partially reversible Li2O formation in ZnO: A critical finding supporting realization of highly reversible metal oxide electrodes

    Science.gov (United States)

    Park, Min-Gu; Sung, Geon-Kyu; Sung, Nark-Eon; Kim, Jae-Hun; Park, Cheol-Min

    2016-10-01

    The electrochemical reaction mechanism of ZnO is investigated to understand its Li insertion/extraction behavior using ex situ X-ray diffraction, extended X-ray absorption fine structure, and high-resolution transmission electron microscopy. Based on these analyses, an interesting partial recombination reaction of ZnO is discovered, which demonstrates that Li2O formed during Li insertion is partially reversible. Additionally, we discover that the control of the partial recombination reaction of the metal oxide is very important for improving reversibility in the first cycle, which is a key finding for realization of highly reversible oxide-based electrode materials. In addition, to enhance the electrochemical performance of the ZnO electrode, a nanostructured ZnO/C composite is prepared by a simple high-energy mechanical milling process. This process allows the electrochemical performance of the ZnO electrode to be evaluated as an anode for rechargeable Li-ion batteries. Electrochemical tests show that the nanocomposite electrode exhibits a high initial charge capacity of 682 mAh g-1, fast rate capability of 371 mAh g-1 at 2 C, and excellent cyclability over 200 cycles.

  2. Fit accuracy of metal partial removable dental prosthesis frameworks fabricated by traditional or light curing modeling material technique: An in vitro study

    Science.gov (United States)

    Anan, Mohammad Tarek M.; Al-Saadi, Mohannad H.

    2015-01-01

    Objective The aim of this study was to compare the fit accuracies of metal partial removable dental prosthesis (PRDP) frameworks fabricated by the traditional technique (TT) or the light-curing modeling material technique (LCMT). Materials and methods A metal model of a Kennedy class III modification 1 mandibular dental arch with two edentulous spaces of different spans, short and long, was used for the study. Thirty identical working casts were used to produce 15 PRDP frameworks each by TT and by LCMT. Every framework was transferred to a metal master cast to measure the gap between the metal base of the framework and the crest of the alveolar ridge of the cast. Gaps were measured at three points on each side by a USB digital intraoral camera at ×16.5 magnification. Images were transferred to a graphics editing program. A single examiner performed all measurements. The two-tailed t-test was performed at the 5% significance level. Results The mean gap value was significantly smaller in the LCMT group compared to the TT group. The mean value of the short edentulous span was significantly smaller than that of the long edentulous span in the LCMT group, whereas the opposite result was obtained in the TT group. Conclusion Within the limitations of this study, it can be concluded that the fit of the LCMT-fabricated frameworks was better than the fit of the TT-fabricated frameworks. The framework fit can differ according to the span of the edentate ridge and the fabrication technique for the metal framework. PMID:26236129

  3. A cracked sheet stiffened by several partially debonded intact or broken stringers. [reinforcement (structures) and structural stability of metal sheets

    Science.gov (United States)

    Arin, K.

    1975-01-01

    The effect of several stringers on the stress intensity factors at the tips of a crack is considered. The stringers which were continuously attached to the plate and placed perpendicular to the crack may be partially debonded due to high stress concentrations. Since the stringers may even break under excessive loading conditions, both intact and broken stringers are considered to investigate the effect of rupture. The continuity of displacements along the bond lines leads to an integral equation which is solved to give the shear stress distribution in the adhesive and the stress intensity factors at the crack tips.

  4. Uncatalysed and potassium-catalysed pyrolysis of the cell-wall constituents of biomass and their model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Nowakowski, Daniel J.; Jones, Jenny M. [Energy and Resources Research Institute, School of Process, Environmental and Materials Engineering (SPEME), University of Leeds, Leeds, LS2 9JT (United Kingdom)

    2008-09-15

    Cell-wall components (cellulose, hemicellulose (oat spelt xylan), lignin (Organosolv)), and model compounds (levoglucosan (an intermediate product of cellulose decomposition) and chlorogenic acid (structurally similar to lignin polymer units)) have been investigated to probe in detail the influence of potassium on their pyrolysis behaviours as well as their uncatalysed decomposition reaction. Cellulose and lignin were pretreated to remove salts and metals by hydrochloric acid, and this dematerialized sample was impregnated with 1% of potassium as potassium acetate. Levoglucosan, xylan and chlorogenic acid were mixed with CH{sub 3}COOK to introduce 1% K. Characterisation was performed using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In addition to the TGA pyrolysis, pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) analysis was introduced to examine reaction products. Potassium-catalysed pyrolysis has a huge influence on the char formation stage and increases the char yields considerably (from 7.7% for raw cellulose to 27.7% for potassium impregnated cellulose; from 5.7% for raw levoglucosan to 20.8% for levoglucosan with CH{sub 3}COOK added). Major changes in the pyrolytic decomposition pathways were observed for cellulose, levoglucosan and chlorogenic acid. The results for cellulose and levoglucosan are consistent with a base catalysed route in the presence of the potassium salt which promotes complete decomposition of glucosidic units by a heterolytic mechanism and favours its direct depolymerization and fragmentation to low molecular weight components (e.g. acetic acid, formic acid, glyoxal, hydroxyacetaldehyde and acetol). Base catalysed polymerization reactions increase the char yield. Potassium-catalysed lignin pyrolysis is very significant: the temperature of maximum conversion in pyrolysis shifts to lower temperature by 70 K and catalysed polymerization reactions increase the char yield from 37% to 51%. A similar trend

  5. All-ceramic and porcelain-fused-to-metal fixed partial dentures: a comparative study by 2D finite element analyses

    Directory of Open Access Journals (Sweden)

    Andréa Barreira Motta

    2007-10-01

    Full Text Available All-ceramic fixed partial dentures (FPDs have an esthetic approach for oral rehabilitation. However, metal-ceramic FPDs are best indicated in the posterior area where the follow-up studies found a lower failure rate. This 2D finite element study compared the stress distribution on 3-unit all-ceramic and metal-ceramic FPDs and identified the areas of major risk of failure. Three FPD models were designed: (1 metal-ceramic FPD; (2 All-ceramic FPD with the veneering porcelain on the occlusal and cervical surface of the abutment tooth; (3 All-ceramic FPD with the veneering porcelain only on the occlusal surface. A 100 N load was applied in an area of 0.5 mm² on the working cusps, following these simulations: (1 on the abutment teeth and the pontic; (2 only on the abutment teeth; and (3 only on the pontic. Relative to the maximum stress values found for the physiological load, all-ceramic FPD with only occlusal veneering porcelain produced the lowest stress value (220 MPa, followed by all-ceramic FPD with cervical veneering porcelain (322 MPa and metal-ceramic FPD (387 MPa. The stress distribution of the load applied on the abutments was significantly better compared to the other two load simulations. The highest principal stress values were low and limited in a small area for the three types of models under this load. When the load was applied on the pontic, the highest stress values appeared on the connector areas between the abutments and pontic. In conclusion, the best stress values and distribution were found for the all-ceramic FPD with the veneering porcelain only on the occlusal surface. However, in under clinical conditions, fatigue conditions and restoration defects must be considered.

  6. Organogel-derived Covalent-Noncovalent Hybrid Polymers as Alkali Metal Ion Scavengers for Partial Deionization of Water.

    Science.gov (United States)

    Prathap, Annamalai; Raju, Cijil; Sureshan, Kana M

    2018-04-12

    We show that crown ethers (CEs) 1-5 congeal both polar and non-polar solvents via their self-assembly through weak non-covalent interactions (NCI) such as CH...O and CH...π interactions. Di-isopropylidene-mannitol (6) is a known gelator that self-assembles through stronger OH...O H-bonding. These two gelators together also congeal non-polar solvents via their individual self-assembly. The gelator 6 self-assembles swiftly to fibers, which act as templates and attract CE to their surface through H-bonding and thereby facilitate their self-assembly through weak NCI. Polymerization of styrene gels made from CE and 6 followed by the washing off of the sacrificial gelator 6 yields robust porous polystyrene-crown ether hybrid matrices (PCH), having pore-exposed CEs. These PCHs were not only efficient in sequestering alkali metal ions from aqueous solutions but also can be recycled. This novel use of organogels for making solid sorbents for metal ion scavenging might be of great interest.

  7. Efficient Removal of Heavy Metals from Polluted Water with High Selectivity for Mercury(II) by 2-Imino-4-thiobiuret-Partially Reduced Graphene Oxide (IT-PRGO).

    Science.gov (United States)

    Awad, Fathi S; AbouZeid, Khaled M; El-Maaty, Weam M Abou; El-Wakil, Ahmad M; El-Shall, M Samy

    2017-10-04

    A novel chelating adsorbent, based on the chemical modification of graphene oxide by functionalization amidinothiourea to form 2-imino-4-thiobiuret-partially reduced graphene oxide (IT-PRGO), is used for the effective extraction of the toxic metal ions Hg(II), Cu(II), Pb(II), Cr(VI), and As(V) from wastewater. FTIR and Raman spectroscopy, XRD, and XPS confirm the successful incorporation of the amidinothiourea groups within the partially reduced GO nanosheets through nucleophilic substitution reactions with the acyl chloride groups in the chemically modified GO. The IT-PRGO adsorbent shows exceptional selectivity for the extraction of Hg(II) with a capacity of 624 mg/g, placing it among the top of carbon-based materials known for the high capacity of Hg(II) removal from aqueous solutions. The maximum sorption capacities for As(V), Cu(II), Cr(VI), and Pb(II) are 19.0, 37.0, 63.0, and 101.5 mg/g, respectively. The IT-PRGO displays a 100% removal of Hg(II) at concentrations up to 100 ppm with 90%, 95%, and 100% removal within 15, 30, and 90 min, respectively, at 50 ppm concentration. In a mixture of six heavy metal ions containing 10 ppm of each ion, the IT-PRGO shows a removal of 3% Zn(II), 4% Ni(II), 9% Cd(II), 21% Cu(II), 63% Pb(II), and 100% Hg(II). A monolayer adsorption behavior is suggested based on the excellent agreement of the experimental sorption isotherms with the Langmuir model. The sorption kinetics can be fitted well to a pseudo-second-order kinetic model which suggests a chemisorption mechanism via the amidinothiourea groups grafted on the reduced graphene oxide nanosheets. Desorption studies demonstrate that the IT-PRGO is easily regenerated with the desorption of the metal ions Hg(II), Cu(II), Pb(II), Cr(VI), and As(V) reaching 96%, 100%, 100%, 96%, and 100%, respectively, from their maximum sorption capacities using different eluents. The IT-PRGO is proposed as a top performing remediation adsorbent for the extraction of heavy metals from waste and

  8. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates

    Science.gov (United States)

    Ackerman, Laura K. G.; Lovell, Matthew M.; Weix, Daniel J.

    2015-08-01

    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  9. Supramolecular Isomers of Metal-Organic Frameworks Derived from a Partially Flexible Ligand with Distinct Binding Motifs

    KAUST Repository

    Abdul Halim, Racha Ghassan

    2016-01-04

    Three novel metal-organic frameworks (MOFs) were isolated upon reacting a heterofunctional ligand 4 (pyrimidin-5 yl)benzoic acid (4,5-pmbc) with mixed valence Cu(I,II) under solvothermal conditions. X-ray crystal structural analysis reveals that the first compound is a layered structure composed of one type of inorganic building block, dinuclear paddlewheel [Cu2(O2C–)4], which are linked through 4,5-pmbc ligands. The two other supramolecular isomers are composed of the same Cu(II) dinuclear paddlewheel and a dinuclear Cu2I2 cluster, which are linked via the 4,5-pmbc linkers to yield two different 3-periodic frameworks with underlying topologies related to lvt and nbo. The observed structural diversity in these structures is due to the distinct coordination modes of the two coordinating moieties (the carboxylate group on the phenyl ring and the N-donor atoms from the pyrimidine moiety).

  10. Synthesis of 2-aminoBODIPYs by palladium catalysed amination.

    Science.gov (United States)

    Alnoman, Rua B; Stachelek, Patrycja; Knight, Julian G; Harriman, Anthony; Waddell, Paul G

    2017-09-20

    Palladium catalysed coupling of the 2-iodoBODIPY 3 with a range of anilines and a primary alkylamine succeeds in generating the corresponding 2-aminoBODIPYs. These 2-aminoBODIPY derivatives are non-emissive and quantum chemical calculations and electrochemistry are consistent with charge transfer from the amine substituent. Attenuation of this charge transfer pathway by conversion of the 1,2-phenylenediamine derivative 9 into the corresponding benzimidazolone 10 restores the fluorescence and has been used as the basis for a fluorescence sensor for phosgene.

  11. Mechanistic Investigation of Molybdate-Catalysed Transfer Hydrodeoxygenation

    DEFF Research Database (Denmark)

    Larsen, Daniel Bo; Petersen, Allan Robertson; Dethlefsen, Johannes Rytter

    2016-01-01

    The molybdate-catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates...... for the transfer HDO of five para-substituted benzylic alcohols was carried out. Density-functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH2...... of benzyl alcohol, which is in line with the mechanism suggested by the DFT study....

  12. Investigation and health risk assessment of heavy metals in soils from partial areas of Daye city, china

    Science.gov (United States)

    Xiao, M. S.; Li, F.; Zhang, J. D.; Lin, S. Y.; Zhuang, Z. Y.; Wu, Z. X.

    2017-05-01

    Heavy metals (Cu and Pb) in four sampling sites from parts areas of Daye city were collected. Concentrations of Cu and Pb in soils in sampling sites were detected, the enrichment degree was measured by geo-accumulation index, and the human health risks were calculated by applying the human health risk assessment model. The results show that the concentrations of Cu and Pb of soils in some areas are much more than Daye City, Hubei Province soil background value. The concentration of Cu and Pb in Xiaganwan soil sample has a higher value and the concentration of Cu (110.17 mg·kg-1) exceeds the soil environmental quality standards. The values of Igeo of Cu and Pb in the soil in some areas of Daye city are 1 except Xiaganwan sample is 2. For human health risk assessment, the non-cancer risk of Cu in three routes of exposure is less than Pb. The non-cancer risk both adults and children are less than 1 and show a general trend of HQ in oral ingestion exposure pathway > HQ in inhalation exposure pathway>HQ in skin contact exposure pathway. It will not cause significant non-carcinogenic health effects on the human body.

  13. X-ray imaging by partially coherent synchrotron light. Application to metallic alloys, tooth dentin and natural rock

    International Nuclear Information System (INIS)

    Zabler, Simon Andreas

    2007-01-01

    The hard spectrum which is available on the BAMline at Berlin's synchrotron BESSY offers the rare opportunity to perform high-resolution X-ray imaging experiments with a partially coherent beam. This thesis work reports on the development of a new tomography system, including Fresnel-propagated imaging, and its application to three specific materials science problems from the fields of engineering materials, biology and earth science. Static and dynamic 2D and 3D images were recorded from a variety of aluminum-based alloys. Coarsening of particle agglomerates (at high solid volume fraction) in liquid solution, as well as rheological properties of semi-solid alloys are thus characterized. Dentin is characterized by a quasi-parallel arrangement of micrometer-sized tubules. This work shows how high-resolution 3D images of water-immersed tooth dentin are recorded, and detailed simulations of the optical wave propagation reveal that Fresnel-images contain additional information about the dense cuff of peritubular dentin surrounding the tubules. The cuff thickness can be extrapolated from the interference fringes that form the propagated images of tubules. Absorption and Fresnel-propagated X-ray tomography are applied to measure samples of different rocks before and after mechanical compression nondestructively. In a first approach, limestone and greywacke are investigated, representing two sedimentary rocks of different grain size. Basalt and granite are tested in a second approach to compare different rock types. Development of cracks is observed in all materials, leading to fracture when increasing mechanical load is applied. In this work, relatively small mm-sized samples are used in order to test a classical fracture model wherein micro-flaws initiate the formation of larger cracks. For the first time, Fresnel-propagated imaging is applied to rock samples, highlighting micrometer-sized intergranular porosity as well as different material phases. The latter is shown

  14. X-ray imaging by partially coherent synchrotron light. Application to metallic alloys, tooth dentin and natural rock

    Energy Technology Data Exchange (ETDEWEB)

    Zabler, Simon Andreas

    2007-10-09

    The hard spectrum which is available on the BAMline at Berlin's synchrotron BESSY offers the rare opportunity to perform high-resolution X-ray imaging experiments with a partially coherent beam. This thesis work reports on the development of a new tomography system, including Fresnel-propagated imaging, and its application to three specific materials science problems from the fields of engineering materials, biology and earth science. Static and dynamic 2D and 3D images were recorded from a variety of aluminum-based alloys. Coarsening of particle agglomerates (at high solid volume fraction) in liquid solution, as well as rheological properties of semi-solid alloys are thus characterized. Dentin is characterized by a quasi-parallel arrangement of micrometer-sized tubules. This work shows how high-resolution 3D images of water-immersed tooth dentin are recorded, and detailed simulations of the optical wave propagation reveal that Fresnel-images contain additional information about the dense cuff of peritubular dentin surrounding the tubules. The cuff thickness can be extrapolated from the interference fringes that form the propagated images of tubules. Absorption and Fresnel-propagated X-ray tomography are applied to measure samples of different rocks before and after mechanical compression nondestructively. In a first approach, limestone and greywacke are investigated, representing two sedimentary rocks of different grain size. Basalt and granite are tested in a second approach to compare different rock types. Development of cracks is observed in all materials, leading to fracture when increasing mechanical load is applied. In this work, relatively small mm-sized samples are used in order to test a classical fracture model wherein micro-flaws initiate the formation of larger cracks. For the first time, Fresnel-propagated imaging is applied to rock samples, highlighting micrometer-sized intergranular porosity as well as different material phases. The latter is

  15. Catalysed fusion: a very different book about CERN

    CERN Multimedia

    CERN Library

    2013-01-01

    Not many books get reviews resulting in headlines like "Steamy novel challenges CERN's serious image", "Love and death at CERN" and so on. But Francis Farley's book "Catalysed Fusion" does not leave its readers untouched.   Those of you who have been around some time will know Farley from when he worked at CERN. For "newcomers", Farley is a well-known physicist who put together the first experiment on the anomalous magnetic moment of the muon and has since taken part in all the experiments relating to this phenomenon. The back cover of his book reads: "A sizzling romance and a romp with subatomic particles at CERN. Love, discovery and adventure in the city where nations meet and beams collide. Life in a large laboratory. As always, the challenges are the same. Who leads? Who follows? Who succeeds? Who gets the credit? Who gets the women or the men? Young Jeremy arrives in CERN and joins the quest ...

  16. Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

    Directory of Open Access Journals (Sweden)

    Mário M. Q. Simões

    2018-03-01

    Full Text Available Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.

  17. Transition metal modified and partially calcined inorganic-organic pillared clays for the adsorption of salicylic acid, clofibric acid, carbamazepine, and caffeine from water.

    Science.gov (United States)

    Cabrera-Lafaurie, Wilman A; Román, Félix R; Hernández-Maldonado, Arturo J

    2012-11-15

    Pharmaceutical and Personal Care Products (PPCPs) are considered emerging contaminants, and their efficient removal from water is going to be a challenging endeavor. Microporous adsorbent materials, including pillared clays, could offer a potential solution if tailored properly. Although pillared clays have been employed previously for the removal of organics, the effective removal of PPCPs will only be possible if their surface and textural properties are manipulated from the bottom-up. This work presents the use of modified inorganic-organic pillared clays (IOCs) for the adsorption of salicylic acid, clofibric acid, carbamazepine, and caffeine. The IOCs have been modified with Co(2+), Cu(2+), or Ni(2+) to induce complexation-like adsorbate-adsorbent interactions at ambient conditions, in an attempt to provide an efficient and yet reversible driving force in the sub-ppm concentration range. Furthermore, the IOCs were partially calcined to increase effective surface area by an order of magnitude while preserving some hydrophobicity. In general, the Ni(2+) IOCs exhibited the greatest interaction with salicylic and clofibric acids, respectively, while the Co(2+) adsorbents excelled at adsorbing caffeine at low concentrations. All of the metal-modified IOCs showed comparable adsorption capacities for the case of carbamazepine, probably due to the lack of availability of particular functional groups in this adsorbate. Copyright © 2012 Elsevier Inc. All rights reserved.

  18. Effect of partial substitution of nickel by tin, aluminum, manganese and palladium on the properties of LaNi5-type metal hydride alloys

    Directory of Open Access Journals (Sweden)

    Souza Elki C.

    2003-01-01

    Full Text Available This work reports studies on the electrochemical behavior of AB5-type hydrogen storage alloys, formed by LaNi(5-xZx, where Z is a metallic element partially replacing Ni, which included Sn, Al, Mn, and Pd. In the case of Mn, some AB6-type structures were also considered. Substitution of a small fraction of Ni by Al, Sn, and Mn (x @ 0.3 leads to an increase of the hydrogen storage capability (HSC, while for Pd there is a decrease of this property. Generally all alloys presenting larger initial HSC exhibit lower stability. A decrease of the hydrogen equilibrium pressure as a function of Mn content is observed for the AB5 alloys and this is related to an increase of the crystalline unit cell volume. Electrochemical impedance measurements show a significant increase of the hydration/dehydration reaction kinetics due to a raise on the active area as a function of the charge/discharge cycle number. It is also seen that the alloys presenting larger HSC are those showing smaller activation energies for the hydrogen oxidation reaction.

  19. Palladium-catalysed cyclisation of alkenols: Synthesis of oxaheterocycles as core intermediates of natural compounds

    Directory of Open Access Journals (Sweden)

    Miroslav Palík

    2014-09-01

    Full Text Available The study of Pd-catalysed cyclisation reactions of alkenols using different catalytic systems is reported. These transformations affect the stereoselective construction of mono- and/or bicyclic oxaheterocyclic derivatives depending on a starting alkenol. The substrate scope and proposed mechanism of Pd-catalysed cyclisation reactions are also discussed. Moreover, the diastereoselective Pd-catalysed cyclisation of appropriate alkenols to tetrahydrofurans and subsequent cyclisation provided properly substituted 2,5-dioxabicyclo[2.2.1]heptane and 2,6-dioxabicyclo[3.2.1]octane, respectively. Such bicyclic ring subunits are found in many natural products including ocellenynes and aurovertines.

  20. Beta-lactam degradation catalysed by Cd2+ ion in methanol.

    Science.gov (United States)

    Martínez, J H; Navarro, P G; Garcia, A A; de las Parras, P J

    1999-08-01

    Kinetic schemes are established for degradation catalysed by Cd2+ ions in methanolic medium for penicillin G, penicillin V and cephalothin, a cephalosporin. Methanolysis of penicillin V and cephalothin occurs with the formation of a single substrate-metal ion intermediate complex, SM, while degradation of penicillin G occurs with the initial formation of two complexes with different stoichiometry, SM and S2M. In each case. degradation is of first order with respect to SM with rate constant values equal to 0.079 min(-1), 0.120 min(-1) and 0.166 min(-1) at 20, 25 and 30 degrees C, respectively, for penicillin G; 0.061 min(-1) at 20 degrees C for penicillin V; and 2.0 x 10(-3) min(-1) at 20 degrees C for cephalothin. Activation energy for the decomposition process of the SM intermediate for penicillin G was calculated to be about 5.5 x 10(4) J/mol. Equilibrium constant values between SM compound and S2M at 20 degrees C (77.1 l/mol), 25 degrees C (45.3 l/mol) and at 30 degrees C (25.7 l/mol) were also calculated as well as the normal enthalpy of this equilibrium. With respect to the reaction products there is evidence that Cd2+ becomes part of their structure, forming complexes between Cd2+ and the product resulting from antibiotic methanolysis (L). Some characteristics of these complexes are discussed.

  1. Bis (imino) pyridine (BIMP) Fe (II) catalyses one-pot green ...

    Indian Academy of Sciences (India)

    pyridine (BIMP) Fe(II) catalyses one-pot green condensation of resorcinol, malononitrile, aromatic aldehydes and cyclohexanone. Saman Damavandi Reza Sandaroos. Volume 124 Issue 2 March 2012 pp 483-486 ...

  2. Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

    2013-01-01

    An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

  3. In Vitro Comparison of Marginal and Internal Fit of Press-on-Metal Ceramic (PoM) Restorations with Zirconium-Supported and Conventional Metal Ceramic Fixed Partial Dentures Before and After Veneering.

    Science.gov (United States)

    Varol, Seda; Kulak-Özkan, Yasemin

    2015-07-01

    To compare marginal and internal fit between 3- and 4-unit press-on-metal (PoM) ceramic, zirconia-supported, and conventional metal ceramic fixed partial dentures (FPDs) before and after veneering. Ten pieces for each 3- and 4-unit MC, IPS InLine PoM, and IPS e.max ZirCAD/Zir Press FPDs were produced. Cross-sections from silicone replicas were examined and measured with a light microscope. Occlusal, axial, intermarginal, and marginal mean adaptation scores of cross-sectioned replicas and means of measurements obtained from 4 sites were calculated independently. Mean values for molars were 78.44 ± 32.01 μm (MC), 89.84 ± 29.20 μm (PoM), and 85.17 ± 28.49 μm (Zir). Premolar values were 76.08 ± 27.92 μm (MC), 89.94 ± 23.49 μm (PoM), and 87.18 ± 28.25 μm (Zir). No difference existed between the means of 3- and 4-unit FPDs except the molar-intermarginal region. The mean value of 4-unit FPDs (93.88 ± 25.41 μm) was less than the 3-unit FPDs (103.68 ± 24.55 μm) at the molar-inter marginal region. A gap increase was observed in all sites except the molar-axio-occlusal region after veneering. According to the mean difference, gap increases at the molar-marginal, molar-intermarginal, and premolar-intermarginal regions were statistically significant. A statistical difference was found at the molar-marginal region for 4-unit MCR (p = 0.041) and 4-unit PoM FPDs (p = 0.042) before and after veneering. Gap increase after veneering of 4-unit metal ceramics at molar-intermarginal, premolar-marginal, and premolar-intermarginal regions (p = 0.020; p = 0.015; p = 0.004) was significant. The gap measurements of the IPS InLine PoM and IPS e.max ZirCAD/Zir Press groups were all clinically acceptable. No studies on marginal and internal fit in the IPS InLine PoM system have been published to date. This study should be supported with future studies. No significant increase was observed after press-veneering the IPS e.max ZirCAD frameworks with an IPS e.max ZirPress material

  4. Palladium-catalysed C-H activation of aliphatic amines to give strained nitrogen heterocycles

    Science.gov (United States)

    McNally, Andrew; Haffemayer, Benjamin; Collins, Beatrice S. L.; Gaunt, Matthew J.

    2014-06-01

    The development of new chemical transformations based on catalytic functionalization of unactivated C-H bonds has the potential to simplify the synthesis of complex molecules dramatically. Transition metal catalysis has emerged as a powerful tool with which to convert these unreactive bonds into carbon-carbon and carbon-heteroatom bonds, but the selective transformation of aliphatic C-H bonds is still a challenge. The most successful approaches involve a `directing group', which positions the metal catalyst near a particular C-H bond, so that the C-H functionalization step occurs via cyclometallation. Most directed aliphatic C-H activation processes proceed through a five-membered-ring cyclometallated intermediate. Considering the number of new reactions that have arisen from such intermediates, it seems likely that identification of distinct cyclometallation pathways would lead to the development of other useful chemical transformations. Here we report a palladium-catalysed C-H bond activation mode that proceeds through a four-membered-ring cyclopalladation pathway. The chemistry described here leads to the selective transformation of a methyl group that is adjacent to an unprotected secondary amine into a synthetically versatile nitrogen heterocycle. The scope of this previously unknown bond disconnection is highlighted through the development of C-H amination and carbonylation processes, leading to the synthesis of aziridines and β-lactams (respectively), and is suggestive of a generic C-H functionalization platform that could simplify the synthesis of aliphatic secondary amines, a class of small molecules that are particularly important features of many pharmaceutical agents.

  5. Metallaphotoredox-catalysed sp3-sp3 cross-coupling of carboxylic acids with alkyl halides

    Science.gov (United States)

    Johnston, Craig P.; Smith, Russell T.; Allmendinger, Simon; MacMillan, David W. C.

    2016-08-01

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp3-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3-sp3 bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp3-sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp3-sp3 coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3-sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for

  6. Partial priapism

    DEFF Research Database (Denmark)

    Høyerup, Peter; Dahl, Claus; Azawi, Nessn Htum

    2014-01-01

    Partial priapism, also called partial segmental thrombosis of the corpus cavernosum, is a rare urological condition. Factors such as bicycle riding, drug usage, penile trauma and haematological diseases have been associated with the condition. Medical treatment with low molecular weight heparin (...... (LMWH) or acetylsalicylic acid is first choice treatment, and surgery is preserved for patients unresponsive to analgesics. In this report we describe the case of a 70-year-old man with partial priapism after blood transfusions treated successfully with LMWH....

  7. Switchable regioselectivity in amine-catalysed asymmetric cycloadditions

    Science.gov (United States)

    Zhou, Zhi; Wang, Zhou-Xiang; Zhou, Yuan-Chun; Xiao, Wei; Ouyang, Qin; Du, Wei; Chen, Ying-Chun

    2017-06-01

    Building small-molecule libraries with structural and stereogenic diversity plays an important role in drug discovery. The development of switchable intermolecular cycloaddition reactions from identical substrates in different regioselective fashions would provide an attractive protocol. However, this also represents a challenge in organic chemistry, because it is difficult to control regioselectivity to afford the products exclusively and at the same time achieve high levels of stereoselectivity. Here, we report the diversified cycloadditions of α‧-alkylidene-2-cyclopentenones catalysed by cinchona-derived primary amines. An asymmetric γ,β‧-regioselective intermolecular [6+2] cycloaddition reaction with 3-olefinic (7-aza)oxindoles is realized through the in situ generation of formal 4-aminofulvenes, while a different β,γ-regioselective [2+2] cycloaddition reaction with maleimides to access fused cyclobutanes is disclosed. In contrast, an intriguing α,γ-regioselective [4+2] cycloaddition reaction is uncovered with the same set of substrates, by employing an unprecedented dual small-molecule catalysis of amines and thiols. All of the cycloaddition reactions exhibit excellent regio- and stereoselectivity, producing a broad spectrum of chiral architectures with high structural diversity and molecular complexity.

  8. Palladium-catalysed anti-Markovnikov selective oxidative amination

    Science.gov (United States)

    Kohler, Daniel G.; Gockel, Samuel N.; Kennemur, Jennifer L.; Waller, Peter J.; Hull, Kami L.

    2018-03-01

    In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to a reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a palladium-catalysed oxidative amination reaction in which the addition of the nitrogen occurs at the less-substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.

  9. Partial priapism

    DEFF Research Database (Denmark)

    Hoyerup, Peter; Azawi, Nessn Htum

    2013-01-01

    With only 34 prior cases in world literature, partial priapism (PP), also called partial segmental thrombosis of the corpus cavernosum, is a rare urological condition. The aetiology and treatment of PP is still unclear, but bicycle riding, trauma, drug usage, sexual intercourse, haematological...

  10. Effect of different surface treatments and retainer designs on the retention of posterior Pd-Ag porcelain-fused-to-metal resin-bonded fixed partial dentures.

    Science.gov (United States)

    Chen, Xiwen; Zhang, Yixin; Zhou, Jinru; Chen, Chenfeng; Zhu, Zhimin; Li, Lei

    2018-02-01

    The aim of this study was to investigate the adhesive property of palladium-silver alloy (Pd-Ag) and the simulated clinical performance of Pd-Ag porcelain-fused-to-metal (PFM), resin-bonded, fixed partial dentures (RBFPDs). A total of 40 Pd-Ag discs (diameter=5 mm) were prepared and divided into the following four groups (n=10): a) No sandblasting, used as a control; and b, 50 µm; c, 110 µm; and d, 250 µm aluminum oxide (Al 2 O 3 ) particles, respectively. Another 50 discs were pre-sandblasted and divided into five groups (n=10) subjected to different treatments: e) Sandblasting, used as a control; f) silane; g) alloy primer; h) silica coating + silane and i) silica coating + alloy primer. All 90 discs were bonded to enamel with Panavia F 2.0 and then subjected to shear bond strength (SBS) testing. The fracture surfaces were examined by scanning electron microscopy. Next, 40 missing maxillary second premolar models were restored with one of the four following RBFPD designs (n=10): I) A premolar occlusal bar combined with molar double rests (MDR); II) both occlusal bars with a wing (OBB); III) a premolar occlusal bar combined with a molar dental band (MDB); and IV) two single rests adjacent to the edentulous space with a wing (SRB) used as a control. All specimens were aged with thermal cycling and mechanical loading. Subsequently, they were loaded until broken. The data were analyzed by one-way analysis of variance. Al 2 O 3 (250 µm) abrasion provided the highest SBS (P<0.05). The alloy primer and silica + silane exhibited increased SBS. Furthermore, fracture analysis revealed that the failure mode varied among the different treatments. Whereas MDB exhibited the highest retention (P<0.05), that of OBB was greater than that of MDR (P<0.05), and the control exhibited the lowest retention. Abrasion with Al 2 O 3 (250 µm) effectively increased the adhesive property of Pd-Ag. Additionally, treatment with the alloy primer and silica coating + silane was able to

  11. C-13 isotopic studies of the surface catalysed reactions of methane

    International Nuclear Information System (INIS)

    Long, M.A.; He, S.J.X.; Adebajo, M.

    1997-01-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  12. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters

    Science.gov (United States)

    Crampton, Andrew S.; Rötzer, Marian D.; Ridge, Claron J.; Schweinberger, Florian F.; Heiz, Ueli; Yoon, Bokwon; Landman, Uzi

    2016-01-01

    The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8–15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the hydrogenation occurs for Ptn (n≥10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity. PMID:26817713

  13. Clinical application of removable partial dentures using thermoplastic resin. Part II: Material properties and clinical features of non-metal clasp dentures

    OpenAIRE

    Fueki, Kenji; Ohkubo, Chikahiro; Yatabe, Masaru; Arakawa, Ichiro; Arita, Masahiro; Ino, Satoshi; Kanamori, Toshikazu; Kawai, Yasuhiko; Kawara, Misao; Komiyama, Osamu; Suzuki, Tetsuya; Nagata, Kazuhiro; Hosoki, Maki; Masumi, Shin-ichi; Yamauchi, Mutsuo

    2014-01-01

    This position paper reviews physical and mechanical properties of thermoplastic resin usedfor non-metal clasp dentures, and describes feature of each thermoplastic resin in clinicalapplication of non-metal clasp dentures and complications based on clinical experience ofexpert panels. Since products of thermoplastic resin have great variability in physical andmechanical properties, clinicians should utilize them with careful consideration of thespecific properties of each product. In general, ...

  14. Partial Cancellation

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. Partial Cancellation. Full Cancellation is desirable. But complexity requirements are enormous. 4000 tones, 100 Users billions of flops !!! Main Idea: Challenge: To determine which cross-talker to cancel on what “tone” for a given victim. Constraint: Total complexity is ...

  15. Iron-catalysed fluoroaromatic coupling reactions under catalytic modulation with 1,2-bis(diphenylphosphino)benzene.

    Science.gov (United States)

    Hatakeyama, Takuji; Kondo, Yoshiyuki; Fujiwara, Yu-Ichi; Takaya, Hikaru; Ito, Shingo; Nakamura, Eiichi; Nakamura, Masaharu

    2009-03-14

    A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.

  16. [Conventional retaining of removable partial dentures

    NARCIS (Netherlands)

    Keltjens, H.M.A.M.; Witter, D.J.; Creugers, N.H.J.

    2009-01-01

    Mechanical and biological criteria have to be met in retaining the metal frame of a removable partial denture. Additionally, a removable partial denture is part of the occlusal interface by the clasps and the denture teeth. With respect to mechanical aspects, all rigid parts of the removable partial

  17. [Removable partial dentures. Oral functions and types

    OpenAIRE

    Creugers, N.H.J.; Baat, C. de

    2009-01-01

    A removable partial denture enables the restoration or improvement of 4 oral functions: aesthetics, mandibular stability, mastication, and speech. However, wearing a removable partial denture should not cause oral comfort to deteriorate. There are 3 types of removable partial dentures: acrylic tissue-supported dentures, dentures with cast metal frameworks en dentures with cast metal frameworks and (semi)precision attachments. Interrupted tooth arches,free-ending tooth arches, and a combinatio...

  18. Proximity effect on the general base catalysed hydrolysis of amide ...

    Indian Academy of Sciences (India)

    the solution state kinetics and equilibria involving poly- dentate phenol–amide ligands and transition metal ions. ∗ ... itored with a Cecil spectrophotometer model CE 7200. (U.K.). The cell block was thermostatted to the .... then acidified with HClO4 to pH 1 and extracted with. CHCl3 at least thrice. All the CHCl3 extracts were.

  19. Partial gigantism

    Directory of Open Access Journals (Sweden)

    М.М. Karimova

    2017-05-01

    Full Text Available A girl with partial gigantism (the increased I and II fingers of the left foot is being examined. This condition is a rare and unresolved problem, as the definite reason of its development is not determined. Wait-and-see strategy is recommended, as well as correcting operations after closing of growth zones, and forming of data pool for generalization and development of schemes of drug and radial therapeutic methods.

  20. Pd(OAc)2/DPPF-catalysed microwave-assisted cyanide-free ...

    Indian Academy of Sciences (India)

    Pd(OAc)2/DPPF-catalysed microwave-assisted cyanide-free synthesis of aryl nitriles. DINESH N SAWANT and BHALCHANDRA M BHANAGE. ∗. Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai 400 019, India e-mail: bhalchandra_bhanage@yahoo.com. MS received 13 April 2013; revised 27 ...

  1. Francis Farley presenting his novel "Catalysed Fusion" in the CERN Library

    CERN Multimedia

    Farley, Irina

    2013-01-01

    "Catalysed Fusion" is described by its author Francis Farley, 92, as a "true-to-life fantasy woven around particle physics" set in 1980s Geneva – "the city where nations meet and particles collide". Farley presented the book in the program "Literature in Focus" on Tuesday 16th April 2013.

  2. Iron(III) porphyrin-catalysed oxidation reactions by m-chloro ...

    Indian Academy of Sciences (India)

    Unknown

    Dedicated to the memory of the late Professor Bhaskar G Maiya. *For correspondence. Iron(III) porphyrin-catalysed oxidation reactions by m-chloro- perbenzoic acid: Nature of reactive intermediates. A AGARWALA, V BAGCHI and D BANDYOPADHYAY*. Department of Chemistry, Indian Institute of Technology, New Delhi ...

  3. Mechanistic aspects of Os(VIII) catalysed oxidation of loop diuretic ...

    Indian Academy of Sciences (India)

    Mechanistic aspects of Os(VIII) catalysed oxidation of loop diuretic drug furosemide by Ag(III) periodate complex in aqueous alkaline medium. SHWETA J MALODEa, NAGARAJ P SHETTIb and SHARANAPPA T NANDIBEWOORa,∗. aPost-Graduate Department of Studies in Chemistry, Karnatak University, Dharwad 580 ...

  4. Organosilane oxidation by water catalysed by large gold nanoparticles in a membrane reactor

    NARCIS (Netherlands)

    Gitis, V.; Beerthuis, R.; Shiju, N.R.; Rothenberg, G.

    2014-01-01

    We show that gold nanoparticles catalyse the oxidation of organosilanes using water as oxidant at ambient conditions. Remarkably, monodispersions of small gold particles (3.5 nm diameter) and large ones (6-18 nm diameter) give equally good conversion rates. This is important because separating large

  5. Ancillary ligand-free copper catalysed hydrohydrazination of terminal alkynes with NH2NH2.

    Science.gov (United States)

    Peltier, Jesse L; Jazzar, Rodolphe; Melaimi, Mohand; Bertrand, Guy

    2016-02-14

    An efficient and selective Cu-catalysed hydrohydrazination of terminal alkynes with parent hydrazine is reported. The methodology tolerates a broad range of functional groups, allows for the synthesis of symmetrical and unsymmetrical azines, and can be extended to hydrazine derivatives and amines.

  6. The role of pellet thermal stability in reactor design for heterogeneously catalysed chemical reactions

    NARCIS (Netherlands)

    Wijngaarden, R.J.; Westerterp, K.R.

    1992-01-01

    For exothermic fluid-phase reactions, a reactor which is cooled at the wall can exhibit multiplicity or parametric sensitivity. Moreover, for heterogeneously catalysed exothermic fluid-phase reactions, each of the catalytically active pellets in the reactor can exhibit multiplicity. Both forms of

  7. Inactivation of barley limit dextrinase inhibitor by thioredoxin-catalysed disulfide reduction

    DEFF Research Database (Denmark)

    Jensen, Johanne Mørch; Hägglund, Per; Christensen, Hans Erik Mølager

    2012-01-01

    Barley limit dextrinase (LD) that catalyses hydrolysis of α-1,6 glucosidic linkages in starch-derived dextrins is inhibited by limit dextrinase inhibitor (LDI) found in mature seeds. LDI belongs to the chloroform/methanol soluble protein family (CM-protein family) and has four disulfide bridges...

  8. Potash alum [KAl (SO 4) 2. 12H 2 O] catalysed esterification of ...

    Indian Academy of Sciences (India)

    A convenient and clean procedure for esterification is reported. Direct condensation of formylphenoxyaliphatic acids with low to high boiling alcohols catalysed by potash alum gave moderate to good yields. This catalyst could be recovered and reused without substantial loss in its catalytic activity and the methodology could ...

  9. Mechanism and Stereoselectivity of Zeolite-catalysed Sugar Isomerisation in Alcohols

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Riisager, Anders; Taarning, Esben

    2016-01-01

    Glucose isomerisation to fructose can occur by different pathways and the mechanism of zeolite-catalysed glucose isomerisation in methanol has remained incompletely understood. Herein, the mechanism is studied using an 1H-13C HSQC NMR assay resolving different fructose isotopomers. We find that z...

  10. Bis(imino)pyridine (BIMP) Fe(II) catalyses one-pot green ...

    Indian Academy of Sciences (India)

    483–486. c Indian Academy of Sciences. Bis(imino)pyridine (BIMP) Fe(II) catalyses one-pot green condensation of resorcinol, malononitrile, aromatic aldehydes and cyclohexanone. SAMAN DAMAVANDIa,∗ and REZA SANDAROOSb. aDepartment of Chemistry, Sarvestan Branch, Islamic Azad University, Sarvestan, Iran.

  11. Cobalt-catalysed C-H carbonylative cyclisation of aliphatic amides.

    Science.gov (United States)

    Williamson, Patrick; Galván, Alicia; Gaunt, Matthew J

    2017-04-01

    A cobalt-catalysed C-H carbonylation of aliphatic carboxamide derivatives is described, employing commercially available Co(ii)-salts in the presence of a silver oxidant. This operationally simple process utilises an atmospheric pressure of CO and generates a range of substituted succinimide products bearing diverse functional groups that can be successfully accessed via this methodology.

  12. On the key role of water in the allylic activation catalysed by Pd (II ...

    Indian Academy of Sciences (India)

    On the key role of water in the allylic activation catalysed by Pd (II) bisphosphinite complexes. RAKESH KUMAR SHARMA and ASHOKA G SAMUELSON*. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012 e-mail: ashoka@ipc.iisc.ernet.in. Abstract. Palladium and platinum ...

  13. Enantioselective Conjugate Addition of Diethylzinc to Chalcones Catalysed by Chiral Ni(II) Aminoalcohol Complexes

    NARCIS (Netherlands)

    Vries, André H.M. de; Jansen, Johan F.G.A.; Feringa, Bernard

    1994-01-01

    Conjugate addition of diethylzinc to chalcones is catalysed by complexes prepared in situ from Ni(acac)2 and cis-exo-N,N-dialkyl-3-aminoisoborneols or (+)-cis-endo-N,N-dimethyl-3-aminoborneol ((+)-DAB) (13b). The products are obtained with enantioselectivities up to 84 %. When scalemic

  14. Potash alum [KAl(SO4)2.12H2O] catalysed esterification of ...

    Indian Academy of Sciences (India)

    Abstract. A convenient and clean procedure for esterification is reported. Direct condensation of formylphe- noxyaliphatic acids with low to high boiling alcohols catalysed by potash alum gave moderate to good yields. This catalyst could be recovered and reused without substantial loss in its catalytic activity and the ...

  15. Hydrolase-catalysed synthesis of peroxycarboxylic acids: Biocatalytic promiscuity for practical applications

    NARCIS (Netherlands)

    Carboni-Oerlemans, Chiara; Dominguez de Maria, Pablo; Tuin, Bernard; Bargeman, Gerrald; van der Meer, Ab; van Gemert, Robert

    2006-01-01

    The enzymatic promiscuity concept involves the possibility that one active site of an enzyme can catalyse several different chemical transformations. A rational understanding of the mechanistic reasons for this catalytic performance could lead to new practical applications. The capability of certain

  16. Mg (ClO 4) 2 catalysed preparation of 1-amidoalkyl-2-naphthols ...

    Indian Academy of Sciences (India)

    A simple, efficient, and practical procedure for the synthesis of amidoalkyl naphthols via multicomponent one-pot reaction of 2-naphthol, aldehydes and amides catalysed by Mg(ClO4)2 is described in high yields. The present work offers several advantages such as high ...

  17. Palladium-catalysed direct cross-coupling of secondary alkyllithium reagents

    NARCIS (Netherlands)

    Vila, Carlos; Giannerini, Massimo; Hornillos, Valentin; Fananas-Mastral, Martin; Feringa, Ben L.

    2014-01-01

    Palladium-catalysed cross-coupling of secondary C(sp(3)) organometallic reagents has been a long-standing challenge in organic synthesis, due to the problems associated with undesired isomerisation or the formation of reduction products. Based on our recently developed catalytic C-C bond formation

  18. Kinetics and mechanism of the base-catalysed reaction of 4 ...

    African Journals Online (AJOL)

    NPMPF) in benzene has been investigated at 27oC and in the presence of functionally similar, but structurally different addenda, namely; imidazole, pyridine and triethylamine. The reaction is catalysed by the nucleophile and imidazole in a linear ...

  19. Computing the correlation between catalyst composition and its performance in the catalysed process

    Czech Academy of Sciences Publication Activity Database

    Holeňa, Martin; Steinfeldt, N.; Baerns, M.; Štefka, David

    2012-01-01

    Roč. 43, 10 August (2012), s. 55-67 ISSN 0098-1354 R&D Projects: GA ČR GA201/08/0802 Institutional support: RVO:67985807 Keywords : catalysed process * catalyst performance * correlation measures * estimating correlation value * analysis of variance * regression trees Subject RIV: IN - Informatics, Computer Science Impact factor: 2.091, year: 2012

  20. Gold(I)-catalysed cascade reactions in the synthesis of 2,3-fused indole derivatives.

    Science.gov (United States)

    Gimeno, Ana; Rodríguez-Gimeno, Alejandra; Cuenca, Ana B; Ramírez de Arellano, Carmen; Medio-Simón, Mercedes; Asensio, Gregorio

    2015-08-11

    A gold(I)-catalysed hydroaminative/arylative cascade for the efficient synthesis of a variety of indole-fused skeletons has been developed. Factors controlling the catalyst loading required in these transformations involving 1,3-unsubstituted indole intermediates have been revealed, allowing isolation of an unprecedented 1,3-dimetallated 3H-indole gold complex characterized by X-ray diffraction.

  1. [Removable partial dentures. Oral functions and types].

    Science.gov (United States)

    Creugers, N H J; de Baat, C

    2009-11-01

    A removable partial denture enables the restoration or improvement of 4 oral functions: aesthetics, mandibular stability, mastication, and speech. However, wearing a removable partial denture should not cause oral comfort to deteriorate. There are 3 types of removable partial dentures: acrylic tissue-supported dentures, dentures with cast metal frameworks en dentures with cast metal frameworks and (semi)precision attachments. Interrupted tooth arches,free-ending tooth arches, and a combination of interrupted as well as free-ending tooth arches can be restored using these dentures. Well-known disadvantages of removable partial dentures are problematic oral hygiene, negative influence on the remaining dentition and limited oral comfort. Due to the advanced possibilities of fixed tooth- or implant-supported partial dentures, whether or not free-ending, or tooth- as well as implant-supported partial dentures, the indication of removable partial dentures is restricted. Nevertheless, for the time being the demand for removable partial dentures is expected to continue.

  2. A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

    KAUST Repository

    Ajitha, Manjaly John

    2016-03-29

    The possibility of direct introduction of a new functionality through C–H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the hetero-aryl substrate (2-phenylpyridine) using phenyl azide as nitrogen source by density functional theory (DFT). For the deprotocyclometallation and protodecyclometallation processes of the title reaction, we propose a stepwise base-assisted mechanism (pathway I) instead of previously reported concerted mechanism (pathway II). In the new mechanism proposed here, 2-phenylpyridine acts as a base in the initial deprotonation step (C-H bond cleavage) and transports the proton towards the final protonation step. In fact, the N-H bond of the strong conjugate acid (formed during initial C-H bond cleavage) considered in pathway I (via TS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (via TS5). The higher activation barrier of TS5 mainly originates from the ring strain of the four membered cyclic transition state. The vital role of base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal catalysed reactions.

  3. Iron(III)-catalysed carbonyl-olefin metathesis

    Science.gov (United States)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.

    2016-05-01

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  4. Clinical application of removable partial dentures using thermoplastic resin. Part II: Material properties and clinical features of non-metal clasp dentures.

    Science.gov (United States)

    Fueki, Kenji; Ohkubo, Chikahiro; Yatabe, Masaru; Arakawa, Ichiro; Arita, Masahiro; Ino, Satoshi; Kanamori, Toshikazu; Kawai, Yasuhiko; Kawara, Misao; Komiyama, Osamu; Suzuki, Tetsuya; Nagata, Kazuhiro; Hosoki, Maki; Masumi, Shin-ichi; Yamauchi, Mutsuo; Aita, Hideki; Ono, Takahiro; Kondo, Hisatomo; Tamaki, Katsushi; Matsuka, Yoshizo; Tsukasaki, Hiroaki; Fujisawa, Masanori; Baba, Kazuyoshi; Koyano, Kiyoshi; Yatani, Hirofumi

    2014-04-01

    This position paper reviews physical and mechanical properties of thermoplastic resin used for non-metal clasp dentures, and describes feature of each thermoplastic resin in clinical application of non-metal clasp dentures and complications based on clinical experience of expert panels. Since products of thermoplastic resin have great variability in physical and mechanical properties, clinicians should utilize them with careful consideration of the specific properties of each product. In general, thermoplastic resin has lower color-stability and higher risk for fracture than polymethyl methacrylate. Additionally, the surface of thermoplastic resin becomes roughened more easily than polymethyl methacrylate. Studies related to material properties of thermoplastic resin, treatment efficacy and follow-up are insufficient to provide definitive conclusions at this time. Therefore, this position paper should be revised based on future studies and a clinical guideline should be provided. Copyright © 2014 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  5. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt(3)M (M=Pt, Ru, Sn, Re, Rh, and Pd).

    Science.gov (United States)

    Xu, Zhen-Feng; Wang, Yixuan

    2011-10-27

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt(3)M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt(3)Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol.

  6. Structural changes of noble metal catalysts during ignition and extinction of the partial oxidation of methane studied by advanced QEXAFS techniques

    DEFF Research Database (Denmark)

    Grunwaldt, Jan-Dierk; Beier, M.; Kimmerle, B.

    2009-01-01

    The dynamics of the ignition and extinction of the catalytic partial oxidation (CPO) of methane to hydrogen and carbon monoxide over Pt-Rh/Al2O3 and Pt/Al2O3 were studied in the subsecond timescale using quick-EXAFS with a novel cam-driven X-ray monochromator employing Si(111) and Si(311) crystal...... of the CPO of methane and are complementing results from time-resolved infrared thermography and full field X-ray microscopy studies....

  7. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols.

    Science.gov (United States)

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J

    2015-12-01

    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  8. Solvent engineering and other reaction design methods for favouring enzyme-catalysed synthesis

    DEFF Research Database (Denmark)

    Zeuner, Birgitte

    important for FAE activity and stability in IL-buffer (15% v/v) systems. The quantum chemistry-based COSMO-RS method was applied for explaining the IL anion effect in terms of hydrogen bonding capacity. Furthermore, the usefulness of COSMO-RS and other thermodynamically based tools in solvent selection...... for FAE-catalysed acylation reactions was reviewed. FAE type A from Aspergillus niger and an FAE from a commercial preparation from Humicola insolens, Depol 740L, could not catalyse the esterification of arabinose or xylose with hydroxycinnamates in IL-buffer systems or in surfactantless microemulsion...... the biocatalytic productivity of 2.5-fold. However, the recyclability of the immobilized enzyme was low. Reusing Tr6 seven times in a membrane reactor increased the trans-sialylation yield on the limiting substrate 1.3-fold, emphasizing the importance of the continuous product removal. Furthermore...

  9. A steric tethering approach enables palladium-catalysed C-H activation of primary amino alcohols

    Science.gov (United States)

    Calleja, Jonas; Pla, Daniel; Gorman, Timothy W.; Domingo, Victoriano; Haffemayer, Benjamin; Gaunt, Matthew J.

    2015-12-01

    Aliphatic primary amines are a class of chemical feedstock essential to the synthesis of higher-order nitrogen-containing molecules, commonly found in biologically active compounds and pharmaceutical agents. New methods for the construction of complex amines remain a continuous challenge to synthetic chemists. Here, we outline a general palladium-catalysed strategy for the functionalization of aliphatic C-H bonds within amino alcohols, an important class of small molecule. Central to this strategy is the temporary conversion of catalytically incompatible primary amino alcohols into hindered secondary amines that are capable of undergoing a sterically promoted palladium-catalysed C-H activation. Furthermore, a hydrogen bond between amine and catalyst intensifies interactions around the palladium and orients the aliphatic amine substituents in an ideal geometry for C-H activation. This catalytic method directly transforms simple, easily accessible amines into highly substituted, functionally concentrated and structurally diverse products, and can streamline the synthesis of biologically important amine-containing molecules.

  10. Microstructural evolution in the partial transient liquid phase diffusion bonding of Zircaloy-4 to stainless steel 321 using active titanium filler metal

    Energy Technology Data Exchange (ETDEWEB)

    Atabaki, M. Mazar, E-mail: m.mazaratabaki@gmail.co [Department of Materials Engineering, Faculty of Mechanical Engineering, University Technology Malaysia, 81310 (Malaysia); Institute for Materials Research, the School of Process, Environmental and Materials Engineering, Faculty of Engineering, University of Leeds, Leeds (United Kingdom)

    2010-11-30

    Microstructural evolution of the partial transient liquid phase diffusion bonded Zircaloy-4 and stainless steel 321 using an active Ti-base interlayer were studied at different temperatures. Additionally, simple analytical models were developed to predict the evolution of the interlayer and intermetallics during the bonding operation. Bonds were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. Precision measurement of the interlayer width was made as a function of the bonding temperature. The liquid film migration occurred as a result of chemical solubility differences between the stable and metastable phases. The formation and growth model of the intermetallic compounds at the interfaces of Zircaloy-4/Ti-base interlayer and stainless steel 321/Ti-base interlayer for controlling the bonding process was studied considering the diffusion kinetics and the thermodynamics. The evolution of the interlayer thickness indicated a good agreement between the calculation and experimental measurement. It was also demonstrated that the low isothermal solidification kinetic was not only due to the enrichment of the liquid phase with the base alloying elements such as Ti and Zr, but also the reduction of solid solubility limit of Cu in the base alloys contributed to the reduction of isothermal solidification kinetic.

  11. Microstructural evolution in the partial transient liquid phase diffusion bonding of Zircaloy-4 to stainless steel 321 using active titanium filler metal

    Science.gov (United States)

    Atabaki, M. Mazar

    2010-11-01

    Microstructural evolution of the partial transient liquid phase diffusion bonded Zircaloy-4 and stainless steel 321 using an active Ti-base interlayer were studied at different temperatures. Additionally, simple analytical models were developed to predict the evolution of the interlayer and intermetallics during the bonding operation. Bonds were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. Precision measurement of the interlayer width was made as a function of the bonding temperature. The liquid film migration occurred as a result of chemical solubility differences between the stable and metastable phases. The formation and growth model of the intermetallic compounds at the interfaces of Zircaloy-4/Ti-base interlayer and stainless steel 321/Ti-base interlayer for controlling the bonding process was studied considering the diffusion kinetics and the thermodynamics. The evolution of the interlayer thickness indicated a good agreement between the calculation and experimental measurement. It was also demonstrated that the low isothermal solidification kinetic was not only due to the enrichment of the liquid phase with the base alloying elements such as Ti and Zr, but also the reduction of solid solubility limit of Cu in the base alloys contributed to the reduction of isothermal solidification kinetic.

  12. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri

    2015-11-30

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

  13. Titania-catalysed oxidative dehydrogenation of ethyl lactate: effective yet selective free-radical oxidation

    NARCIS (Netherlands)

    Ramos-Fernandez, E.V.; Geels, N.J.; Shiju, N.R.; Rothenberg, G.

    2014-01-01

    We research here the catalytic oxidative dehydrogenation of ethyl lactate, as an alternative route to ethyl pyruvate. Testing various solid catalysts (Fe2O3, TiO2, V2O5/MgO-Al2O3, ZrO2, CeO2 and ZnO), we find that simple and inexpensive TiO2 efficiently catalyses this reaction under mild conditions.

  14. FeCl3-catalysed Zn-mediated allylation of cyclic enol ethers in water

    Indian Academy of Sciences (India)

    FeCl3-catalysed Zn-mediated allylation of cyclic enol ethers in water. P CHAKRABORTY and ... To a stirred mixture of dihydropyran (84.2mg,. 1.0 mmol), water (5 ... 2b (syn/anti = 1:1) was prepared from dihydropyran and 1b following the procedure described for com- pound 2a. Viscous oil. Rf = 0.21 (30% ethyl acetate. 509 ...

  15. Rieske non-heme iron-dependent oxygenases catalyse diverse reactions in natural product biosynthesis.

    Science.gov (United States)

    Perry, Christopher; de Los Santos, Emmanuel L C; Alkhalaf, Lona M; Challis, Gregory L

    2018-04-13

    Covering: up to the end of 2017The roles played by Rieske non-heme iron-dependent oxygenases in natural product biosynthesis are reviewed, with particular focus on experimentally characterised examples. Enzymes belonging to this class are known to catalyse a range of transformations, including oxidative carbocyclisation, N-oxygenation, C-hydroxylation and C-C desaturation. Examples of such enzymes that have yet to be experimentally investigated are also briefly described and their likely functions are discussed.

  16. Rapid assembly of functionalised spirocyclic indolines by palladium-catalysed dearomatising diallylation of indoles with allyl acetate

    OpenAIRE

    Dhankher, P.; Benhamou, L.; Sheppard, T. D.

    2014-01-01

    Herein, we report the application of allyl acetate to the palladium-catalysed dearomatising diallylation of indoles. The reaction can be carried out by using a readily available palladium catalyst at room temperature, and can be applied to a wide range of substituted indoles to provide access to the corresponding 3,3-diallylindolinines. These compounds are versatile synthetic intermediates that readily undergo Ugi reactions or proline-catalysed asymmetric Mannich reactions. Alternatively, acy...

  17. Single and multi-component adsorption of salicylic acid, clofibric acid, carbamazepine and caffeine from water onto transition metal modified and partially calcined inorganic-organic pillared clay fixed beds.

    Science.gov (United States)

    Cabrera-Lafaurie, Wilman A; Román, Félix R; Hernández-Maldonado, Arturo J

    2015-01-23

    Fixed-beds of transition metal (Co(2+), Ni(2+) or Cu(2+)) inorganic-organic pillared clays (IOCs) were prepared to study single- and multi-component non-equilibrium adsorption of a set of pharmaceutical and personal care products (PPCPs: salicylic acid, clofibric acid, carbamazepine and caffeine) from water. Adsorption capacities for single components revealed that the copper(II) IOCs have better affinity toward salicylic and clofibric acid. However, multi-component adsorption tests showed a considerable decrease in adsorption capacity for the acids and an unusual selectivity toward carbamazepine depending on the transition metal. This was attributed to a combination of competition between PPCPs for adsorption sites, adsorbate-adsorbate interactions, and plausible pore blocking caused by carbamazepine. The cobalt(II) IOC bed that was partially calcined to fractionate the surfactant moiety showcased the best selectivity toward caffeine, even during multi-component adsorption. This was due to a combination of a mildly hydrophobic surface and interaction between the PPCP and cobalt(II). In general, the tests suggest that these IOCs may be a potential solution for the removal of PPCPs if employed in a layered-bed configuration, to take care of families of adsorbates in a sequence that would produce sharpened concentration wavefronts. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Direct formation of a current collector layer on a partially reduced graphite oxide film using sputter-assisted metal deposition to fabricate high-power micro-supercapacitor electrodes

    Science.gov (United States)

    Byun, Segi; Yu, Jin

    2016-03-01

    When a reduced graphite oxide (RGO) freestanding film is fabricated on a supercapacitor cell via compression onto a current collector, there are gaps between the film and the current collector, even if the cell is carefully assembled. These gaps can induce increases in the electrical series resistance (ESR) of the cell, resulting in degradation of the cell's electrochemical performance. Here, to effectively reduce the ESR of the supercapacitor, metal sputtering deposition is introduced. This enables the direct formation of the current collector layer on a partially reduced GO (pRGO) film, the model system. Using metal sputtering, a nickel (Ni) layer with a thickness formed on the pRGO film. The pRGO film sustains its film form with high packing density (∼1.31 g cm-3). Furthermore, the Ni-sputtered pRGO film with optimized Ni thickness exhibits remarkable enhancement of its electrochemical performance. This includes a superior rate capability and semi-permanent cycle life compared with the untreated pRGO film. This is due to the significant decrease in the ESR of the film.

  19. Lipase catalysed biodiesel synthesis with integrated glycerol separation in continuously operated microchips connected in series.

    Science.gov (United States)

    Šalić, Anita; Tušek, Ana Jurinjak; Sander, Aleksandra; Zelić, Bruno

    2018-02-05

    Although the application of microreactors in different processes has been extensively explored in recent decades, microreactors continue to be underexplored in the context of the enzyme-catalysed process for biodiesel production. Due to their numerous advantages, microreactors could become the next step in the development of a biodiesel production process characterised by sustainability, cost-effectiveness and energy efficiency. In this investigation, biodiesel production was catalysed by lipase from Thermomyces lanuginosus (Lipolase L100). Edible sunflower oil was used as a model substrate in order to investigate the process. After optimal process conditions had been determined, waste-cooking oil was used for biodiesel production to make the production process more sustainable. Three different substrate-feeding strategies were investigated and finally an optimal strategy was proposed. In all the investigated systems, fatty acids methyl esters (FAME) content was higher than 95% and obtained in a significantly shorter time (less than 2 h) compared to the batch process in which biodiesel production was catalysed by lipase (C = 95%, t = 96 h). After the optimal biodiesel production system had been proposed, an integrated system with two microchips connected in series was developed. The first microchip was used for biodiesel production and the second for simultaneous purification i.e. glycerol separation. Finally, purified biodiesel was produced with glycerol content below the detection limit. Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Glass fiber-reinforced thermoplastics for use in metal-free removable partial dentures: combined effects of fiber loading and pigmentation on color differences and flexural properties.

    Science.gov (United States)

    Tanimoto, Yasuhiro; Nagakura, Manamu; Nishiyama, Norihiro

    2018-02-20

    The purpose of this study was to investigate the combined effects of fiber loading and pigmentation on the color differences and flexural properties of glass fiber-reinforced thermoplastics (GFRTPs), for use in non-metal clasp dentures (NMCDs). The GFRTPs consisted mainly of E-glass fibers, a polypropylene matrix, and a coloring pigment: the GFRTPs with various fiber loadings (0, 10, and 20mass%) and pigmentations (0, 1, 2, and 4mass%) were fabricated by using an injection molding. The color differences of GFRTPs were measured based on the Commission Internationale de l'Eclairage (CIE) Lab color system, by comparing with a commercially available NMCD. The flexural properties of GFRTPs were evaluated by using a three-point bending test, according to International Standards Organization (ISO) specification number 20795-1. The visible colors of GFRTPs with pigment contents of 2mass% were acceptable for gingival color, and the glass fibers harmonized well with the resins. The ΔE* values of the GFRTPs with pigment contents of 2mass% obtained by using the CIE Lab system were lowest at all fiber loadings. For GFRTPs with fiber contents of 10 and 20mass% at 2mass% pigment content, these GFRTPs surpassed the ISO 20795-1 specification regarding flexural strength (> 60MPa) and modulus (> 1.5GPa). A combination of the results of color difference evaluation and mechanical examination indicates that the GFRTPs with fiber contents of 10 or 20mass%, and with pigment contents of 2mass% have acceptable esthetic appearance and sufficient rigidity for NMCDs. Copyright © 2018 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  1. Catalytic and substrate promiscuity: distinct multiple chemistries catalysed by the phosphatase domain of receptor protein tyrosine phosphatase.

    Science.gov (United States)

    Srinivasan, Bharath; Marks, Hanna; Mitra, Sreyoshi; Smalley, David M; Skolnick, Jeffrey

    2016-07-15

    The presence of latent activities in enzymes is posited to underlie the natural evolution of new catalytic functions. However, the prevalence and extent of such substrate and catalytic ambiguity in evolved enzymes is difficult to address experimentally given the order-of-magnitude difference in the activities for native and, sometimes, promiscuous substrate/s. Further, such latent functions are of special interest when the activities concerned do not fall into the domain of substrate promiscuity. In the present study, we show a special case of such latent enzyme activity by demonstrating the presence of two mechanistically distinct reactions catalysed by the catalytic domain of receptor protein tyrosine phosphatase isoform δ (PTPRδ). The primary catalytic activity involves the hydrolysis of a phosphomonoester bond (C─O─P) with high catalytic efficiency, whereas the secondary activity is the hydrolysis of a glycosidic bond (C─O─C) with poorer catalytic efficiency. This enzyme also displays substrate promiscuity by hydrolysing diester bonds while being highly discriminative for its monoester substrates. To confirm these activities, we also demonstrated their presence on the catalytic domain of protein tyrosine phosphatase Ω (PTPRΩ), a homologue of PTPRδ. Studies on the rate, metal-ion dependence, pH dependence and inhibition of the respective activities showed that they are markedly different. This is the first study that demonstrates a novel sugar hydrolase and diesterase activity for the phosphatase domain (PD) of PTPRδ and PTPRΩ. This work has significant implications for both understanding the evolution of enzymatic activity and the possible physiological role of this new chemistry. Our findings suggest that the genome might harbour a wealth of such alternative latent enzyme activities in the same protein domain that renders our knowledge of metabolic networks incomplete. © 2016 The Author(s). published by Portland Press Limited on behalf of the

  2. [Acrylic resin removable partial dentures].

    Science.gov (United States)

    de Baat, C; Witter, D J; Creugers, N H J

    2011-01-01

    An acrylic resin removable partial denture is distinguished from other types of removable partial dentures by an all-acrylic resin base which is, in principle, solely supported by the edentulous regions of the tooth arch and in the maxilla also by the hard palate. When compared to the other types of removable partial dentures, the acrylic resin removable partial denture has 3 favourable aspects: the economic aspect, its aesthetic quality and the ease with which it can be extended and adjusted. Disadvantages are an increased risk of caries developing, gingivitis, periodontal disease, denture stomatitis, alveolar bone reduction, tooth migration, triggering of the gag reflex and damage to the acrylic resin base. Present-day indications are ofa temporary or palliative nature or are motivated by economic factors. Special varieties of the acrylic resin removable partial denture are the spoon denture, the flexible denture fabricated of non-rigid acrylic resin, and the two-piece sectional denture. Furthermore, acrylic resin removable partial dentures can be supplied with clasps or reinforced by fibers or metal wires.

  3. Removable partial dentures: clinical concepts.

    Science.gov (United States)

    Bohnenkamp, David M

    2014-01-01

    This article provides a review of the traditional clinical concepts for the design and fabrication of removable partial dentures (RPDs). Although classic theories and rules for RPD designs have been presented and should be followed, excellent clinical care for partially edentulous patients may also be achieved with computer-aided design/computer-aided manufacturing technology and unique blended designs. These nontraditional RPD designs and fabrication methods provide for improved fit, function, and esthetics by using computer-aided design software, composite resin for contours and morphology of abutment teeth, metal support structures for long edentulous spans and collapsed occlusal vertical dimensions, and flexible, nylon thermoplastic material for metal-supported clasp assemblies. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. Catalysed fusion

    CERN Document Server

    Farley, Francis

    2012-01-01

    A sizzling romance and a romp with subatomic particles at CERN. Love, discovery and adventure in the city where nations meet and beams collide. Life in a large laboratory. As always, the challenges are the same. Who leads? Who follows? Who succeeds? Who gets the credit? Who gets the women or the men? Young Jeremy arrives in CERN and joins the quest for green energy. Coping with baffling jargon and manifold dangers, he is distracted by radioactive rats, lovely ladies and an unscrupulous rival. Full of doubts and hesitations, he falls for a dazzling Danish girl, who leads him astray. His brilliant idea leads to a discovery and a new route to cold fusion. But his personal life is scrambled. Does it bring fame or failure? Tragedy or triumph?

  5. The doping effect of fluorinated aromatic solvents on the rate of ruthenium-catalysed olefin metathesis.

    Science.gov (United States)

    Samojłowicz, Cezary; Bieniek, Michał; Pazio, Aleksandra; Makal, Anna; Woźniak, Krzysztof; Poater, Albert; Cavallo, Luigi; Wójcik, Jacek; Zdanowski, Konrad; Grela, Karol

    2011-11-11

    A study concerning the effect of using a fluorinated aromatic solvent as the medium for olefin metathesis reactions catalysed by ruthenium complexes bearing N-heterocyclic carbene ligands is presented. The use of fluorinated aromatic hydrocarbons (FAH) as solvents for olefin metathesis reactions catalysed by standard commercially available ruthenium pre-catalysts allows substantially higher yields of the desired products to be obtained, especially in the case of demanding polyfunctional molecules, including natural and biologically active compounds. Interactions between the FAH and the second-generation ruthenium catalysts, which apparently improve the efficiency of the olefin metathesis transformation, have been studied by X-ray structure analysis and computations, as well as by carrying out a number of metathesis experiments. The optimisation of reaction conditions by using an FAH can be regarded as a complementary approach for the design of new improved ruthenium catalysts. Fluorinated aromatic solvents are an attractive alternative medium for promoting challenging olefin metathesis reactions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. EtfA catalyses the formation of dipicolinic acid in Clostridium perfringens.

    Science.gov (United States)

    Orsburn, Benjamin C; Melville, Stephen B; Popham, David L

    2010-01-01

    Dipicolinic acid (DPA) is a major component of bacterial endospores, comprising 5-15% of the spore dry weight, and is important for spore stability and resistance properties. The biosynthetic precursor to DPA, dihydro-dipicolinic acid (DHDPA), is produced by DHDPA synthase within the lysine biosynthesis pathway. In Bacillus subtilis, and most other bacilli and clostridia, DHDPA is oxidized to DPA by the products of the spoVF operon. Analysis of the genomes of the clostridia in Cluster I, including the pathogens Clostridium perfringens, Clostridium botulinum and Clostridium tetani, has shown that no spoVF orthologues exist in these organisms. DPA synthase was purified from extracts of sporulating C. perfringens cells. Peptide sequencing identified an electron transfer flavoprotein, EtfA, in this purified protein fraction. A C. perfringens strain with etfA inactivated is blocked in late stage sporulation and produces < or = 11% of wild-type DPA levels. C. perfringens EtfA was expressed in and purified from Escherichia coli, and this protein catalysed DPA formation in vitro. The sequential production of DHDPA and DPA in C. perfringens appears to be catalysed by DHDPA synthase followed by EtfA. Genome sequence data and the taxonomy of spore-forming species suggest that this may be the ancestral mechanism for DPA synthesis.

  7. SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis

    Science.gov (United States)

    Ohashi, Masao; Liu, Fang; Hai, Yang; Chen, Mengbin; Tang, Man-Cheng; Yang, Zhongyue; Sato, Michio; Watanabe, Kenji; Houk, K. N.; Tang, Yi

    2017-09-01

    Pericyclic reactions—which proceed in a concerted fashion through a cyclic transition state—are among the most powerful synthetic transformations used to make multiple regioselective and stereoselective carbon-carbon bonds. They have been widely applied to the synthesis of biologically active complex natural products containing contiguous stereogenic carbon centres. Despite the prominence of pericyclic reactions in total synthesis, only three naturally existing enzymatic examples (the intramolecular Diels-Alder reaction, and the Cope and the Claisen rearrangements) have been characterized. Here we report a versatile S-adenosyl-L-methionine (SAM)-dependent enzyme, LepI, that can catalyse stereoselective dehydration followed by three pericyclic transformations: intramolecular Diels-Alder and hetero-Diels-Alder reactions via a single ambimodal transition state, and a retro-Claisen rearrangement. Together, these transformations lead to the formation of the dihydropyran core of the fungal natural product, leporin. Combined in vitro enzymatic characterization and computational studies provide insight into how LepI regulates these bifurcating biosynthetic reaction pathways by using SAM as the cofactor. These pathways converge to the desired biosynthetic end product via the (SAM-dependent) retro-Claisen rearrangement catalysed by LepI. We expect that more pericyclic biosynthetic enzymatic transformations remain to be discovered in naturally occurring enzyme ‘toolboxes’. The new role of the versatile cofactor SAM is likely to be found in other examples of enzyme catalysis.

  8. Click synthesis of 1,4-disubstituted-1,2,3-triazoles catalysed by CuO ...

    Indian Academy of Sciences (India)

    Click synthesis of 1,4-disubstituted-1,2,3-triazoles catalysed by. CuO–CeO2 nanocomposite in the presence of amberlite-supported azide. JALAL ALBADIa,∗, JAFAR ABBASI SHIRANb and AZAM MANSOURNEZHADc. aBehbahan Khatam Alanbia University of Technology, Behbahan 6361647189, Iran. bFaculty of Science ...

  9. Bioacetilação de álcoois catalisada por Saccharum officinarum Bioacetylation of alcohols catalysed by Saccharum officinarum

    Directory of Open Access Journals (Sweden)

    João Carlos C. Assunção

    2009-01-01

    Full Text Available Lipase-catalysed esterifications of alcohols using immobilized enzyme system from sugar cane (Saccharum officinarum as biocatalyst afforded the corresponding esters in considerable yields (68-93%. Under optimized conditions, the material was utilized for reactions of acetylation with several advantage. It also investigated the possibility of reuse of immobilized enzymes of S. officinarum as biocatalyst under optimal reaction conditions.

  10. Isotopic effects in mechanistic studies of biotransformations of fluorine derivatives of L-alanine catalysed by L-alanine dehydrogenase

    International Nuclear Information System (INIS)

    Szymańska-Majchrzak, Jolanta; Pałka, Katarzyna; Kańska, Marianna

    2017-01-01

    Synthesis of 3-fluoro-[2- 2 H]-L-alanine (3-F-[ 2 H]-L-Ala) in reductive amination of 3-fluoropyruvic acid catalysed by L-alanine dehydrogenase (AlaDH) was described. Fluorine derivative was used to study oxidative deamination catalysed by AlaDH applied kinetic (for 3-F-L-Ala in H 2 O - KIE’s on V max : 1.1; on V max /K M : 1.2; for 3-F-L-Ala in 2 H 2 O – on V max : 1.4; on V max /K M : 2.1) and solvent isotope effect methods (for 3-F-L-Ala - SIE’s on V max : 1.0; on V max /K M : 0.87; for 3-F-[2- 2 H]-L-Ala – on V max : 1.4; on V max /K M : 1.5). Studies explain some details of reaction mechanism. - Highlights: • Synthesis of 3-fluoro-[2- 2 H]-L-alanine was performed. • The reactions were catalysed using the enzyme L-alanine dehydrogenase. • Performed reactions involved fluorinated analogues of L-alanine. • Solvent isotope effects of deuterium were determined. • Kinetic isotope effects were determined for obtained 3-fluoro-L-alanine. • The mechanism of reaction catalysed by L-alanine dehydrogenase was proposed.

  11. Experimental and kinetic modelling studies on the acid-catalysed hydrolysis of the water hyacinth plant to levulinic acid

    NARCIS (Netherlands)

    Girisuta, B.; Danon, B.; Manurung, R.; Janssen, L. P. B. M.; Heeres, H. J.

    2008-01-01

    A comprehensive experimental and modelling study on the acid-catalysed hydrolysis of the water hyacinth plant (Eichhornia crassipes) to optimise the yield of levulinic acid (LA) is reported (T = 150-175 degrees C, C-H2SO4 - 0.1-1 M, water hyacinth intake = 1-5 wt%). At high acid concentrations (>

  12. Palladium-catalysed telomerisation of isoprene with glycerol and polyethylene glycol: A facile route to new terpene derivatives

    NARCIS (Netherlands)

    Gordillo, A.; Durán Páchon, L.; de Jesus, E.; Rothenberg, G.

    2009-01-01

    We present here the first example of the telomerisation of isoprene with glycerol and polyethylene glycol (PEG-200), opening a facile route to new terpene structures, based on a combination of renewable and petroleum-based feedstocks. The reaction is catalysed by a palladium-carbene complex.

  13. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme

    DEFF Research Database (Denmark)

    Gallage, Nethaji J; Hansen, Esben H; Kannangara, Rubini

    2014-01-01

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside...... into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes......-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression...

  14. Enzyme catalysed production of sialylated human milk oligosaccharides and galactooligosaccharides by Trypanosoma cruzi trans-sialidase

    DEFF Research Database (Denmark)

    Holck, Jesper; Larsen, Dorte Møller; Michalak, Malwina

    2014-01-01

    A Trypanosoma cruzi trans-sialidase (E.C. 3.2.1.18) was cloned into Pichia pastoris and expressed. The pH and temperature optimum of the enzyme was determined as pH 5.7 and 30°C. Using casein glycomacropeptide (CGMP) and lactose as sialyl-donor and acceptor respectively, the optimal donor....../acceptor ratio for the trans-sialidase catalysed 3′-sialyllactose production was found to be 1:4. Quantitative amounts of 3′-sialyllactose were produced from CGMP and lactose at a yield of 40mg/g CGMP. The 3′-sialyllactose obtained exerted a stimulatory effect on selected probiotic strains, including different...

  15. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  16. Lipase-catalysed ester synthesis in solvent-free oil system: is it esterification or transesterification?

    Science.gov (United States)

    Sun, Jingcan; Yu, Bin; Curran, Philip; Liu, Shao-Quan

    2013-12-01

    Ester synthesis was carried out in a solvent-free system of lipase, coconut oil and ethanol or fusel alcohols to ascertain the reaction mechanism. During ester formation, octanoic and decanoic acids increased initially and then decreased gradually, indicating that ester production was a two-step reaction consisting of hydrolysis and esterification, rather than alcoholysis. With ethanol as the alcohol substrate, added butyric acid inhibited ester synthesis. However, when fusel alcohols were used as the alcohol substrate, no significant inhibitory effect by butyric acid was observed. Added octanoic acid did not show any adverse effect on the synthesis of corresponding esters. The results suggest that polarity of the reactants determines lipase activity. This study provides the first evidence on the mechanism of immobilised lipase-catalysed ester synthesis in a solvent-free system involving both hydrolysis and esterification. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

    KAUST Repository

    Gómez-Suárez, Adrián

    2015-12-13

    Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water.

    Science.gov (United States)

    Wang, Yanliang; Deng, Weiping; Wang, Binju; Zhang, Qinghong; Wan, Xiaoyue; Tang, Zhenchen; Wang, Ye; Zhu, Chun; Cao, Zexing; Wang, Guichang; Wan, Huilin

    2013-01-01

    The direct transformation of cellulose, which is the main component of lignocellulosic biomass, into building-block chemicals is the key to establishing biomass-based sustainable chemical processes. Only limited successes have been achieved for such transformations under mild conditions. Here we report the simple and efficient chemocatalytic conversion of cellulose in water in the presence of dilute lead(II) ions, into lactic acid, which is a high-value chemical used for the production of fine chemicals and biodegradable plastics. The lactic acid yield from microcrystalline cellulose and several lignocellulose-based raw biomasses is >60% at 463 K. Both theoretical and experimental studies suggest that lead(II) in combination with water catalyses a series of cascading steps for lactic acid formation, including the isomerization of glucose formed via the hydrolysis of cellulose into fructose, the selective cleavage of the C3-C4 bond of fructose to trioses and the selective conversion of trioses into lactic acid.

  19. Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes

    Science.gov (United States)

    Sydor, Paulina K.; Barry, Sarah M.; Odulate, Olanipekun M.; Barona-Gomez, Francisco; Haynes, Stuart W.; Corre, Christophe; Song, Lijiang; Challis, Gregory L.

    2011-05-01

    Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically powerful implementation of C-H activation reactions in nature. Here, we show that Rieske oxygenase-like enzymes mediate regio- and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalysed by non-haem iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio- and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective man-made C-H activation catalysts.

  20. Real-Time Monitoring of Enzyme-Catalysed Reactions using Deep UV Resonance Raman Spectroscopy.

    Science.gov (United States)

    Westley, Chloe; Fisk, Heidi; Xu, Yun; Hollywood, Katherine A; Carnell, Andrew J; Micklefield, Jason; Turner, Nicholas J; Goodacre, Royston

    2017-05-23

    For enzyme-catalysed biotransformations, continuous in situ detection methods minimise the need for sample manipulation, ultimately leading to more accurate real-time kinetic determinations of substrate(s) and product(s). We have established for the first time an on-line, real-time quantitative approach to monitor simultaneously multiple biotransformations based on UV resonance Raman (UVRR) spectroscopy. To exemplify the generality and versatility of this approach, multiple substrates and enzyme systems were used involving nitrile hydratase (NHase) and xanthine oxidase (XO), both of which are of industrial and biological significance, and incorporate multistep enzymatic conversions. Multivariate data analysis of the UVRR spectra, involving multivariate curve resolution-alternating least squares (MCR-ALS), was employed to effect absolute quantification of substrate(s) and product(s); repeated benchmarking of UVRR combined with MCR-ALS by HPLC confirmed excellent reproducibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water

    Science.gov (United States)

    Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F. Y.; Luan, Tiangang

    2015-08-01

    Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment.

  2. Direct rate assessment of laccase catalysed radical formation in lignin by electron paramagnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Munk, Line; Andersen, Mogens Larsen; Meyer, Anne S.

    2017-01-01

    Laccases (EC 1.10.3.2) catalyse removal of an electron and a proton from phenolic hydroxyl groups, including phenolic hydroxyls in lignins, to form phenoxy radicals during reduction of O2. We employed electron paramagnetic resonance spectroscopy (EPR) for real time measurement of such catalytic...... to suspensions of the individual lignin samples produced immediate time and enzyme dose dependent increases in intensity in the EPR signal with g-values in the range 2.0047–2.0050 allowing a direct quantitative monitoring of the radical formation and thus allowed laccase enzyme kinetics assessment on lignin...... formation than the Tv laccase on all three types of lignin substrates. When comparing the equal laccase dose rates on the three lignin substrates the enzymatic radical formation rate on the wheat straw lignin residue was consistently higher than those of the organosolv lignins. The pH-temperature optimum...

  3. Nocardia globerula NHB-2 nitrilase catalysed biotransformation of 4-cyanopyridine to isonicotinic acid.

    Science.gov (United States)

    Sharma, Nitya Nand; Sharma, Monica; Bhalla, Tek Chand

    2012-04-26

    Isonicotinic acid (INA) is an important pyridine derivative used in the manufacture of isoniazid (antituberculosatic drug) and other pharmaceutically important drugs. Nitrilase catalysed processes for the synthesis of pharmaceutically important acids from their corresponding nitriles are promising alternative over the cumbersome, hazardous, and energy demanding chemical processes. Nitrilase of Nocardia globerula NHB-2 (NitNHB2) is expressed in presence of isobutyronitrile in the growth medium (1.0% glucose, 0.5% peptone, 0.3% beef extract, and 0.1 % yeast extract, pH 7.5). NitNHB2 hydrolyses 4-cyanopyridine (4-CP) to INA without accumulation of isonicotinamide, which is common in the reaction catalysed via fungal nitrilases. The NitNHB2 suffers from substrate inhibition effect and hydrolysing activity up to 250 mM 4-CP was recorded. Complete conversion of 200 mM 4-CP to INA was achieved in 40 min using resting cell concentration corresponding to 10 U mL-1 nitrilase activity in the reaction. Substrate inhibition effect in the fed batch reaction (200 mM substrate feed/40min) led to formation of only 729 mM INA. In a fed batch reaction (100 mM 4-CP/20min), substrate inhibition effect was encountered after 7th feed and a total of 958 mM INA was produced in 400 min. The fed batch reaction scaled up to 1 L and 100% hydrolysis of 700 mM of 4-CP to INA at 35°C achieved in 140 min. The rate of INA production was 21.1 g h-1 mgDCW-1. This is the fastest biotransformation process ever reported for INA production with time and space productivity of 36 g L-1 h-1 using a bacterial nitrilase.

  4. Laccase catalysed grafting of phenolic onto xylan to improve its applicability in films

    Science.gov (United States)

    Pei, Jicheng; Wang, Bing; Zhang, Fangdong; Li, Zhongyang; Yin, Yunbei; Zhang, Dongxu

    2015-07-01

    Xylan can be tailored for various value-added applications. However, its use in aqueous systems is hampered by its complex structure, and small molecular weight. This research aimed at improving the xylan molecular weight and changing its structure. Laccase-catalysed oxidation of 4-coumaric acid (PCA), ferulic acid (FA), syringaldehyde (SD), and vanillin (VA) onto xylan was grafted to study the changes in its structure, tensile properties, and antibacterial activities. A Fourier transform infrared (FTIR) spectrum analyser was used to observe the changes in functional groups of xylan. The results showed a band at 1635 cm-1 corresponding to the stretching vibration of conjugated carbonyl carboxy hemoglobin and a benzene ring structure were strengthened; the appearance of a new band between 1200 cm-1 and 1270 cm-1 corresponding to alkyl ethers on the aryl C-O stretching vibration was due to the fact that during the grafting process, the number of benzene ring structures increased and covalent connections occurred between phenols and xylan. The reaction mechanism for the laccase-catalysed oxidation of phenol compounds onto xylan was preliminary explored by 13C-NMR. The results showed that PCA-xylan, FA-xylan graft poly onto xylan by Cγ ester bond, SD-xylan graft poly onto xylan by ether bond and an ester bond, and VD-xylan graft poly onto xylan by ether bond. The film strength of xylan derivatives has been significantly increased, especially for the PCA-xylan derivative. The increases in tensile stress at break, tensile strength, tensile yield stress, and Young's modulus were: 24.04%, 31.30%, 55.56%, and 28.21%, respectively. After laccase/phenolics were modified, xylan had a good antibacterial effect to E. coli, Corynebacterium glutamicum, and Bacillus subtilis. The SD-xylan, FA-xylan, and PCA-xylan showed a greater efficacy against E. coli, Corynebacterium glutamicum, and Bacillus subtilis, respectively.

  5. Esthetic double-structure fixed partial dentures.

    Science.gov (United States)

    Ravasini, G; Ugolini, G; Ravasini, F

    1996-04-01

    A new technical procedure for fixed partial dentures and single inlays allows the use of a metal supporting structure with independent ceramic coverage. The advantages of the technique are the bonding of metal to beveled dentinal margins with conventional cement and the acid-etched resin composite cementation of the ceramic, which permits more conservative preparation of the teeth. The complexity of the structure, the laboratory costs, and the doubling of the cementation procedures are the main disadvantages of the technique.

  6. Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilov, Konstantin N [Department of Chemistry, S.A. Esenin Ryazan State Pedagogical University, Ryazan (Russian Federation); Bondarev, Oleg G; Polosukhin, Aleksei I [A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow (Russian Federation)

    2004-07-31

    The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

  7. A gold-catalysed imine-propargylamine cascade sequence: synthesis of 3-substituted-2,5-dimethylpyrazines and the reaction mechanism.

    Science.gov (United States)

    Alcaide, Benito; Almendros, Pedro; Alonso, José M; Fernández, Israel; Gómez-Campillos, Gonzalo; Torres, M Rosario

    2014-05-07

    The gold-catalysed coupling reaction between propargylamine-derived imines and propargylamine exclusively afforded pyrazines. Besides, in order to understand the mechanism of this sequence, deuterium labeling and computational studies have been performed.

  8. Silver-catalysed azide-alkyne cycloaddition (AgAAC): assessing the mechanism by density functional theory calculations

    Science.gov (United States)

    Banerji, Biswadip; Chandrasekhar, K.; Killi, Sunil Kumar; Pramanik, Sumit Kumar; Uttam, Pal; Sen, Sudeshna; Maiti, Nakul Chandra

    2016-09-01

    `Click reactions' are the copper catalysed dipolar cycloaddition reaction of azides and alkynes to incorporate nitrogens into a cyclic hydrocarbon scaffold forming a triazole ring. Owing to its efficiency and versatility, this reaction and the products, triazole-containing heterocycles, have immense importance in medicinal chemistry. Copper is the only known catalyst to carry out this reaction, the mechanism of which remains unclear. We report here that the `click reactions' can also be catalysed by silver halides in non-aqueous medium. It constitutes an alternative to the well-known CuAAC click reaction. The yield of the reaction varies on the type of counter ion present in the silver salt. This reaction exhibits significant features, such as high regioselectivity, mild reaction conditions, easy availability of substrates and reasonably good yields. In this communication, the findings of a new catalyst along with the effect of solvent and counter ions will help to decipher the still obscure mechanism of this important reaction.

  9. Experimental and kinetic modelling studies on the acid-catalysed hydrolysis of the water hyacinth plant to levulinic acid.

    Science.gov (United States)

    Girisuta, B; Danon, B; Manurung, R; Janssen, L P B M; Heeres, H J

    2008-11-01

    A comprehensive experimental and modelling study on the acid-catalysed hydrolysis of the water hyacinth plant (Eichhornia crassipes) to optimise the yield of levulinic acid (LA) is reported (T=150-175 degrees CH2SO4 = 0.1-1M, water hyacinth intake=1-5wt%). At high acid concentrations (>0.5M), LA was the major organic acid whereas at low acid concentrations (acid instead of LA was favoured. The highest yield of LA was 53mol% (35wt%) based on the amount of C6-sugars in the water hyacinth (T=175 degrees CH2SO4 =1M , water hyacinth intake=1wt%). The LA yield as a function of the process conditions was modelled using a kinetic model originally developed for the acid-catalysed hydrolysis of cellulose and good agreement between the experimental and modelled data was obtained.

  10. Flavan-3-ols isolated from some medicinal plants inhibiting COX-1 and COX-2 catalysed prostaglandin biosynthesis.

    Science.gov (United States)

    Noreen, Y; Serrano, G; Perera, P; Bohlin, L

    1998-08-01

    Extracts from the four plant species Atuna racemosa Raf. ssp. racemosa, Syzygium corynocarpum (A. Gray) C. Muell., Syzygium malaccense (L.) Merr. & Perry and Vantanea peruviana Macbr., traditionally used for inflammatory conditions, were fractionated using a cyclooxygenase-1 catalysed prostaglandin biosynthesis in vitro assay. The flavan-3-ol derivatives (+)-catechin, (+)-gallocatechin, 4'-O-Me-ent-gallocatechin, ouratea-catechin and ouratea-proanthocynidin A were isolated as active principles. The IC50 values ranged from 3.3 microM to 138 microM whilst indomethacin under the same test conditions had an IC50 value of 1.1 microM. The flavonol rhamnosides mearnsitrin, myricitrin and quercitrin were also isolated. When further tested for inhibitory effect on cyclooxygenase-2 catalysed prostaglandin biosynthesis, the five flavan-3-ol derivatives exhibited from equal to weaker inhibitory potencies, as compared to their cyclooxygenase-1 inhibitory effects. The flavonol rhamnosides were inactive towards both enzymes.

  11. Understanding titanium-catalysed radical-radical reactions: a DFT study unravels the complex kinetics of ketone-nitrile couplings.

    Science.gov (United States)

    Streuff, Jan; Himmel, Daniel; Younas, Sara L

    2018-04-03

    The computational investigation of a titanium-catalysed reductive radical-radical coupling is reported. The results match the conclusions from an earlier experimental study and enable a further interpretation of the previously observed complex reaction kinetics. Furthermore, the interplay between neutral and cationic reaction pathways in titanium(iii)-catalysed reactions is investigated for the first time. The results show that hydrochloride additives and reaction byproducts play an important role in the respective equilibria. A full reaction profile is assembled and the computed activation barrier is found to be in reasonable agreement with the experiment. The conclusions are of fundamental importance to the field of low-valent titanium catalysis and the understanding of related catalytic radical-radical coupling reactions.

  12. An efficient one-pot multi component synthesis of polyhydroquinoline derivatives through Hantzsch reaction catalysed by Gadolinium triflate

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2017-02-01

    Full Text Available Gadolinium(III trifluoromethanesulfonate (Gadolinium triflate Gd(OTf3 catalysed efficient Hantzsch reaction via four-component coupling reactions of aldehydes, 5,5-dimethyl-1,3-cyclohexaedione (dimedone, ethyl acetoacetate and ammonium acetate at ambient temperature was described as the preparation of polyhydroquinoline derivatives. The process presented here is operationally simple, environmentally benign and has excellent yield. Furthermore, the catalyst can be recovered conveniently and reused efficiently.

  13. Appearance and distribution of regioisomers in metallo- and serine-protease-catalysed acylation of sucrose in N,N-dimethylformamide

    DEFF Research Database (Denmark)

    Lie, Aleksander; Meyer, Anne S.; Pedersen, Lars Haastrup

    2014-01-01

    The appearance and distribution of monoester regioisomers were investigated in the virtually irreversible acylation of sucrose with the enol ester, vinyl laurate, as acyl donor catalysed by serine proteases and a metalloprotease in the hydrophilic, aprotic solvent N,N-dimethylformamide. Sucrose l...... without protein in the reaction mixture appeared to be catalysed in the presence of aluminosilicate molecular sieves. Non-catalytic protein in the reaction medium seemed to lower the catalytic activity of the molecular sieves....

  14. Direct metal laser sintering: a digitised metal casting technology.

    Science.gov (United States)

    Venkatesh, K Vijay; Nandini, V Vidyashree

    2013-12-01

    Dental technology is undergoing advancements at a fast pace and technology is being imported from various other fields. One such imported technology is direct metal laser sintering technology for casting metal crowns. This article will discuss the process of laser sintering for making metal crowns and fixed partial dentures with a understanding of their pros and cons.

  15. An ecotoxicological study on tin- and bismuth-catalysed PDMS based coatings containing a surface-active polymer.

    Science.gov (United States)

    Pretti, Carlo; Oliva, Matteo; Mennillo, Elvira; Barbaglia, Martina; Funel, Marco; Reddy Yasani, Bhaskar; Martinelli, Elisa; Galli, Giancarlo

    2013-12-01

    Novel films were prepared by condensation curing reaction of a poly(dimethyl siloxane) (PDMS) matrix with bismuth neodecanoate and dibutyltin diacetate catalysts. An ecotoxicological study was performed on the leachates of the coatings using the bacterium Vibrio fischeri, the unicellular alga Dunaliella tertiolecta, the crustacean Artemia salina and the fish Sparus aurata (larvae) as testing organisms. A copper-based self-polishing commercial paint was also tested as reference. The results showed that the tin-catalysed coatings and the copper paint were highly toxic against at least two of the four test organisms, whereas bismuth-catalysed coatings did not show any toxic effect. Moreover, the same biological assessment was also carried out on PDMS coatings containing a surface-active fluorinated polymer. The toxicity of the entire polymeric system resulted only from the tin catalyst used for the condensation curing reaction, as the bismuth catalysed coatings incorporating the surface-active polymer remained atoxic toward all the tested organisms. © 2013 Elsevier Inc. All rights reserved.

  16. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme

    Science.gov (United States)

    Gallage, Nethaji J.; Hansen, Esben H.; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-01-01

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco. PMID:24941968

  17. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme.

    Science.gov (United States)

    Gallage, Nethaji J; Hansen, Esben H; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-06-19

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco.

  18. Organising nursing practice into care models that catalyse quality: A clinical nurse leader case study.

    Science.gov (United States)

    Bender, Miriam; Spiva, LeeAnna; Su, Wei; Hites, Lisle

    2018-02-09

    To determine the power of a conceptual clinical nurse leader practice model to explain the care model's enactment and trajectory in real world settings. How nursing, organised into specific models of care, functions as an organisational strategy for quality is not well specified. Clinical nurse leader integrated care delivery is one emerging model with growing adoption. A recently validated clinical nurse leader practice model conceptualizes the care model's characteristics and hypothesizes their mechanisms of action. Pattern matching case study design and mixed methods were used to determine how the care model's constructs were operationalized in one regional United States health system that integrated clinical nurse leaders into their care delivery system in 2010. The findings confirmed the empirical presence of all clinical nurse leader practice model constructs and provided a rich description of how the health system operationalized the constructs in practice. The findings support the hypothesized model pathway from Clinical Nurse Leader structuring to Clinical Nurse Leader practice and outcomes. The findings indicate analytic generalizability of the clinical nurse leader practice model. Nursing practice organised to focus on microsystem care processes can catalyse multidisciplinary engagement with, and consistent enactment of, quality practices. The model has great potential for transferability across diverse health systems. © 2018 John Wiley & Sons Ltd.

  19. Biodiesel Derive Bio-oil of Hermetia illucens Pre-pupae Catalysed by Sulphonated Biochar

    Science.gov (United States)

    Yoong Leong, Siew; Chong, Soo Shin; Chin, Kah Seng

    2018-03-01

    This study investigates the development of biochar catalyst from bamboo applied for biodiesel synthesis. A non-conventional biodiesel feedstock was used in the in-situ transesterification reaction. This non-conventional feedstock is obtained from an insect's fly, the Hermetia illucens fly. Biochar derived from bamboo has been investigated as a promising catalyst for biodiesel synthesis. The biochar acid catalysts were prepared by sulphonation via impregnation with concentrated sulphuric acid. The prepared catalysts were investigated for their performance to catalyse in-situ transesterification via ultra-sonication of Hermetia illucens bio-oil. The effects of carbonisation time (1 hour and 2 hour) and temperature (400°C, 500°C and 600°C) as well as catalyst loading (5-20 wt% on oil basis) on the transesterification yield were studied. Result showed that the highest yield of FAME obtained was 95.6% with catalyst loading of 15 wt% carbonized at 500°C for 2 hours. Sharp band of methyl ester functional groups were observed in the FTIR spectra at 1735-1750cm-1. The composition of this methyl ester was further deduced using gas chromatography and the fatty acid was predominantly lauric acid.

  20. Response surface methodological approach for optimizing production of geranyl propionate catalysed by carbon nanotubes nanobioconjugates

    International Nuclear Information System (INIS)

    Mohamad, NurRoyhaila; Mahat, Naji Arafat; Wahab, Roswanira Abdul; Huyop, Fahrul; Aboul-Enein, Hassan Youssef

    2015-01-01

    Terpene esters of short-chain fatty acids are essential oils that have big importance in food, cosmetic and pharmaceutical industries as flavours and fragrances. Geraniol and citronellol are the most important substances. Considering the everincreasing demand for such products, their enzymatic production from natural raw materials by using environmentally friendly and economically attractive processes may prove advantageous. In this contribution, we would like to present an alternative option for the production of geranyl propionate using nanobioconjugates consisting of Candida rugosa lipase adsorbed onto multi-walled carbon nanotubes (CRL-MWCNTs). We investigated the effects of incubation time, temperature, solvent log P and substrate molar ratio, and determined the optimum conditions. The yield of geranyl propionate catalysed by CRL-MWCNTs nanobioconjugates was significantly influenced by two factors, namely, temperature and time of the reaction. Under the optimum reaction conditions of 55 C, solvent n-heptane (log P D 4.0), geraniol to propionic acid molar ratio of 5:1 and reaction time of 6 h, the use of CRL-MWCNTs resulted in 51.3% production of geranyl propionate. Therefore, the investigation revealed that geranyl propionate was successfully synthesized under mild conditions with reasonably high yield within a short period of time. The CRL-MWCNTs nanobioconjugates demonstrated a potential as economical and environmentally smarter biocatalysts for the production of geranyl propionate. Keywords: nanobioconjugates

  1. Pd-catalysed ligand-enabled carboxylate-directed highly regioselective arylation of aliphatic acids

    Science.gov (United States)

    Zhu, Yan; Chen, Xiaolan; Yuan, Chunchen; Li, Guobao; Zhang, Jingyu; Zhao, Yingsheng

    2017-04-01

    α-amino acids bearing aromatic side chains are important synthetic units in the synthesis of peptides and natural products. Although various β-C-H arylation methodologies for amino acid derivatives involving the assistance of directing groups have been extensively developed, syntheses that directly employ N-protected amino acids as starting materials remain rare. Herein, we report an N-acetylglycine-enabled Pd-catalysed carboxylate-directed β-C(sp3)-H arylation of aliphatic acids. In this way, various non-natural amino acids can be directly prepared from phthaloylalanine in one step in good to excellent yields. Furthermore, a series of aliphatic acids have been shown to be amenable to this transformation, affording β-arylated propionic acid derivatives in moderate to good yields. More importantly, this ligand-enabled direct β-C(sp3)-H arylation could be easily scaled-up to 10 g under reflux conditions, highlighting the potential utility of this synthetic method.

  2. Asymmetric Suzuki-Miyaura coupling of heterocycles via Rhodium-catalysed allylic arylation of racemates

    Science.gov (United States)

    Schäfer, Philipp; Palacin, Thomas; Sidera, Mireia; Fletcher, Stephen P.

    2017-06-01

    Using asymmetric catalysis to simultaneously form carbon-carbon bonds and generate single isomer products is strategically important. Suzuki-Miyaura cross-coupling is widely used in the academic and industrial sectors to synthesize drugs, agrochemicals and biologically active and advanced materials. However, widely applicable enantioselective Suzuki-Miyaura variations to provide 3D molecules remain elusive. Here we report a rhodium-catalysed asymmetric Suzuki-Miyaura reaction with important partners including aryls, vinyls, heteroaromatics and heterocycles. The method can be used to couple two heterocyclic species so the highly enantioenriched products have a wide array of cores. We show that pyridine boronic acids are unsuitable, but they can be halogen-modified at the 2-position to undergo reaction, and this halogen can then be removed or used to facilitate further reactions. The method is used to synthesize isoanabasine, preclamol, and niraparib--an anticancer agent in several clinical trials. We anticipate this method will be a useful tool in drug synthesis and discovery.

  3. Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate.

    Science.gov (United States)

    North, Michael; Omedes-Pujol, Marta

    2010-11-03

    Propylene carbonate can be used as a green solvent for the asymmetric synthesis of cyanohydrin trimethylsilyl ethers from aldehydes and trimethylsilyl cyanide catalysed by VO(salen)NCS, though reactions are slower in this solvent than the corresponding reactions carried out in dichloromethane. A mechanistic study has been undertaken, comparing the catalytic activity of VO(salen)NCS in propylene carbonate and dichloromethane. Reactions in both solvents obey overall second-order kinetics, the rate of reaction being dependent on the concentration of both the aldehyde and trimethylsilyl cyanide. The order with respect to VO(salen)NCS was determined and found to decrease from 1.2 in dichloromethane to 1.0 in propylene carbonate, indicating that in propylene carbonate, VO(salen)NCS is present only as a mononuclear species, whereas in dichloromethane dinuclear species are present which have previously been shown to be responsible for most of the catalytic activity. Evidence from ⁵¹V NMR spectroscopy suggested that propylene carbonate coordinates to VO(salen)NCS, blocking the free coordination site, thus inhibiting its Lewis acidity and accounting for the reduction in catalytic activity. This explanation was further supported by a Hammett analysis study, which indicated that Lewis base catalysis made a much greater contribution to the overall catalytic activity of VO(salen)NCS in propylene carbonate than in dichloromethane.

  4. Co(salen catalysed oxidation of synthetic lignin-like polymer: Co(salen effects

    Directory of Open Access Journals (Sweden)

    Liu Jing

    2012-01-01

    Full Text Available In this paper, Co(salen [salen = N, N’-bis(salicylideneethylenediamine] complex was studied as oxygen activators for the catalytic oxidation of a lignin model polymer using water as the solvent, with molecular oxygen and hydrogen peroxide as the oxidants. The effect of Co(salen on oxidation was tested by spectroscopic methods (FTIR, 13C-NMR and GC-MS. The reactions catalysed by Co(salen included Cα-alcohol oxidation, Cα-Cβ side chain cleavage, demethoxylation, aromatic ring cleavage, and β-O-4 cleavage. In addition to the mechanistic information obtained, the effect of Co(salen suggests that Co(salen can be important for the catalytic oxidation, as they affect the oxidation of lignin model polymer. The reaction performed in the presence of Co(salen was more efficient than without it. The formation of aldehyde in the catalytic oxidation, as shown by GC-MS, could be identified as the mechanism of oxidative cleavage of the β-O-4 bonds.

  5. Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates

    Science.gov (United States)

    Gao, Bing; Zhang, Linda; Zheng, Qinheng; Zhou, Feng; Klivansky, Liana M.; Lu, Jianmei; Liu, Yi; Dong, Jiajia; Wu, Peng; Sharpless, K. Barry

    2017-11-01

    Polysulfates and polysulfonates possess exceptional mechanical properties making them potentially valuable engineering polymers. However, they have been little explored due to a lack of reliable synthetic access. Here we report bifluoride salts (Q+[FHF]-, where Q+ represents a wide range of cations) as powerful catalysts for the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl silyl ethers and aryl fluorosulfates (or alkyl sulfonyl fluorides). The bifluoride salts are significantly more active in catalysing the SuFEx reaction compared to organosuperbases, therefore enabling much lower catalyst-loading (down to 0.05 mol%). Using this chemistry, we are able to prepare polysulfates and polysulfonates with high molecular weight, narrow polydispersity and excellent functional group tolerance. The process is practical with regard to the reduced cost of catalyst, polymer purification and by-product recycling. We have also observed that the process is not sensitive to scale-up, which is essential for its future translation from laboratory research to industrial applications.

  6. Palladium-catalysed transannular C-H functionalization of alicyclic amines

    Science.gov (United States)

    Topczewski, Joseph J.; Cabrera, Pablo J.; Saper, Noam I.; Sanford, Melanie S.

    2016-03-01

    Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

  7. Natural spectroscopic hydrogen isotope transfer in alcohol dehydrogenase-catalysed reduction

    International Nuclear Information System (INIS)

    Ben-Li Zhang; Pionnier, S.

    2002-01-01

    The enantiomeric purity of natural α-mono deuterated enantiomers, (R) and (S)ethanol-1-d 1 , in the alcohol produced by sugar fermentation with yeast was studied by 2 H NMR using their esters derived from optical mandelic acid. The results of isotope tracing experiments show that the transfer pathways of the two eantiotopic hydrogens of the methylene group are different. It was observed that (S)-deuterium comes only from the medium water. The (R)-deuterium transferred by NADH in alcohol dehydrogenase reduction of the acetaldehyde is complex origin. Some of them originates from carbon bound hydrogen of the sugar, especially from C(4) position of glucose and most of them comes from water. Only a small portion of the NADH deuterium is incorporated indirectly from water through enzyme catalysed exchange between the pro-S site of NADH and flavin. When a carbonyl compound (ethyl acetoacetate) was reduced under the same conditions during the alcoholic fermentation, among the NADH-transferred deuterium, only a small portion comes from water while most comes from the unexchangeable positions of the glucose. (author)

  8. Glycolysis of carbon fiber-epoxy unidirectional mat catalysed by sodium hydroxide

    Science.gov (United States)

    Zaini, Mariana Binti Mohd; Badri, Khairiah Haji

    2014-09-01

    This study was conducted to recycle carbon fibre-epoxy (CFRP) composite in woven sheet/ mat form. The CFRP was recycled through glycolysis with polyethlyene glycol (PEG 200) as the solvent. The CFRP was loaded into the solvent at a ratio of 4:1 (w/w). PEG200 was diluted with water to a ratio of 80:20 (v/v). This reaction was catalysed by sodium hydroxide (NaOH) solution with varying concentrations at 1.5, 1.7 and 1.9% (w/v). The glycolysis was conducted at 180-190 °C. The recovered CF (rCF) was analysed using Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX) while the degraded solution was analysed using FTIR and the epoxy content was determined. The FTIR spectrum of the rCF exhibited the disappearance of the COC peak belonged to epoxy and supported by the SEM micrographs that showed clear rCF. On the other hand, the analysed filtrate detected the disappearance of oxygen peak element in the EDX spectrum for all rCF samples. This gave an indication that the epoxy resin has been removed from the surface of the carbon fiber.

  9. Glycolysis of carbon fiber-epoxy unidirectional mat catalysed by sodium hydroxide

    International Nuclear Information System (INIS)

    Zaini, Mariana Binti Mohd; Badri, Khairiah Haji

    2014-01-01

    This study was conducted to recycle carbon fibre-epoxy (CFRP) composite in woven sheet/ mat form. The CFRP was recycled through glycolysis with polyethlyene glycol (PEG 200) as the solvent. The CFRP was loaded into the solvent at a ratio of 4:1 (w/w). PEG200 was diluted with water to a ratio of 80:20 (v/v). This reaction was catalysed by sodium hydroxide (NaOH) solution with varying concentrations at 1.5, 1.7 and 1.9% (w/v). The glycolysis was conducted at 180-190 °C. The recovered CF (rCF) was analysed using Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX) while the degraded solution was analysed using FTIR and the epoxy content was determined. The FTIR spectrum of the rCF exhibited the disappearance of the COC peak belonged to epoxy and supported by the SEM micrographs that showed clear rCF. On the other hand, the analysed filtrate detected the disappearance of oxygen peak element in the EDX spectrum for all rCF samples. This gave an indication that the epoxy resin has been removed from the surface of the carbon fiber

  10. Partial differential equations

    Indian Academy of Sciences (India)

    been a regular stream of high quality work done in these areas. Talking of elliptic partial differen- tial equations, important contributions have been made in the ...... [6] Evans L C 1992 Periodic homogenisation of certain fully nonlinear partial differential equations; Proc. Roy. Soc. Edinburgh Sect. A 120 No. 3–4, 245–265.

  11. Characterization and Structure Prediction of Partial Length Protein Sequences of pcoA, pcoR and chrB Genes from Heavy Metal Resistant Bacteria from the Klip River, South Africa

    Directory of Open Access Journals (Sweden)

    Patience Chihomvu

    2015-04-01

    Full Text Available The Klip River has suffered from severe anthropogenic effects from industrial activities such as mining. Long-term exposure to heavy metal pollution has led to the development of heavy metal resistant strains of Pseudomonas sp. KR23, Lysinibacillus sp. KR25, and E. coli KR29. The objectives of this study were to characterize the genetics of copper and chromate resistance of the isolates. Copper and chromate resistance determinants were cloned and sequenced. Open reading frames (ORFs related to the genes CopA and CopR were identified in E. coli KR29, PcoA in Lysinibacillus sp. KR25 and none related to chromate resistance were detected. The 3D-models predicted by I-TASSER disclose that the PcoA proteins consist of β-sheets, which form a part of the cupredoxin domain of the CopA copper resistance family of genes. The model for PcoR_29 revealed the presence of a helix turn helix; this forms part of a DNA binding protein, which is part of a heavy metal transcriptional regulator. The bacterial strains were cured using ethidium bromide. The genes encoding for heavy metal resistance and antibiotic resistance were found to be located on the chromosome for both Pseudomonas sp. (KR23 and E. coli (KR29. For Lysinibacillus (KR25 the heavy metal resistance determinants are suspected to be located on a mobile genetic element, which was not detected using gel electrophoresis.

  12. The Lausanne Institutional Biobank: a new resource to catalyse research in personalised medicine and pharmaceutical sciences.

    Science.gov (United States)

    Mooser, Vincent; Currat, Christine

    2014-01-01

    Breakthrough technologies which now enable the sequencing of individual genomes will irreversibly modify the way diseases are diagnosed, predicted, prevented and treated. For these technologies to reach their full potential requires, upstream, access to high-quality biomedical data and samples from large number of properly informed and consenting individuals and, downstream, the possibility to transform the emerging knowledge into a clinical utility. The Lausanne Institutional Biobank was designed as an integrated, highly versatile infrastructure to harness the power of these emerging technologies and catalyse the discovery and development of innovative therapeutics and biomarkers, and advance the field of personalised medicine. Described here are its rationale, design and governance, as well as parallel initiatives which have been launched locally to address the societal, ethical and technological issues associated with this new bio-resource. Since January 2013, inpatients admitted at Lausanne CHUV University Hospital have been systematically invited to provide a general consent for the use of their biomedical data and samples for research, to complete a standardised questionnaire, to donate a 10-ml sample of blood for future DNA extraction and to be re-contacted for future clinical trials. Over the first 18 months of operation, 14,459 patients were contacted, and 11,051 accepted to participate in the study. This initial 18-month experience illustrates that a systematic hospital-based biobank is feasible; it shows a strong engagement in research from the patient population in this University Hospital setting, and the need for a broad, integrated approach for the future of medicine to reach its full potential.

  13. Kinetics of acyl transfer reactions in organic media catalysed by Candida antarctica lipase B.

    Science.gov (United States)

    Martinelle, M; Hult, K

    1995-09-06

    The acyl transfer reactions catalysed by Candida antartica lipase B in organic media followed a bi-bi ping-pong mechanism, with competitive substrate inhibition by the alcohols used as acyl acceptors. The effect of organic solvents on Vm and Km was investigated. The Vm values in acetonitrile was 40-50% of those in heptane. High Km values in acetonitrile compared to those in heptane could partly be explained by an increased solvation of the substrates in acetonitrile. Substrate solvation caused a 10-fold change in substrate specificity, defined as (Vm/Km)ethyl octanoate/(Vm/Km)octanoic acid, going from heptane to acetonitrile. Deacylation was the rate determining step for the acyl transfer in heptane with vinyl- and ethyl octanoate as acyl donors and (R)-2-octanol as acyl acceptor. With 1-octanol, a rate determining deacylation step in heptane was indicated using the same acyl donors. Using 1-octanol as acceptor in heptane, S-ethyl thiooctanoate had a 25- to 30-fold lower Vm/Km value and vinyl octanoate a 4-fold higher Vm/Km value than that for ethyl octanoate. The difference showed to be a Km effect for vinyl octanoate and mainly a Km effect for S-ethyl thiooctanoate. The Vm values of the esterification of octanoic acid with different alcohols was 10-30-times lower than those for the corresponding transesterification of ethyl octanoate. The low activity could be explained by a low pH around the enzyme caused by the acid or a withdrawing of active enzyme by nonproductive binding by the acid.

  14. Catalyse homogène supportée Supported Homogeneous Catalysis

    Directory of Open Access Journals (Sweden)

    Commereuc D.

    2006-11-01

    Full Text Available Les catalyseurs complexes de coordination en phase homogène offrent des performances d'activité et de sélectivité en général meilleures que celles des catalyseurs hétérogènes obtenus par les méthodes plus classiques de dépôt par voie thermique. Ils posent cependant, en raison de leur valeur plus élevée, des problèmes de récupération ou de recyclage. Le coût de la voie homogène entraîne alors bien souvent le choix de la méthode hétérogène classique, au détriment de performances plus séduisantes. On envisage ici les solutions offertes par la catalyse homogène supportée, ainsi que les difficultés rencontrées lors de la synthèse et de l'utilisation de ce type nouveau de catalyseur. Complex homogeneous-phase coordination catalysts generally have better activity and selectivity performances than those of heterogeneous catalysts produced by more conventional methods of thermal depositing. However, because of their higher value they raise problems of recovery or recycling. The cost of homogeneous catalysis thus often leads to the choice of the conventional heterogeneous method, to the detriment of more attractive performances. This article takes up the solutions offered by supported homogeneous catalysis as well as the difficulties encountered during the synthesis and use of this new type of catalyst.

  15. Creating a climate that catalyses healthcare innovation in the United Kingdom - learning lessons from international innovators.

    Science.gov (United States)

    Cresswell, Kathrin; Cunningham-Burley, Sarah; Sheikh, Aziz

    2017-01-25

    The United Kingdom (UK) lags behind other high-income countries in relation to technological innovation in healthcare. In order to inform UK strategy on how to catalyse innovation, we sought to understand what national strategies can help to promote a climate for innovation in healthcare settings by extracting lessons for the UK from international innovators. We undertook a series of qualitative semi-structured interviews with senior international innovators from a range of health related policy, care/service delivery, commercial and academic backgrounds. Thematic analysis helped to explore how different stakeholder groups could facilitate/inhibit innovation at individual, organisational, and wider societal levels. We conducted 14 interviews and found that a conducive climate for healthcare innovation comprised of national/regional strategies stimulating commercial competition, promoting public/private relationships, and providing central direction (e.g. incentives for adoption and regulation through standards) without being restrictive. Organisational attitudes with a willingness to experiment and to take risks were also seen as important, but a bottom-up approach to innovation, based on the identification of clinical need, was seen as a crucial first step to construct relevant national policies.  There is now a need to create mechanisms through which frontline National Health Service staff in relation can raise ideas/concerns and suggest opportunities for improvement, and then build national innovation environments that seek to address these needs. This should be accompanied by creating competitive health technology markets to stimulate a commercial environment that attracts high-quality health information technology experts and innovators working in partnership with staff and patients.

  16. Solvent-free lipase catalysed synthesis of diacylgycerols as low-calorie food ingredients

    Directory of Open Access Journals (Sweden)

    Luis eVazquez

    2016-02-01

    Full Text Available Problems derived from obesity and overweight have recently promoted the development of fat substitutes and other low-calorie foods. On the one hand, fats with short and medium chain fatty acids are a source of quick energy, easily hydrolyzable and hardly stored as fat. Furthermore, 1,3-diacylglycerols are not hydrolyzed to 2-monoacylglycerols in the gastrointestinal tract, reducing the formation of chylomicron and lowers the serum level of triacylglycerols by decreasing its re-synthesis in the enterocyte and its metabolism and absorption by the enterocyte are limited in comparison with the TAG, reducing chylomicron formation. In this work these two effects were combined to synthesize short and medium chain 1,3 diacylglycerols, leading to a product with great potential as for their low-calorie properties. Lipase catalysed transesterification reactions were performed between short and medium chain fatty acid ethyl esters and glycerol. Different variables were investigated such as the type of biocatalyst, the molar ratio FAEE:glycerol, the adsorption of glycerol on silica gel or the addition of lecithin. Best reaction conditions were evaluated considering the conversion intopercentage of 1,3-DAG produced and the reaction rate. Except Novozym 435 (Candida antarctica, other lipases required the adsorption of glycerol on silica gel to form acylglycerols. Lipases that gave the best results with adsorption were Novozym 435 and Lipozyme RM IM (Rhizomucor miehei with 52% and 60.7% of DAG at 32 h, respectively. Because of its specificity for sn-1 and sn-3 positions, lipases leading to a higher proportion of 1,3-DAG vs 1,2-DAG were Lipozyme RM IM (39.8% and 20.9%, respectively and Lipase PLG (Alcaligenes sp. (35.9% and 19.3%, respectively. By adding 1% (w/w of lecithin to the reaction with Novozym 435 and raw glycerol the reaction rate was considerably increased from 41.7% to 52.8% DAG at 24 h.

  17. DEVICE FOR CONTROL OF OXYGEN PARTIAL PRESSURE

    Science.gov (United States)

    Bradner, H.; Gordon, H.S.

    1957-12-24

    A device is described that can sense changes in oxygen partial pressure and cause a corresponding mechanical displacement sufficient to actuate meters, valves and similar devices. A piston and cylinder arrangement contains a charge of crystalline metal chelate pellets which have the peculiar property of responding to variations in the oxygen content of the ambient atmosphere by undergoing a change in dimension. A lever system amplifies the relative displacement of the piston in the cylinder, and actuates the controlled valving device. This partial pressure oxygen sensing device is useful in controlled chemical reactions or in respiratory devices such as the oxygen demand meters for high altitude aircraft.

  18. Successful removable partial dentures.

    Science.gov (United States)

    Lynch, Christopher D

    2012-03-01

    Removable partial dentures (RPDs) remain a mainstay of prosthodontic care for partially dentate patients. Appropriately designed, they can restore masticatory efficiency, improve aesthetics and speech, and help secure overall oral health. However, challenges remain in providing such treatments, including maintaining adequate plaque control, achieving adequate retention, and facilitating patient tolerance. The aim of this paper is to review the successful provision of RPDs. Removable partial dentures are a successful form of treatment for replacing missing teeth, and can be successfully provided with appropriate design and fabrication concepts in mind.

  19. Hyperbolic partial differential equations

    CERN Document Server

    Witten, Matthew

    1986-01-01

    Hyperbolic Partial Differential Equations III is a refereed journal issue that explores the applications, theory, and/or applied methods related to hyperbolic partial differential equations, or problems arising out of hyperbolic partial differential equations, in any area of research. This journal issue is interested in all types of articles in terms of review, mini-monograph, standard study, or short communication. Some studies presented in this journal include discretization of ideal fluid dynamics in the Eulerian representation; a Riemann problem in gas dynamics with bifurcation; periodic M

  20. Beginning partial differential equations

    CERN Document Server

    O'Neil, Peter V

    2011-01-01

    A rigorous, yet accessible, introduction to partial differential equations-updated in a valuable new edition Beginning Partial Differential Equations, Second Edition provides a comprehensive introduction to partial differential equations (PDEs) with a special focus on the significance of characteristics, solutions by Fourier series, integrals and transforms, properties and physical interpretations of solutions, and a transition to the modern function space approach to PDEs. With its breadth of coverage, this new edition continues to present a broad introduction to the field, while also addres

  1. Acceptability of maxillary major connectors in removable partial ...

    African Journals Online (AJOL)

    Conclusions: The metal bar major connector was the most acceptable maxillary major connector while acrylic resin plate was more acceptable than metal plate maxillary major connector. It also confirmed the influence of connector design on patient acceptance of removable partial denture. African Health Sciences Vol.

  2. Partial knee replacement

    Science.gov (United States)

    ... candidate for partial knee replacement and what the success rate is for your condition. Alternative Names Unicompartmental ... ADAM Health Solutions. About MedlinePlus Site Map FAQs Customer Support Get email updates Subscribe to RSS Follow ...

  3. Partial knee replacement - slideshow

    Science.gov (United States)

    ... medlineplus.gov/ency/presentations/100225.htm Partial knee replacement - series—Normal anatomy To use the sharing features ... M. Editorial team. Related MedlinePlus Health Topics Knee Replacement A.D.A.M., Inc. is accredited by ...

  4. Beginning partial differential equations

    CERN Document Server

    O'Neil, Peter V

    2014-01-01

    A broad introduction to PDEs with an emphasis on specialized topics and applications occurring in a variety of fields Featuring a thoroughly revised presentation of topics, Beginning Partial Differential Equations, Third Edition provides a challenging, yet accessible,combination of techniques, applications, and introductory theory on the subjectof partial differential equations. The new edition offers nonstandard coverageon material including Burger's equation, the telegraph equation, damped wavemotion, and the use of characteristics to solve nonhomogeneous problems. The Third Edition is or

  5. Partial dynamical symmetry

    International Nuclear Information System (INIS)

    Alhassid, Y.; Leviatan, A.

    1993-01-01

    A novel symmetry structure, partial dynamical symmetry is introduced. The Hamiltonian is not invariant under the transformations of a group G and irreps of G are mixed in its eigenstates. it possesses, however, a partial set of eigenstates which do have good symmetry and can be labeled by irreps of G. A general algorithm to construct such Hamiltonians for a semi-simple group G is presented. (Author) 6 refs

  6. B-doping of vapour-liquid-solid grown Au-catalysed and Al-catalysed Si nanowires: effects of B2H6 gas during Si nanowire growth and B-doping by a post-synthesis in situ plasma process

    International Nuclear Information System (INIS)

    Whang, S-J; Lee, S; Chi, D-Z; Yang, W-F; Cho, B-J; Liew, Y-F; Kwong, D-L

    2007-01-01

    In this study, B-doping of vapour-liquid-solid (VLS) grown Si nanowires was studied. First, the different effects of B 2 H 6 gas on nanowire structures during VLS growth of both Au-catalysed and Al-catalysed Si nanowires were investigated. While Au-catalysed Si nanowires grown with B 2 H 6 gas reveal significant morphological changes, resulting in cone-shaped nanowires, structures comparable to un-doped nanowires were observed from Al-catalysed Si nanowires, which may be explained by thermodynamic properties of Au and Al catalyst in the presence of boron. In addition, successful incorporation of boron and controllability of its concentration in Si nanowires, maintaining the structural quality of the nanowires, was achieved by a post-synthesis in situ plasma B 2 H 6 doping process

  7. Coordinence en catalyse hétèrogène appliquée Coordination in Applied Heterogeneous Catalysis

    Directory of Open Access Journals (Sweden)

    Montarnal R.

    2006-11-01

    Full Text Available L'exposé concerne l'activation des paraffines et des oléfines en présence d'hydrogène sur les métaux du groupe VIII. L'activation des paraffines fait intervenir les voies d'hydrogénolyse, d'isomérisation et de cyclisation. La profondeur d'hydrogénolyse permet de proposer un classement des métaux selon l'ordre croissant de la force de la liaison, paraffine chimisorbée-métal Pd-Pt-Ir-Rh-Ru-Os-Ni-Co-Fe L'activité spécifique d'hydrogénolyse, portée alors en fonction de la force de cette liaison, passe par un maximum autour de la position de Rh - Ru - Os. Les activités d'isomérisation et de cyclisation passent, par un maximum, pour la position de Pt. On retrouve ainsi la notion de force optimale de chimisorption pour catalyser une transformation précise. Sur la base des notions développées par Pearson, on peut alors considérer que la paraffine chimisorbée intervient plutôt en qualité de base «dure» de telle façon que la force de la liaison paraffine métal, augmente avec le caractère «dur» du métal. L'effet des ligands dans la sphère de coordination du site catalytique est ensuite analysé, en distinguant les ligands introduits lors de la préparation du catalyseur et ceux amenés par la phase réactionnelle. Les modifications ainsi apportées au caractère « dur ou mou » du site catalytique, conduisent à prévoir le sens de variation de l'activité d'hdrogénolyse ou de cyclisation. L'expérience confirme en gros les prévisions. L'étude de l'activation des oléfines est limitée au cas de l'éthylène, pour lequel on examine l'activité de l'hydrogénation et de l'échange éthylène-deutérium. La valeur de la multiplicité de cet échange permet de proposer un classement des métaux selon l'ordre croissant de la force de la liaison oléfine-métal Fe - Co-Ni-Ru-Rh-Os-Ir-Pt L'activité d'hydrogénation portée alors en fonction de la force de cette liaison, passe par un maximum autour (également de la position

  8. N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

    KAUST Repository

    Guo, Hao

    2015-11-16

    An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

  9. Scope and limitations of chiral bis(oxazoline) ligands in the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes

    DEFF Research Database (Denmark)

    Østergaard, N.; Jensen, Jakob Feldthusen; Tanner, David Ackland

    2001-01-01

    A series of derivatives of 3-methyl-2-buten-1-ol has been used to test the scope and limitations of the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes by ethyl diazoacetate in the presence of C-2-symmetric bis(oxazoline) ligands. In the best case, a trans/cis ratio of 91......:9, with 92% ee for the major isomer, was obtained from the reaction of the p-methoxybenzoate derivative. The highest ee was 95%, for the trans isomer of a 80:20 diastereomer mixture (acetate derivative)....

  10. Removable partial dentures: use of rapid prototyping.

    Science.gov (United States)

    Lima, Julia Magalhaes Costa; Anami, Lilian Costa; Araujo, Rodrigo Maximo; Pavanelli, Carlos A

    2014-10-01

    The CAD/CAM technology associated with rapid prototyping (RP) is already widely used in the fabrication of all-ceramic fixed prostheses and in the biomedical area; however, the use of this technology for the manufacture of metal frames for removable dentures is new. This work reports the results of a literature review conducted on the use of CAD/CAM and RP in the manufacture of removable partial dentures. © 2014 by the American College of Prosthodontists.

  11. Alanine aminotransferase catalyses the breakdown of alanine after hypoxia in Arabidopsis thaliana.

    Science.gov (United States)

    Miyashita, Yo; Dolferus, Rudy; Ismond, Kathleen P; Good, Allen G

    2007-03-01

    Alanine aminotransferase (AlaAT) catalyses the reversible transfer of an amino group from glutamate to pyruvate to form 2-oxoglutarate and alanine. The regulation of AlaAT in several plant species has been studied in response to low-oxygen stress, light and nitrogen application. In this study, induction of Arabidopsis AlaAT1 and AlaAT2 during hypoxia was observed at the transcriptional level, and an increase in enzyme activity was detected in hypoxically treated roots. In addition, the tissue-specific expression of AlaAT1 and AlaAT2 was analysed using promoter:GUS fusions. The GUS staining patterns indicated that both AlaAT genes are expressed predominantly in vascular tissues. We manipulated AlaAT expression to determine the relative importance of this enzyme in low-oxygen stress tolerance and nitrogen metabolism. This was done by analysing T-DNA mutants and over-expressing barley AlaAT in Arabidopsis. The AlaAT1 knockout mutant (alaat1-1) showed a dramatic reduction in AlaAT activity, suggesting that AlaAT1 is the major AlaAT isozyme in Arabidopsis. Over-expression of barley AlaAT significantly increased the AlaAT activity in the transgenic plants. These plants were analysed for metabolic changes over a period of hypoxic stress and during their subsequent recovery. The results showed that alaat1-1 plants accumulate more alanine than wild-type plants during the early phase of hypoxia, and the decline in accumulated alanine was delayed in the alaat1-1 line during the post-hypoxia recovery period. When alanine was supplied as the nitrogen source, alaat1-1 plants utilized alanine less efficiently than wild-type plants did. These results indicate that the primary role of AlaAT1 is to break down alanine when it is in excess. Therefore, AlaAT appears to be crucial for the rapid conversion of alanine to pyruvate during recovery from low-oxygen stress.

  12. Algebraic partial Boolean algebras

    CERN Document Server

    Smith, D

    2003-01-01

    Partial Boolean algebras, first studied by Kochen and Specker in the 1960s, provide the structure for Bell-Kochen-Specker theorems which deny the existence of non-contextual hidden variable theories. In this paper, we study partial Boolean algebras which are 'algebraic' in the sense that their elements have coordinates in an algebraic number field. Several of these algebras have been discussed recently in a debate on the validity of Bell-Kochen-Specker theorems in the context of finite precision measurements. The main result of this paper is that every algebraic finitely-generated partial Boolean algebra B(T) is finite when the underlying space H is three-dimensional, answering a question of Kochen and showing that Conway and Kochen's infinite algebraic partial Boolean algebra has minimum dimension. This result contrasts the existence of an infinite (non-algebraic) B(T) generated by eight elements in an abstract orthomodular lattice of height 3. We then initiate a study of higher-dimensional algebraic partial...

  13. Methanol partial oxidation reformer

    Science.gov (United States)

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  14. Partial differential equations

    CERN Document Server

    Evans, Lawrence C

    2010-01-01

    This text gives a comprehensive survey of modern techniques in the theoretical study of partial differential equations (PDEs) with particular emphasis on nonlinear equations. The exposition is divided into three parts: representation formulas for solutions; theory for linear partial differential equations; and theory for nonlinear partial differential equations. Included are complete treatments of the method of characteristics; energy methods within Sobolev spaces; regularity for second-order elliptic, parabolic, and hyperbolic equations; maximum principles; the multidimensional calculus of variations; viscosity solutions of Hamilton-Jacobi equations; shock waves and entropy criteria for conservation laws; and, much more.The author summarizes the relevant mathematics required to understand current research in PDEs, especially nonlinear PDEs. While he has reworked and simplified much of the classical theory (particularly the method of characteristics), he primarily emphasizes the modern interplay between funct...

  15. Production of uranium hexafluoride by the catalysed fluorox process: pilot plant and supporting bench-scale studies

    International Nuclear Information System (INIS)

    Janov, J.; Charlton, B.G.; LePage, A.H.; Vilkaitis, V.K.

    1982-04-01

    The feasibility of producing UF 6 by the catalysed reaction of UF 4 with oxygen (the Fluorox process) was investigated in a 150 mm diameter fluidised bed reactor and in supporting bench-scale experiments. The rate of the Fluorox reaction in batch experiments was increased by an order of magnitude with 1 to 5 per cent catalyst (containing 3 to 4 per cent platinum on alumina). The maximum UF 6 production rate at 650 deg. C was 0.9 kg h -1 . However, the platinum catalyst was completely poisoned after production of only 1 and 20 kg UF 6 per kg of catalyst when using respectively French and British UF 4 . Regeneration of the catalyst was demonstrated to be technically feasible by washing with water or ammonium oxalate solution or treating with hydrogen and hydrogen fluoride at 350-650 deg. C. However, since the very fast rate of poisoning would necessitate higher catalyst concentrations and/or frequent regeneration, the catalysed Fluorox process in unlikely to be economically competitive with the direct fluorination of UF 4

  16. Rapid assembly of functionalised spirocyclic indolines by palladium-catalysed dearomatising diallylation of indoles with allyl acetate.

    Science.gov (United States)

    Dhankher, Persis; Benhamou, Laure; Sheppard, Tom D

    2014-10-06

    Herein, we report the application of allyl acetate to the palladium-catalysed dearomatising diallylation of indoles. The reaction can be carried out by using a readily available palladium catalyst at room temperature, and can be applied to a wide range of substituted indoles to provide access to the corresponding 3,3-diallylindolinines. These compounds are versatile synthetic intermediates that readily undergo Ugi reactions or proline-catalysed asymmetric Mannich reactions. Alternatively, acylation of the 3,3-diallylindolinines with an acid chloride or a chloroformate, followed by treatment with aluminium chloride, enables 2,3-diallylindoles to be prepared. By using ring-closing metathesis, functionalised spirocyclic indoline scaffolds can be accessed from the Ugi products, and a dihydrocarbazole can be prepared from the corresponding 2,3-diallylindole. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  17. A novel Dps-type protein from insect gut bacteria catalyses hydrolysis and synthesis of N-acyl amino acids.

    Science.gov (United States)

    Ping, Liyan; Büchler, Rita; Mithöfer, Axel; Svatos, Ales; Spiteller, Dieter; Dettner, Konrad; Gmeiner, Sophie; Piel, Jörn; Schlott, Bernhard; Boland, Wilhelm

    2007-06-01

    A novel type of a microbial N-acyl amino acid hydrolase (AAH) from insect gut bacteria was purified, cloned and functionally characterized. The enzyme was obtained from Microbacterium arborescens SE14 isolated from the foregut of larvae of the generalist herbivore Spodoptera exigua. The substrates of AAH are N-acyl-glutamines previously reported to elicit plant defence reactions after introduction into the leaf during feeding. The isolated AAH catalyses the hydrolysis of the amide bond (K(m) = 36 micromol l(-1)) and, less efficient, the formation (K(m) = 3 mmol l(-1)) of the elicitor active N-acyl amino acids. The AAH from M. arborescens SE14 shows no homology to known fatty acyl amidases (EC 3.5.1.4) but belongs to the family of Dps proteins (DNA-binding protein from starved cell). In line with other DPS proteins AAH is a homododecamer (monomer 17 181 Da) and contains iron atoms (c. 1-16 iron atoms per subunit). Unlike genuine DPS proteins the enzyme does not significantly bind DNA. Amino acid hydrolase is the first member of the DPS family that catalyses the cleavage or formation of amide bonds. The participation of a microbial enzyme in the homeostasis of N-acyl-glutamines in the insect gut adds further complexity to the interaction between plants and their herbivores.

  18. Multicomponent Synthesis of Isoindolinone Frameworks via RhIII -Catalysed in situ Directing Group-Assisted Tandem Oxidative Olefination/Michael Addition.

    Science.gov (United States)

    Wang, Liang; Liu, Xi; Liu, Jian-Biao; Shen, Jun; Chen, Qun; He, Ming-Yang

    2018-04-04

    A Rh III -catalysed three-component synthesis of isoindolinone frameworks via direct assembly of benzoyl chlorides, o-aminophenols and activated alkenes has been developed. The process involves in situ generation of o-aminophenol (OAP)-based bidentate directing group (DG), Rh III -catalysed tandem ortho C-H olefination and subsequent cyclization via aza-Michael addition. This protocol exhibits good chemoselectivity and functional group tolerance. Computational studies showed that the presence of hydroxyl group on the N-aryl ring could enhance the chemoselectivity of the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Achard, Thierry

    2016-01-01

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

  20. Fundamental partial compositeness

    DEFF Research Database (Denmark)

    Sannino, Francesco; Strumia, Alessandro; Tesi, Andrea

    2016-01-01

    We construct renormalizable Standard Model extensions, valid up to the Planck scale, that give a composite Higgs from a new fundamental strong force acting on fermions and scalars. Yukawa interactions of these particles with Standard Model fermions realize the partial compositeness scenario. Unde...

  1. Partial Remission Definition

    DEFF Research Database (Denmark)

    Andersen, Marie Louise Max; Hougaard, Philip; Pörksen, Sven

    2014-01-01

    OBJECTIVE: To validate the partial remission (PR) definition based on insulin dose-adjusted HbA1c (IDAA1c). SUBJECTS AND METHODS: The IDAA1c was developed using data in 251 children from the European Hvidoere cohort. For validation, 129 children from a Danish cohort were followed from the onset...

  2. Partially Hidden Markov Models

    DEFF Research Database (Denmark)

    Forchhammer, Søren Otto; Rissanen, Jorma

    1996-01-01

    Partially Hidden Markov Models (PHMM) are introduced. They differ from the ordinary HMM's in that both the transition probabilities of the hidden states and the output probabilities are conditioned on past observations. As an illustration they are applied to black and white image compression where...

  3. Partial Ileal Bypass Undone

    NARCIS (Netherlands)

    Beynen, A.C.; Schouten, J.A.; Hoitsma, H.F.W.

    1984-01-01

    Partial ileal bypass (PIB) for the treatment of hypercholesterolaemia was introduced 20 years ago. About 110 cases have been described. We know of only 1 case of restoration of intestinal continuity; no details were given. We report here the second case of PIB in the Netherlands; the operation

  4. Partially ordered models

    NARCIS (Netherlands)

    Fernandez, R.; Deveaux, V.

    2010-01-01

    We provide a formal definition and study the basic properties of partially ordered chains (POC). These systems were proposed to model textures in image processing and to represent independence relations between random variables in statistics (in the later case they are known as Bayesian networks).

  5. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

    OpenAIRE

    Xu, Zhen-Feng; Wang, Yixuan

    2011-01-01

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker th...

  6. New chiral ligands in asymmetric catalysis. Application in stabilization of metal nanoparticles

    OpenAIRE

    Axet Martí, M. Rosa

    2006-01-01

    Thesis M. Rosa AxetThis thesis deals with the development and application of diphosphite ligands derived from carbohydrates to rhodium-catalysed asymmetric hydroformylation and hydrogenation reactions. The use of various carbohydrate derivative ligands as stabilisers of metal nanoparticles is also studied. The synthesis and the characterisation of the series of diphosphite ligands are described in Chapter 2. The results of the asymmetric hydroformylation of styrene and related vinyl arenes ar...

  7. Algebraic partial Boolean algebras

    Science.gov (United States)

    Smith, Derek

    2003-04-01

    Partial Boolean algebras, first studied by Kochen and Specker in the 1960s, provide the structure for Bell-Kochen-Specker theorems which deny the existence of non-contextual hidden variable theories. In this paper, we study partial Boolean algebras which are 'algebraic' in the sense that their elements have coordinates in an algebraic number field. Several of these algebras have been discussed recently in a debate on the validity of Bell-Kochen-Specker theorems in the context of finite precision measurements. The main result of this paper is that every algebraic finitely-generated partial Boolean algebra B(T) is finite when the underlying space Script H is three-dimensional, answering a question of Kochen and showing that Conway and Kochen's infinite algebraic partial Boolean algebra has minimum dimension. This result contrasts the existence of an infinite (non-algebraic) B(T) generated by eight elements in an abstract orthomodular lattice of height 3. We then initiate a study of higher-dimensional algebraic partial Boolean algebras. First, we describe a restriction on the determinants of the elements of B(T) that are generated by a given set T. We then show that when the generating set T consists of the rays spanning the minimal vectors in a real irreducible root lattice, B(T) is infinite just if that root lattice has an A5 sublattice. Finally, we characterize the rays of B(T) when T consists of the rays spanning the minimal vectors of the root lattice E8.

  8. Algebraic partial Boolean algebras

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Derek [Math Department, Lafayette College, Easton, PA 18042 (United States)

    2003-04-04

    Partial Boolean algebras, first studied by Kochen and Specker in the 1960s, provide the structure for Bell-Kochen-Specker theorems which deny the existence of non-contextual hidden variable theories. In this paper, we study partial Boolean algebras which are 'algebraic' in the sense that their elements have coordinates in an algebraic number field. Several of these algebras have been discussed recently in a debate on the validity of Bell-Kochen-Specker theorems in the context of finite precision measurements. The main result of this paper is that every algebraic finitely-generated partial Boolean algebra B(T) is finite when the underlying space H is three-dimensional, answering a question of Kochen and showing that Conway and Kochen's infinite algebraic partial Boolean algebra has minimum dimension. This result contrasts the existence of an infinite (non-algebraic) B(T) generated by eight elements in an abstract orthomodular lattice of height 3. We then initiate a study of higher-dimensional algebraic partial Boolean algebras. First, we describe a restriction on the determinants of the elements of B(T) that are generated by a given set T. We then show that when the generating set T consists of the rays spanning the minimal vectors in a real irreducible root lattice, B(T) is infinite just if that root lattice has an A{sub 5} sublattice. Finally, we characterize the rays of B(T) when T consists of the rays spanning the minimal vectors of the root lattice E{sub 8}.

  9. La catalyse enzymatique en milieu organique Enzymatic Catalysis in Organic Media

    Directory of Open Access Journals (Sweden)

    Monot F.

    2006-11-01

    Full Text Available L'environnement naturel des enzymes étant de nature aqueuse, leurs applications industrielles se sont en général limitées à des réactions mettant en jeu des substrats solubles dans l'eau. Depuis quelques années, la possibilité de faire fonctionner des enzymes dans des milieux hydrophobes (hydrocarbures, solvants organiques a été mise en évidence, engendrant ainsi de nombreux travaux visant, d'une part à mieux comprendre les mécanismes permettant aux enzymes de rester actives dans un tel environnement et, d'autre part à explorer les nouvelles applications envisageables. Les produits pétroliers constituant par excellence le domaine des molécules hydrophobes, le présent article se propose de faire le point sur ces deux aspects, compréhension et intérêt de la catalyse enzymatique en milieu organique. Nous détaillerons ainsi les vues actuelles sur le fonctionnement des enzymes dans des solvants organiques, les différents modes de mise en oeuvre possibles et, à travers une revue de leurs applications potentielles, les principaux systèmes enzymatiques utilisés. The extension of enzymatic catalysis, classically carried out in aqueous media, to organic media can be first ascribed to the possibility of using substrates that are poorly soluble or insoluble in water. In biphasic media consisting of an aqueous phase containing the enzyme in solution and of a non water-miscible organic solvent, the enzyme is kept in a suitable aqueous environment. A variant biphasic system consists in creating reverse micelles by the addition of a surfactant in order to increase the interfacial area and thus to improve the transfers between the aqueous phase where the enzyme is located and the organic phase. In these two cases, the partition coefficient of the different reactants plays a crucial role by governing the rates and yields of reaction. Microaqueous media constitute a new system for biocatalysis in organic media. In this case, a solid enzyme

  10. Iron(III) porphyrin-catalysed oxidation reactions by m-chloro ...

    Indian Academy of Sciences (India)

    Unknown

    1. McLain J, Lee J and Groves J T 2000 In Biomimetic oxidations catalyzed by transition metal complexes. (ed.) Meunier B (London: Imperial College Press) pp. 91–169. 2. Meunier B 1992 Chem. Rev. 92 1411. 3. Dolphin D and Traylor T G 1997 Acc. Chem. Res. 30. 251. 4. Sheldon R A 1994 Metalloporphyrins in catalytic.

  11. Partial quantum logics revisited

    Science.gov (United States)

    Vetterlein, Thomas

    2011-01-01

    Partial Boolean algebras (PBAs) were introduced by Kochen and Specker as an algebraic model reflecting the mutual relationships among quantum-physical yes-no tests. The fact that not all pairs of tests are compatible was taken into special account. In this paper, we review PBAs from two sides. First, we generalise the concept, taking into account also those yes-no tests which are based on unsharp measurements. Namely, we introduce partial MV-algebras, and we define a corresponding logic. Second, we turn to the representation theory of PBAs. In analogy to the case of orthomodular lattices, we give conditions for a PBA to be isomorphic to the PBA of closed subspaces of a complex Hilbert space. Hereby, we do not restrict ourselves to purely algebraic statements; we rather give preference to conditions involving automorphisms of a PBA. We conclude by outlining a critical view on the logico-algebraic approach to the foundational problem of quantum physics.

  12. Partially composite Higgs models

    DEFF Research Database (Denmark)

    Alanne, Tommi; Buarque Franzosi, Diogo; Frandsen, Mads T.

    2018-01-01

    We study the phenomenology of partially composite-Higgs models where electroweak symmetry breaking is dynamically induced, and the Higgs is a mixture of a composite and an elementary state. The models considered have explicit realizations in terms of gauge-Yukawa theories with new strongly...... interacting fermions coupled to elementary scalars and allow for a very SM-like Higgs state. We study constraints on their parameter spaces from vacuum stability and perturbativity as well as from LHC results and find that requiring vacuum stability up to the compositeness scale already imposes relevant...... constraints. A small part of parameter space around the classically conformal limit is stable up to the Planck scale. This is however already strongly disfavored by LHC results. in different limits, the models realize both (partially) composite-Higgs and (bosonic) technicolor models and a dynamical extension...

  13. Arthroscopic partial medial meniscectomy

    Directory of Open Access Journals (Sweden)

    Dašić Žarko

    2011-01-01

    Full Text Available Background/Aim. Meniscal injuries are common in professional or recreational sports as well as in daily activities. If meniscal lesions lead to physical impairment they usually require surgical treatment. Arthroscopic treatment of meniscal injuries is one of the most often performed orthopedic operative procedures. Methods. The study analyzed the results of arthroscopic partial medial meniscectomy in 213 patients in a 24-month period, from 2006, to 2008. Results. In our series of arthroscopically treated medial meniscus tears we noted 78 (36.62% vertical complete bucket handle lesions, 19 (8.92% vertical incomplete lesions, 18 (8.45% longitudinal tears, 35 (16.43% oblique tears, 18 (8.45% complex degenerative lesions, 17 (7.98% radial lesions and 28 (13.14% horisontal lesions. Mean preoperative International Knee Documentation Committee (IKDC score was 49.81%, 1 month after the arthroscopic partial medial meniscectomy the mean IKDC score was 84.08%, and 6 months after mean IKDC score was 90.36%. Six months after the procedure 197 (92.49% of patients had good or excellent subjective postoperative clinical outcomes, while 14 (6.57% patients subjectively did not notice a significant improvement after the intervention, and 2 (0.93% patients had no subjective improvement after the partial medial meniscectomy at all. Conclusion. Arthroscopic partial medial meniscetomy is minimally invasive diagnostic and therapeutic procedure and in well selected cases is a method of choice for treatment of medial meniscus injuries when repair techniques are not a viable option. It has small rate of complications, low morbidity and fast rehabilitation.

  14. Corrosion-resistant metal surfaces

    Science.gov (United States)

    Sugama, Toshifumi [Wading River, NY

    2009-03-24

    The present invention relates to metal surfaces having thereon an ultrathin (e.g., less than ten nanometer thickness) corrosion-resistant film, thereby rendering the metal surfaces corrosion-resistant. The corrosion-resistant film includes an at least partially crosslinked amido-functionalized silanol component in combination with rare-earth metal oxide nanoparticles. The invention also relates to methods for producing such corrosion-resistant films.

  15. Cobalt-Porphyrin-Catalysed Intramolecular Ring-Closing C-H Amination of Aliphatic Azides: A Nitrene-Radical Approach to Saturated Heterocycles

    NARCIS (Netherlands)

    Kuijpers, P.F.; Tiekink, M.J.; Breukelaar, W.B.; Broere, D.L.J.; van Leest, N.P.; van der Vlugt, J.I.; Reek, J.N.H.; de Bruin, B.

    2017-01-01

    Cobalt-porphyrin-catalysed intramolecular ring-closing C−H bond amination enables direct synthesis of various N-heterocycles from aliphatic azides. Pyrrolidines, oxazolidines, imidazolidines, isoindolines and tetrahydroisoquinoline can be obtained in good to excellent yields in a single reaction

  16. Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

    Science.gov (United States)

    Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

    2017-06-01

    The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

  17. Développement de cathodes microbiennes catalysant la réduction du dioxygène

    OpenAIRE

    Debuy, Sandra

    2015-01-01

    Depuis 2002 a émergé le concept de « catalyse électromicrobienne ». Cette même année, une équipe du LGC a démontré un phénomène de transfert d’électrons entre un biofilm aérobie marin et une cathode d’acier inoxydable. A partir de ces biofilms a été isolée une souche bactérienne, Algoriphagus yeomjeoni, pouvant former un biofilm électroactif monoespèce. Les objectifs de ce travail ont été de rechercher cette capacité à réduire du dioxygène chez des bactéries marines mais également chez une so...

  18. Synthesis of a precursor dipeptide of RGDS (Arg-Gly-Asp-Ser) catalysed by the industrial protease alcalase.

    Science.gov (United States)

    Hou, Rui-Zhen; Yang, Yan; Li, Gang; Huang, Yi-Bing; Wang, Hua; Liu, Yun-Jia; Xu, Li; Zhang, Xue-Zhong

    2006-05-01

    Synthesis of Bz-Arg-Gly-NH(2) (N-benzoylargininylglycinamide) [a precursor dipeptide of RGDS (Arg-Gly-Asp-Ser)] catalysed by protease in water/organic co-solvent systems was studied. Starting substrates were N-benzoyl-L-arginine ethyl ester hydrochloride (acyl donor) and glycinamide (nucleophile). Acetonitrile was selected as the organic solvent. Alcalase, an industrial alkaline protease, was applied to the synthesis of the target dipeptide. The conditions of the synthesis reaction were optimized by examining the effects of several factors, including water content, temperature, pH, molar ratio of the substrates and reaction time, on the yield of Bz-Arg-Gly-NH(2). The optimum conditions were established to be pH 10.0, 45 degrees C, in acetonitrile/0.1 M Na(2)CO(3)/NaHCO(3) buffer system (90:10, v/v) for 1 h with a dipeptide yield of 82.9%.

  19. A direct approach to amines with remote stereocentres by enantioselective CuH-catalysed reductive relay hydroamination

    Science.gov (United States)

    Zhu, Shaolin; Niljianskul, Nootaree; Buchwald, Stephen L.

    2016-02-01

    Amines with remote stereocentres (stereocentres that are three or more bonds away from the C-N bond) are important structural elements in many pharmaceutical agents and natural products. However, previously reported methods to prepare these compounds in an enantioselective manner are indirect and require multistep synthesis. Here, we report a copper-hydride-catalysed, enantioselective synthesis of γ- or δ-chiral amines from readily available allylic alcohols, esters and ethers using a reductive relay hydroamination strategy (a net reductive process in which an amino group is installed at a site remote from the original carbon-carbon double bond). The protocol was suitable for substrates containing a wide range of functional groups and provided remote chiral amine products with high levels of regio- and enantioselectivity. Sequential amination of substrates containing several carbon-carbon double bonds could be achieved, demonstrating the high chemoselectivity of this process.

  20. Microwave-assisted facile and rapid Friedel-Crafts benzoylation of arenes catalysed by bismuth trifluoromethanesulfonate

    DEFF Research Database (Denmark)

    Tran, Phoung Hoang; Hansen, Poul Erik; Pham, Thuy Than

    2014-01-01

    The catalytic activity of metal triflates was investigated in Friedel–Crafts benzoylation under microwave irradiation. Friedel–Crafts benzoylation with benzoyl chloride of a variety of arenes containing electron-rich and electron-poor rings using bismuth triflate under microwave irradiation is de...... is described. This method allows the preparation of aryl ketones under solventless conditions in good to excellent yields and short reaction time. Bismuth triflate was easily recovered and reused five times without significant loss of the catalytic activity....

  1. Arabidopsis thaliana Y-family DNA polymerase eta catalyses translesion synthesis and interacts functionally with PCNA2.

    Science.gov (United States)

    Anderson, Heather J; Vonarx, Edward J; Pastushok, Landon; Nakagawa, Mayu; Katafuchi, Atsushi; Gruz, Petr; Di Rubbo, Antonio; Grice, Desma M; Osmond, Megan J; Sakamoto, Ayako N; Nohmi, Takehiko; Xiao, Wei; Kunz, Bernard A

    2008-09-01

    Upon blockage of chromosomal replication by DNA lesions, Y-family polymerases interact with monoubiquitylated proliferating cell nuclear antigen (PCNA) to catalyse translesion synthesis (TLS) and restore replication fork progression. Here, we assessed the roles of Arabidopsis thaliana POLH, which encodes a homologue of Y-family polymerase eta (Poleta), PCNA1 and PCNA2 in TLS-mediated UV resistance. A T-DNA insertion in POLH sensitized the growth of roots and whole plants to UV radiation, indicating that AtPoleta contributes to UV resistance. POLH alone did not complement the UV sensitivity conferred by deletion of yeast RAD30, which encodes Poleta, although AtPoleta exhibited cyclobutane dimer bypass activity in vitro, and interacted with yeast PCNA, as well as with Arabidopsis PCNA1 and PCNA2. Co-expression of POLH and PCNA2, but not PCNA1, restored normal UV resistance and mutation kinetics in the rad30 mutant. A single residue difference at site 201, which lies adjacent to the residue (lysine 164) ubiquitylated in PCNA, appeared responsible for the inability of PCNA1 to function with AtPoleta in UV-treated yeast. PCNA-interacting protein boxes and an ubiquitin-binding motif in AtPoleta were found to be required for the restoration of UV resistance in the rad30 mutant by POLH and PCNA2. These observations indicate that AtPoleta can catalyse TLS past UV-induced DNA damage, and links the biological activity of AtPoleta in UV-irradiated cells to PCNA2 and PCNA- and ubiquitin-binding motifs in AtPoleta.

  2. Redox process catalysed by growing crystal-strengite, FePO4,2H2O, crystallizing from solution with iron(II) and hydroxylamine

    Science.gov (United States)

    Lundager Madsen, Hans Erik

    2014-09-01

    In an attempt to grow pure crystals of the iron(II) phosphate vivianite, Fe3(PO4)2,8H2O, from a solution of Mohr's salt, Fe(NH4)2(SO4)2,6H2O, added to a solution of ammonium phosphate, hydroxylammonium chloride, NH3OHCl, was added to the iron(II) stock solution to eliminate oxidation of iron(II) by oxygen from the air. However, the effect turned out to be the opposite of the expected: whereas hydroxylamine reduces iron(III) in bulk solution, it acted as a strong oxidant in the presence of growing iron phosphate crystals, causing the crystallization of the iron(III) phosphate strengite, FePO4,2H2O, as the only solid phase. Evidently the crystal surface catalyses oxidation of iron(II) by hydroxylamine. The usual composite kinetics of spiral growth and surface nucleation was found. The surface-nucleation part yielded edge free energy λ in the range 12-45 pJ/m, virtually independent of temperature and in the range typical for phosphates of divalent metals. The scatter of values for λ presumably arises from contributions from different crystal forms to the overall growth rate. The low mean value points to strong adsorption of iron(II), which is subsequently oxidized at the crystal surface, forming strengite. The state of the system did not tend to thermodynamic equilibrium, but to a metastable state, presumably controlled by the iron(II) rich surface layer of the crystal. In addition to crystal growth, it was possible to measure nucleation kinetics by light scattering (turbidimetry). A point of transition from heterogeneous to homogeneous nucleation was found, and from the results for the homogeneous domain a rather precise value of crystal surface free energy γ=55 mJ/m2 was found. This is a relatively low value as well, indicating that the redox process plays a role already at the nucleation stage.

  3. Partial differential equations

    CERN Document Server

    Agranovich, M S

    2002-01-01

    Mark Vishik's Partial Differential Equations seminar held at Moscow State University was one of the world's leading seminars in PDEs for over 40 years. This book celebrates Vishik's eightieth birthday. It comprises new results and survey papers written by many renowned specialists who actively participated over the years in Vishik's seminars. Contributions include original developments and methods in PDEs and related fields, such as mathematical physics, tomography, and symplectic geometry. Papers discuss linear and nonlinear equations, particularly linear elliptic problems in angles and gener

  4. Partial differential equations

    CERN Document Server

    Sloan, D; Süli, E

    2001-01-01

    /homepage/sac/cam/na2000/index.html7-Volume Set now available at special set price ! Over the second half of the 20th century the subject area loosely referred to as numerical analysis of partial differential equations (PDEs) has undergone unprecedented development. At its practical end, the vigorous growth and steady diversification of the field were stimulated by the demand for accurate and reliable tools for computational modelling in physical sciences and engineering, and by the rapid development of computer hardware and architecture. At the more theoretical end, the analytical insight in

  5. Partially ordered algebraic systems

    CERN Document Server

    Fuchs, Laszlo

    2011-01-01

    Originally published in an important series of books on pure and applied mathematics, this monograph by a distinguished mathematician explores a high-level area in algebra. It constitutes the first systematic summary of research concerning partially ordered groups, semigroups, rings, and fields. The self-contained treatment features numerous problems, complete proofs, a detailed bibliography, and indexes. It presumes some knowledge of abstract algebra, providing necessary background and references where appropriate. This inexpensive edition of a hard-to-find systematic survey will fill a gap i

  6. Elliptic partial differential equations

    CERN Document Server

    Han, Qing

    2011-01-01

    Elliptic Partial Differential Equations by Qing Han and FangHua Lin is one of the best textbooks I know. It is the perfect introduction to PDE. In 150 pages or so it covers an amazing amount of wonderful and extraordinary useful material. I have used it as a textbook at both graduate and undergraduate levels which is possible since it only requires very little background material yet it covers an enormous amount of material. In my opinion it is a must read for all interested in analysis and geometry, and for all of my own PhD students it is indeed just that. I cannot say enough good things abo

  7. Partial differential equations

    CERN Document Server

    Friedman, Avner

    2008-01-01

    This three-part treatment of partial differential equations focuses on elliptic and evolution equations. Largely self-contained, it concludes with a series of independent topics directly related to the methods and results of the preceding sections that helps introduce readers to advanced topics for further study. Geared toward graduate and postgraduate students of mathematics, this volume also constitutes a valuable reference for mathematicians and mathematical theorists.Starting with the theory of elliptic equations and the solution of the Dirichlet problem, the text develops the theory of we

  8. Partial differential equations

    CERN Document Server

    Levine, Harold

    1997-01-01

    The subject matter, partial differential equations (PDEs), has a long history (dating from the 18th century) and an active contemporary phase. An early phase (with a separate focus on taut string vibrations and heat flow through solid bodies) stimulated developments of great importance for mathematical analysis, such as a wider concept of functions and integration and the existence of trigonometric or Fourier series representations. The direct relevance of PDEs to all manner of mathematical, physical and technical problems continues. This book presents a reasonably broad introductory account of the subject, with due regard for analytical detail, applications and historical matters.

  9. Nonelliptic Partial Differential Equations

    CERN Document Server

    Tartakoff, David S

    2011-01-01

    This book provides a very readable description of a technique, developed by the author years ago but as current as ever, for proving that solutions to certain (non-elliptic) partial differential equations only have real analytic solutions when the data are real analytic (locally). The technique is completely elementary but relies on a construction, a kind of a non-commutative power series, to localize the analysis of high powers of derivatives in the so-called bad direction. It is hoped that this work will permit a far greater audience of researchers to come to a deep understanding of this tec

  10. A generic process of growing aligned carbon nanotube arrays on metals and metal alloys

    International Nuclear Information System (INIS)

    Parthangal, Prahalad M; Cavicchi, Richard E; Zachariah, Michael R

    2007-01-01

    Aligned carbon nanotube (CNT) arrays are integral towards the development of several applications such as field emission, interconnects in silicon technology, and chemical and biological sensing. Even though the synthesis of CNTs has been described extensively in the literature, there has not been significant success in growing uniform, well-aligned CNT arrays on pure metal surfaces other than metals that catalyse CNT growth themselves. In this paper, we describe a method of growing aligned CNT arrays on a variety of pure metals, metal alloys, and conductive ceramics using a bimetallic iron/alumina composite catalyst at low temperatures (550 to 700 deg. C). We believe that the addition of alumina to the iron catalyst significantly reduces catalyst-metal underlayer interactions that have traditionally proven to be a barrier for the growth of CNTs on metals. The alumina also minimizes surface diffusion of iron and allows the formation of a high density of uniformly dispersed catalyst nanoparticles to act as nucleation sites for well-aligned CNT arrays. Despite the presence of non-conducting alumina from the catalyst, the contact resistance between the CNTs and the metal underlayer was observed to be quite low, emphasizing the usefulness of this approach to practical applications. Our process was successful in growing aligned CNTs even on commercial steel plates and may be applicable for substrates of any shape or size

  11. Experts' Understanding of Partial Derivatives Using the Partial Derivative Machine

    Science.gov (United States)

    Roundy, David; Weber, Eric; Dray, Tevian; Bajracharya, Rabindra R.; Dorko, Allison; Smith, Emily M.; Manogue, Corinne A.

    2015-01-01

    Partial derivatives are used in a variety of different ways within physics. Thermodynamics, in particular, uses partial derivatives in ways that students often find especially confusing. We are at the beginning of a study of the teaching of partial derivatives, with a goal of better aligning the teaching of multivariable calculus with the needs of…

  12. Metal-metal-hofteproteser

    DEFF Research Database (Denmark)

    Ulrich, Michael; Overgaard, Søren; Penny, Jeannette

    2014-01-01

    In Denmark 4,456 metal-on-metal (MoM) hip prostheses have been implanted. Evidence demonstrates that some patients develope adverse biological reactions causing failures of MoM hip arthroplasty. Some reactions might be systemic. Failure rates are associated with the type and the design of the Mo...

  13. Unilateral removable partial dentures.

    Science.gov (United States)

    Goodall, W A; Greer, A C; Martin, N

    2017-01-27

    Removable partial dentures (RPDs) are widely used to replace missing teeth in order to restore both function and aesthetics for the partially dentate patient. Conventional RPD design is frequently bilateral and consists of a major connector that bridges both sides of the arch. Some patients cannot and will not tolerate such an extensive appliance. For these patients, bridgework may not be a predictable option and it is not always possible to provide implant-retained restorations. This article presents unilateral RPDs as a potential treatment modality for such patients and explores indications and contraindications for their use, including factors relating to patient history, clinical presentation and patient wishes. Through case examples, design, material and fabrication considerations will be discussed. While their use is not widespread, there are a number of patients who benefit from the provision of unilateral RPDs. They are a useful treatment to have in the clinician's armamentarium, but a highly-skilled dental team and a specific patient presentation is required in order for them to be a reasonable and predictable prosthetic option.

  14. Tutorial on Online Partial Evaluation

    Directory of Open Access Journals (Sweden)

    William R. Cook

    2011-09-01

    Full Text Available This paper is a short tutorial introduction to online partial evaluation. We show how to write a simple online partial evaluator for a simple, pure, first-order, functional programming language. In particular, we show that the partial evaluator can be derived as a variation on a compositionally defined interpreter. We demonstrate the use of the resulting partial evaluator for program optimization in the context of model-driven development.

  15. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  16. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  17. Type-Directed Partial Evaluation

    DEFF Research Database (Denmark)

    Danvy, Olivier

    1998-01-01

    Type-directed partial evaluation uses a normalization function to achieve partial evaluation. These lecture notes review its background, foundations, practice, and applications. Of specific interest is the modular technique of offline and online type-directed partial evaluation in Standard ML of ...

  18. Type-Directed Partial Evaluation

    DEFF Research Database (Denmark)

    Danvy, Olivier

    1998-01-01

    Type-directed partial evaluation uses a normalization function to achieve partial evaluation. These lecture notes review its background, foundations, practice, and applications. Of specific interest is the modular technique of offline and online type-directed partial evaluation in Standard ML...

  19. Partial symmetries in nuclear spectroscopy

    International Nuclear Information System (INIS)

    Leviatan, A.

    1996-01-01

    The notions of exact, dynamical and partial symmetries are discussed in relation to nuclear spectroscopy. Explicit forms of Hamiltonians with partial SU(3) symmetry are presented in the framework of the interacting boson model of nuclei. An analysis of the resulting spectrum and electromagnetic transitions demonstrates the relevance of such partial symmetry to the spectroscopy of axially deformed nuclei. (Author)

  20. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

    Directory of Open Access Journals (Sweden)

    Matthieu Jouffroy

    2014-10-01

    Full Text Available The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2.

  1. Elliptic partial differential equations

    CERN Document Server

    Volpert, Vitaly

    If we had to formulate in one sentence what this book is about it might be "How partial differential equations can help to understand heat explosion, tumor growth or evolution of biological species". These and many other applications are described by reaction-diffusion equations. The theory of reaction-diffusion equations appeared in the first half of the last century. In the present time, it is widely used in population dynamics, chemical physics, biomedical modelling. The purpose of this book is to present the mathematical theory of reaction-diffusion equations in the context of their numerous applications. We will go from the general mathematical theory to specific equations and then to their applications. Mathematical anaylsis of reaction-diffusion equations will be based on the theory of Fredholm operators presented in the first volume. Existence, stability and bifurcations of solutions will be studied for bounded domains and in the case of travelling waves. The classical theory of reaction-diffusion equ...

  2. Applied partial differential equations

    CERN Document Server

    Logan, J David

    2004-01-01

    This primer on elementary partial differential equations presents the standard material usually covered in a one-semester, undergraduate course on boundary value problems and PDEs. What makes this book unique is that it is a brief treatment, yet it covers all the major ideas: the wave equation, the diffusion equation, the Laplace equation, and the advection equation on bounded and unbounded domains. Methods include eigenfunction expansions, integral transforms, and characteristics. Mathematical ideas are motivated from physical problems, and the exposition is presented in a concise style accessible to science and engineering students; emphasis is on motivation, concepts, methods, and interpretation, rather than formal theory. This second edition contains new and additional exercises, and it includes a new chapter on the applications of PDEs to biology: age structured models, pattern formation; epidemic wave fronts, and advection-diffusion processes. The student who reads through this book and solves many of t...

  3. Fundamental partial compositeness

    Energy Technology Data Exchange (ETDEWEB)

    Sannino, Francesco [CP-Origins and Danish IAS, University of Southern Denmark,Campusvej 55 (Denmark); Strumia, Alessandro [Dipartimento di Fisica dell’Università di Pisa and INFN,Pisa (Italy); Theory Division, CERN,Geneva (Switzerland); Tesi, Andrea [Department of Physics, Enrico Fermi Institute, University of Chicago,Chicago, IL 60637 (United States); Vigiani, Elena [Dipartimento di Fisica dell’Università di Pisa and INFN,Pisa (Italy)

    2016-11-07

    We construct renormalizable Standard Model extensions, valid up to the Planck scale, that give a composite Higgs from a new fundamental strong force acting on fermions and scalars. Yukawa interactions of these particles with Standard Model fermions realize the partial compositeness scenario. Under certain assumptions on the dynamics of the scalars, successful models exist because gauge quantum numbers of Standard Model fermions admit a minimal enough ‘square root’. Furthermore, right-handed SM fermions have an SU(2){sub R}-like structure, yielding a custodially-protected composite Higgs. Baryon and lepton numbers arise accidentally. Standard Model fermions acquire mass at tree level, while the Higgs potential and flavor violations are generated by quantum corrections. We further discuss accidental symmetries and other dynamical features stemming from the new strongly interacting scalars. If the same phenomenology can be obtained from models without our elementary scalars, they would reappear as composite states.

  4. Partial pressure gauges

    CERN Document Server

    Peter, G J

    2007-01-01

    The determination of partial pressures in vacuum systems is usually performed by mass spectrometers. The most common type is the QMS. Quadrupole mass spectrometers were developed decades ago and have been used by vacuum specialists as a diagnostic tool since then. In the first part of the paper the principles of these mass spectrometers are briefly reviewed together with the key features of the instruments. This is necessary to operate these instruments. In the second part the boundary conditions which arise from the application as residual gas analyser in UHV/XHV plants are described. These lead to special versions of mass spectrometers. Results obtained with these instruments and typical artefacts in mass spectra obtained in the UHV are discussed.

  5. Fundamental partial compositeness

    CERN Document Server

    Sannino, Francesco

    2016-01-01

    We construct renormalizable Standard Model extensions, valid up to the Planck scale, that give a composite Higgs from a new fundamental strong force acting on fermions and scalars. Yukawa interactions of these particles with Standard Model fermions realize the partial compositeness scenario. Successful models exist because gauge quantum numbers of Standard Model fermions admit a minimal enough 'square root'. Furthermore, right-handed SM fermions have an SU(2)$_R$-like structure, yielding a custodially-protected composite Higgs. Baryon and lepton numbers arise accidentally. Standard Model fermions acquire mass at tree level, while the Higgs potential and flavor violations are generated by quantum corrections. We further discuss accidental symmetries and other dynamical features stemming from the new strongly interacting scalars. If the same phenomenology can be obtained from models without our elementary scalars, they would reappear as composite states.

  6. Carbon dioxide hydrogenation catalysed by well-defined Mn(i) PNP pincer hydride complexes† †Electronic supplementary information (ESI) available: Experimental procedures, NMR and IR spectra, atomic coordinates for DFT optimized structures and computational details, and crystallographic data for 2. CCDC 1520528. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00209b Click here for additional data file. Click here for additional data file.

    Science.gov (United States)

    Bertini, Federica; Glatz, Mathias; Gorgas, Nikolaus; Stöger, Berthold; Peruzzini, Maurizio; Veiros, Luis F.

    2017-01-01

    The catalytic reduction of carbon dioxide is of great interest for its potential as a hydrogen storage method and to use carbon dioxide as C-1 feedstock. In an effort to replace expensive noble metal-based catalysts with efficient and cheap earth-abundant counterparts, we report the first example of Mn(i)-catalysed hydrogenation of CO2 to HCOOH. The hydride Mn(i) catalyst [Mn(PNPNH-iPr)(H)(CO)2] showed higher stability and activity than its Fe(ii) analogue. TONs up to 10 000 and quantitative yields were obtained after 24 h using DBU as the base at 80 °C and 80 bar total pressure. At catalyst loadings as low as 0.002 mol%, TONs greater than 30 000 could be achieved in the presence of LiOTf as the co-catalyst, which are among the highest activities reported for base-metal catalysed CO2 hydrogenations to date. PMID:28970889

  7. Algorithms over partially ordered sets

    DEFF Research Database (Denmark)

    Baer, Robert M.; Østerby, Ole

    1969-01-01

    We here study some problems concerned with the computational analysis of finite partially ordered sets. We begin (in § 1) by showing that the matrix representation of a binary relationR may always be taken in triangular form ifR is a partial ordering. We consider (in § 2) the chain structure...... in partially ordered sets, answer the combinatorial question of how many maximal chains might exist in a partially ordered set withn elements, and we give an algorithm for enumerating all maximal chains. We give (in § 3) algorithms which decide whether a partially ordered set is a (lower or upper) semi...

  8. Robot-assisted partial nephrectomy: Superiority over laparoscopic partial nephrectomy.

    Science.gov (United States)

    Shiroki, Ryoichi; Fukami, Naohiko; Fukaya, Kosuke; Kusaka, Mamoru; Natsume, Takahiro; Ichihara, Takashi; Toyama, Hiroshi

    2016-02-01

    Nephron-sparing surgery has been proven to positively impact the postoperative quality of life for the treatment of small renal tumors, possibly leading to functional improvements. Laparoscopic partial nephrectomy is still one of the most demanding procedures in urological surgery. Laparoscopic partial nephrectomy sometimes results in extended warm ischemic time and severe complications, such as open conversion, postoperative hemorrhage and urine leakage. Robot-assisted partial nephrectomy exploits the advantages offered by the da Vinci Surgical System to laparoscopic partial nephrectomy, equipped with 3-D vision and a better degree in the freedom of surgical instruments. The introduction of the da Vinci Surgical System made nephron-sparing surgery, specifically robot-assisted partial nephrectomy, safe with promising results, leading to the shortening of warm ischemic time and a reduction in perioperative complications. Even for complex and challenging tumors, robotic assistance is expected to provide the benefit of minimally-invasive surgery with safe and satisfactory renal function. Warm ischemic time is the modifiable factor during robot-assisted partial nephrectomy to affect postoperative kidney function. We analyzed the predictive factors for extended warm ischemic time from our robot-assisted partial nephrectomy series. The surface area of the tumor attached to the kidney parenchyma was shown to significantly affect the extended warm ischemic time during robot-assisted partial nephrectomy. In cases with tumor-attached surface area more than 15 cm(2) , we should consider switching robot-assisted partial nephrectomy to open partial nephrectomy under cold ischemia if it is imperative. In Japan, a nationwide prospective study has been carried out to show the superiority of robot-assisted partial nephrectomy to laparoscopic partial nephrectomy in improving warm ischemic time and complications. By facilitating robotic technology, robot-assisted partial nephrectomy

  9. Metal-metal-hofteproteser

    DEFF Research Database (Denmark)

    Ulrich, Michael; Overgaard, Søren; Penny, Jeannette

    2014-01-01

    In Denmark 4,456 metal-on-metal (MoM) hip prostheses have been implanted. Evidence demonstrates that some patients develope adverse biological reactions causing failures of MoM hip arthroplasty. Some reactions might be systemic. Failure rates are associated with the type and the design of the Mo......M hip implant. A Danish surveillance programme has been initiated addressing these problems....

  10. Production and partial purification of extracellular tannase by ...

    African Journals Online (AJOL)

    End-product repression was also studied with inclusion of gallic acid to the growth medium. Enrichment with various additives of metal ions and detergents resulted in inhibition of tannase production. The enzyme was partially purified using ammonium sulfate precipitation followed by the use of DEAE-cellulose. SDS-PAGE ...

  11. Fiber-reinforced composites in fixed partial dentures | Garoushi ...

    African Journals Online (AJOL)

    ... to whether FRC prostheses will replace metal-ceramic or full-ceramic prostheses, attention should be focused on the additional treatment options brought by the use of fibers. However, more clinical experience is needed. Keywords: fiber-reinforced composite, fixed partial dentures, particulate resin composite, framework

  12. Estimation of vapour pressure and partial pressure of subliming ...

    Indian Academy of Sciences (India)

    Administrator

    substance due to the flowing gas in the thermogravimetric analysis (TGA) apparatus was taken into account. ... the partial pressure, V the volume, n number of moles (of the vapour), R the universal gas constant and T the .... Figure 7. Molar concentration of vanadium metal as a func- tion of temperature at different pressures.

  13. Partially supervised speaker clustering.

    Science.gov (United States)

    Tang, Hao; Chu, Stephen Mingyu; Hasegawa-Johnson, Mark; Huang, Thomas S

    2012-05-01

    Content-based multimedia indexing, retrieval, and processing as well as multimedia databases demand the structuring of the media content (image, audio, video, text, etc.), one significant goal being to associate the identity of the content to the individual segments of the signals. In this paper, we specifically address the problem of speaker clustering, the task of assigning every speech utterance in an audio stream to its speaker. We offer a complete treatment to the idea of partially supervised speaker clustering, which refers to the use of our prior knowledge of speakers in general to assist the unsupervised speaker clustering process. By means of an independent training data set, we encode the prior knowledge at the various stages of the speaker clustering pipeline via 1) learning a speaker-discriminative acoustic feature transformation, 2) learning a universal speaker prior model, and 3) learning a discriminative speaker subspace, or equivalently, a speaker-discriminative distance metric. We study the directional scattering property of the Gaussian mixture model (GMM) mean supervector representation of utterances in the high-dimensional space, and advocate exploiting this property by using the cosine distance metric instead of the euclidean distance metric for speaker clustering in the GMM mean supervector space. We propose to perform discriminant analysis based on the cosine distance metric, which leads to a novel distance metric learning algorithm—linear spherical discriminant analysis (LSDA). We show that the proposed LSDA formulation can be systematically solved within the elegant graph embedding general dimensionality reduction framework. Our speaker clustering experiments on the GALE database clearly indicate that 1) our speaker clustering methods based on the GMM mean supervector representation and vector-based distance metrics outperform traditional speaker clustering methods based on the “bag of acoustic features” representation and statistical

  14. Efficient one-pot enzymatic synthesis of alpha-(1 -> 4)-glucosidic disaccharides through a coupled reaction catalysed by Lactobacillus acidophilus NCFM maltose phosphorylase

    DEFF Research Database (Denmark)

    Nakai, Hiroyuki; Dilokpimol, Adiphol; Abou Hachem, Maher

    2010-01-01

    Lactobacillus acidophilus NCFM maltose phosphorylase (LaMalP) of glycoside hydrolase family 65 catalysed enzymatic synthesis of alpha-(1 -> 4)-glucostdic disacchandes from maltose and five monosacchandes in a coupled phosphorolysis/reverse phosphorolysis one-pot reaction Thus phosphorolysis...... of maltose to 0-glucose I -phosphate circumvented addition of costly 0-glucose 1-phosphate for reverse phosphorolysis with different monosacchande acceptors, resulting in 91%, 89%, 88%, 86% and 84% yield of alpha-a-glucopyranosyl-(1 4)-N-acetyl-a-glucosain inopyranose IN-acetyl-maltosamine I, alpha......-fucose and 0.5 M xylose in 02 M phosphate-citrate p1-I 62 These current yields of 0.27-0.34 g of disaccharide products from 10 mL reaction mixtures are easy to scale up and moreover the strategy can be applied to large-scale production of other oligosacchandes from low-cost disacchandes as catalysed...

  15. Pd(II)-catalysed meta-C–H functionalizations of benzoic acid derivatives

    Science.gov (United States)

    Li, Shangda; Cai, Lei; Ji, Huafang; Yang, Long; Li, Gang

    2016-01-01

    Benzoic acids are highly important structural motifs in drug molecules and natural products. Selective C–H bond functionalization of benzoic acids will provide synthetically useful tools for step-economical organic synthesis. Although direct ortho-C–H functionalizations of benzoic acids or their derivatives have been intensely studied, the ability to activate meta-C–H bond of benzoic acids or their derivatives in a general manner via transition-metal catalysis has been largely unsuccessful. Although chelation-assisted meta-C–H functionalization of electron-rich arenes was reported, chelation-assisted meta-C–H activation of electron-poor arenes such as benzoic acid derivatives remains a formidable challenge. Herein, we report a general protocol for meta-C–H olefination of benzoic acid derivatives using a nitrile-based sulfonamide template. A broad range of benzoic acid derivatives are meta-selectively olefinated using molecular oxygen as the terminal oxidant. The meta-C–H acetoxylation, product of which is further transformed at the meta-position, is also reported. PMID:26813919

  16. Kraft lignin depolymerisation by based catalysed degradation (BCD) - The effect of process parameters on conversion degree and structural features of BCD fractions

    OpenAIRE

    Schmiedl, Schmiedl; Böringer, Sarah; Schweppe, Rainer; Liitiä, Tiina; Rovio, Stella; Tamminen, Tarja; Rencoret, Jorge; Gutiérrez Suárez, Ana; Río Andrade, José Carlos del; Río Andrade, José Carlos del

    2014-01-01

    The objective of the study is the generation of oxy-aromatic compounds (monomer, oligomer) from Eucalyptus- Kraft-lignin via multi-stage processes. These processes (1st base catalysed degradation & 2nd separation of the organic phase from reactor water) have to be feasible in bio refineries & in new Pulp-mill bio refineries as a new technology module. The Eucalyptus-Kraft-lignin (Suzano Pulp & Paper) was used for catalyzed conversion into oxy aromatics. Subsequently, the effect of process par...

  17. Partial Actions and Power Sets

    Directory of Open Access Journals (Sweden)

    Jesús Ávila

    2013-01-01

    Full Text Available We consider a partial action (X,α with enveloping action (T,β. In this work we extend α to a partial action on the ring (P(X,Δ,∩ and find its enveloping action (E,β. Finally, we introduce the concept of partial action of finite type to investigate the relationship between (E,β and (P(T,β.

  18. Optimisation of flavour ester biosynthesis in an aqueous system of coconut cream and fusel oil catalysed by lipase.

    Science.gov (United States)

    Sun, Jingcan; Yu, Bin; Curran, Philip; Liu, Shao-Quan

    2012-12-15

    Coconut cream and fusel oil, two low-cost natural substances, were used as starting materials for the biosynthesis of flavour-active octanoic acid esters (ethyl-, butyl-, isobutyl- and (iso)amyl octanoate) using lipase Palatase as the biocatalyst. The Taguchi design method was used for the first time to optimize the biosynthesis of esters by a lipase in an aqueous system of coconut cream and fusel oil. Temperature, time and enzyme amount were found to be statistically significant factors and the optimal conditions were determined to be as follows: temperature 30°C, fusel oil concentration 9% (v/w), reaction time 24h, pH 6.2 and enzyme amount 0.26 g. Under the optimised conditions, a yield of 14.25mg/g (based on cream weight) and signal-to-noise (S/N) ratio of 23.07 dB were obtained. The results indicate that the Taguchi design method was an efficient and systematic approach to the optimisation of lipase-catalysed biological processes. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Sn-Beta zeolites with borate salts catalyse the epimerization of carbohydrates via an intramolecular carbon shift.

    Science.gov (United States)

    Gunther, William R; Wang, Yuran; Ji, Yuewei; Michaelis, Vladimir K; Hunt, Sean T; Griffin, Robert G; Román-Leshkov, Yuriy

    2012-01-01

    Carbohydrate epimerization is an essential technology for the widespread production of rare sugars. In contrast to other enzymes, most epimerases are only active on sugars substituted with phosphate or nucleotide groups, thus drastically restricting their use. Here we show that Sn-Beta zeolite in the presence of sodium tetraborate catalyses the selective epimerization of aldoses in aqueous media. Specifically, a 5 wt% aldose (for example, glucose, xylose or arabinose) solution with a 4:1 aldose:sodium tetraborate molar ratio reacted with catalytic amounts of Sn-Beta yields near-equilibrium epimerization product distributions. The reaction proceeds by way of a 1,2 carbon shift wherein the bond between C-2 and C-3 is cleaved and a new bond between C-1 and C-3 is formed, with C-1 moving to the C-2 position with an inverted configuration. This work provides a general method of performing carbohydrate epimerizations that surmounts the main disadvantages of current enzymatic and inorganic processes.

  20. Facile Combustion Synthesis of Carbon-Supported Titanium Oxynitride to Catalyse Oxygen Reduction Reaction in Acidic Media

    International Nuclear Information System (INIS)

    Chisaka, Mitsuharu; Ando, Yuta; Muramoto, Hirokazu

    2015-01-01

    A facile route for synthesis of nitrogen-doped TiO 2 supported on carbon black (TiO x N y –C) to catalyse oxygen reduction reaction in acidic media, was developed without forming bulky TiN. This protocol involved modification of an inexpensive “solution phase combustion” process used for production of nitrogen and fluorine codoped TiO 2 photocatalysts. Fluorine-free TiO x N y particles were successfully supported on carbon by adding the carbon support to the precursor dispersion containing titanium tetrafluoride and urea with stirring at 523 K, followed by pyrolysis under N 2 gas as a modification of the photocatalyst synthesis. The catalyst activity depended on the pyrolysis temperature, where the optimal activity was achieved by pyrolysis at 1073–1123 K. The active sites are proposed to be rutile TiO 2 doped with nitrogen atoms containing oxygen defects. The developed synthesis route requires less than half of the time required for our previous protocol utilizing two-step pyrolysis under a mixture of H 2 /O 2 /N 2 gas and NH 3 -gas and is also significantly more economical.

  1. Dilute phosphoric acid-catalysed hydrolysis of municipal bio-waste wood shavings using autoclave parr reactor system.

    Science.gov (United States)

    Orozco, Angela M; Al-Muhtaseb, Ala'a H; Albadarin, Ahmad B; Rooney, David; Walker, Gavin M; Ahmad, Mohammad N M

    2011-10-01

    The visibility of using municipal bio-waste, wood shavings, as a potential feedstock for ethanol production was investigated. Dilute acid hydrolysis of wood shavings with H₃PO₄ was undertaken in autoclave parr reactor. A combined severity factor (CSF) was used to integrate the effects of hydrolysis times, temperature and acid concentration into a single variable. Xylose concentration reached a maximum value of 17 g/100 g dry mass corresponding to a yield of 100% at the best identified conditions of 2.5 wt.% H₃PO₄, 175 °C and 10 min reaction time corresponding to a CSF of 1.9. However, for glucose, an average yield of 30% was obtained at 5 wt.% H₃PO₄, 200 °C and 10 min. Xylose production increased with increasing temperature and acid concentration, but its transformation to the degradation product furfural was also catalysed by those factors. The maximum furfural formed was 3 g/100 g dry mass, corresponding to the 24% yield. Copyright © 2011 Elsevier Ltd. All rights reserved.

  2. Control of chemical chaos through medium viscosity in a batch ferroin-catalysed Belousov-Zhabotinsky reaction.

    Science.gov (United States)

    Budroni, Marcello A; Calabrese, Ilaria; Miele, Ylenia; Rustici, Mauro; Marchettini, Nadia; Rossi, Federico

    2017-12-13

    In this paper we show that the active interplay of nonlinear kinetics and transport phenomena in a chemical oscillator can be exploited to induce and control chaos. To this aim we use as a model system the ferroin-catalysed Belousov-Zhabotinsky (BZ) oscillating reaction, which is known to evolve to characteristic chaotic transient dynamics when carried out under batch and unstirred conditions. In particular, chemical chaos was found to appear and disappear by following a Ruelle-Takens-Newhouse (RTN) scenario. Here we use medium viscosity as a bifurcation parameter to tune the reaction-diffusion-convection (RDC) interplay and force the reaction in a specific sequence of dynamical regimes: either (i) periodic → quasi-periodic → chaotic or (ii) periodic → quasi-periodic or (iii) only periodic. The medium viscosity can be set by adding different amounts of surfactant (sodium dodecyl sulphate), known to have a little impact on the reaction mechanism, above its critical micelle concentration. Experimental results are supported by means of numerical simulations of a RDC model, which combines self-sustained oscillations to the related chemically-induced buoyancy convection.

  3. Aspergillus nidulans α-galactosidase of glycoside hydrolase family 36 catalyses the formation of α-galacto-oligosaccharides by transglycosylation

    DEFF Research Database (Denmark)

    Nakai, Hiroyuki; Baumann, Martin; Petersen, B. O.

    2010-01-01

    The α-galactosidase from Aspergillus nidulans (AglC) belongs to a phylogenetic cluster containing eukaryotic α-galactosidases and α-galacto-oligosaccharide synthases of glycoside hydrolase family 36 (GH36). The recombinant AglC, produced in high yield (0.65 g·L−1 culture) as His-tag fusion...... in Escherichia coli, catalysed efficient transglycosylation with α-(1→6) regioselectivity from 40 mm 4-nitrophenol α-d-galactopyranoside, melibiose or raffinose, resulting in a 37–74% yield of 4-nitrophenol α-d-Galp-(1→6)-d-Galp, α-d-Galp-(1→6)-α-d-Galp-(1→6)-d-Glcp and α-d-Galp-(1→6)-α-d-Galp-(1→6)-d-Glcp-(α1→β......2)-d-Fruf (stachyose), respectively. Furthermore, among 10 monosaccharide acceptor candidates (400 mm) and the donor 4-nitrophenol α-d-galactopyranoside (40 mm), α-(1→6) linked galactodisaccharides were also obtained with galactose, glucose and mannose in high yields of 39–58%. AglC did...

  4. Arabidopsis IRE1 catalyses unconventional splicing of bZIP60 mRNA to produce the active transcription factor

    KAUST Repository

    Nagashima, Yukihiro

    2011-07-01

    IRE1 plays an essential role in the endoplasmic reticulum (ER) stress response in yeast and mammals. We found that a double mutant of Arabidopsis IRE1A and IRE1B (ire1a/ire1b) is more sensitive to the ER stress inducer tunicamycin than the wild-type. Transcriptome analysis revealed that genes whose induction was reduced in ire1a/ire1b largely overlapped those in the bzip60 mutant. We observed that the active form of bZIP60 protein detected in the wild-type was missing in ire1a/ire1b. We further demonstrated that bZIP60 mRNA is spliced by ER stress, removing 23 ribonucleotides and therefore causing a frameshift that replaces the C-terminal region of bZIP60 including the transmembrane domain (TMD) with a shorter region without a TMD. This splicing was detected in ire1a and ire1b single mutants, but not in the ire1a/ire1b double mutant. We conclude that IRE1A and IRE1B catalyse unconventional splicing of bZIP60 mRNA to produce the active transcription factor.

  5. [Acrylic resin removable partial dentures

    NARCIS (Netherlands)

    Baat, C. de; Witter, D.J.; Creugers, N.H.J.

    2011-01-01

    An acrylic resin removable partial denture is distinguished from other types of removable partial dentures by an all-acrylic resin base which is, in principle, solely supported by the edentulous regions of the tooth arch and in the maxilla also by the hard palate. When compared to the other types of

  6. Partial Epilepsy with Auditory Features

    Directory of Open Access Journals (Sweden)

    J Gordon Millichap

    2004-07-01

    Full Text Available The clinical characteristics of 53 sporadic (S cases of idiopathic partial epilepsy with auditory features (IPEAF were analyzed and compared to previously reported familial (F cases of autosomal dominant partial epilepsy with auditory features (ADPEAF in a study at the University of Bologna, Italy.

  7. Load transfer characteristics of unilateral distal extension removable partial dentures with polyacetal resin supporting components.

    Science.gov (United States)

    Jiao, T; Chang, T; Caputo, A A

    2009-03-01

    To photoelastically examine load transfer by unilateral distal extension removable partial dentures with supporting and retentive components made of the lower stiffness polyacetal resins. A mandibular photoelastic model, with edentulous space distal to the right second premolar and missing the left first molar, was constructed to determine the load transmission characteristics of a unilateral distal extension base removable partial denture. Individual simulants were used for tooth structure, periodontal ligament, and alveolar bone. Three designs were fabricated: a major connector and clasps made from polyacetal resin, a metal framework as the major connector with polyacetal resin clasp and denture base, and a traditional metal framework I-bar removable partial denture. Simulated posterior bilateral and unilateral occlusal loads were applied to the removable partial dentures. Under bilateral and left side unilateral loading, the highest stress was observed adjacent to the left side posterior teeth with the polyacetal removable partial denture. The lowest stress was seen with the traditional metal framework. Unilateral loads on the right edentulous region produced similar distributed stress under the denture base with all three designs but a somewhat higher intensity with the polyacetal framework. The polyacetal resin removable partial denture concentrated the highest stresses to the abutment and the bone. The traditional metal framework I-bar removable partial denture most equitably distributed force. The hybrid design that combined a metal framework and polyacetal clasp and denture base may be a viable alternative when aesthetics are of primary concern.

  8. Enantiospecific kinking of DNA by a partially intercalating metal complex

    KAUST Repository

    Reymer, Anna

    2012-01-01

    Opposite enantiomers of [Ru(phenanthroline) 3] 2+ affect the persistence length of DNA differently, a long speculated effect of helix kinking. Our molecular dynamics simulations confirm a substantial change of duplex secondary structure produced by wedge-intercalation of one but not the other enantiomer. This effect is exploited by several classes of DNA operative proteins. © The Royal Society of Chemistry 2012.

  9. Cast Partial Denture versus Acrylic Partial Denture for Replacement of Missing Teeth in Partially Edentulous Patients

    Directory of Open Access Journals (Sweden)

    Pramita Suwal

    2017-03-01

    Full Text Available Aim: To compare the effects of cast partial denture with conventional all acrylic denture in respect to retention, stability, masticatory efficiency, comfort and periodontal health of abutments. Methods: 50 adult partially edentulous patient seeking for replacement of missing teeth having Kennedy class I and II arches with or without modification areas were selected for the study. Group-A was treated with cast partial denture and Group-B with acrylic partial denture. Data collected during follow-up visit of 3 months, 6 months, and 1 year by evaluating retention, stability, masticatory efficiency, comfort, periodontal health of abutment. Results: Chi-square test was applied to find out differences between the groups at 95% confidence interval where p = 0.05. One year comparison shows that cast partial denture maintained retention and stability better than acrylic partial denture (p< 0.05. The masticatory efficiency was significantly compromising from 3rd month to 1 year in all acrylic partial denture groups (p< 0.05. The comfort of patient with cast partial denture was maintained better during the observation period (p< 0.05. Periodontal health of abutment was gradually deteriorated in all acrylic denture group (p

  10. Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulphidic marine sediments

    Energy Technology Data Exchange (ETDEWEB)

    Glass, DR. Jennifer [California Institute of Technology, Pasadena; Yu, DR. Hang [California Institute of Technology, Pasadena; Steele, Joshua [California Institute of Technology, Pasadena; Dawson, Katherine [California Institute of Technology, Pasadena; Sun, S [University of California, San Diego; Chourey, Karuna [ORNL; Pan, Chongle [ORNL; Hettich, Robert {Bob} L [ORNL; Orphan, V [California Institute of Technology, Pasadena

    2013-01-01

    Microbes have obligate requirements for trace metals in metalloenzymes that catalyse important biogeochemical reactions. In anoxic methane- and sulphiderich environments, microbes may have unique adaptations for metal acquisition and utilization because of decreased bioavailability as a result of metal sulphide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulphidic (> 1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5 270 nM), cobalt (0.5 6 nM), molybdenum (10 5600 nM) and tungsten (0.3 8 nM) in Hydrate Ridge sediment porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalysing anaerobic oxidation of methane (AOM) utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulphate-reducing bacteria. Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrophilic microorganisms. Overall, our data suggest that AOM consortia use specialized biochemical strategies to overcome the challenges of metal availability in sulphidic environments.

  11. A spinach O-acetylserine(thiollyase homologue, SoCSaseLP, suppresses cysteine biosynthesis catalysed by other enzyme isoforms

    Directory of Open Access Journals (Sweden)

    Miki Noda

    2016-06-01

    Full Text Available An enzyme, O-acetylserine(thiollyase (OASTL, also known as O-acetylserine sulfhydrylase or cysteine synthase (CSase, catalyses the incorporation of sulfide into O-acetylserine and produces cysteine. We previously identified a cDNA encoding an OASTL-like protein from Spinacia oleracea, (SoCSaseLP, but a recombinant SoCSaseLP produced in Escherichia coli did not show OASTL activity. The exon-intron structure of the SoCSaseLP gene shared conserved structures with other spinach OASTL genes. The SoCSaseLP and a Beta vulgaris homologue protein, KMT13462, comprise a unique clade in the phylogenetic tree of the OASTL family. Interestingly, when the SoCSaseLP gene was expressed in tobacco plants, total OASTL activity in tobacco leaves was reduced. This reduction in total OASTL activity was most likely caused by interference by SoCSaseLP with cytosolic OASTL. To investigate the possible interaction of SoCSaseLP with a spinach cytosolic OASTL isoform SoCSaseA, a pull-down assay was carried out. The recombinant glutathione S-transferase (GST-SoCSaseLP fusion protein was expressed in E. coli together with the histidine-tagged SoCSaseA protein, and the protein extract was subjected to glutathione affinity chromatography. The histidine-tagged SoCSaseA was co-purified with the GST-SoCSaseLP fusion protein, indicating the binding of SoCSaseLP to SoCSaseA. Consistent with this interaction, the OASTL activity of the co-purified SoCSaseA was reduced compared with the activity of SoCSaseA that was purified on its own. These results strongly suggest that SoCSaseLP negatively regulates the activity of other cytosolic OASTL family members by direct interaction.

  12. Implementation of steady state approximation for modelling of reaction kinetic of UV catalysed hydrogen peroxide oxidation of starch

    Science.gov (United States)

    Kumoro, Andri Cahyo; Retnowati, Diah Susetyo; Ratnawati, Budiyati, Catarina Sri

    2015-12-01

    With regard to its low viscosity, high stability, clarity, film forming and binding properties, oxidised starch has been widely used in various applications specifically in the food, paper, textile, laundry finishing and binding materials industries. A number of methods have been used to produce oxidised starch through reactions with various oxidizing agents, such as hydrogen peroxide, air oxygen, ozone, bromine, chromic acid, permanganate, nitrogen dioxide and hypochlorite. Unfortunately, most of previous works reported in the literatures were focused on the study of reaction mechanism and physicochemical properties characterization of the oxidised starches produced without investigation of the reaction kinetics of the oxidation process. This work aimed to develop a simple kinetic model for UV catalysed hydrogen peroxide oxidation of starch through implementation of steady state approximation for the radical reaction rates. The model was then verified using experimental data available in the literature. The model verification revealed that the proposed model shows its good agreement with the experimental data as indicated by an average absolute relative error of only 2.45%. The model also confirmed that carboxyl groups are oxidised further by hydroxyl radical. The carbonyl production rate was found to follow first order reaction with respect to carbonyl concentration. Similarly, carboxyl production rate also followed first order reaction with respect to carbonyl concentration. The apparent reaction rate constant for carbonyl formation and oxidation were 6.24 × 104 s-1 and 1.01 × 104 M-1.s-1, respectively. While apparent reaction rate constant for carboxyl oxidation was 4.86 × 104 M-1.s-1.

  13. Physics of partially ionized plasmas

    CERN Document Server

    Krishan, Vinod

    2016-01-01

    Plasma is one of the four fundamental states of matter; the other three being solid, liquid and gas. Several components, such as molecular clouds, diffuse interstellar gas, the solar atmosphere, the Earth's ionosphere and laboratory plasmas, including fusion plasmas, constitute the partially ionized plasmas. This book discusses different aspects of partially ionized plasmas including multi-fluid description, equilibrium and types of waves. The discussion goes on to cover the reionization phase of the universe, along with a brief description of high discharge plasmas, tokomak plasmas and laser plasmas. Various elastic and inelastic collisions amongst the three particle species are also presented. In addition, the author demonstrates the novelty of partially ionized plasmas using many examples; for instance, in partially ionized plasma the magnetic induction is subjected to the ambipolar diffusion and the Hall effect, as well as the usual resistive dissipation. Also included is an observation of kinematic dynam...

  14. Introduction to partial differential equations

    CERN Document Server

    Greenspan, Donald

    2000-01-01

    Designed for use in a one-semester course by seniors and beginning graduate students, this rigorous presentation explores practical methods of solving differential equations, plus the unifying theory underlying the mathematical superstructure. Topics include basic concepts, Fourier series, second-order partial differential equations, wave equation, potential equation, heat equation, approximate solution of partial differential equations, and more. Exercises appear at the ends of most chapters. 1961 edition.

  15. New metals

    International Nuclear Information System (INIS)

    Bergqvist, U.

    1983-12-01

    The aim of this report is to estimate the exposure to various metals and metal compounds and discuss the available information of the possible toxic effects of these metals and compounds. In the first section, some metals are defined as those with either a large or a fast increasing exposure to living organisms. The available information on toxicity is discussed in the second section. In the third section interesting metals are defined as compounds having a large exposure and an apparent insufficient knowledge of their possible toxic effects. Comments on each of these metals are also to be found in the third section. (G.B.)

  16. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  17. The copper-catalysed Suzuki-Miyaura coupling of alkylboron reagents: disproportionation of anionic (alkyl)(alkoxy)borates to anionic dialkylborates prior to transmetalation.

    Science.gov (United States)

    Basnet, Prakash; Thapa, Surendra; Dickie, Diane A; Giri, Ramesh

    2016-09-25

    We report the first example of Cu(I)-catalysed coupling of alkylboron reagents with aryl and heteroaryl iodides that affords products in good to excellent yields. Preliminary mechanistic studies with alkylborates indicate that the anionic (alkoxy)(alkyl)borates, generated from alkyllithium and alkoxyboron reagents, undergo disproportionation to anionic dialkylborates and that both anionic alkylborates are active for transmetalation to a Cu(I)-catalyst. Results from a radical clock experiment and the Hammett plot imply that the reaction likely proceeds via a non-radical pathway.

  18. Revisiting the Brønsted acid catalysed hydrolysis kinetics of polymeric carbohydrates in ionic liquids by in situ ATR-FTIR spectroscopy

    DEFF Research Database (Denmark)

    Kunov-Kruse, Andreas Jonas; Riisager, Anders; Shunmugavel, Saravanamurugan

    2013-01-01

    A new versatile method to measure rates and determine activation energies for the Brønsted acid catalysed hydrolysis of cellulose and cellobiose (and other polymeric carbohydrates) in ionic liquids is demonstrated by following the C–O stretching band of the glycoside bond with in situ ATR......-FTIR. An activation energy in excellent agreement with the literature was determined for cellulose hydrolysis, whereas a distinctly lower activation energy was determined for cellobiose hydrolysis. The methodology also allowed to independently determine activation energies for the formation of 5-hydroxymethylfurfural...

  19. Metal lagging

    International Nuclear Information System (INIS)

    Lemercier, Guy.

    1974-01-01

    The metal lagging described is characterized by the fact that it is formed of closed sacks composed of an elastic metal mass, compressed in an outer envelope made of a fine mesh metal fabric. The metal mass is composed of stainless steel wool stuffed into the envelope. This lagging is particularly intended for the thermal protection of the end slab of LMFBR type reactors [fr

  20. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  1. Silicone metalization

    Energy Technology Data Exchange (ETDEWEB)

    Maghribi, Mariam N. (Livermore, CA); Krulevitch, Peter (Pleasanton, CA); Hamilton, Julie (Tracy, CA)

    2008-12-09

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  2. Parachute technique for partial penectomy

    Directory of Open Access Journals (Sweden)

    Fernando Korkes

    2010-04-01

    Full Text Available PURPOSE: Penile carcinoma is a rare but mutilating malignancy. In this context, partial penectomy is the most commonly applied approach for best oncological results. We herein propose a simple modification of the classic technique of partial penectomy, for better cosmetic and functional results. TECHNIQUE: If partial penectomy is indicated, the present technique can bring additional benefits. Different from classical technique, the urethra is spatulated only ventrally. An inverted "V" skin flap with 0.5 cm of extension is sectioned ventrally. The suture is performed with vicryl 4-0 in a "parachute" fashion, beginning from the ventral portion of the urethra and the "V" flap, followed by the "V" flap angles and than by the dorsal portion of the penis. After completion of the suture, a Foley catheter and light dressing are placed for 24 hours. CONCLUSIONS: Several complex reconstructive techniques have been previously proposed, but normally require specific surgical abilities, adequate patient selection and staged procedures. We believe that these reconstructive techniques are very useful in some specific subsets of patients. However, the technique herein proposed is a simple alternative that can be applied to all men after a partial penectomy, and takes the same amount of time as that in the classic technique. In conclusion, the "parachute" technique for penile reconstruction after partial amputation not only improves the appearance of the penis, but also maintains an adequate function.

  3. Partial breast radiation therapy - external beam

    Science.gov (United States)

    Carcinoma of the breast - partial radiation therapy; Partial external beam radiation - breast; Intensity-modulated radiation therapy - breast cancer; IMRT - breast cancer WBRT; Adjuvant partial breast - IMRT; APBI - IMRT; ...

  4. Enzyme catalysed tandem reactions

    OpenAIRE

    Oroz-Guinea, Isabel; García-Junceda, Eduardo

    2013-01-01

    To transfer to the laboratory, the excellent efficiency shown by enzymes in Nature, biocatalysis, had to mimic several synthetic strategies used by the living organisms. Biosynthetic pathways are examples of tandem catalysis and may be assimilated in the biocatalysis field for the use of isolated multi-enzyme systems in the homogeneous phase. The concurrent action of several enzymes that work sequentially presents extraordinary advantages from the synthetic point of view, since it permits a r...

  5. Enzyme catalysed tandem reactions.

    Science.gov (United States)

    Oroz-Guinea, Isabel; García-Junceda, Eduardo

    2013-04-01

    To transfer to the laboratory, the excellent efficiency shown by enzymes in Nature, biocatalysis, had to mimic several synthetic strategies used by the living organisms. Biosynthetic pathways are examples of tandem catalysis and may be assimilated in the biocatalysis field for the use of isolated multi-enzyme systems in the homogeneous phase. The concurrent action of several enzymes that work sequentially presents extraordinary advantages from the synthetic point of view, since it permits a reversible process to become irreversible, to shift the equilibrium reaction in such a way that enantiopure compounds can be obtained from prochiral or racemic substrates, reduce or eliminate problems due to product inhibition or prevent the shortage of substrates by dilution or degradation in the bulk media, etc. In this review we want to illustrate the developments of recent studies involving in vitro multi-enzyme reactions for the synthesis of different classes of organic compounds. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Partially composite Goldstone Higgs boson

    DEFF Research Database (Denmark)

    Alanne, Tommi; Franzosi, Diogo Buarque; Frandsen, Mads T.

    2017-01-01

    We consider a model of dynamical electroweak symmetry breaking with a partially composite Goldstone Higgs boson. The model is based on a strongly interacting fermionic sector coupled to a fundamental scalar sector via Yukawa interactions. The SU(4)×SU(4) global symmetry of these two sectors...... is broken to a single SU(4) via Yukawa interactions. Electroweak symmetry breaking is dynamically induced by condensation due to the strong interactions in the new fermionic sector which further breaks the global symmetry SU(4)→Sp(4). The Higgs boson arises as a partially composite state which is an exact...... Goldstone boson in the limit where SM interactions are turned off. Terms breaking the SU(4) global symmetry explicitly generate a mass for the Goldstone Higgs boson. The model realizes in different limits both (partially) composite Higgs and (bosonic) technicolor models, thereby providing a convenient...

  7. Cardiac asystole in partial seizures.

    Science.gov (United States)

    Scott, C A; Fish, D R

    2000-06-01

    Literature review shows many anecdotal case reports of cardiac asystole in ictal recordings of partial seizures. We have reviewed our data from the last five years, of patients who are being assessed for epilepsy surgery and found 2 out of more than 1,500 complex partial seizures, recorded in 589 consecutive patients, showing a significant period of asystole (13 and 15 seconds). Our previous studies of cardiac and respiratory parameters during partial seizures showed that a central apnoea occurred in 39%. It is probable that sudden death during seizures is due to the interaction of both cardiac and respiratory irregularities. Although rare (occurrence cardiac asystole occurring in an epilepsy monitoring unit highlights the need for resuscitation equipment to be readily available and for trained nursing staff. Furthermore, it is important to recognize that the semiology of seizures may be affected by the consequences of secondary cardiac asystole.

  8. partial replacement of partial replacement of cement with bagasse

    African Journals Online (AJOL)

    eobe

    4. CONCLUSION. CONCLUSION. CONCLUSION. 1. BA as a partial replacement for cement will help to solve environmental problems encountered in urban settings where Bagasse is disposed; hence this can help in the actualization of the phrase. “waste to wealth”. 2. The desirable properties of aggregates used in this.

  9. Partial pressure analysis of plasmas

    International Nuclear Information System (INIS)

    Dylla, H.F.

    1984-11-01

    The application of partial pressure analysis for plasma diagnostic measurements is reviewed. A comparison is made between the techniques of plasma flux analysis and partial pressure analysis for mass spectrometry of plasmas. Emphasis is given to the application of quadrupole mass spectrometers (QMS). The interface problems associated with the coupling of a QMS to a plasma device are discussed including: differential-pumping requirements, electromagnetic interferences from the plasma environment, the detection of surface-active species, ion source interactions, and calibration procedures. Example measurements are presented from process monitoring of glow discharge plasmas which are useful for cleaning and conditioning vacuum vessels

  10. Elements of partial differential equations

    CERN Document Server

    Sneddon, Ian Naismith

    1957-01-01

    Geared toward students of applied rather than pure mathematics, this volume introduces elements of partial differential equations. Its focus is primarily upon finding solutions to particular equations rather than general theory.Topics include ordinary differential equations in more than two variables, partial differential equations of the first and second orders, Laplace's equation, the wave equation, and the diffusion equation. A helpful Appendix offers information on systems of surfaces, and solutions to the odd-numbered problems appear at the end of the book. Readers pursuing independent st

  11. Basic linear partial differential equations

    CERN Document Server

    Treves, Francois

    1975-01-01

    Focusing on the archetypes of linear partial differential equations, this text for upper-level undergraduates and graduate students features most of the basic classical results. The methods, however, are decidedly nontraditional: in practically every instance, they tend toward a high level of abstraction. This approach recalls classical material to contemporary analysts in a language they can understand, as well as exploiting the field's wealth of examples as an introduction to modern theories.The four-part treatment covers the basic examples of linear partial differential equations and their

  12. Comparative study of antioxidant, metal chelating and antiglycation activities of Momordica charantia flesh and pulp fractions.

    Science.gov (United States)

    Ghous, Tahseen; Aziz, Nouman; Mehmood, Zahid; Andleeb, Saiqa

    2015-07-01

    Momordica charantia is commonly used as a vegetable and folk medicine in most parts of South Asia. This study aims to determine and compare the antioxidant, metal chelating and antiglycation activities of aqueous extracts of M. charantia fruit flesh (MCF) and fruit pulp (MCP) fractions. Our results show that MCP has pronounced DPPH and ABTS radical scavenging potential compared to MCF. In the antiglycation assay both fractions illustrated considerable inhibitory activities against the formation of AGEs induced by glucose with an efficacy of 75 and 67% with 150 μl of MCP and MCF extracts respectively, almost equal to 0.3mM amino guanidine. Results for metal catalysed protein fragmentation and autoxidative and glycoxidation assays demonstrate that MCF and MCP inhibited metal catalysed protein fragmentation. The percentage of relative standard deviation for three replicate measurements of 150 μl of MCF and MCP was < 3.0% for antiglycation. The antioxidant assays with regression values of MCP (0.981 and 0.991) and MCF (0.967 and 0.999) were also recorded. We conclude that both extracts possess high antioxidant and antiglycation activities and are equally good sources of antioxidant and antiglycating agents.

  13. The base catalysed hydrolysis of methyl paraben: a test reaction for flow microcalorimeters used for determination of both kinetic and thermodynamic parameters

    Energy Technology Data Exchange (ETDEWEB)

    O' Neill, M.A.A.; Beezer, A.E.; Labetoulle, C.; Nicolaides, L.; Mitchell, J.C.; Orchard, J.A.; Connor, J.A.; Kemp, R.B.; Olomolaiye, D

    2003-03-24

    The results of an inter/intra-laboratory study into a test and reference reaction for isothermal microcalorimeters, the imidazole catalysed hydrolysis of triacetin, have been reported in a recent paper [Thermochim. Acta 380 (2001) 13]. The results and conclusions drawn from this study have been extended to a consideration of the need for a similar test and reference reaction for isothermal microcalorimeters operating in flow mode. This paper reports the findings of a preliminary inter/intra-laboratory study of the base catalysed hydrolysis of methyl 4-hydroxy benzoate (methyl paraben) and its suitability as a test and reference reaction. The derived values for the hydrolysis reaction were (3.15{+-}0.11)x10{sup -4} s{sup -1} and -50.5{+-}4.3 kJ mol{sup -1} for the rate constant and enthalpy, respectively. It is also reported how such a test and reference reaction can be used to validate the thermal output from a LKB 10-700-1 and Thermometric Thermal Activity Monitor (TAM) 2277-202 flow microcalorimeters.

  14. Synchronizing Strategies under Partial Observability

    DEFF Research Database (Denmark)

    Larsen, Kim Guldstrand; Laursen, Simon; Srba, Jiri

    2014-01-01

    Embedded devices usually share only partial information about their current configurations as the communication bandwidth can be restricted. Despite this, we may wish to bring a failed device into a given predetermined configuration. This problem, also known as resetting or synchronizing words, has...

  15. Characterization of Partial Intrinsic Symmetries

    NARCIS (Netherlands)

    Shehu, Aurela; Brunton, Alan; Wuhrer, Stefanie; Wand, Michael

    2014-01-01

    We present a mathematical framework and algorithm for characterizing and extracting partial intrinsic symmetries of surfaces, which is a fundamental building block for many modern geometry processing algorithms. Our goal is to compute all “significant” symmetry information of the shape, which we

  16. 75__Abdulazeez_Partial purification

    African Journals Online (AJOL)

    User

    pharmaceutical industry, carboxymethylated st. (CMS) is used as disintegrant in tablets and been reported .... The Amino Acid profile of the partially purified peptide was determined using methods described by Benitez ..... North America, Mexico and Central America. Botanical Institute of Texas, Fort Worth,. Texas, United ...

  17. Adaptive Partially Hidden Markov Models

    DEFF Research Database (Denmark)

    Forchhammer, Søren Otto; Rasmussen, Tage

    1996-01-01

    Partially Hidden Markov Models (PHMM) have recently been introduced. The transition and emission probabilities are conditioned on the past. In this report, the PHMM is extended with a multiple token version. The different versions of the PHMM are applied to bi-level image coding....

  18. Timed Testing under Partial Observability

    DEFF Research Database (Denmark)

    David, Alexandre; Larsen, Kim Guldstrand; Li, Shuhao

    2009-01-01

    observability of SUT using a set of predicates over the TGA state space, and specify the test purposes in Computation Tree Logic (CTL) formulas. A recently developed partially observable timed game solver is used to generate winning strategies, which are used as test cases. We propose a conformance testing...

  19. Partially molten magma ocean model

    International Nuclear Information System (INIS)

    Shirley, D.N.

    1983-01-01

    The properties of the lunar crust and upper mantle can be explained if the outer 300-400 km of the moon was initially only partially molten rather than fully molten. The top of the partially molten region contained about 20% melt and decreased to 0% at 300-400 km depth. Nuclei of anorthositic crust formed over localized bodies of magma segregated from the partial melt, then grew peripherally until they coverd the moon. Throughout most of its growth period the anorthosite crust floated on a layer of magma a few km thick. The thickness of this layer is regulated by the opposing forces of loss of material by fractional crystallization and addition of magma from the partial melt below. Concentrations of Sr, Eu, and Sm in pristine ferroan anorthosites are found to be consistent with this model, as are trends for the ferroan anorthosites and Mg-rich suites on a diagram of An in plagioclase vs. mg in mafics. Clustering of Eu, Sr, and mg values found among pristine ferroan anorthosites are predicted by this model

  20. Variable Selection via Partial Correlation.

    Science.gov (United States)

    Li, Runze; Liu, Jingyuan; Lou, Lejia

    2017-07-01

    Partial correlation based variable selection method was proposed for normal linear regression models by Bühlmann, Kalisch and Maathuis (2010) as a comparable alternative method to regularization methods for variable selection. This paper addresses two important issues related to partial correlation based variable selection method: (a) whether this method is sensitive to normality assumption, and (b) whether this method is valid when the dimension of predictor increases in an exponential rate of the sample size. To address issue (a), we systematically study this method for elliptical linear regression models. Our finding indicates that the original proposal may lead to inferior performance when the marginal kurtosis of predictor is not close to that of normal distribution. Our simulation results further confirm this finding. To ensure the superior performance of partial correlation based variable selection procedure, we propose a thresholded partial correlation (TPC) approach to select significant variables in linear regression models. We establish the selection consistency of the TPC in the presence of ultrahigh dimensional predictors. Since the TPC procedure includes the original proposal as a special case, our theoretical results address the issue (b) directly. As a by-product, the sure screening property of the first step of TPC was obtained. The numerical examples also illustrate that the TPC is competitively comparable to the commonly-used regularization methods for variable selection.

  1. Implementing circularity using partial evaluation

    DEFF Research Database (Denmark)

    Lawall, Julia Laetitia

    2001-01-01

    of an imperative C-like language, by extending the language with a new construct, persistent variables. We show that an extension of partial evaluation can eliminate persistent variables, producing a staged C program. This approach has been implemented in the Tempo specializer for C programs, and has proven useful...

  2. Migrating Partial Seizures of Infancy

    Directory of Open Access Journals (Sweden)

    J Gordon Millichap

    2013-06-01

    Full Text Available A national surveillance study in conjunction with the British Paediatric Neurology Unit was undertaken to further define the clinical, pathological and molecular genetic features of migrating partial seizures of infancy (MPSI, a rare early infantile epileptic encephalopathy with poor prognosis.

  3. Transition-metal-free chemo- and regioselective vinylation of azaallyls

    Science.gov (United States)

    Li, Minyan; Gutierrez, Osvaldo; Berritt, Simon; Pascual-Escudero, Ana; Yeşilçimen, Ahmet; Yang, Xiaodong; Adrio, Javier; Huang, Georgia; Nakamaru-Ogiso, Eiko; Kozlowski, Marisa C.; Walsh, Patrick J.

    2017-10-01

    Direct C(sp3)-C(sp2) bond formation under transition-metal-free conditions offers an atom-economical, inexpensive and environmentally benign alternative to traditional transition-metal-catalysed cross-coupling reactions. A new chemo- and regioselective coupling protocol between 3-aryl-substituted-1,1-diphenyl-2-azaallyl derivatives and vinyl bromides has been developed. This is the first transition-metal-free cross-coupling of azaallyls with vinyl bromide electrophiles and delivers allylic amines in excellent yields (up to 99%). This relatively simple and mild protocol offers a direct and practical strategy for the synthesis of high-value allylic amine building blocks that does not require the use of transition metals, special initiators or photoredox catalysts. Radical clock experiments, electron paramagnetic resonance studies and density functional theory calculations point to an unprecedented substrate-dependent coupling mechanism. Furthermore, an electron paramagnetic resonance signal was observed when the N-benzyl benzophenone ketimine was subjected to silylamide base, supporting the formation of radical species upon deprotonation. The unique mechanisms outlined herein could pave the way for new approaches to transition-metal-free C-C bond formations.

  4. Antimicrobial resistance challenged with metal-based antimicrobial macromolecules.

    Science.gov (United States)

    Abd-El-Aziz, Alaa S; Agatemor, Christian; Etkin, Nola

    2017-02-01

    Antimicrobial resistance threatens the achievements of science and medicine, as it deactivates conventional antimicrobial therapeutics. Scientists respond to the threat by developing new antimicrobial platforms to prevent and treat infections from these resistant strains. Metal-based antimicrobial macromolecules are emerging as an alternative to conventional platforms because they combine multiple mechanisms of action into one platform due to the distinctive properties of metals. For example, metals interact with intracellular proteins and enzymes, and catalyse various intracellular processes. The macromolecular architecture offers a means to enhance antimicrobial activity since several antimicrobial moieties can be conjugated to the scaffold. Further, these macromolecules can be fabricated into antimicrobial materials for contact-killing medical implants, fabrics, and devices. As volatilization or leaching out of the antimicrobial moieties from the macromolecular scaffold is reduced, these medical implants, fabrics, and devices can retain their antimicrobial activity over an extended period. Recent advances demonstrate the potential of metal-based antimicrobial macromolecules as effective platforms that prevent and treat infections from resistant strains. In this review these advances are thoroughly discussed within the context of examples of metal-based antimicrobial macromolecules, their mechanisms of action and biocompatibility. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. High-performance heterogeneous catalysis with surface-exposed stable metal nanoparticles.

    Science.gov (United States)

    Huang, Ning; Xu, Yanhong; Jiang, Donglin

    2014-11-27

    Protection of metal nanoparticles from agglomeration is critical for their functions and applications. The conventional method for enhancing their stability is to cover them with passivation layers to prevent direct contact. However, the presence of a protective shell blocks exposure of the metal species to reactants, thereby significantly impeding the nanoparticles' utility as catalysts. Here, we report that metal nanoparticles can be prepared and used in a surface-exposed state that renders them inherently catalytically active. This strategy is realised by spatial confinement and electronic stabilisation with a dual-module mesoporous and microporous three-dimensional π-network in which surface-exposed nanoparticles are crystallised upon in situ reduction. The uncovered palladium nanoparticles serve as heterogeneous catalysts that are exceptionally active in water, catalyse unreactive aryl chlorides for straightforward carbon-carbon bond formation and are stable for repeated use in various types of cross couplings. Therefore, our results open new perspectives in developing practical heterogeneous catalysts.

  6. Metallic nanomesh

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Zhifeng; Sun, Tianyi; Guo, Chuanfei

    2018-02-20

    A transparent flexible nanomesh having at least one conductive element and sheet resistance less than 300.OMEGA./.quadrature. when stretched to a strain of 200% in at least one direction. The nanomesh is formed by depositing a sacrificial film, depositing, etching, and oxidizing a first metal layer on the film, etching the sacrificial film, depositing a second metal layer, and removing the first metal layer to form a nanomesh on the substrate.

  7. 32 CFR 751.13 - Partial payments.

    Science.gov (United States)

    2010-07-01

    ... voucher and all other information related to the partial payment shall be placed in the claim file. Action... 32 National Defense 5 2010-07-01 2010-07-01 false Partial payments. 751.13 Section 751.13 National... Claims Against the United States § 751.13 Partial payments. (a) Partial payments when hardship exists...

  8. VLSI metallization

    CERN Document Server

    Einspruch, Norman G; Gildenblat, Gennady Sh

    1987-01-01

    VLSI Electronics Microstructure Science, Volume 15: VLSI Metallization discusses the various issues and problems related to VLSI metallization. It details the available solutions and presents emerging trends.This volume is comprised of 10 chapters. The two introductory chapters, Chapter 1 and 2 serve as general references for the electrical and metallurgical properties of thin conducting films. Subsequent chapters review the various aspects of VLSI metallization. The order of presentation has been chosen to follow the common processing sequence. In Chapter 3, some relevant metal deposition tec

  9. First-principles molecular dynamics for metals

    International Nuclear Information System (INIS)

    Fernando, G.W.; Qian, G.; Weinert, M.; Davenport, J.W.

    1989-01-01

    A Car-Parrinello-type first-principles molecular-dynamics approach capable of treating the partial occupancy of electronic states that occurs at the Fermi level in a metal is presented. The algorithms used to study metals are both simple and computationally efficient. We also discuss the connection between ordinary electronic-structure calculations and molecular-dynamics simulations as well as the role of Brillouin-zone sampling. This extension should be useful not only for metallic solids but also for solids that become metals in their liquid and/or amorphous phases

  10. Trace metal speciation: Finally, correctly addressing trace metal issues

    International Nuclear Information System (INIS)

    Donard, O.F.X.

    2001-01-01

    The history of the development of trace metal speciation was discussed and the reasons behind the relatively slow widespread acceptance of its importance were presented. Partially, this was due to the lack of availability of commercial instrumentation and partly to the drive towards improving sensitivity in analytical chemistry which had focused attention on total concentration determinations. The sophistication and control of analytical instrumentation is now such that the spotlight must be turned onto the chemical species of an element present in a sample since this is what governs its behaviour in the biosphere. Indeed, several companies are currently considering the introduction of instrumentation specifically designed for metal species determination

  11. Characterization of two genes encoding metal tolerance proteins from Beta vulgaris subspecies maritima that confers manganese tolerance in yeast

    DEFF Research Database (Denmark)

    Erbasol, Isil; Bozdag, Gonensin Ozan; Koc, Ahmet

    2013-01-01

    Manganese (Mn) is an essential micronutrient in plants. However increased Mn levels are toxic to plant cells. Metal tolerance proteins (MTPs), member of cation diffusion facilitator protein (CDF) family, have important roles in metal homeostatis in different plant species and catalyse efflux...... in planta localization and function as the Arabidopsis Mn-CDF homolog AtMTP11 and this conservation shows the evolutionary importance of these vesicular proteins in heavy metal homeostatis among plant species....... of excess metal ions. In this study, we identified and characterized two MTP genes from Beta vulgaris spp. maritima (B. v. ssp. maritima). Overexpression of these two genes provided Mn tolerance in yeast cells. Sequence analyses displayed BmMTP10 and BmMTP11as members of the Mn-CDF family. Functional...

  12. The marketing of partial hospitalization.

    Science.gov (United States)

    Millsap, P; Brown, E; Kiser, L; Pruitt, D

    1987-09-01

    Health-care professionals are currently operating in the context of a rapidly changing health-care delivery system, including the move away from inpatient services to outpatient services in order to control costs. Those who practice in partial-hospital settings are in a position to offer effective, cost-efficient services; however, there continue to be obstacles which hinder appropriate utilization of the modality. The development and use of a well-designed marketing plan is one strategy for removing these obstacles. This paper presents a brief overview of the marketing process, ideas for developing a marketing plan, and several examples of specific marketing strategies as well as ways to monitor their effectiveness. Partial-hospital providers must take an active role in answering the calls for alternative sources of psychiatric care. A comprehensive, education-oriented marketing approach will increase the public's awareness of such alternatives and enable programs to survive in a competitive environment.

  13. Partial scram incident in FBTR

    International Nuclear Information System (INIS)

    Usha, S.; Pillai, C.P.; Muralikrishna, G.

    1989-01-01

    Evaluation of a partial scram incident occurred at the Fast Breeder Test Reactor at Kalpakkam was carried out. Based on the observations of the experiments it was ascertained that the nonpersistant order was due to superimposed noise component on the channel that was close to the threshold and had resulted in intermittent supply to electro-magnetic (EM) coils. Owing to a larger discharge time and a smaller charge time, the EM coils got progressively discharged. It was confirmed that during the incident, partial scram took place since the charging and discharging patterns of the EM coils are dissimilar and EM coils of rods A, E and F had discharged faster than others for noise component of a particular duty cycle. However, nonlatching of scram order was because of the fact that noise pulse duration was less than latching time. (author)

  14. Dynamics of partial differential equations

    CERN Document Server

    Wayne, C Eugene

    2015-01-01

    This book contains two review articles on the dynamics of partial differential equations that deal with closely related topics but can be read independently. Wayne reviews recent results on the global dynamics of the two-dimensional Navier-Stokes equations. This system exhibits stable vortex solutions: the topic of Wayne's contribution is how solutions that start from arbitrary initial conditions evolve towards stable vortices. Weinstein considers the dynamics of localized states in nonlinear Schrodinger and Gross-Pitaevskii equations that describe many optical and quantum systems. In this contribution, Weinstein reviews recent bifurcations results of solitary waves, their linear and nonlinear stability properties, and results about radiation damping where waves lose energy through radiation.   The articles, written independently, are combined into one volume to showcase the tools of dynamical systems theory at work in explaining qualitative phenomena associated with two classes of partial differential equ...

  15. Introduction to partial differential equations

    CERN Document Server

    Borthwick, David

    2016-01-01

    This modern take on partial differential equations does not require knowledge beyond vector calculus and linear algebra. The author focuses on the most important classical partial differential equations, including conservation equations and their characteristics, the wave equation, the heat equation, function spaces, and Fourier series, drawing on tools from analysis only as they arise.Within each section the author creates a narrative that answers the five questions: (1) What is the scientific problem we are trying to understand? (2) How do we model that with PDE? (3) What techniques can we use to analyze the PDE? (4) How do those techniques apply to this equation? (5) What information or insight did we obtain by developing and analyzing the PDE? The text stresses the interplay between modeling and mathematical analysis, providing a thorough source of problems and an inspiration for the development of methods.

  16. Solvency ii. partial internal model

    OpenAIRE

    Baltrėnas, Rokas

    2016-01-01

    Solvency II. Partial Internal Model Solvency is one of the most important characteristics of the insurance company. Sufficient solvency ratio ensures long–term performance of the company and the necessary protection of policyholders. The new solvency assessment framework (Solvency II) came into force across the EU on 1 January 2016. It is based on a variety of risk evaluation modules, so it better reflects the real state of the company’s solvency. Under the Solvency II insurance company’s sol...

  17. Exact dynamical and partial symmetries

    Energy Technology Data Exchange (ETDEWEB)

    Leviatan, A, E-mail: ami@phys.huji.ac.il [Racah Institute of Physics, The Hebrew University, Jerusalem 91904 (Israel)

    2011-03-01

    We discuss a hierarchy of broken symmetries with special emphasis on partial dynamical symmetries (PDS). The latter correspond to a situation in which a non-invariant Hamiltonian accommodates a subset of solvable eigenstates with good symmetry, while other eigenstates are mixed. We present an algorithm for constructing Hamiltonians with this property and demonstrate the relevance of the PDS notion to nuclear spectroscopy, to quantum phase transitions and to mixed systems with coexisting regularity and chaos.

  18. Exact dynamical and partial symmetries

    International Nuclear Information System (INIS)

    Leviatan, A

    2011-01-01

    We discuss a hierarchy of broken symmetries with special emphasis on partial dynamical symmetries (PDS). The latter correspond to a situation in which a non-invariant Hamiltonian accommodates a subset of solvable eigenstates with good symmetry, while other eigenstates are mixed. We present an algorithm for constructing Hamiltonians with this property and demonstrate the relevance of the PDS notion to nuclear spectroscopy, to quantum phase transitions and to mixed systems with coexisting regularity and chaos.

  19. [Benign partial epilepsies of childhood].

    Science.gov (United States)

    Palencia, R

    To carry out, by means of a literature review, an update of the entities that can be included within the group of benign partial epilepsies of childhood. Among partial epilepsies with onset in the first stages of life, a group extended in the last years with a favourable course and a trend to reverse, even spontaneously, has been identified. Some of these entities have a genetic origin but we do not know the mechanisms by which these epilepsies show a self limited course, which have given rise to the denomination of epilepsy that comes and goes; nevertheless, an evolution to other more complex forms is also possible. Benign partial epilepsies of childhood constitute a wide group of conditions of varied semiology, usually with a good prognosis even without treatment. Occasionally, these epilepsies may show a more unfavourable course with a worsening, in spite of medication, and the appearance of neurologic and neuropsychologic disorders. All these aspects must be known and considered by the physician in charge of these patients management.

  20. Signature of Metallic Behavior in the Metal-Organic Frameworks M3(hexaiminobenzene)2(M = Ni, Cu).

    Science.gov (United States)

    Dou, Jin-Hu; Sun, Lei; Ge, Yicong; Li, Wenbin; Hendon, Christopher H; Li, Ju; Gul, Sheraz; Yano, Junko; Stach, Eric A; Dincă, Mircea

    2017-10-04

    The two-dimensionally connected metal-organic frameworks (MOFs) Ni 3 (HIB) 2 and Cu 3 (HIB) 2 (HIB = hexaiminobenzene) are bulk electrical conductors and exhibit ultraviolet-photoelectron spectroscopy (UPS) signatures expected of metallic solids. Electronic band structure calculations confirm that in both materials the Fermi energy lies in a partially filled delocalized band. Together with additional structural characterization and microscopy data, these results represent the first report of metallic behavior and permanent porosity coexisting within a metal-organic framework.

  1. Heavy metal

    African Journals Online (AJOL)

    of spawning, resistance to diseases and social acceptability (Pillay, 1993). This study aimed at determining the carbohydrate reserves and heavy metal accumulation of the Nile tilapia, Oreochromis miloticus after treatment with heavy metals such as lead, copper and zinc. 2. Materials and Methods. Test organism: Nile tilapia ...

  2. Plasma metallization

    International Nuclear Information System (INIS)

    Crowther, J.M.

    1997-09-01

    Many methods are currently used for the production of thin metal films. However, all of these have drawbacks associated with them, for example the need for UHV conditions, high temperatures, exotic metal precursors, or the inability to coat complex shaped objects. Reduction of supported metal salts by non-isothermal plasma treatment does not suffer from these drawbacks. In order to produce and analyse metal films before they become contaminated, a plasma chamber which could be attached directly to a UHV chamber with XPS capability was designed and built. This allowed plasma treatment of supported metal salts and surface analysis by XPS to be performed without exposure of the metal film to the atmosphere. Non-equilibrium plasma treatment of Nylon 66 supported gold(lll) chloride using hydrogen as the feed gas resulted in a 95% pure gold film, the remaining 5% of the film being carbon. If argon or helium were used as the feed gases during plasma treatment the resultant gold films were 100% pure. Some degree of surface contamination of the films due to plasma treatment was observed but was easily removed by argon ion cleaning. Hydrogen plasma reduction of glass supported silver(l) nitrate and palladium(ll) acetate films reveals that this metallization technique is applicable to a wide variety of metal salts and supports, and has also shown the ability of plasma reduction to retain the complex 'fern-like' structures seen for spin coated silver(l) nitrate layers. Some metal salts are susceptible to decomposition by X-rays. The reduction of Nylon 66 supported gold(lll) chloride films by soft X-rays to produce nanoscopic gold particles has been studied. The spontaneous reduction of these X-ray irradiated support gold(lll) chloride films on exposure to the atmosphere to produce gold rich metallic films has also been reported. (author)

  3. Correlations in a partially degenerate electron plasma

    Energy Technology Data Exchange (ETDEWEB)

    Chihara, Junzo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-03-01

    The density-functional theory proves that an ion-electron mixture can be treated as a one-component liquid interacting only via a pairwise interaction in the evaluation of the ion-ion radial distribution function (RDF), and provides a set of integral equations: one is an integral equation for the ion-ion RDF and another for an effective ion-ion interaction, which depends on the ion-ion RDF. This formulation gives a set of integral equation to calculate plasma structures with combined use of the electron-electron correlations in a partially degenerate electron plasma. Therefore, it is important for this purpose to determine the electron-electron correlations at a arbitrary temperature. Here, they are calculated by the quantal version of the hypernetted chain (HNC) equation. On the basis of the jellium-vacancy model, the ionic and electronic structures of rubidium are calculated for the range from liquid metal to plasma states by increasing the temperature at the fixed density using the electron-correlation results. (author)

  4. The fate of heavy metals during combustion and gasification of contaminated biomass—A brief review

    Energy Technology Data Exchange (ETDEWEB)

    Nzihou, Ange, E-mail: ange.nzihou@mines-albi.fr [Université de Toulouse, Mines Albi, CNRS, Centre RAPSODEE, Campus Jarlard, F-81013 Albi cedex 09 (France); Stanmore, Brian [Formerly of the University of Queensland, Brisbane, QLD 4072 (Australia)

    2013-07-15

    Highlights: ► A review on metal behaviour during the thermal treatment of contamined biomass. ► Wide range of biomass waste reported. ► Distribution of metals in the ash, and in the sub-micron particles discussed. -- Abstract: The literature on the presence of heavy metals in contaminated wastes is reviewed. Various categories of materials produced from domestic and industrial activities are included, but municipal solid waste, which is a more complex material, is excluded. This review considers among the most abundant the following materials – wood waste including demolition wood, phytoremediation scavengers and chromated copper arsenate (CCA) timber, sludges including de-inking sludge and sewage sludge, chicken litter and spent pot liner. The partitioning of the metals in the ashes after combustion or gasification follows conventional behaviour, with most metals retained, and higher concentrations in the finer sizes due to vaporisation and recondensation. The alkali metals have been shown to catalyse the biomass conversion, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent in biomass is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. Because the metals are predominantly found in the ash, the effectiveness of their removal depends on the efficiency of the collection of particulates. The potential for disposal into soil depends on the initial concentration in the feed material.

  5. Ethnographic Evidence of an Emerging Transnational Arts Practice?: Perspectives on U.K. and Mexican Participatory Artists' Processes for Catalysing Change, and Facilitating Health and Flourishing.

    Science.gov (United States)

    Raw, Anni

    2014-03-01

    This article reports new ethnographic research exploring community-based, participatory arts practice in Northern England and Mexico City. Noting the value of an ethnographic approach, the study investigated whether commonalities discovered in practitioners' approaches are significant enough to constitute a generalisable participatory arts methodology, transcending significant contextual differences, and recognisable across national boundaries. Shared characteristics emerged in practitioners' modes of engagement with groups, and strategies for catalysing change; clear convergences from which a core methodology in community-based participatory arts for change is distilled. It suggests the opening of liminal spaces in which participants can reflect, rehearsing fresh ways of engaging in transformative dialogues in relation to the world in which they live. This article presents the study findings as a grounded characterisation of 'participatory arts practice': a complex but potentially powerful mechanism, in use within numerous community health projects, and evident in diverse settings, despite little or no exchange of ideas between practitioners.

  6. Online UV-visible spectroscopy and multivariate curve resolution as powerful tool for model-free investigation of laccase-catalysed oxidation.

    Science.gov (United States)

    Kandelbauer, A; Kessler, W; Kessler, R W

    2008-03-01

    The laccase-catalysed transformation of indigo carmine (IC) with and without a redox active mediator was studied using online UV-visible spectroscopy. Deconvolution of the mixture spectra obtained during the reaction was performed on a model-free basis using multivariate curve resolution (MCR). Thereby, the time courses of educts, products, and reaction intermediates involved in the transformation were reconstructed without prior mechanistic assumptions. Furthermore, the spectral signature of a reactive intermediate which could not have been detected by a classical hard-modelling approach was extracted from the chemometric analysis. The findings suggest that the combined use of UV-visible spectroscopy and MCR may lead to unexpectedly deep mechanistic evidence otherwise buried in the experimental data. Thus, although rather an unspecific method, UV-visible spectroscopy can prove useful in the monitoring of chemical reactions when combined with MCR. This offers a wide range of chemists a cheap and readily available, highly sensitive tool for chemical reaction online monitoring.

  7. Synthesis of Structurally Diverse 2,3-Fused Indoles via Microwave-Assisted AgSbF6-Catalysed Intramolecular Difunctionalization of o-Alkynylanilines

    Science.gov (United States)

    Huang, Yuanqiong; Yang, Yan; Song, Hongjian; Liu, Yuxiu; Wang, Qingmin

    2015-08-01

    2,3-Fused indoles are found in numerous natural products and drug molecules. Although several elegant methods for the synthesis of this structural motif have been reported, long reaction times and harsh conditions are sometimes required, and the yields tend to be low. Herein, we report a microwave method for straightforward access to various types of 2,3-fused indoles via AgSbF6-catalysed intramolecular difunctionalization of o-alkynylanilines. AgSbF6 played a role in both the hydroamination step and the imine-formation step. This method, which exhibited excellent chemoselectivity (no ring-fused 1,2-dihydroquinolines were formed), was used for formal syntheses of the natural products conolidine and ervaticine and the antihistamine drug latrepirdine.

  8. NMR studies on mechanism of isomerisation of fructose 6-phosphate to glucose 6-phosphate catalysed by phosphoglucose isomerase from Thermococcus kodakarensis.

    Science.gov (United States)

    Abbas, Shahzada Nadeem; Mok, Kenneth Hun; Rashid, Naeem; Xie, Yongjing; Ruether, Manuel; O'Brien, John; Akhtar, Muhammad

    2016-06-01

    The fate of hydrogen atoms at C-2 of glucose 6-phosphate (G6P) and C-1 of fructose 6-phosphate (F6P) was studied in the reaction catalysed by phosphoglucose isomerase from Thermococcus kodakarensis (TkPGI) through 1D and 2D NMR methods. When the reaction was performed in (2)H2O the hydrogen atoms in the aforementioned positions were exchanged with deuterons indicating that the isomerization occurred by a cis-enediol intermediate involving C-1 pro-R hydrogen of F6P. These features are similar to those described for phosphoglucose isomerases from rabbit muscle and Pyrococcus furiosus. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Theoretical investigation of the Friedlander reaction catalysed by CuBTC: Concerted effect of the adjacent Cu2+ sites

    Czech Academy of Sciences Publication Activity Database

    Položij, M.; Pérez-Mayoral, E.; Čejka, Jiří; Hermann, J.; Nachtigall, P.

    2013-01-01

    Roč. 204, APR 2013 (2013), s. 101-107 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : Friedlander reaction * Metal Organic Framework (MOF) * CuBTC Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.309, year: 2013

  10. Glucose and Fructose to Platform Chemicals: Understanding the Thermodynamic Landscapes of Acid-Catalysed Reactions Using High-Level ab Initio Methods

    Energy Technology Data Exchange (ETDEWEB)

    Assary, Rajeev S.; Kim, Taijin; Low, John; Greeley, Jeffrey P.; Curtiss, Larry A.

    2012-12-28

    Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2–OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2–OH position, which includes a C–C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future.

  11. Target cells for cytochrome p450-catalysed irreversible binding of 7,12-dimethylbenz[a]anthracene (DMBA) in rodent adrenal glands.

    Science.gov (United States)

    Lindhe, Orjan; Granberg, Lizette; Brandt, Ingvar

    2002-08-01

    7,12-Dimethylbenz[a]anthracene (DMBA) is an adrenocorticolytic agent that causes apoplexy (haemorrhage) and massive necrosis in the adrenal cortex in rat. Several explanations regarding the origin of toxicity have been proposed. Huggins and Morii (J Exp Med 114:741-60, 1961) suggested that the cells of the inner adrenal cortex are the primary target, whereas Horváth and Kovács (Pathol Eur 8:43-59, 1973) suggested the vascular endothelium as being the origin of toxicity. In the present study, cultured precision-cut tissue slices were used to localize target cells for irreversible [(3)H]DMBA binding in rat and mouse adrenal cortex. The sites of binding were confirmed by autoradiography in vivo. Irreversible [(3)H]DMBA binding was confined to zona fasciculata/reticularis cells in rat (but not in mouse) adrenal cortex. Pronounced binding was observed in clusters of cells (focal binding), localized predominantly in zona reticularis of rat. [(3)H]DMBA binding in zona fasciculata/reticularis cells was inhibited by the cytochrome p450 1A/B (CYP1A/B) inhibitors ellipticine, alpha-naphthoflavone, and 1-ethynylpyrene. The CYP11B1-inhibitor metyrapone did not reduce [(3)H]DMBA binding. In CYP1-induced (PCB 126-treated) rats and mice, intense irreversible [(3)H]DMBA binding was found also in endothelial cells of the adrenal cortex. The endothelial binding was abolished by the CYP1 inhibitors but remained unaffected by metyrapone. We conclude that the metabolic activation in adrenal parenchymal cells is presumably catalysed by CYP1B1, whereas CYP1A1 presumably catalyses the activation in endothelial cells. We suggest that the adrenocorticolytic effect of DMBA is the result of a dual mode of action, targeting both endothelial and parenchymal cells in the rat adrenal cortex.

  12. 'Scaling-up is a craft not a science': Catalysing scale-up of health innovations in Ethiopia, India and Nigeria.

    Science.gov (United States)

    Spicer, Neil; Bhattacharya, Dipankar; Dimka, Ritgak; Fanta, Feleke; Mangham-Jefferies, Lindsay; Schellenberg, Joanna; Tamire-Woldemariam, Addis; Walt, Gill; Wickremasinghe, Deepthi

    2014-11-01

    Donors and other development partners commonly introduce innovative practices and technologies to improve health in low and middle income countries. Yet many innovations that are effective in improving health and survival are slow to be translated into policy and implemented at scale. Understanding the factors influencing scale-up is important. We conducted a qualitative study involving 150 semi-structured interviews with government, development partners, civil society organisations and externally funded implementers, professional associations and academic institutions in 2012/13 to explore scale-up of innovative interventions targeting mothers and newborns in Ethiopia, the Indian state of Uttar Pradesh and the six states of northeast Nigeria, which are settings with high burdens of maternal and neonatal mortality. Interviews were analysed using a common analytic framework developed for cross-country comparison and themes were coded using Nvivo. We found that programme implementers across the three settings require multiple steps to catalyse scale-up. Advocating for government to adopt and finance health innovations requires: designing scalable innovations; embedding scale-up in programme design and allocating time and resources; building implementer capacity to catalyse scale-up; adopting effective approaches to advocacy; presenting strong evidence to support government decision making; involving government in programme design; invoking policy champions and networks; strengthening harmonisation among external programmes; aligning innovations with health systems and priorities. Other steps include: supporting government to develop policies and programmes and strengthening health systems and staff; promoting community uptake by involving media, community leaders, mobilisation teams and role models. We conclude that scale-up has no magic bullet solution - implementers must embrace multiple activities, and require substantial support from donors and governments in

  13. Resonant Auger studies of metallic systems

    International Nuclear Information System (INIS)

    Coulthard, I.; Antel, W. J. Jr.; Frigo, S. P.; Freeland, J. W.; Moore, J.; Calaway, W. S.; Pellin, M. J.; Mendelsohn, M.; Sham, T. K.; Naftel, S. J.

    2000-01-01

    Results of resonant Auger spectroscopy experimental are presented for Cu, Co, and oxidized Al. Sublifetime narrowing of Auger spectra and generation of sublifetime narrowed absorption spectra constructed from Auger yield measurements were observed. Resonant Auger yields are used to identify three chemical states of oxidized Al. Partial absorption yield spectra were derived giving detailed electronic information and thickness information for the various chemical states of the bulk metal, the passivating aluminum oxide layer, and the metal-oxide interface region. In addition, the total absorption yield spectrum for the oxidized Al sample was constructed from the partial yield data, supporting the consistency of our method. (c) 2000 American Vacuum Society

  14. Laparoscopic Partial Hepatectomy: Animal Experiments

    Directory of Open Access Journals (Sweden)

    Haruhiro Inoue

    1995-01-01

    Full Text Available As a first step in firmly establishing laparoscopic hepatectomy, we introduce a porcine model of laparoscopic partial hepatectomy. This procedure has been successfully performed under the normal-pressure or low-pressure pneumoperitoneum condition supported by the full-thickness abdominal wall lifting technique. An ultrasonic dissector combined with electrocautery, newly developed by Olympus Optical Corporation (Japan was effectively utilized in facilitating safe and smooth incisions into the liver parenchyma. Although indications for this procedure seem to be limited only to peripheral lesions and not to central lesions, clinical application of this method may be useful for some patients in the near future.

  15. Partial differential equations an introduction

    CERN Document Server

    Colton, David

    2004-01-01

    Intended for a college senior or first-year graduate-level course in partial differential equations, this text offers students in mathematics, engineering, and the applied sciences a solid foundation for advanced studies in mathematics. Classical topics presented in a modern context include coverage of integral equations and basic scattering theory. This complete and accessible treatment includes a variety of examples of inverse problems arising from improperly posed applications. Exercises at the ends of chapters, many with answers, offer a clear progression in developing an understanding of

  16. Single Tooth Replacement Using InCeram Resin Bonded Fixed Partial Denture: A Clinical Report.

    OpenAIRE

    Elnaz Moslehifard; Farzaneh Farid

    2014-01-01

    This clinical report describes a treatment option for replacement of a missing mandibular anterior tooth using InCeram resin bonded fixed partial denture (RBFPD). The conventional approach for replacing mandibular incisors dictates the placement of either a conventional porcelain-fused-to-metal (PFM) bridge, Maryland bridge, or fiber-reinforced composite veneer bridge and several appearance-related disadvantages have been reported in the use of a prosthesis that incorporates a metal substruct...

  17. Complex partial seizures: cerebellar metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Theodore, W.H.; Fishbein, D.; Deitz, M.; Baldwin, P.

    1987-07-01

    We used positron emission tomography (PET) with (/sup 18/F)2-deoxyglucose to study cerebellar glucose metabolism (LCMRglu) and the effect of phenytoin (PHT) in 42 patients with complex partial seizures (CPS), and 12 normal controls. Mean +/- SD patient LCMRglu was 6.9 +/- 1.8 mg glucose/100 g/min (left = right), significantly lower than control values of 8.5 +/- 1.8 (left, p less than 0.006), and 8.3 +/- 1.6 (right, p less than 0.02). Only four patients had cerebellar atrophy on CT/MRI; cerebellar LCMRglu in these was 5.5 +/- 1.5 (p = 0.054 vs. total patient sample). Patients with unilateral temporal hypometabolism or EEG foci did not have lateralized cerebellar hypometabolism. Patients receiving phenytoin (PHT) at the time of scan and patients with less than 5 years total PHT exposure had lower LCMRglu, but the differences were not significant. There were weak inverse correlations between PHT level and cerebellar LCMRglu in patients receiving PHT (r = -0.36; 0.05 less than p less than 0.1), as well as between length of illness and LCMRglu (r = -0.22; 0.05 less than p less than 0.1). Patients with complex partial seizures have cerebellar hypometabolism that is bilateral and due only in part to the effect of PHT.

  18. Metals 2000

    Energy Technology Data Exchange (ETDEWEB)

    Allison, S.W.; Rogers, L.C.; Slaughter, G. [Oak Ridge National Lab., TN (United States); Boensch, F.D. [6025 Oak Hill Lane, Centerville, OH (United States); Claus, R.O.; de Vries, M. [Virginia Polytechnic Inst. and State Univ., Blacksburg, VA (United States)

    1993-05-01

    This strategic planning exercise identified and characterized new and emerging advanced metallic technologies in the context of the drastic changes in global politics and decreasing fiscal resources. In consideration of a hierarchy of technology thrusts stated by various Department of Defense (DOD) spokesmen, and the need to find new and creative ways to acquire and organize programs within an evolving Wright Laboratory, five major candidate programs identified are: C-17 Flap, Transport Fuselage, Mach 5 Aircraft, 4.Fighter Structures, and 5. Missile Structures. These results were formed by extensive discussion with selected major contractors and other experts, and a survey of advanced metallic structure materials. Candidate structural applications with detailed metal structure descriptions bracket a wide variety of uses which warrant consideration for the suggested programs. An analysis on implementing smart skins and structures concepts is given from a metal structures perspective.

  19. Temporary metal stents in bladder outflow obstruction.

    Science.gov (United States)

    Yachia, D

    1997-12-01

    The use of stents in the management of prostatic obstruction started in 1980 with the development of the "partial catheter" by Fabian in Germany. Since then, a variety of metals and biostable and biodegradable polymers have been made into temporary or permanent stents for the management of infravesical obstructions such as benign or malignant prostatic enlargement, bladder neck stenoses, or urethral strictures. This paper is an overview of two generations of temporary metal stents used in the patients with infravesical obstruction.

  20. Male patients with partial androgen insensitivity syndrome

    DEFF Research Database (Denmark)

    Hellmann, Philip; Christiansen, Peter; Johannsen, Trine Holm

    2012-01-01

    To describe the natural history of phenotype, growth and gonadal function in patients with partial androgen insensitivity syndrome.......To describe the natural history of phenotype, growth and gonadal function in patients with partial androgen insensitivity syndrome....

  1. Approximations of Stochastic Partial Differential Equations

    OpenAIRE

    Di Nunno, Giulia; Zhang, Tusheng

    2014-01-01

    In this paper we show that solutions of stochastic partial differ- ential equations driven by Brownian motion can be approximated by stochastic partial differential equations forced by pure jump noise/random kicks. Applications to stochastic Burgers equations are discussed.

  2. Abstract methods in partial differential equations

    CERN Document Server

    Carroll, Robert W

    2012-01-01

    Detailed, self-contained treatment examines modern abstract methods in partial differential equations, especially abstract evolution equations. Suitable for graduate students with some previous exposure to classical partial differential equations. 1969 edition.

  3. Metal carbides

    International Nuclear Information System (INIS)

    Wells, A.F.

    1988-01-01

    From the viewpoint of general crystal chemistry principles and on the base of modern data the structural chemistry of metal carbides is presented. The classification deviding metal carbides into 4 groups depending on chemical and physical properties is presented. The features of the crystal structure of carbides of alkali alkaline earth, transition, 4 f- and 5f-elements and their effect on physical and chemical properties are considered

  4. PARALLEL SOLUTION METHODS OF PARTIAL DIFFERENTIAL EQUATIONS

    Directory of Open Access Journals (Sweden)

    Korhan KARABULUT

    1998-03-01

    Full Text Available Partial differential equations arise in almost all fields of science and engineering. Computer time spent in solving partial differential equations is much more than that of in any other problem class. For this reason, partial differential equations are suitable to be solved on parallel computers that offer great computation power. In this study, parallel solution to partial differential equations with Jacobi, Gauss-Siedel, SOR (Succesive OverRelaxation and SSOR (Symmetric SOR algorithms is studied.

  5. Some existence problems regarding partial Latin squares

    OpenAIRE

    Aryapoor, Masood

    2014-01-01

    Latin squares are interesting combinatorial objects with many applications. When working with Latin squares, one is sometimes led to deal with partial Latin squares, a generalization of Latin squares. One of the problems regarding partial Latin square and with applications to Latin squares is whether a partial Latin square with a given set of conditions exists. The goal of this article is to introduce some problems of this kind and answer some existence questions regarding partial Latin squares

  6. [Removable partial dentures. Oral functions and types

    NARCIS (Netherlands)

    Creugers, N.H.J.; Baat, C. de

    2009-01-01

    A removable partial denture enables the restoration or improvement of 4 oral functions: aesthetics, mandibular stability, mastication, and speech. However, wearing a removable partial denture should not cause oral comfort to deteriorate. There are 3 types of removable partial dentures: acrylic

  7. Partial Dynamical Symmetry in Deformed Nuclei

    International Nuclear Information System (INIS)

    Leviatan, A.

    1996-01-01

    We discuss the notion of partial dynamical symmetry in relation to nuclear spectroscopy. Explicit forms of Hamiltonians with partial SU(3) symmetry are presented in the framework of the interacting boson model of nuclei. An analysis of the resulting spectrum and electromagnetic transitions demonstrates the relevance of such partial symmetry to the spectroscopy of axially deformed nuclei. copyright 1996 The American Physical Society

  8. Partial Dynamical Symmetry in Deformed Nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Leviatan, A. [Racah Institute of Physics, The Hebrew University, Jerusalem 91904 (Israel)

    1996-07-01

    We discuss the notion of partial dynamical symmetry in relation to nuclear spectroscopy. Explicit forms of Hamiltonians with partial SU(3) symmetry are presented in the framework of the interacting boson model of nuclei. An analysis of the resulting spectrum and electromagnetic transitions demonstrates the relevance of such partial symmetry to the spectroscopy of axially deformed nuclei. {copyright} {ital 1996 The American Physical Society.}

  9. Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

    Science.gov (United States)

    Lennon, David; Winfield, John M

    2017-01-28

    Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

  10. Separation of peroxidases from Miscanthus x giganteus, their partial characterisation and application for degradation of dyes.

    Science.gov (United States)

    Dragana, Robajac; Nikola, Gligorijević; Željko, Dželetović; Gordana, Andrejić; Olgica, Nedić

    2017-11-01

    Due to wide applicative potential of peroxidases (POXs), the search for novel sources and forms, possibly with better characteristics and performances, is justified. In this study, POXs from Miscanthus x giganteus rhizomes grown in chernozem-like soil and mine tailings were examined. Higher activity of POXs in samples originating from the metal-contaminated soil was found. The quantity of acidic isoforms was much greater than basic. The rates of reactions catalysed by acidic POX isoforms decreased slightly at 50 °C, whereas stability of basic isoforms was affected at 40 °C. Concentrations of Zn, Mn and Fe were higher in rhizomes grown in mine tailings, and negatively correlated with the concentration of proteins. Basic POX isoforms effectively degraded CBB R250, while Amidoblack 10b was predominantly degraded by acidic isoforms. Thus, Miscanthus x giganteus can be used as a source of POXs which can be applied for dye decomposition and, possibly, waste water management. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  11. Partially coherent isodiffracting pulsed beams

    Science.gov (United States)

    Koivurova, Matias; Ding, Chaoliang; Turunen, Jari; Pan, Liuzhan

    2018-02-01

    We investigate a class of isodiffracting pulsed beams, which are superpositions of transverse modes supported by spherical-mirror laser resonators. By employing modal weights that, for stationary light, produce a Gaussian Schell-model beam, we extend this standard model to pulsed beams. We first construct the two-frequency cross-spectral density function that characterizes the spatial coherence in the space-frequency domain. By assuming a power-exponential spectral profile, we then employ the generalized Wiener-Khintchine theorem for nonstationary light to derive the two-time mutual coherence function that describes the space-time coherence of the ensuing beams. The isodiffracting nature of the laser resonator modes permits all (paraxial-domain) calculations at any propagation distance to be performed analytically. Significant spatiotemporal coupling is revealed in subcycle, single-cycle, and few-cycle domains, where the partial spatial coherence also leads to reduced temporal coherence even though full spectral coherence is assumed.

  12. Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum

    Science.gov (United States)

    Jackson, Colleen; Smith, Graham T.; Inwood, David W.; Leach, Andrew S.; Whalley, Penny S.; Callisti, Mauro; Polcar, Tomas; Russell, Andrea E.; Levecque, Pieter; Kramer, Denis

    2017-06-01

    Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50-100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

  13. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    Science.gov (United States)

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C.; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with π-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

  14. Recent Developments in Microbiological Approaches for Securing Mine Wastes and for Recovering Metals from Mine Waters

    Directory of Open Access Journals (Sweden)

    D. Barrie Johnson

    2014-04-01

    Full Text Available Mining of metals and coals generates solid and liquid wastes that are potentially hazardous to the environment. Traditional methods to reduce the production of pollutants from mining and to treat impacted water courses are mostly physico-chemical in nature, though passive remediation of mine waters utilizes reactions that are catalysed by microorganisms. This paper reviews recent advances in biotechnologies that have been proposed both to secure reactive mine tailings and to remediate mine waters. Empirical management of tailings ponds to promote the growth of micro-algae that sustain populations of bacteria that essentially reverse the processes involved in the formation of acid mine drainage has been proposed. Elsewhere, targeted biomineralization has been demonstrated to produce solid products that allow metals present in mine waters to be recovered and recycled, rather than to be disposed of in landfill.

  15. Protein Labelling with Versatile Phosphorescent Metal Complexes for Live Cell Luminescence Imaging.

    Science.gov (United States)

    Connell, Timothy U; James, Janine L; White, Anthony R; Donnelly, Paul S

    2015-09-28

    To take advantage of the luminescent properties of d(6) transition metal complexes to label proteins, versatile bifunctional ligands were prepared. Ligands that contain a 1,2,3-triazole heterocycle were synthesised using Cu(I) catalysed azide-alkyne cycloaddition "click" chemistry and were used to form phosphorescent Ir(III) and Ru(II) complexes. Their emission properties were readily tuned, by changing either the metal ion or the co-ligands. The complexes were tethered to the metalloprotein transferrin using several conjugation strategies. The Ir(III)/Ru(II)-protein conjugates could be visualised in cancer cells using live cell imaging for extended periods without significant photobleaching. These versatile phosphorescent protein-labelling agents could be widely applied to other proteins and biomolecules and are useful alternatives to conventional organic fluorophores for several applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum.

    Science.gov (United States)

    Jackson, Colleen; Smith, Graham T; Inwood, David W; Leach, Andrew S; Whalley, Penny S; Callisti, Mauro; Polcar, Tomas; Russell, Andrea E; Levecque, Pieter; Kramer, Denis

    2017-06-22

    Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50-100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

  17. Partial dynamical systems, fell bundles and applications

    CERN Document Server

    Exel, Ruy

    2017-01-01

    Partial dynamical systems, originally developed as a tool to study algebras of operators in Hilbert spaces, has recently become an important branch of algebra. Its most powerful results allow for understanding structural properties of algebras, both in the purely algebraic and in the C*-contexts, in terms of the dynamical properties of certain systems which are often hiding behind algebraic structures. The first indication that the study of an algebra using partial dynamical systems may be helpful is the presence of a grading. While the usual theory of graded algebras often requires gradings to be saturated, the theory of partial dynamical systems is especially well suited to treat nonsaturated graded algebras which are in fact the source of the notion of "partiality". One of the main results of the book states that every graded algebra satisfying suitable conditions may be reconstructed from a partial dynamical system via a process called the partial crossed product. Running in parallel with partial dynamica...

  18. Tunable morphological properties of silver enriched platinum allied nanoparticles and their catalysed reduction of p-nitrophenol

    International Nuclear Information System (INIS)

    Adekoya, Joseph Adeyemi; Dare, Enock Olugbenga; Mesubi, Michael Adediran

    2014-01-01

    A robust polymer based and polyol mediated procedure to synthesize nanobimetallic particles has been modified to produce core–shell and alloy Ag/Pt nanoparticles with tunable properties. Novel three-dimensional (3D) quasi nanocubes entangled in nanowebs were produced by rapid solution phase transformation with hot addition of absolute ethanol. The optical characterization showed extinction of plasmon resonance band occurring with incremental feeding ratio of Pt source in all cases. Transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) images revealed that the shape, size and size distribution of as-prepared silver platinum nanoparticles depended on the stabilizer or capping agent, mole ratio of metal ion sources, temperature and time of reaction. Meanwhile, catalytic activity was highest in the reduction of p-nitrophenol in the presence of polyvinylpyrrolidone/diethylene glycol stabilized Ag/Pt nanoparticles. (paper)

  19. Tunable morphological properties of silver enriched platinum allied nanoparticles and their catalysed reduction of p-nitrophenol

    Science.gov (United States)

    Adeyemi Adekoya, Joseph; Olugbenga Dare, Enock; Adediran Mesubi, Michael

    2014-09-01

    A robust polymer based and polyol mediated procedure to synthesize nanobimetallic particles has been modified to produce core-shell and alloy Ag/Pt nanoparticles with tunable properties. Novel three-dimensional (3D) quasi nanocubes entangled in nanowebs were produced by rapid solution phase transformation with hot addition of absolute ethanol. The optical characterization showed extinction of plasmon resonance band occurring with incremental feeding ratio of Pt source in all cases. Transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) images revealed that the shape, size and size distribution of as-prepared silver platinum nanoparticles depended on the stabilizer or capping agent, mole ratio of metal ion sources, temperature and time of reaction. Meanwhile, catalytic activity was highest in the reduction of p-nitrophenol in the presence of polyvinylpyrrolidone/diethylene glycol stabilized Ag/Pt nanoparticles.

  20. Geometric frustration of icosahedron in metallic glasses.

    Science.gov (United States)

    Hirata, A; Kang, L J; Fujita, T; Klumov, B; Matsue, K; Kotani, M; Yavari, A R; Chen, M W

    2013-07-26

    Icosahedral order has been suggested as the prevalent atomic motif of supercooled liquids and metallic glasses for more than half a century, because the icosahedron is highly close-packed but is difficult to grow, owing to structure frustration and the lack of translational periodicity. By means of angstrom-beam electron diffraction of single icosahedra, we report experimental observation of local icosahedral order in metallic glasses. All the detected icosahedra were found to be distorted with partially face-centered cubic symmetry, presenting compelling evidence on geometric frustration of local icosahedral order in metallic glasses.

  1. Clinical Fit of Partial Removable Dental Prostheses Based on Alginate or Polyvinyl Siloxane Impressions.

    NARCIS (Netherlands)

    Fokkinga, W.A.; Witter, D.J.; Bronkhorst, E.M.; Creugers, N.H.J.

    2017-01-01

    PURPOSE: The aim of this study was to analyze the clinical fit of metal-frame partial removable dental prostheses (PRDPs) based on custom trays used with alginate or polyvinyl siloxane impression material. MATERIALS AND METHODS: Fifth-year students of the Nijmegen Dental School made 25 correct

  2. Dual catalyst bed concept for catalytic partial oxidation of methane to synthesis gas

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    A system with two catalyst beds instead of one single metal catalyst bed is proposed for catalytic partial oxidation of methane (CPOM) to synthesis gas. In this dual catalyst bed system, an irreducible stable oxide, such as yttrium-stabilized zirconia (YSZ), is used in the first catalyst bed to

  3. Partially decomposed PVP as a surface modification of ZnO, CdO ...

    Indian Academy of Sciences (India)

    Infrared spectra confirmed the PVP–metal complexation and partial decomposition of the polymer. ... and morphology impact; further, P-CdS induced 71% antibiotic degradation after 10 h of illumination with visible light compared with only 48% for P-ZnS, 29% for P-ZdO and 20% for P-CdO due to improved light absorption.

  4. Metal dusting: kinetically or thermodynamically controlled?

    NARCIS (Netherlands)

    Hermse, C.G.M.

    2011-01-01

    The current paper determines whether the rate of the metal dusting reaction is kinetically or thermodynamically controlled at 600 degrees Celsius. This is done by varying the gas composition, specifically the CO partial pressure and the carbon activity, and comparing the degradation rates of alloy

  5. Investigating oral health-related quality of life and self-perceived satisfaction with partial dentures.

    Science.gov (United States)

    Abuzar, Menaka A; Kahwagi, Esperance; Yamakawa, Takeshi

    2012-05-01

    To investigate the prevalence and severity of oral health-related quality of life in patients treated with removable partial dentures at a publicly-funded dental hospital. The association between patients' demographic profiles, denture-related, variables and oral health-related quality of life was also investigated. A questionnaire was designed to investigate the use and satisfaction of removable partial dentures, and oral health-related quality of life of removable partial denture wearers using the Oral Health Impact Profile-14. The questionnaire was administered to 740 randomly-selected patients who received removable partial dentures during 2005-2008. The response rate was 31.35%. Non-parametric tests and a logistic regression model were used to analyze the association between denture-related variables and oral health-related quality of life. A question on symptoms unrelated to dentures was also analyzed. The Oral Health Impact Profile-14 prevalence calculated was 43.1%. The removable partial denture experience and frequency of use was inversely associated with Oral Health Impact Profile-14 scores. Metal-based removable partial dentures were associated with lower Oral Health Impact Profile prevalence and severity scores. No significant association was found between demographic profile, circumstance for provision of removable partial dentures and Oral Health Impact Profile-14 score. The participants of this study indicated that perceived denture performance, removable partial dentures material, experience, and frequency of use are associated with oral health-related quality of life. © 2012 Blackwell Publishing Asia Pty Ltd.

  6. Flavour from partially resolved singularities

    Energy Technology Data Exchange (ETDEWEB)

    Bonelli, G. [International School of Advanced Studies (SISSA) and INFN, Sezione di Trieste, via Beirut 2-4, 34014 Trieste (Italy)]. E-mail: bonelli@sissa.it; Bonora, L. [International School of Advanced Studies (SISSA) and INFN, Sezione di Trieste, via Beirut 2-4, 34014 Trieste (Italy); Ricco, A. [International School of Advanced Studies (SISSA) and INFN, Sezione di Trieste, via Beirut 2-4, 34014 Trieste (Italy)

    2006-06-15

    In this Letter we study topological open string field theory on D-branes in a IIB background given by non-compact CY geometries O(n)-bar O(-2-n) on P{sup 1} with a singular point at which an extra fiber sits. We wrap N D5-branes on P{sup 1} and M effective D3-branes at singular points, which are actually D5-branes wrapped on a shrinking cycle. We calculate the holomorphic Chern-Simons partition function for the above models in a deformed complex structure and find that it reduces to multi-matrix models with flavour. These are the matrix models whose resolvents have been shown to satisfy the generalized Konishi anomaly equations with flavour. In the n=0 case, corresponding to a partial resolution of the A{sub 2} singularity, the quantum superpotential in the N=1 unitary SYM with one adjoint and M fundamentals is obtained. The n=1 case is also studied and shown to give rise to two-matrix models which for a particular set of couplings can be exactly solved. We explicitly show how to solve such a class of models by a quantum equation of motion technique.

  7. metal alkoxides

    Indian Academy of Sciences (India)

    substituent effects in the head-to-tail double insertion reactions observed ... an internal standard. The yield of diphenyl carbodii- mide was further verified by isolating it as diphenyl urea after hydrolysis. The organic fraction obtained in the catalytic metathesis .... insertion of PhNCO into metal alkoxide 1a to generate. Table 1.

  8. Metallic glasses

    NARCIS (Netherlands)

    Schaafsma, Arjen Sybren

    1981-01-01

    It is shown in section 7.1. that the influence of topological disorder on the range of magnetic interactions in ferromagnetic transition metal-metalloid (TM-M) glasses, is much less than often assumed. This is demonstrated via a study of the temperature dependence of the average iron hyperfine field

  9. A single methyltransferase YefA (RlmCD) catalyses both m5U747 and m5U1939 modifications in Bacillus subtilis 23S rRNA

    DEFF Research Database (Denmark)

    Desmolaize, Benoit; Fabret, Céline; Brégeon, Damien

    2011-01-01

    Escherichia coli possesses three paralogues. These comprise the methyltransferases TrmA that targets U54 in tRNAs, RlmC that modifies U747 in 23S rRNA and RlmD that is specific for U1939 in 23S rRNA. The tRNAs and rRNAs of the Gram-positive bacterium Bacillus subtilis have the same three m(5)U modifications....... However, as previously shown, the m(5)U54 modification in B. subtilis tRNAs is catalysed in a fundamentally different manner by the folate-dependent enzyme TrmFO, which is unrelated to the E. coli TrmA. Here, we show that methylation of U747 and U1939 in B. subtilis rRNA is catalysed by a single enzyme...

  10. Dacite formation on Vesta: Partial melting of the eucritic crust

    Science.gov (United States)

    Hahn, Timothy M.; Lunning, Nicole G.; MCSween, Harry Y.; Bodnar, Robert J.; Taylor, Lawrence A.

    2017-06-01

    The Dominion Range 2010 howardite pairing group contains an evolved lithic clast of dacite composition. The dacite contains an assemblage of plagioclase, quartz, and augite, with minor pigeonite, troilite, ilmenite, FeNi metal, K-feldspar, and phosphates. Primary augite occurs as >1 mm oikocrysts enclosing plagioclase. Quartz is abundant, comprising approximately 30% of the clast. Textural and geochemical characteristics support the hypothesis that the dacite is a primary igneous lithology, and represents a partial melt of the eucritic crust. Numerical modeling (MELTS) suggests 10-20% partial melting of a Juvinas source could have produced the dacite lithology; quantitative trace element modeling further supports crustal partial melting as the magma source for the dacite. The dacite likely formed as evolved-melt pockets, and thus represents a volumetrically minor lithology in the Vestan crust, although its formation provides direct support for a genetic relationship between Stannern and residual trend eucrites, and is the first identification of residual eucrite complementary melts. We propose the dacite clast is the first characterized sample of tertiary crust on Vesta.

  11. THE IMPACT OF PARTIAL CRYSTALLIZATION ON THE PERMEATION PROPERTIES BULK AMORPHOUS GLASS HYDROGEN SEPARATION MEMBRANES

    Energy Technology Data Exchange (ETDEWEB)

    Brinkman, K; Paul Korinko, P; Thad Adams, T; Elise Fox, E; Arthur Jurgensen, A

    2008-11-25

    It is recognized that hydrogen separation membranes are a key component of the emerging hydrogen economy. A potentially exciting material for membrane separations are bulk metallic glass materials due to their low cost, high elastic toughness and resistance to hydrogen 'embrittlement' as compared to crystalline Pd-based membrane systems. However, at elevated temperatures and extended operation times structural changes including partial crystallinity may appear in these amorphous metallic systems. A systematic evaluation of the impact of partial crystallinity/devitrification on the diffusion and solubility behavior in multi-component Metallic Glass materials would provide great insight into the potential of these materials for hydrogen applications. This study will report on the development of time and temperature crystallization mapping and their use for interpretation of 'in-situ' hydrogen permeation at elevated temperatures.

  12. The fate of heavy metals during combustion and gasification of contaminated biomass-a brief review.

    Science.gov (United States)

    Nzihou, Ange; Stanmore, Brian

    2013-07-15

    The literature on the presence of heavy metals in contaminated wastes is reviewed. Various categories of materials produced from domestic and industrial activities are included, but municipal solid waste, which is a more complex material, is excluded. This review considers among the most abundant the following materials - wood waste including demolition wood, phytoremediation scavengers and chromated copper arsenate (CCA) timber, sludges including de-inking sludge and sewage sludge, chicken litter and spent pot liner. The partitioning of the metals in the ashes after combustion or gasification follows conventional behaviour, with most metals retained, and higher concentrations in the finer sizes due to vaporisation and recondensation. The alkali metals have been shown to catalyse the biomass conversion, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent in biomass is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. Because the metals are predominantly found in the ash, the effectiveness of their removal depends on the efficiency of the collection of particulates. The potential for disposal into soil depends on the initial concentration in the feed material. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Partial migration in fishes: causes and consequences

    DEFF Research Database (Denmark)

    Chapman, B.B.; Hulthén, K.; Brodersen, J.

    2012-01-01

    Partial migration, where only some individuals from a population migrate, has been widely reported in a diverse range of animals. In this paper, what is known about the causes and consequences of partial migration in fishes is reviewed. Firstly, the ultimate and proximate drivers of partial...... migration are reflected upon: what ecological factors can shape the evolution of migratory dimorphism? How is partial migration maintained over evolutionary timescales? What proximate mechanisms determine whether an individual is migratory or remains resident? Following this, the consequences of partial...... with a reflection on the future opportunities in this field, and the avenues of research that are likely to be fruitful to shed light on the enduring puzzle of partial migration in fishes...

  14. Extracellular palladium-catalysed dealkylation of 5-fluoro-1-propargyl-uracil as a bioorthogonally activated prodrug approach.

    Science.gov (United States)

    Weiss, Jason T; Dawson, John C; Macleod, Kenneth G; Rybski, Witold; Fraser, Craig; Torres-Sánchez, Carmen; Patton, E Elizabeth; Bradley, Mark; Carragher, Neil O; Unciti-Broceta, Asier

    2014-01-01

    A bioorthogonal organometallic reaction is a biocompatible transformation undergone by a synthetic material exclusively through the mediation of a non-biotic metal source; a selective process used to label biomolecules and activate probes in biological environs. Here we report the in vitro bioorthogonal generation of 5-fluorouracil from a biologically inert precursor by heterogeneous Pd(0) catalysis. Although independently harmless, combined treatment of 5-fluoro-1-propargyl-uracil and Pd(0)-functionalized resins exhibits comparable antiproliferative properties to the unmodified drug in colorectal and pancreatic cancer cells. Live-cell imaging and immunoassay studies demonstrate that the cytotoxic activity of the prodrug/Pd(0)-resin combination is due to the in situ generation of 5-fluorouracil. Pd(0)-resins can be carefully implanted in the yolk sac of zebrafish embryos and display excellent biocompatibility and local catalytic activity. The in vitro efficacy shown by this masking/activation strategy underlines its potential to develop a bioorthogonally activated prodrug approach and supports further in vivo investigations.

  15. Partial differential equations of mathematical physics

    CERN Document Server

    Sobolev, S L

    1964-01-01

    Partial Differential Equations of Mathematical Physics emphasizes the study of second-order partial differential equations of mathematical physics, which is deemed as the foundation of investigations into waves, heat conduction, hydrodynamics, and other physical problems. The book discusses in detail a wide spectrum of topics related to partial differential equations, such as the theories of sets and of Lebesgue integration, integral equations, Green's function, and the proof of the Fourier method. Theoretical physicists, experimental physicists, mathematicians engaged in pure and applied math

  16. First partial Siberian snake test during acceleration

    International Nuclear Information System (INIS)

    Varzar, S.M.; Alexeeva, L.V.; Blinov, B.B.

    1995-01-01

    The authors studied the acceleration of a spin-polarized beam through a depolarizing resonance using a partial Siberian snake. They accelerated polarized protons from 95 to 140 MeV while ramping a 10% partial Siberian snake along with the acceleration cycle. The 10% partial snake suppressed all observable depolarization during acceleration due to the Gγ=2 imperfection depolarizing resonance which occurred near 108 MeV. However, 20% and 30% partial Siberian snakes apparently moved an intrinsic depolarization resonance, normally near 177 MeV, into this energy range; this caused some interesting but not-yet-fully understood depolarization

  17. Axial stress corrosion cracking forming method to metal tube

    International Nuclear Information System (INIS)

    Araki, Kumiko

    1998-01-01

    Generally, it is more difficult in a metal tube, to intentionally cause a stress corrosion cracking in axial direction than in circumferential direction. In the present invention, a bevel is formed on a metal tube and welding is conducted in circumferential direction along the bevel, and welding is conducted in axial direction partially to the portion welded in circumferential direction. Namely, a bevel is formed in circumferential direction to an abutting portion of thick-walled metal tubes with each other, welding is conducted in circumferential direction along the bevel, and welding is conducted in axial direction partially to a portion welded in circumferential direction. With such procedures, since tensile stress in the circumferential direction is increased partially at a portion welded in axial direction, stress corrosion cracking is caused in axial direction at the portion. Then, stress corrosion cracking in axial direction can thus be formed on the thick-walled metal tube. (N.H.)

  18. Olefins hydro-formylation catalysed by rhodium complexes using ionic liquids; Hydroformylation des olefines par les complexes du rhodium dans les liquides ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Favre, F.

    2000-10-26

    Biphasic long chain olefins hydro-formylation catalysed by rhodium complexes using ionic liquids allows a selective reaction and an easy separation of the products from the catalyst. This study reports the synthesis of ionic liquids that were used as the catalyst's solvent. Their physical and chemical properties (melting point, solubility of organic substrates) can be varied with the structure of the organic cation (imidazolium, pyridinium, pyrrolydinium) and with its substituents (nature, length, number). It depends also on the nature of the inorganic anion (hexa-fluoro-phosphate, tetrafluoroborate, tri-fluoro-acetate, triflate, bistriflylamidure...). The use of phosphorus ligands bearing ionic functions proved to be efficient to maintain the onerous rhodium catalyst in the ionic liquid phase. Phosphines, phosphites and phosphinites including anionic (sulfonate, carboxylate) or cationic (imidazolium, pyridinium, guanidinium, phosphonium) groups have been synthesised. Finally, the influences of the ligand and of the ionic liquid on the catalytic system performances are described. Selectivities in aldehydes and reaction rates proved to be highly dependent on the nature of the ligand and of the ionic liquid. The different possibilities of recycling the ionic phase containing the rhodium catalyst have been also studied. (author)

  19. The plant cell-wall enzyme AtXTH3 catalyses covalent cross-linking between cellulose and cello-oligosaccharide

    Science.gov (United States)

    Shinohara, Naoki; Sunagawa, Naoki; Tamura, Satoru; Yokoyama, Ryusuke; Ueda, Minoru; Igarashi, Kiyohiko; Nishitani, Kazuhiko

    2017-04-01

    Cellulose is an economically important material, but routes of its industrial processing have not been fully explored. The plant cell wall - the major source of cellulose - harbours enzymes of the xyloglucan endotransglucosylase/hydrolase (XTH) family. This class of enzymes is unique in that it is capable of elongating polysaccharide chains without the requirement for activated nucleotide sugars (e.g., UDP-glucose) and in seamlessly splitting and reconnecting chains of xyloglucan, a naturally occurring soluble analogue of cellulose. Here, we show that a recombinant version of AtXTH3, a thus far uncharacterized member of the Arabidopsis XTH family, catalysed the transglycosylation between cellulose and cello-oligosaccharide, between cellulose and xyloglucan-oligosaccharide, and between xyloglucan and xyloglucan-oligosaccharide, with the highest reaction rate observed for the latter reaction. In addition, this enzyme formed cellulose-like insoluble material from a soluble cello-oligosaccharide in the absence of additional substrates. This newly found activity (designated “cellulose endotransglucosylase,” or CET) can potentially be involved in the formation of covalent linkages between cellulose microfibrils in the plant cell wall. It can also comprise a new route of industrial cellulose functionalization.

  20. Enantioselective Arylation of N-Tosylimines by Phenylboronic Acid Catalysed by a Rhodium/Diene Complex: Reaction Mechanism from Density Functional Theory.

    Science.gov (United States)

    Sieffert, Nicolas; Boisson, Julien; Py, Sandrine

    2015-06-26

    A DFT study of the reaction mechanism of the rhodium-catalysed enantioselective arylation of (E)-N-propylidene-4-methyl-benzenesulfonamide by phenylboronic acid [Lin et al J. Am. Chem. Soc. 2011, 133, 12394] is reported. The catalyst ([{Rh(OH)(diene)}2]) includes a chiral diene ligand and the reaction is conducted in 1,4-dioxane in the presence of drying agents (4 Å molecular sieves). Because phenylboronic acid is in equilibrium with phenylboroxin and water under the reaction conditions, three catalytic cycles are proposed that differ in the way the transmetallation and the release of the product are brought about, depending on the availability of phenylboronic acid, water and boroxin in the reaction medium. Based on computations, a new mechanism for the title reaction is proposed, in which phenylboronic acid plays the double role of "aryl source" and proton donor. This path does not require the presence of adventitious water molecules, in keeping with a reaction conducted in a dry medium. Comparisons with the generally accepted mechanism for arylation of enones proposed by Hayashi and co-workers (J. Am. Chem. Soc. 2002, 124, 5052) show that the latter mechanism is less favourable and is not expected to operate in the case of the N-tosylimine substrate considered herein. Finally, the possibility that phenylboroxin is the aryl source has also been investigated, but is not found to be competitive. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Transport property of novel sono-catalysed LiCF sub 3 SO sub 3 doped SiO sub 2 -PEG ormolyte

    CERN Document Server

    Jung, H Y; Wi, C J; Whang, C M

    2003-01-01

    Transport property of a novel sono-catalysed LiCF sub 3 SO sub 3 doped SiO sub 2 -10 wt% PEG ormolyte is reported. The ormolyte was synthesized by sol-gel method by varying the LiCF sub 3 SO sub 3 concentration [Li/O] from 0 to 0.1 in mole. The composition with [Li/O] = 0.05 exhibited the highest conductivity (sigma sub 2 sub 5 sub d eg sub C = 2.4x10 sup - sup 4 S cm sup - sup 1) with an enhancement of 10 sup 3 from that of the host matrix: SiO sub 2 -10 wt% PEG sono gel and has been referred to as 'optimum conducting composition (OCC)'. The direct determination of Li sup + ion mobility (mu)/mobile ion concentration (n) indicated that the enhancement was due to the increase in mu and n both. The temperature dependence of sigma, mu and n were carried out for the OCC samples in order to evaluate the respective energies involved in different thermally activated processes and to understand the ion transport mechanism. The ion transference number (t sub i sub o sub n) measurement inferred the ions as the sole cha...

  2. Biotransformation optimization of betulin into betulinic acid production catalysed by cultured Armillaria luteo-virens Sacc ZJUQH100-6 cells.

    Science.gov (United States)

    Liu, J; Fu, M L; Chen, Q H

    2011-01-01

    Betulinic acid has attracted attention in terms of its important biological and pharmacological characteristics. The main objective of this work was to optimize the variables of biotransformation process in order to enhance betulinic acid production from betulin catalysed by fungus Armillaria luteo-virens Sacc ZJUQH100-6. Fractional factorial design and response surface methodology were applied to optimize the main parameters that affect betulinic acid production in the growing-cells system. Results indicated that the addition of Tween 80 and substrate concentration were identified as the significant factors on betulinic acid formation, and the central composite experimental design was then adopted to derive a statistical model for optimizing biotransformation conditions. The optimum conditions were observed at pH 6·0, 0·57% Tween 80, 15 mg l(-1) betulin and at 3 days of stage of inoculation. Under the optimized conditions, the highest productivity of betulinic acid predicted was 9·32%, which increased by 74·53% in comparison with that of the nonoptimized. The verified experiment revealed that the model can well simulate betulin biotransformation. Moreover, the bioconversion of betulin and betulin-28-monooxygenase activities was compared between the optimized and the nonoptimized conditions. Current data imply that betulinic acid production from betulin can be effectively enhanced through biotransformation optimization strategy. © 2010 The Authors. Journal of Applied Microbiology © 2010 The Society for Applied Microbiology.

  3. Deuterium and tritium labelling of aromatic hydrocarbons by zeolite-catalysed exchange with perdeuteriobenzene, tritiated benzene, and [p-3H]toluene

    International Nuclear Information System (INIS)

    Long, M.A.; Garnett, J.L.; Williams, P.G.

    1984-01-01

    Three hydrogen zeolites, HNaY, H-Mordenite, and HZSM-5, have been employed as catalysts for hydrogen isotope exchange reactions. The zeolites catalysed exchange between the isotope sources perdeuteriobenzene, tritiated benzene, and [p- 3 H]toluene, and a wide range of organic substrates, thus providing a useful labelling technique. The extent and orientation of exchange in reaction products were assessed through the techniques of radio-gas chromatography, mass spectrometry, and 3 H n.m.r. spectroscopy. Substituted benzenoid compounds were non-specifically labelled in the aromatic centres at temperatures from 40 to 175 deg C, but heterocyclic compounds and alkanes were not exchanged. A series of competitive exchange experiments gave an insight into the reasons for the lack of reactivity of some substrates. Inspection of the multiple exchange parameters and relative rates of exchange of substrates of different bulk suggested correlations between zeolite pore sizes, substrate reactivity, and labelling patterns. Consideration of these experimental results together with those from redistribution reactions with [p- 3 H]toluene led to interpretation of results in terms of acid exchange mechanisms, where these mechanisms are mediated by the constraints of zeolite pore geometry. (author)

  4. Fluorescence in situ hybridization and sequential catalysed reporter deposition (2C-FISH for the flow cytometric sorting of freshwater ultramicrobacteria

    Directory of Open Access Journals (Sweden)

    Stefan M Neuenschwander

    2015-03-01

    Full Text Available Flow cytometric sorting is a powerful tool to physically separate cells within mixed microbial communities. If combined with phylogenetic staining (fluorescence in situ hybridization, FISH it allows to specifically sort defined genotypic microbial populations from complex natural samples. However, the targeted enrichment of freshwater ultramicrobacteria, such as members of the LD12 clade of Alphaproteobacteria (SAR11-IIIb, is still challenging. Current FISH protocols, even in combination with signal amplification by catalysed reporter deposition (CARD, are not sufficiently sensitive for the distinction of these bacteria from background noise by flow cytometry, presumably due to their low ribosome content and small cell sizes. We, therefore, modified a CARD based flow sorting protocol with the aim of increasing its sensitivity to a level sufficient for ultramicrobacteria. This was achieved by a second signal amplification step mediated by horseradish peroxidase labelled antibodies targeted to the fluorophores that were previously deposited by CARD-FISH staining. The protocol was tested on samples from an oligo-mesotrophic lake. Ultramicrobacteria affiliated with LD12 Alphaproteobacteria could be successfully sorted to high purity by flow cytometry. The ratios of median fluorescence signal to background ranged around 20, and hybridization rates determined by flow cytometry were comparable to those obtained by fluorescence microscopy. Potential downstream applications of our modified cell staining approach range from the analysis of microdiversity within 16S rRNA-defined populations to that of functional properties, such as the taxon-specific incorporation rates of organic substrates.

  5. Corrosion of valve metals

    International Nuclear Information System (INIS)

    Draley, J.E.

    1976-01-01

    A general survey related to the corrosion of valve metals or film-forming metals. The way these metals corrode with some general examples is described. Valve metals form relatively perfect oxide films with little breakdown or leakage when anodized

  6. Metal phosphides

    International Nuclear Information System (INIS)

    Uehlls, A.

    1987-01-01

    The structure of phosphides of the most of elements: alkali, alkaline earth, rare earth, transition metals, actinides, indium, beryllium, cadmium forming the variety of formulae and types of structures, is considered. The ways of P atom combination in phosphides vary from single atoms (ions P 3- in compounds of electropositive elements) through one-, two-dimensional complexes P n up to three-dimensional (charged) grids. In all phosphides, containing the systems of bound atoms of phosphorus, certain or all from these atoms form less than three bonds P-P. The formation of one bond P-P by every atom leads to group P 2 found as P 2 4- ion in diphosphides of transition metals with the structure of the pyrite or marcasite type (RuP 2 ). LaP, SmP, ThP, UP, ZrP form structural type NaCl

  7. Catalytic partial oxidation of pyrolysis oils

    Science.gov (United States)

    Rennard, David Carl

    2009-12-01

    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

  8. Partial order in the non-Fermi-liquid phase of MnSi.

    Science.gov (United States)

    Pfleiderer, C; Reznik, D; Pintschovius, L; Löhneysen, H V; Garst, M; Rosch, A

    2004-01-15

    Only a few metallic phases have been identified in pure crystalline materials. These include normal, ferromagnetic and antiferromagnetic metals, systems with spin and charge density wave order, and superconductors. Fermi-liquid theory provides a basis for the description of all of these phases. It has been suggested that non-Fermi-liquid phases of metals may exist in some heavy-fermion compounds and oxide materials, but the discovery of a characteristic microscopic signature of such phases presents a major challenge. The transition-metal compound MnSi above a certain pressure (p(c) = 14.6 kbar) provides what may be the cleanest example of an extended non-Fermi-liquid phase in a three-dimensional metal. The bulk properties of MnSi suggest that long-range magnetic order is suppressed at p(c) (refs 7-12). Here we report neutron diffraction measurements of MnSi, revealing that sizeable quasi-static magnetic moments survive far into the non-Fermi-liquid phase. These moments are organized in an unusual pattern with partial long-range order. Our observation supports the existence of novel metallic phases with partial ordering of the conduction electrons (reminiscent of liquid crystals), as proposed for the high-temperature superconductors and heavy-fermion compounds.

  9. Laparoscopic partial nephrectomy for endophytic hilar tumors

    DEFF Research Database (Denmark)

    Di Pierro, G B; Tartaglia, N; Aresu, L

    2014-01-01

    To analyze feasibility and outcomes of laparoscopic partial nephrectomy (LPN) for endophytic hilar tumors in low-intermediate (ASA I-II) risk patients.......To analyze feasibility and outcomes of laparoscopic partial nephrectomy (LPN) for endophytic hilar tumors in low-intermediate (ASA I-II) risk patients....

  10. Partial purification and characterization of metalloprotease of ...

    African Journals Online (AJOL)

    USER

    2013-07-31

    Jul 31, 2013 ... We partially purified extracellular metalloprotease of a halotolerant alkaliphilic bacterium isolated from coastal sediment of Goa, India, which was identified as Bacillus cereus strain CS1 based on biochemical characteristics and 16S rDNA sequence. Zymogram of partially purified enzyme clearly revealed ...

  11. Mathematical Modelling of Intraretinal Oxygen Partial Pressure ...

    African Journals Online (AJOL)

    Purpose: The aim of our present work is to develop a simple steady state model for intraretinal oxygen partial pressure distribution and to investigate the effect of various model parameters on the partial pressure distribution under adapted conditions of light and darkness.. Method: A simple eight-layered mathematical model ...

  12. On partially saturated formations of finite groups

    International Nuclear Information System (INIS)

    Ballester-Bolinches, Adolfo; Calvo, Clara; Shemetkov, L A

    2007-01-01

    Various types of partially saturated formations and connections between them are considered. It is shown that partially saturated formations can be characterized as classes of finite groups with generalized central series. A theorem on the decomposition of an FG-module into a sum of two submodules with special properties is proved. Bibliography: 26 titles.

  13. Zero ischemia laparoscopic partial thulium laser nephrectomy.

    LENUS (Irish Health Repository)

    Thomas, Arun Z

    2013-11-01

    Laser technology presents a promising alternative to achieve tumor excision and renal hemostasis with or without hilar occlusion, yet its use in partial nephrectomy has not been significantly evaluated. We prospectively evaluated the thulium:yttrium-aluminum-garnet laser in laparoscopic partial nephrectomy (LPN) in our institution over a 1-year period.

  14. Memoization in Type-Directed Partial Evaluation

    DEFF Research Database (Denmark)

    Balat, Vincent; Danvy, Olivier

    2002-01-01

    the functions and type-directed partial evaluation provides a convenient setting to obtain the normal form of their composition. However, off-the-shelf type-directed partial evaluation turns out to yield gigantic normal forms. We identify that this gigantism is due to redundancies, and that these redundancies...

  15. Enhancing Energy Efficient TCP by Partial Reliability

    NARCIS (Netherlands)

    Donckers, L.; Smit, Gerardus Johannes Maria; Havinga, Paul J.M.; Smit, L.T.

    We present a study on the effects on a mobile system's energy efficiency of enhancing, with partial reliability, our energy efficient TCP variant (E/sup 2/TCP) (see Donckers, L. et al., Proc. 2nd Asian Int. Mobile Computing Conf. - AMOC2002, p.18-28, 2002). Partial reliability is beneficial for

  16. Generalized partial dynamical symmetry in nuclei.

    Science.gov (United States)

    Leviatan, A; Isacker, P Van

    2002-11-25

    We introduce the notion of a generalized partial dynamical-symmetry for which part of the eigenstates have part of the dynamical symmetry. This general concept is illustrated with the example of Hamiltonians with a partial dynamical O(6) symmetry in the framework of the interacting boson model. The resulting spectrum and electromagnetic transitions are compared with empirical data in 162Dy.

  17. Partial dynamical symmetry in a fermion system

    Science.gov (United States)

    Escher; Leviatan

    2000-02-28

    The relevance of the partial dynamical symmetry concept for an interacting fermion system is demonstrated. Hamiltonians with partial SU(3) symmetry are presented in the framework of the symplectic shell model of nuclei and shown to be closely related to the quadrupole-quadrupole interaction. Implications are discussed for the deformed light nucleus 20Ne.

  18. Generalized partial dynamical symmetry in nuclei

    International Nuclear Information System (INIS)

    Leviatan, A.; Isacker, P. van

    2002-01-01

    We introduce the notion of a generalized partial dynamical-symmetry for which part of the eigenstates have part of the dynamical symmetry. This general concept is illustrated with the example of Hamiltonians with a partial dynamical O(6) symmetry in the framework of the interacting boson model. The resulting spectrum and electromagnetic transitions are compared with empirical data in Dy 162

  19. Partial purification and biochemical characterization of acid ...

    African Journals Online (AJOL)

    Mung bean (Vigna radiata) is one of the important crops of the North Eastern Region of India. In the present study, acid phosphatase enzyme was isolated and partially purified from germinated local mung bean seeds. The sequential partial purification process was performed using ammonium sulphate precipitation method.

  20. Oxidoreductase activities of polyclonal IgGs from the sera of Wistar rats are better activated by combinations of different metal ions.

    Science.gov (United States)

    Tolmacheva, Anna S; Zaksas, Nataliya P; Buneva, Valentina N; Vasilenko, Nataliya L; Nevinsky, Georgy A

    2009-01-01

    It was shown that IgGs purified from the sera of healthy Wistar rats contain several different bound Me2+ ions and oxidize 3,3'-diaminobenzidine through a H2O2-dependent peroxidase and H2O2-independent oxidoreductase activity. IgGs have lost these activities after removing the internal metal ions by dialysis against EDTA. External Cu2+ or Fe2+ activated significantly both activities of non-dialysed IgGs containing different internal metals (Fe > or = Pb > or = Zn > or = Cu > or = Al > or = Ca > or = Ni > or = Mn > Co > or = Mg) showing pronounced biphasic dependencies corresponding to approximately 0.1-2 and approximately 2-5 mM of Me2+, while the curves for Mn2+ were nearly linear. Cu2+ alone significantly stimulated both the peroxidase and oxidoreductase activities of dialysed IgGs only at high concentration (> or = 2 mM), while Mn2+ weakly activated peroxidase activity at concentration >3 mM but was active in the oxidoreductase oxidation at a low concentration (ions taken separately; the rates of the oxidation reactions, catalysed by non-dialysed and dialysed IgGs, became comparable. Mg2+, Co2+ and Ni2+ markedly activated the Cu2+-dependent oxidation reactions catalysed by dialysed IgGs, while Ca2+ inhibited these reactions. A possible role of the second metal in the oxidation reactions is discussed. Copyright 2008 John Wiley & Sons, Ltd.

  1. effect of partial re effect of partial replacement of sand wi placement ...

    African Journals Online (AJOL)

    eobe

    yahoo.com. ABSTRACT. This work investigated the effect of partial replacement of sand with quarry dust on the. This work investigated the effect of partial replacement of sand with quarry dust on the compressive strength, compressive strength,.

  2. Some New Metrics Based on Partial Fidelity and Partial Super-Fidelity

    International Nuclear Information System (INIS)

    Wu Zhao-Qi; Zhu Chuan-Xi; Zhang Xiao-Zhi

    2014-01-01

    In this paper, we introduce some new metrics between quantum states based on partial fidelity and partial super-fidelity and discuss their properties. We show that the new metrics are useful measures in quantum information processing. (general)

  3. Development of Partial Discharging Simulation Test Equipment

    Science.gov (United States)

    Kai, Xue; Genghua, Liu; Yan, Jia; Ziqi, Chai; Jian, Lu

    2017-12-01

    In the case of partial discharge training for recruits who lack of on-site work experience, the risk of physical shock and damage of the test equipment may be due to the limited skill level and improper operation by new recruits. Partial discharge simulation tester is the use of simulation technology to achieve partial discharge test process simulation, relatively true reproduction of the local discharge process and results, so that the operator in the classroom will be able to get familiar with and understand the use of the test process and equipment.The teacher sets up the instrument to display different partial discharge waveforms so that the trainees can analyze the test results of different partial discharge types.

  4. A prospective evaluation of zirconia anterior partial fixed dental prostheses: Clinical results after seven years.

    Science.gov (United States)

    Solá-Ruíz, Maria Fernanda; Agustin-Panadero, Rubén; Fons-Font, Antonio; Labaig-Rueda, Carlos

    2015-06-01

    Because of the high mechanical strength of zirconium dioxide, the metal in fixed partial prostheses can now be replaced. However, the material is susceptible to aging or hydrothermal degradation and to chipping of the feldspathic veneer. The purpose of this prospective study was to evaluate the survival (without failure) and success (survival without any complication or failure) rate and clinical efficacy of anterior zirconia partial fixed dental prostheses. Twenty-seven anterior partial fixed dental prostheses of 3 to 6 units were fabricated. All participants were examined after 1 month and 6 months, then annually for 7 years. Three partial fixed dental prostheses failed and had to be removed: 2 because of secondary caries, which increased failure significantly (P=.001) and 1 because of severe chipping. Six partial fixed dental prostheses had complications: 2 debonded, 3 had chipping, and 1 had periapical pathology. All veneer porcelain fractures occurred in 6-unit fixed partial prostheses (P=.002). The clinical success rate was 88.8% after the 7-year follow-up. The clinical behavior of partial fixed dental prostheses with a zirconium dioxide core in the anterior region provides an adequate medium-term survival rate. The main cause of failure was secondary caries. The most frequent complication was chipping, which was directly related to the number of units of the prosthesis. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  5. Correlation between factors associated with the removable partial dentures use and Candida spp. in saliva.

    Science.gov (United States)

    Gusmão, João Milton Rocha; Ferreira dos Santos, Silvana Soleo; Neisser, Maximiliano Piero; Jorge, Antônio Olavo Cardoso; Faria, Ms Ivan

    2011-12-01

    To correlate the presence and number of Candida spp. in the saliva of wearers of removable partial dentures retained with precision attachments with the proportion of metal/acrylic resin present in the dentures. Saliva samples from 40 removable partial denture wearers (test) and one paired sample of individuals, non-wearers of any type of removable denture (control) were collected, seeded, and the colony forming units of Candida counted and identified. The metal/acrylic resin proportion of each denture was quantified, using silicone plates pressed over each denture. Candida spp. was found in the saliva of 80% of the individuals in the test group and 65% of the control, with C. albicans being the most prevalent species. The test group presented with the highest number of colony forming units of Candida per ml of saliva, and there was weak correlation between this number and the metal and resin area of the denture (Pearson's coefficient of correlation). Greater prevalence and a higher number of colony forming units of Candida per ml of saliva occurred in removable partial denture wearers (p = 0.04) with a weak positive correlation between the metal and resin area and the number of colony forming units of Candida per ml of saliva. However, this correlation was more significant for the area of resin. © 2010 The Gerodontology Society and John Wiley & Sons A/S.

  6. Glassy metals

    CERN Document Server

    Russew, Krassimir

    2016-01-01

    The topics discussed in this book focus on fundamental problems concerning the structural relaxation of amorphous metallic alloys, above all the possibility of studying it on the basis of viscous flow behavior and its relation to rheological anomalies, such as bend stress relaxation, thermal expansion, specific heat, density changes, and crystallization. Most relaxation studies deal with the relaxation changes of a single definite material property, and not with a wider spectrum of physical properties integrated into a common framework. This book shows that it is possible to describe these property changes on the basis of a more comprehensive theoretical understanding of their mechanism.

  7. Chalcopyrite—bearer of a precious, non-precious metal

    Science.gov (United States)

    Kimball, Bryn E.

    2013-01-01

    The mineral chalcopyrite (CuFeS2) is the world's most abundant source of copper, a metal component in virtually every piece of electrical equipment. It is the main copper mineral in several different ore deposit types, the most important of which are porphyry deposits. Chalcopyrite is unstable at the Earth's surface, so it weathers from sulphide outcrops and mine waste piles, contributing acid and dissolved copper to what is known as acid rock drainage. If not prevented, dissolved copper from chalcopyrite weathering will be transported downstream, potentially harming ecosystems along the way. Pristine areas are becoming targets for future copper supply as we strive to meet ever-increasing demands for copper by developed and developing nations. Additionally, our uses for copper are expanding to include technology such as solar energy production. This has lead to the processing of increasingly lower grade ores, which is possible, in part, due to advances in bio-leaching (i.e. metal extraction catalysed by micro-organisms). Although copper is plentiful, it is still a nonrenewable resource. Future copper supply promises to fall short of demand and the volatility of the copper market may continue if we do not prioritize copper use and improve copper recycling and ore extraction efficiency.

  8. Mechanochemical processing for metals and metal alloys

    Science.gov (United States)

    Froes, Francis H.; Eranezhuth, Baburaj G.; Prisbrey, Keith

    2001-01-01

    A set of processes for preparing metal powders, including metal alloy powders, by ambient temperature reduction of a reducible metal compound by a reactive metal or metal hydride through mechanochemical processing. The reduction process includes milling reactants to induce and complete the reduction reaction. The preferred reducing agents include magnesium and calcium hydride powders. A process of pre-milling magnesium as a reducing agent to increase the activity of the magnesium has been established as one part of the invention.

  9. Structural evidence for the partially oxidized dipyrromethene and dipyrromethanone forms of the cofactor of porphobilinogen deaminase: structures of the Bacillus megaterium enzyme at near-atomic resolution

    International Nuclear Information System (INIS)

    Azim, N.; Deery, E.; Warren, M. J.; Wolfenden, B. A. A.; Erskine, P.; Cooper, J. B.; Coker, A.; Wood, S. P.; Akhtar, M.

    2014-01-01

    The enzyme porphobilinogen deaminase (PBGD; hydroxymethylbilane synthase; EC 2.5.1.61) catalyses a key early step in the biosynthesis of tetrapyrroles in which four molecules of the monopyrrole porphobilinogen are condensed to form a linear tetrapyrrole. Two near-atomic resolution structures of PBGD from B. megaterium are reported that demonstrate the time-dependent accumulation of partially oxidized forms of the cofactor, including one that possesses a tetrahedral C atom in the terminal pyrrole ring. The enzyme porphobilinogen deaminase (PBGD; hydroxymethylbilane synthase; EC 2.5.1.61) catalyses an early step of the tetrapyrrole-biosynthesis pathway in which four molecules of the monopyrrole porphobilinogen are condensed to form a linear tetrapyrrole. The enzyme possesses a dipyrromethane cofactor, which is covalently linked by a thioether bridge to an invariant cysteine residue (Cys241 in the Bacillus megaterium enzyme). The cofactor is extended during the reaction by the sequential addition of the four substrate molecules, which are released as a linear tetrapyrrole product. Expression in Escherichia coli of a His-tagged form of B. megaterium PBGD has permitted the X-ray analysis of the enzyme from this species at high resolution, showing that the cofactor becomes progressively oxidized to the dipyrromethene and dipyrromethanone forms. In previously solved PBGD structures, the oxidized cofactor is in the dipyromethenone form, in which both pyrrole rings are approximately coplanar. In contrast, the oxidized cofactor in the B. megaterium enzyme appears to be in the dipyrromethanone form, in which the C atom at the bridging α-position of the outer pyrrole ring is very clearly in a tetrahedral configuration. It is suggested that the pink colour of the freshly purified protein is owing to the presence of the dipyrromethene form of the cofactor which, in the structure reported here, adopts the same conformation as the fully reduced dipyrromethane form

  10. A γ-lactamase from cereal infecting Fusarium spp. catalyses the first step in the degradation of the benzoxazolinone class of phytoalexins.

    Science.gov (United States)

    Kettle, Andrew J; Carere, Jason; Batley, Jacqueline; Benfield, Aurelie H; Manners, John M; Kazan, Kemal; Gardiner, Donald M

    2015-10-01

    The benzoxazolinone class of phytoalexins are released by wheat, maize, rye and other agriculturally important species in the Poaceae family upon pathogen attack. Benzoxazolinones show antimicrobial effects on plant pathogens, but certain fungi have evolved mechanisms to actively detoxify these compounds which may contribute to the virulence of the pathogens. In many Fusarium spp. a cluster of genes is thought to be involved in the detoxification of benzoxazolinones. However, only one enzyme encoded in the cluster has been unequivocally assigned a role in this process. The first step in the detoxification of benzoxazolinones in Fusarium spp. involves the hydrolysis of a cyclic ester bond. This reaction is encoded by the FDB1 locus in F. verticillioides but the underlying gene is yet to be cloned. We previously proposed that FDB1 encodes a γ-lactamase, and here direct evidence for this is presented. Expression analyses in the important wheat pathogen F. pseudograminearum demonstrated that amongst the three predicted γ-lactamase genes only the one designated as FDB1, part of the proposed benzoxazolinone cluster in F. pseudograminearum, was strongly responsive to exogenous benzoxazolinone application. Analysis of independent F. pseudograminearum and F. graminearum FDB1 gene deletion mutants, as well as biochemical assays, demonstrated that the γ-lactamase enzyme, encoded by FDB1, catalyses the first step in detoxification of benzoxazolinones. Overall, our results support the notion that Fusarium pathogens that cause crown rot and head blight on wheat have adopted strategies to overcome host-derived chemical defences. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. Optimisation and Characterisation of Lipase-Catalysed Synthesis of a Kojic Monooleate Ester in a Solvent-Free System by Response Surface Methodology.

    Directory of Open Access Journals (Sweden)

    Khairulazhar Jumbri

    Full Text Available Kojic acid is widely used to inhibit the browning effect of tyrosinase in cosmetic and food industries. In this work, synthesis of kojic monooleate ester (KMO was carried out using lipase-catalysed esterification of kojic acid and oleic acid in a solvent-free system. Response Surface Methodology (RSM based on central composite rotatable design (CCRD was used to optimise the main important reaction variables, such as enzyme amount, reaction temperature, substrate molar ratio, and reaction time along with immobilised lipase from Candida Antarctica (Novozym 435 as a biocatalyst. The RSM data indicated that the reaction temperature was less significant in comparison to other factors for the production of a KMO ester. By using this statistical analysis, a quadratic model was developed in order to correlate the preparation variable to the response (reaction yield. The optimum conditions for the enzymatic synthesis of KMO were as follows: an enzyme amount of 2.0 wt%, reaction temperature of 83.69°C, substrate molar ratio of 1:2.37 (mmole kojic acid:oleic acid and a reaction time of 300.0 min. Under these conditions, the actual yield percentage obtained was 42.09%, which is comparably well with the maximum predicted value of 44.46%. Under the optimal conditions, Novozym 435 could be reused for 5 cycles for KMO production percentage yield of at least 40%. The results demonstrated that statistical analysis using RSM can be used efficiently to optimise the production of a KMO ester. Moreover, the optimum conditions obtained can be applied to scale-up the process and minimise the cost.

  12. Exploring the atmospheric chemistry of O2SO3− and assessing the maximum turnover number of ion-catalysed H2SO4 formation

    Directory of Open Access Journals (Sweden)

    N. Bork

    2013-04-01

    Full Text Available It has recently been demonstrated that the O2SO3− ion forms in the atmosphere as a natural consequence of ionizing radiation. Here, we present a density functional theory-based study of the reactions of O2SO3− with O3. The most important reactions are (a oxidation to O2SO3− and (b cluster decomposition into SO3, O2 and O3−. The former reaction is highly exothermic, and the nascent O2SO3− will rapidly decompose into SO4− and O2. If the origin of O2SO3− is SO2 oxidation by O3−, the latter reaction closes a catalytic cycle wherein SO2 is oxidized to SO3. The relative rate between the two major sinks for O2SO3− is assessed, thereby providing a measure of the maximum turnover number of ion-catalysed SO2 oxidation, i.e. how many SO2 can be oxidized per free electron. The rate ratio between reactions (a and (b is significantly altered by the presence or absence of a single water molecule, but reaction (b is in general much more probable. Although we are unable to assess the overall importance of this cycle in the real atmosphere due to the unknown influence of CO2 and NOx, we roughly estimate that ion-induced catalysis may contribute with several percent of H2SO4 levels in typical CO2-free and low NOx reaction chambers, e.g. the CLOUD chamber at CERN.

  13. Management of long span partially edentulous maxilla with fixed removable denture prosthesis

    Directory of Open Access Journals (Sweden)

    Mahilan I Jeyavalan

    2012-01-01

    Full Text Available Restoration of a long span partially edentulous maxilla with tooth supported prosthesis is challenging because of inherent anatomic limitations and unfavourable biomechanics present after the loss of teeth. A tooth supported fixed-removable prosthesis is a treatment option for restoration of such long span partially edentulous maxillary arches. This prosthesis meets the requirements for esthetics, phonetics, comfort, and hygiene, as well as favourable biomechanical stress distribution to the remaining natural tooth abutments. This article presents a procedure for fabrication of a fixed-removable prosthesis that has cement-retained custom cast bar metal substructure and a ball attachment retained removable superstructure prosthesis.

  14. Partial differential equations for scientists and engineers

    CERN Document Server

    Farlow, Stanley J

    1993-01-01

    Most physical phenomena, whether in the domain of fluid dynamics, electricity, magnetism, mechanics, optics, or heat flow, can be described in general by partial differential equations. Indeed, such equations are crucial to mathematical physics. Although simplifications can be made that reduce these equations to ordinary differential equations, nevertheless the complete description of physical systems resides in the general area of partial differential equations.This highly useful text shows the reader how to formulate a partial differential equation from the physical problem (constructing th

  15. Method for partially coating laser diode facets

    Science.gov (United States)

    Dholakia, Anil R. (Inventor)

    1990-01-01

    Bars of integral laser diode devices cleaved from a wafer are placed with their p regions abutting and n regions abutting. A thin BeCu mask having alternate openings and strips of the same width as the end facets is used to mask the n region interfaces so that multiple bars can be partially coated over their exposed p regions with a reflective or partial reflective coating. The partial coating permits identification of the emitting facet from the fully coated back facet during a later device mounting procedure.

  16. Prosthetic management of the partial foot amputee.

    Science.gov (United States)

    Yonclas, Peter P; O'donnell, Casey J

    2005-07-01

    Partial foot amputations provide advantages and challenges to the patient confronting loss of limb and the rehabilitation team. The partial foot amputation offers the potential for retention of plantar load-bearing tissues that are capable of tolerating the forces involved in weight bearing; this can allow the patient to ambulate with or without a prosthesis. Because of the complexity of the foot-ankle complex and the multiple types of partial foot amputations encountered, choosing the appropriate prosthesis can be challenging. This article explains some of the rationale and common options available for the different levels of amputation.

  17. Metal filled porous carbon

    Science.gov (United States)

    Gross, Adam F [Los Angeles, CA; Vajo, John J [West Hills, CA; Cumberland, Robert W [Malibu, CA; Liu, Ping [Irvine, CA; Salguero, Tina T [Encino, CA

    2011-03-22

    A porous carbon scaffold with a surface and pores, the porous carbon scaffold containing a primary metal and a secondary metal, where the primary metal is a metal that does not wet the surface of the pores of the carbon scaffold but wets the surface of the secondary metal, and the secondary metal is interspersed between the surface of the pores of the carbon scaffold and the primary metal.

  18. Allergic reactions associated with metal alloys in porcelain-fused-to-metal fixed prosthodontic devices-A systematic review.

    Science.gov (United States)

    Levi, Lauren; Barak, Shlomo; Katz, Joseph

    2012-01-01

    To systematically review the allergic reactions associated with metal alloys in porcelain-fused-to-metal (PFM) fixed prosthetic devices. After reviewing the titles and abstracts of the articles as well as removing duplicates, 22 articles were considered relevant. PubMed, Web of Science, ScienceDirect, and Google Scholar from 1970 to 2012 were evaluated, and randomized studies, review articles, case reports, cross-sectional surveys, and abstracts were included. Conference papers and posters were excluded. Although reported, allergic reactions to metallic alloys in the context of PFM devices are not well documented. Allergic reactions to high noble and noble metal alloy cores of palladium and gold and to base metal alloys nickel and cobalt in the context of PFM fixed partial dentures (FPDs) are reported. Each type of metal is associated with a different rate of allergic reactions, which may be attributed to the extent of corrosion of the alloy, population exposure, and the biologic environment. Because few studies document allergic reactions to metals that comprise PFM crowns and partial dentures, further research in this field is necessary to determine the frequency and type of reactions elicited. Though allergic reactions to metal alloys used in dentistry are well documented, only few articles focus on the correlation between FPDs and metal allergies. Thus, this paper surveys case reports of hypersensitivity reactions linked to FPDs and reviews the current literature on allergic reactions to the metallic elements comprising those devices.

  19. Electric arc, water jet cutting of metals

    International Nuclear Information System (INIS)

    Bruening, D.

    1991-01-01

    For thermal dismantling and cutting of metallic components, as electric arc, water jet cutting method was developed that can be used for underwater cutting work up to a depth of 20 m. Short-circuiting of a continuously fed electrode wire in contact with the metal generates an electric arc which induces partial melting of the metal, and the water jet surrounding the wire rinses away the molten material, thus making a continuous kerf in the material. The method was also tested and modified to allow larger area, surface cutting and removal of metallic surface coatings. This is achieved by melting parts of the surface with the electric arc and subsequent rinsing by the water jet. The cutting and melting depth for surface removal can be accurately controlled by the operating parameters chosen. (orig./DG) [de

  20. Fiber-reinforced composites in fixed partial dentures

    Directory of Open Access Journals (Sweden)

    Vallittu P

    2006-08-01

    Full Text Available Fiber-reinforced composite resin (FRC prostheses offer the advantages of good esthetics, minimal invasive treatment, and an ability to bond to the abutment teeth, thereby compensating for less-than-optimal abutment tooth retention and resistance form. These prostheses are composed of two types of composite materials: fiber composites to build the framework and hybrid or microfill particulate composites to create the external veneer surface. This review concentrates on the use of fiber reinforcement in the fabrication of laboratory or chairside-made composite-fixed partial dentures of conventional preparation. Other applications of FRC in dentistry are briefly mentioned. The possibilities fiber reinforcement technology offers must be emphasized to the dental community. Rather than limiting discussion to whether FRC prostheses will replace metal-ceramic or full-ceramic prostheses, attention should be focused on the additional treatment options brought by the use of fibers. However, more clinical experience is needed.

  1. Accelerated decarburization of Fe-C metal alloys

    Science.gov (United States)

    Pal, Uday B.; Sadoway, Donald R.

    1997-01-01

    A process for improving the rate of metal production and FeO utilization in a steelmaking process or a process combining iron-making and steelmaking in a single reactor that uses or generates Fe-C metal alloy droplets submerged in an FeO-containing slag. The process involves discharging a charge build-up (electron accumulation) in the slag at the slag-metal alloy interface by means of an electron conductor connected between the metal alloy droplets and a gas at a gas-slag interface, said gas having an oxygen partial pressure of at least about 0.01 atmosphere.

  2. Introduction to partial differential equations with applications

    CERN Document Server

    Zachmanoglou, E C

    1988-01-01

    This text explores the essentials of partial differential equations as applied to engineering and the physical sciences. Discusses ordinary differential equations, integral curves and surfaces of vector fields, the Cauchy-Kovalevsky theory, more. Problems and answers.

  3. Science Academies' Refresher Course on Partial Differential ...

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 22; Issue 4. Science Academies' Refresher Course on Partial Differential Equations and their Applications (PDEA-2017). Information and Announcements Volume 22 Issue 4 April 2017 pp 429-429 ...

  4. Hospital Outpatient PPS Partial Hospitalization Program LDS

    Data.gov (United States)

    U.S. Department of Health & Human Services — Hospital Outpatient Prospective Payment System (OPPS) Partial Hospitalization Program LDS This file contains select claim level data and is derived from 2010 claims...

  5. Clustering stocks using partial correlation coefficients

    Science.gov (United States)

    Jung, Sean S.; Chang, Woojin

    2016-11-01

    A partial correlation analysis is performed on the Korean stock market (KOSPI). The difference between Pearson correlation and the partial correlation is analyzed and it is found that when conditioned on the market return, Pearson correlation coefficients are generally greater than those of the partial correlation, which implies that the market return tends to drive up the correlation between stock returns. A clustering analysis is then performed to study the market structure given by the partial correlation analysis and the members of the clusters are compared with the Global Industry Classification Standard (GICS). The initial hypothesis is that the firms in the same GICS sector are clustered together since they are in a similar business and environment. However, the result is inconsistent with the hypothesis and most clusters are a mix of multiple sectors suggesting that the traditional approach of using sectors to determine the proximity between stocks may not be sufficient enough to diversify a portfolio.

  6. Partial Actions, Paradoxicality and Topological full Groups

    DEFF Research Database (Denmark)

    Scarparo, Eduardo

    uniform Roe algebra is finite. In Article C, we analyze the C*-algebra generated by the Koopman representation of a topological full group, showing, in particular, that it is not AF andhas real rank zero. We also prove that if G is a finitely generated, elementary amenable group, and C*(G) has real rank......We study how paradoxicality properties affect the way groups partially acton topological spaces and C*-algebras. We also investigate the real rank zero and AF properties for certain classes of group C*-algebras. Specifically, in article A, we characterize supramenable groups in terms of existence...... of invariant probability measures for partial actions on compact Hausdorff spaces and existence of tracial states on partial crossed products. These characterizations show that, in general, one cannot decompose a partial crossed product of a C*-algebra by a semidirect product of groups as two iterated...

  7. Partial Differential Equations Modeling and Numerical Simulation

    CERN Document Server

    Glowinski, Roland

    2008-01-01

    This book is dedicated to Olivier Pironneau. For more than 250 years partial differential equations have been clearly the most important tool available to mankind in order to understand a large variety of phenomena, natural at first and then those originating from human activity and technological development. Mechanics, physics and their engineering applications were the first to benefit from the impact of partial differential equations on modeling and design, but a little less than a century ago the Schrödinger equation was the key opening the door to the application of partial differential equations to quantum chemistry, for small atomic and molecular systems at first, but then for systems of fast growing complexity. Mathematical modeling methods based on partial differential equations form an important part of contemporary science and are widely used in engineering and scientific applications. In this book several experts in this field present their latest results and discuss trends in the numerical analy...

  8. Partial Safety Factors for Rubble Mound Breakwaters

    DEFF Research Database (Denmark)

    Sørensen, John Dalsgaard; Burcharth, H. F.; Christiani, E.

    1995-01-01

    On the basis of the failure modes formulated in the various subtasks calibration of partial safety factors are described in this paper. The partial safety factors can be used to design breakwaters under quite different design conditions, namely probabilities of failure from 0.01 to 0.4, design...... lifetimes from 20 to 100 years and different qualities of wave data. A code of practice where safety is taken into account using partial safety factors is called a level I code. The partial safety factors are calibrated using First Order Reliability Methods (FORM, see Madsen et al. [1]) where...... the reliability is measured by reliability indices. For all significant failure modes limit state functions are formulated and uncertain quantities are modelled by stochastic variables. In section 2 the most important failure modes are mentioned and statistical models for the uncertain parameters are described...

  9. Pragmatics of type-directed partial evaluation

    DEFF Research Database (Denmark)

    Danvy, Olivier

    1996-01-01

    the user to annotate arrow types with effect information. It is achieved by delimiting and abstracting control, comparably to continuation-based specialization in direct style. It enables type-directed partial evaluation of programs with effects (e.g., a definitional lambda-interpreter for an imperative...... and Schwichtenberg's normalization algorithm for the simply typed lambda-calculus. Type-directed partial evaluation thus can be used to specialize a compiled, closed program, given its type. Since Similix, let-insertion is a cornerstone of partial evaluators for call-by-value procedural languages with computational...... effects (such as divergence). It prevents the duplication of residual computations, and more generally maintains the order of dynamic side effects in the residual program. This article describes the extension of type-directed partial evaluation to insert residual let expressions. This extension requires...

  10. Neurotoxicity of metals.

    Science.gov (United States)

    Caito, Samuel; Aschner, Michael

    2015-01-01

    Metals are frequently used in industry and represent a major source of toxin exposure for workers. For this reason governmental agencies regulate the amount of metal exposure permissible for worker safety. While essential metals serve physiologic roles, metals pose significant health risks upon acute and chronic exposure to high levels. The central nervous system is particularly vulnerable to metals. The brain readily accumulates metals, which under physiologic conditions are incorporated into essential metalloproteins required for neuronal health and energy homeostasis. Severe consequences can arise from circumstances of excess essential metals or exposure to toxic nonessential metal. Herein, we discuss sources of occupational metal exposure, metal homeostasis in the human body, susceptibility of the nervous system to metals, detoxification, detection of metals in biologic samples, and chelation therapeutic strategies. The neurologic pathology and physiology following aluminum, arsenic, lead, manganese, mercury, and trimethyltin exposures are highlighted as classic examples of metal-induced neurotoxicity. © 2015 Elsevier B.V. All rights reserved.

  11. Respiratory functions after partial laryngectomy surgery

    Directory of Open Access Journals (Sweden)

    Mehmet Gökhan Demir

    2016-01-01

    Conclusions: In our study, various degrees of restrictive and/or obstructive findings were observed in the respiratory functions after partial surgeries. It was determined that such findings increased as long as the amount of the removed larynx tissue increased. We recommend that patients undergo a respiratory function test after partial laryngectomy and treated according to the findings as restrictive and obstructive findings affect patients' survival.

  12. Pancharatnam geometric phase originating from successive partial ...

    Indian Academy of Sciences (India)

    Pancharatnam connection [1,2] dictates that ψp is in phase ψ0. The partial projection effects a ... up to a real multiplier. Here again, ψf is in phase with ψp but relative to ψ0, has a .... For the third partial projection of strength t3 and an azimuth angle φ13 to effect a triangle closure for both initial states |z〉 and | − z〉, we derive ...

  13. The Sounds of Metal

    DEFF Research Database (Denmark)

    Grund, Cynthia M.

    2015-01-01

    Two, I propose that this framework allows for at least a theoretical distinction between the way in which extreme metal – e.g. black metal, doom metal, funeral doom metal, death metal – relates to its sound as music and the way in which much other music may be conceived of as being constituted...

  14. Detection of improvement in the masticatory function from old to new removable partial dentures using mixing ability test.

    Science.gov (United States)

    Asakawa, A; Fueki, K; Ohyama, T

    2005-09-01

    The aim of this study was to determine the sensitivity of the Mixing Ability Test to detect improvement of masticatory function in subjects on transition from old to new removable partial dentures. Thirty-two subjects (seven males, 25 females, mean age 65.0 years) with distal extension partially edentulous area in mandible and/or maxilla participated in the study. The following reasons were presented for replacing the old removable partial dentures with new ones: fracture and/or poor fitness of retainers, extraction of abutment teeth, poor fitness of denture base, severe wear of artificial teeth and request for metal base dentures. Masticatory function with old and new removable partial dentures after an adaptation period (mean 27.4 weeks) was evaluated by the Mixing Ability Test. Subjects were asked to masticate five two-coloured wax cubes with each removable partial denture. Mixing Ability Index was obtained from the colour mixture and shape of the masticated cubes. Wilcoxon signed-rank test was used to test the difference of Mixing Ability Indexes between old and new removable partial dentures. The mixing ability indexes with new removable partial dentures (mean+/- s.d.: 0.70+/- 0.68) was significantly higher (Premovable partial dentures (-0.11+/-1.13). The results suggest that the Mixing Ability Test was capable of detecting improvement in masticatory function with new removable partial dentures.

  15. An optical coherence tomography investigation of materials defects in ceramic fixed partial dental prostheses

    Science.gov (United States)

    Sinescu, Cosmin; Negrutiu, Meda; Hughes, Michael; Bradu, Adrian; Todea, Carmen; Rominu, Mihai; Laissue, Philippe L.; Podoleanu, Adrian Gh.

    2008-04-01

    Metal ceramic and integral ceramic fixed partial prostheses are mainly used in the frontal part of the dental arch because for esthetics reasons. The masticatory stress may induce fractures of the bridges. There are several factors that are associated with the stress state created in ceramic restorations, including: thickness of ceramic layers, mechanical properties of the materials, elastic modulus of the supporting substrate material, direction, magnitude and frequency of applied load, size and location of occlusal contact areas, residual stresses induced by processing or pores, restoration-cement interfacial defects and environmental defects. The fractures of these bridges lead to functional, esthetic and phonetic disturbances which finally render the prosthetic treatment inefficient. The purpose of this study is to evaluate the capability of optical coherence tomography (OCT) in detection and analysis of possible material defects in metal-ceramic and integral ceramic fixed partial dentures.

  16. Metallothionein expression during liver regeneration after partial hepatectomy in cadmium-pretreated rats

    Energy Technology Data Exchange (ETDEWEB)

    Margeli, A.P. (Dept. of Forensic Medicine and Toxicology, School of Medicine, Univ. of Athens (Greece)); Theocharis, S.E. (Dept. of Forensic Medicine and Toxicology, School of Medicine, Univ. of Athens (Greece)); Yannacou, N.N. (Dept. of Forensic Medicine and Toxicology, School of Medicine, Univ. of Athens (Greece)); Spiliopoulou, C. (Dept. of Forensic Medicine and Toxicology, School of Medicine, Univ. of Athens (Greece)); Koutselinis, A. (Dept. of Forensic Medicine and Toxicology, School of Medicine, Univ. of Athens (Greece))

    1994-10-01

    Metallothionein is a low molecular mass protein inducible mainly by heavy metals, having high affinity for binding cadmium, zinc and copper. In the present study we investigated the expression of metallothionein in regenerating liver, at different time intervals, in cadmium pretreated partially hepatectomized rats. Liver metallothionein is highly expressed during regeneration induced by partial hepatectomy in rats, providing zinc within the rapidly growing tissue. Cadmium pretreatment caused inhibition of the first peak of liver regeneration, while metallothionein expression was markedly more prominent in the liver residues of cadmium-pretreated rats. These results demonstrate that although metallothionein able to bind temporarily metal ions as zinc and cadmium has been highly expressed, the liver regenerative process was inhibited possibly due to the effects of cadmium on other pivotal events necessary to the DNA replication. (orig.)

  17. Study on Thixojoining Process Using Partial Remelting Method

    Directory of Open Access Journals (Sweden)

    M. N. Mohammed

    2013-01-01

    Full Text Available Cold-work tool steel is considered to be a nonweldable metal due to its high percentage content of carbon and alloy elements. The application of a new process of the semisolid joining of two dissimilar metals is proposed. AISI D2 cold-work tool steel was thixojoined to 304 stainless steel by using a partial remelting method. After thixojoining, microstructural examination including metallographic analysis, energy dispersive spectroscopy (EDS, and Vickers hardness tests was performed. From the results, metallographic analyses along the joint interface between semisolid AISI D2 and stainless steel showed a smooth transition from one to another and neither oxides nor microcracking was observed. Hardness values obtained from the points in the diffusion zone were much higher than those in the 304 stainless steel but lower than those in the AISI D2 tool steel. The study revealed that a new type of nonequilibrium diffusion interfacial structure was constructed at the interface of the two different types of steel. The current work successfully confirmed that avoidance of a dendritic microstructure in the semisolid joined zone and high bonding quality components can be achieved without the need for force or complex equipment when compared to conventional welding processes.

  18. Metal polish poisoning

    Science.gov (United States)

    Metal polishes are used to clean metals, including brass, copper, or silver. This article discusses the harmful effects from swallowing metal polish. This article is for information only. DO NOT use ...

  19. Metal-phosphate binders

    Science.gov (United States)

    Howe, Beth Ann [Lewistown, IL; Chaps-Cabrera, Jesus Guadalupe [Coahuila, MX

    2009-05-12

    A metal-phosphate binder is provided. The binder may include an aqueous phosphoric acid solution, a metal-cation donor including a metal other than aluminum, an aluminum-cation donor, and a non-carbohydrate electron donor.

  20. System and method for producing metallic iron

    Science.gov (United States)

    Englund, David J.; Schlichting, Mark; Meehan, John; Crouch, Jeremiah; Wilson, Logan

    2014-07-29

    A method of production of metallic iron nodules comprises assembling a hearth furnace having a moveable hearth comprising refractory material and having a conversion zone and a fusion zone, providing a hearth material layer comprising carbonaceous material on the refractory material, providing a layer of reducible material comprising and iron bearing material arranged in discrete portions over at least a portion of the hearth material layer, delivering oxygen gas into the hearth furnace to a ratio of at least 0.8:1 ponds of oxygen to pounds of iron in the reducible material to heat the conversion zone to a temperature sufficient to at least partially reduce the reducible material and to heat the fusion zone to a temperature sufficient to at least partially reduce the reducible material, and heating the reducible material to form one or more metallic iron nodules and slag.