Highly Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Catalyzed by Stereogenic-at-Mo Adamantylimido Complexes

PubMed Central

Ibrahem, Ismail; Yu, Miao; Schrock, Richard R.; Hoveyda, Amir H.

2009-01-01

The first highly Z- and enantioselective class of ring-opening/cross-metathesis (ROCM) reactions is presented. Transformations are promoted in the presence of <2 mol % of chiral stereogenic-at-Mo monoaryloxide complexes, which bear an adamantylimido ligand and are prepared and used in situ. Reactions involve meso oxabicyclic substrates and afford the desired pyrans in 50–85% yield and in up to >98:<2 enantiomer ratio (er). Importantly, the desired chiral pyrans are thus obtained bearing a Z olefin either exclusively (>98:<2 Z:E) or predominantly (≥87:13 Z:E). PMID:19249833

Nobel Chemistry in the Laboratory: Synthesis of a Ruthenium Catalyst for Ring-Closing Olefin Metathesis--An Experiment for the Advanced Inorganic or Organic Laboratory

ERIC Educational Resources Information Center

Greco, George E.

2007-01-01

An experiment for the upper-level undergraduate laboratory is described in which students synthesize a ruthenium olefin metathesis catalyst, then use the catalyst to carry out the ring-closing metathesis of diethyl diallylmalonate. The olefin metathesis reaction was the subject of the 2005 Nobel Prize in chemistry. The catalyst chosen for this…

Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products.

PubMed

Schmidt, Bernd; Kunz, Oliver

2013-01-01

Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60 Fullerenes.

PubMed

Martínez, Juan Pablo; Vummaleti, Sai Vikrama Chaitanya; Falivene, Laura; Nolan, Steven P; Cavallo, Luigi; Solà, Miquel; Poater, Albert

2016-05-04

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium indenylidene “1st generation” olefin metathesis catalysts containing triisopropyl phosphite

PubMed Central

Guidone, Stefano; Nahra, Fady; Slawin, Alexandra M Z

2015-01-01

Summary The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands. PMID:26425210

Bimolecular Coupling as a Vector for Decomposition of Fast-Initiating Olefin Metathesis Catalysts.

PubMed

Bailey, Gwendolyn A; Foscato, Marco; Higman, Carolyn S; Day, Craig S; Jensen, Vidar R; Fogg, Deryn E

2018-06-06

The correlation between rapid initiation and rapid decomposition in olefin metathesis is probed for a series of fast-initiating, phosphine-free Ru catalysts: the Hoveyda catalyst HII, RuCl 2 (L)(═CHC 6 H 4 - o-O i Pr); the Grela catalyst nG (a derivative of HII with a nitro group para to O i Pr); the Piers catalyst PII, [RuCl 2 (L)(═CHPCy 3 )]OTf; the third-generation Grubbs catalyst GIII, RuCl 2 (L)(py) 2 (═CHPh); and dianiline catalyst DA, RuCl 2 (L)( o-dianiline)(═CHPh), in all of which L = H 2 IMes = N,N'-bis(mesityl)imidazolin-2-ylidene. Prior studies of ethylene metathesis have established that various Ru metathesis catalysts can decompose by β-elimination of propene from the metallacyclobutane intermediate RuCl 2 (H 2 IMes)(κ 2 -C 3 H 6 ), Ru-2. The present work demonstrates that in metathesis of terminal olefins, β-elimination yields only ca. 25-40% propenes for HII, nG, PII, or DA, and none for GIII. The discrepancy is attributed to competing decomposition via bimolecular coupling of methylidene intermediate RuCl 2 (H 2 IMes)(═CH 2 ), Ru-1. Direct evidence for methylidene coupling is presented, via the controlled decomposition of transiently stabilized adducts of Ru-1, RuCl 2 (H 2 IMes)L n (═CH 2 ) (L n = py n' ; n' = 1, 2, or o-dianiline). These adducts were synthesized by treating in situ-generated metallacyclobutane Ru-2 with pyridine or o-dianiline, and were isolated by precipitating at low temperature (-116 or -78 °C, respectively). On warming, both undergo methylidene coupling, liberating ethylene and forming RuCl 2 (H 2 IMes)L n . A mechanism is proposed based on kinetic studies and molecular-level computational analysis. Bimolecular coupling emerges as an important contributor to the instability of Ru-1, and a potentially major pathway for decomposition of fast-initiating, phosphine-free metathesis catalysts.

The Influence of the Anionic Counter-Ion on the Activity of Ammonium Substituted Hoveyda-Type Olefin Metathesis Catalysts in Aqueous Media

NASA Astrophysics Data System (ADS)

Gułajski, Łukasz; Grela, Karol

Polar olefin metathesis catalysts, bearing an ammonium group are presented. The electron withdrawing ammonium group not only activates the catalysts electronically, but at the same time makes the catalysts more hydrophilic. Catalysts can be therefore efficiently used not only in traditional media, such as methylene chloride and toluene, but also in technical-grade alcohols, alcohol— water mixtures and in neat water. Finally, in this overview the influence of the anionic counter-ion on the activity of ammonium substituted Hoveyda-type olefin metathesis catalysts in aqueous media is presented.

Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands.

PubMed

Pribisko, Melanie A; Ahmed, Tonia S; Grubbs, Robert H

2014-12-14

Two new Ru-based metathesis catalysts, 3 and 4 , have been synthesized for the purpose of comparing their catalytic properties to those of their cis -selective nitrate analogues, 1 and 2 . Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2 , they maintained high cis -selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis -selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer.

Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

PubMed

Meng, Xiangtao; Edgar, Kevin J

2015-11-05

Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands

PubMed Central

Pribisko, Melanie A.; Ahmed, Tonia S.; Grubbs, Robert H.

2014-01-01

Two new Ru-based metathesis catalysts, 3 and 4, have been synthesized for the purpose of comparing their catalytic properties to those of their cis-selective nitrate analogues, 1 and 2. Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2, they maintained high cis-selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis-selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer. PMID:25484484

Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

NASA Astrophysics Data System (ADS)

Mauldin, Timothy C.

Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution

Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of P-Stereogenic, Z-Configured Bicyclo[7.3.1]- and Bicyclo[8.3.1]phosphates.

PubMed

Markley, Jana L; Maitra, Soma; Hanson, Paul R

2016-02-05

A phosphate tether-mediated ring-closing metathesis (RCM) study to the synthesis of Z-configured, P-stereogenic bicyclo[7.3.1]- and bicyclo[8.3.1]phosphates is reported. Investigations suggest that C3-substitution, olefin substitution, and proximity of the forming olefin to the bridgehead carbon of the bicyclic affect the efficiency and stereochemical outcome of the RCM event. This study demonstrates the utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol-containing dienes in the generation of macrocyclic phosphates with potential synthetic and biological utility.

An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands.

PubMed

Getty, Kendra; Delgado-Jaime, Mario Ulises; Kennepohl, Pierre

2007-12-26

Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.

Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis

PubMed Central

Sattely, Elizabeth S.; Meek, Simon J.; Malcolmson, Steven J.; Schrock, Richard R.; Hoveyda, Amir H.

2010-01-01

A total synthesis of the Aspidosperma alkaloid quebrachamine in racemic form is first described. A key catalytic ring-closing metathesis of an achiral triene is used to establish the all-carbon quaternary stereogenic center and the tetracyclic structure of the natural product; the catalytic transformation proceeds with reasonable efficiency through the use of existing achiral Ru or Mo catalysts. Ru- or Mo-based chiral olefin metathesis catalysts have proven to be inefficient and entirely nonselective in cases where the desired product is observed. In the present study, the synthesis route thus serves as a platform for the discovery of new olefin metathesis catalysts that allow for efficient completion of an enantioselective synthesis of quebrachamine. Accordingly, on the basis of mechanistic principles, stereogenic-at-Mo complexes bearing only monodentate ligands have been designed. The new catalysts provide significantly higher levels of activity than observed with the previously reported Ru- or Mo-based complexes. Enantiomerically enriched chiral alkylidenes are generated through diastereoselective reactions involving achiral Mo-based bispyrrolides and enantiomerically pure silyl-protected binaphthols. Such chiral catalysts initiate the key enantioselective ring-closing metathesis step in the total synthesis of quebrachamine efficiently (1 mol % loading, 22 °C, 1 h, >98% conversion, 84% yield) and with high selectivity (98:2 er, 96% ee). PMID:19113867

Shell Higher Olefins Process.

ERIC Educational Resources Information Center

Lutz, E. F.

1986-01-01

Shows how olefin isomerization and the exotic olefin metathesis reaction can be harnessed in industrial processes. Indicates that the Shell Higher Olefins Process makes use of organometallic catalysts to manufacture alpha-olefins and internal carbon-11 through carbon-14 alkenes in a flexible fashion that can be adjusted to market needs. (JN)

Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

ERIC Educational Resources Information Center

Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

2007-01-01

A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

Synthesis of all-hydrocarbon stapled α-helical peptides by ring-closing olefin metathesis.

PubMed

Kim, Young-Woo; Grossmann, Tom N; Verdine, Gregory L

2011-06-01

This protocol provides a detailed procedure for the preparation of stapled α-helical peptides, which have proven their potential as useful molecular probes and as next-generation therapeutics. Two crucial features of this protocol are (i) the construction of peptide substrates containing hindered α-methyl, α-alkenyl amino acids and (ii) the ring-closing olefin metathesis (RCM) of the resulting resin-bound peptide substrates. The stapling systems described in this protocol, namely bridging one or two turns of an α-helix, are highly adaptable to most peptide sequences, resulting in favorable RCM kinetics, helix stabilization and promotion of cellular uptake.

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

NASA Astrophysics Data System (ADS)

Nguyen, Thach T.; Koh, Ming Joo; Mann, Tyler J.; Schrock, Richard R.; Hoveyda, Amir H.

2017-12-01

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity—namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products—and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis.

PubMed

Nguyen, Thach T; Koh, Ming Joo; Mann, Tyler J; Schrock, Richard R; Hoveyda, Amir H

2017-12-20

Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity-namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products-and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

Metathesis of alkanes and related reactions.

PubMed

Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

2010-02-16

of olefins or the selective transformation of ethylene into propylene. Alkane metathesis represents a powerful tool for making progress in a variety of areas, perhaps most notably in the petroleum and petrochemical fields. Modern civilization is currently confronting a host of problems that relate to energy production and its effects on the environment, and judicious application of alkane metathesis to the processing of fuels such as crude oil and natural gas may well afford solutions to these difficulties.

Synthesis by ring-closing alkyne metathesis with selective hydrogenation, and olfactory comparison of (7E)- and (7Z)-cyclohexadec-7-enone (Aurelione(®) ).

PubMed

Mathys, Marion; Kraft, Philip

2014-10-01

Both C=C-bond isomers of cyclohexadec-7-enone (6, Aurelione(®) ) were selectively synthesized via cyclohexadec-7-ynol (16) by ring-closing alkyne metathesis of icosa-2,18-diyn-9-ol (15), employing an in situ-formed catalyst from Mo(CO)6 and 4-(trifluoromethyl)phenol. Pyridinium chlorochromate (PCC) oxidation and subsequent Lindlar hydrogenation afforded the (7Z)-configured isomer (7Z)-6, while hydrosilylation of the intermediate cyclohexadec-7-ynone (17), followed by desilylation, provided the (7E)-configured cyclohexadec-7-enone ((7E)-6). The substrate for the alkyne metathesis was prepared from cycloheptanone (7) by cycloaddition of chloromethylcarbene to its trimethylsilyl enol ether 8, and subsequent ring enlargement of the adduct 9 under rearrangement to 2-methylcyclooct-2-enone (10), which was subjected to Weitz-Scheffer epoxidation and Eschenmoser-Ohloff fragmentation to non-7-ynal (12). Its reaction with the Grignard reagent of 11-bromoundec-2-yne (14), prepared from the corresponding alcohol 13 by Appel-Lee bromination, furnished the icosa-2,18-diyn-9-ol (15). While both isomers of cyclohexadec-7-enone (6) possess warm and powdery musk odors with tobacco-type ambery accents, (7Z)-6 is more animalic and waxy, whereas (7E)-6 was found to be more floral, sweet, and hay-like in tonality. Interestingly, however, with odor detection thresholds of 2.0 ng/l air and 2.3 ng/l air, respectively, both (7Z)-6 and (7E)-6 were found to be almost identical in their odor strength, with the (7Z)-6 being only very slightly more powerful. Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich.

Nonproductive events in ring-closing metathesis using ruthenium catalysts.

PubMed

Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

2010-06-30

The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

Controlled Ring-Opening Metathesis Polymerization by Molybdenum and Tungsten Alkylidene Complexes

DTIC Science & Technology

1988-07-29

weights and low polydispersities (as low as 1.03) consistent with a living catalyst system employing 50, 100, 200, and 400 eq of monomer. The reactions are...secondary metathesis of polymer chains Bulky alkoxide ligands Wittig-like reaction Ring-opening metathesis polymerization (ROMP) Feast monomer Cyclic...olefins Retro Diels-Alder reaction Norbornene (NBE) Low temperature column chromatography Endo-,endo-5,6-dicarbomethoxynorbornene Discrete, soluble

Metathesis Activity Encoded in the Metallacyclobutane Carbon-13 NMR Chemical Shift Tensors

PubMed Central

2017-01-01

Metallacyclobutanes are an important class of organometallic intermediates, due to their role in olefin metathesis. They can have either planar or puckered rings associated with characteristic chemical and physical properties. Metathesis active metallacyclobutanes have short M–Cα/α′ and M···Cβ distances, long Cα/α′–Cβ bond length, and isotropic 13C chemical shifts for both early d0 and late d4 transition metal compounds for the α- and β-carbons appearing at ca. 100 and 0 ppm, respectively. Metallacyclobutanes that do not show metathesis activity have 13C chemical shifts of the α- and β-carbons at typically 40 and 30 ppm, respectively, for d0 systems, with upfield shifts to ca. −30 ppm for the α-carbon of metallacycles with higher dn electron counts (n = 2 and 6). Measurements of the chemical shift tensor by solid-state NMR combined with an orbital (natural chemical shift, NCS) analysis of its principal components (δ11 ≥ δ22 ≥ δ33) with two-component calculations show that the specific chemical shift of metathesis active metallacyclobutanes originates from a low-lying empty orbital lying in the plane of the metallacyclobutane with local π*(M–Cα/α′) character. Thus, in the metathesis active metallacyclobutanes, the α-carbons retain some residual alkylidene character, while their β-carbon is shielded, especially in the direction perpendicular to the ring. Overall, the chemical shift tensors directly provide information on the predictive value about the ability of metallacyclobutanes to be olefin metathesis intermediates. PMID:28776018

Assessment of density functional methods for the study of olefin metathesis catalysed by ruthenium alkylidene complexes

NASA Astrophysics Data System (ADS)

Śliwa, Paweł; Handzlik, Jarosław

2010-06-01

Performance of 31 DFT methods in thermochemistry of olefin metathesis involving the model catalyst (PH 3) 2(Cl) 2Ru dbnd CH 2 is studied using the CCSD(T) reference energies. The best methods are M06, ωB97X-D and PBE0, followed by MPW1B95, LC-ωPBE, M05-2X and B1B95. Among 20 functionals tested in reproduction of experimental PCy 3 dissociation energy for the Grubbs catalyst (H 2IMes)(PCy 3)(Cl) 2Ru dbnd CHPh, the M06-class and M05-2X methods are most accurate. ωB97X-D overestimates the dissociation energy, whereas MPW1B95, LC-ωPBE, PBE0 and B1B95 underestimate it, similarly to other methods, which give larger errors. LC-ωPBE, B1B95, MPW1B95 and PBE0 provide the best geometries.

Methods of making organic compounds by metathesis

DOEpatents

Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

2015-09-01

Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

A two-color fluorogenic carbene complex for tagging olefins via metathesis reaction

NASA Astrophysics Data System (ADS)

Wirtz, Marcel; Grüter, Andreas; Heib, Florian; Huch, Volker; Zapp, Josef; Herten, Dirk-Peter; Schmitt, Michael; Jung, Gregor

2015-12-01

We describe a fluorogenic ruthenium (II) carbene complex in which the chromophore is directly connected to the metal center. The compound introduces a boron dipyrromethene (BODIPY) moiety into target double bonds by metathesis. Tagging of terminal double bonds is demonstrated on immobilized styrene units on a glass surface. We also show that two compounds with distinguishable fluorescence properties are formed in the model reaction with styrene. The outcome of the metathesis reaction is characterized by 19F-NMR, optical spectroscopy, and, finally, single-molecule trajectories. This labeling scheme, in our perception, is of particular interest in the fields of interfacial science and biorthogonal ligation in combination with super-resolution imaging.

About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

PubMed Central

Mutlu, Hatice; Montero de Espinosa, Lucas; Türünç, Oĝuz

2010-01-01

Summary We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET) polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS. PMID:21160555

Low Catalyst Loadings in Olefin Metathesis: Synthesis of Nitrogen Heterocycles by Ring Closing Metathesis

PubMed Central

Kuhn, Kevin M.; Champagne, Timothy M.; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C.; Grubbs, Robert H.; Pederson, Richard L.

2010-01-01

(eq 1) A series of ruthenium catalysts have been screened under ring closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate-series could be run neat, the six-membered carbamate-series could be run at 1.0 M concentrations and the seven-membered carbamate-series worked best at 0.2 M to 0.05 M concentrations. PMID:20141172

Methods of refining natural oils and methods of producing fuel compositions

DOEpatents

Firth, Bruce E; Kirk, Sharon E; Gavaskar, Vasudeo S

2015-11-04

A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent selected from the group consisting of phosphorous acid, phosphinic acid, and a combination thereof; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

Metathesis-mediated synthesis of (R)-10-methyl-2-tridecanone, the southern corn rootworm pheromone.

PubMed

Shikichi, Yasumasa; Mori, Kenji

2012-01-01

(R)-10-Methyl-2-tridecanone, the female sex pheromone of the southern corn rootworm (Diabrotica undecimpunctata howardi Barber), was synthesized in 9 steps from methyl (S)-3-hydroxy-2-methylpropanoate in a 15.7% overall yield. Olefin cross metathesis between (R)-6-methyl-1-nonene and 5-hexen-2-one employing Grubbs' first-generation catalyst was the key step of the synthesis.

Alkene metathesis: the search for better catalysts.

PubMed

Deshmukh, Prashant H; Blechert, Siegfried

2007-06-28

Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

A tandem cross-metathesis/semipinacol rearrangement reaction.

PubMed

Plummer, Christopher W; Soheili, Arash; Leighton, James L

2012-05-18

An efficient and (E)-selective synthesis of a 6-alkylidenebicyclo[3.2.1]octan-8-one has been developed. The key step is a tandem cross-metathesis/semipinacol rearrangement reaction, wherein the Hoveyda-Grubbs II catalyst, or more likely a derivative thereof, serves as the Lewis acid for the rearrangement. Despite the fact that both the starting alkene and the cross-metathesis product are viable rearrangement substrates, only the latter rearranges, suggesting that the Lewis acidic species is generated only after the cross-metathesis reaction is complete.

Z-Selective Metathesis Homocoupling of 1,3-Dienes by Molybdenum and Tungsten Monoaryloxide Pyrrolide (MAP) Complexes

PubMed Central

Townsend, Erik M.; Schrock, Richard R.; Hoveyda, Amir H.

2012-01-01

Molybdenum or tungsten MAP complexes that contain OHIPT as the aryloxide (hexaisopropylterphenoxide) are effective catalysts for homocoupling of simple (E)-1,3-dienes to give (E,Z,E)-trienes in high yield and with high Z selectivities. A vinylalkylidene MAP species was shown to have the expected syn structure in an X-ray study. MAP catalysts that contain OHMT (hexamethylterphenoxide) are relatively inefficient. PMID:22734508

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters.

PubMed

Thomas, Bryce N; Moon, Patrick J; Yin, Shengkang; Brown, Alex; Lundgren, Rylan J

2018-01-07

A well-defined Ir-allyl complex catalyzes the Z -selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E -products typically observed in metal-mediated coupling reactions to enable the synthesis of Z , E -dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir-carbene and Ir-allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E-H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt 3 .

Methods of refining natural oils, and methods of producing fuel compositions

DOEpatents

Firth, Bruce E.; Kirk, Sharon E.

2015-10-27

A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent that comprises nitric acid; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

Stereoselectivity of supported alkene metathesis catalysts: a goal and a tool to characterize active sites.

PubMed

Copéret, Christophe

2011-01-05

Stereoselectivity in alkene metathesis is a challenge and can be used as a tool to study active sites under working conditions. This review describes the stereochemical relevance and problems in alkene metathesis (kinetic vs. thermodynamic issues), the use of (E/Z) ratio at low conversions as a tool to characterize active sites of heterogeneous catalysts and finally to propose strategies to improve catalysts based on the current state of the art.

Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane.

PubMed

Samantaray, Manoja K; Kavitake, Santosh; Morlanés, Natalia; Abou-Hamad, Edy; Hamieh, Ali; Dey, Raju; Basset, Jean-Marie

2017-03-08

Two compatible organometallic complexes, W(Me) 6 (1) and TiNp 4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO 2-700 ) to synthesize the well-defined bimetallic precatalyst [(≡Si-O-)W(Me) 5 (≡Si-O-)Ti(Np) 3 ] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in 1 H- 1 H multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(≡Si-O-)W(Me) 5 ] (3), with a TON of 98, for propane metathesis at 150 °C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by β-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 °C) using a well-defined bimetallic system prepared via the SOMC approach.

Precision Aliphatic Polyesters with Alternating Microstructures via Cross-Metathesis Polymerization: An Event of Sequence Control.

PubMed

Li, Zi-Long; Zeng, Fu-Rong; Ma, Ji-Mei; Sun, Lin-Hao; Zeng, Zhen; Jiang, Hong

2017-06-01

Sequence-regulated polymerization is realized upon sequential cross-metathesis polymerization (CMP) and exhaustive hydrogenation to afford precision aliphatic polyesters with alternating sequences. This strategy is particularly suitable for the arrangement of well-known monomer units including glycolic acid, lactic acid, and caprolactic acid on polymer chain in a predetermined sequence. First of all, structurally asymmetric monomers bearing acrylate and α-olefin terminuses are generated in an efficient and straightforward fashion. Subsequently, cross-metathesis (co)polymerization of M1 and M2 using the Hoveyda-Grubbs second-generation catalyst (HG-II) furnishes P1-P3, respectively. Finally, hydrogenation yields the desired saturated polyesters HP1-HP3. It is noteworthy that the ε-caprolactone-derived unit is generated in situ rather than introduced to tailor-made monomers prior to CMP. NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) results verify the microstructural periodicity of these precision polyesters. Differential scanning calorimetry (DSC) results reflect that polyesters without methyl side groups exhibit crystallinity, and unsaturated polyester samples show higher glass transition temperatures than their hydrogenated counterparts owing to structural rigidity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cross enyne metathesis of para-substituted styrenes: a kinetic study of enyne metathesis.

PubMed

Giessert, Anthony J; Diver, Steven T

2005-01-20

[Reaction: see text] The intermolecular enyne metathesis between alkynes and styrene derivatives was developed to study electronic effects in enyne metathesis. A Hammett plot for the overall reaction, catalyst initiation and vinyl carbene turnover was determined with the second generation Grubbs ruthenium carbene catalyst.

Methods of refining and producing dibasic esters and acids from natural oil feedstocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snead, Thomas E; Cohen, Steven A; Gildon, Demond L

2015-04-07

Methods are provided for refining natural oil feedstocks and producing dibasic esters and/or dibasic acids. The methods comprise reacting a terminal olefin with an internal olefin in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In certain embodiments, the olefin esters are formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having olefin esters.

Methods of refining and producing dibasic esters and acids from natural oil feedstocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.

2016-03-15

Methods are provided for refining natural oil feedstocks and producing dibasic esters and/or dibasic acids. The methods comprise reacting a terminal olefin with an internal olefin in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In certain embodiments, the olefin esters are formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having olefin esters.

Methods of refining and producing dibasic esters and acids from natural oil feedstocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.

Methods and systems for making dibasic esters and/or dibasic acids using metathesis are generally disclosed. In some embodiments, the methods comprise reacting a terminal olefin ester with an internal olefin ester in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In some embodiments, the terminal olefin ester or the internal olefin ester are derived from a renewable feedstock, such as a natural oil feedstock. In some such embodiments, the natural oil feedstock, or a transesterified derivative thereof, is metathesized to make the terminal olefin ester or the internal olefin ester.

Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines

PubMed Central

Pfister, Kai F.; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J.

2017-01-01

Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering. PMID:28630908

Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines.

PubMed

Pfister, Kai F; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J

2017-06-01

Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering.

E- or Z-Selective synthesis of 4-fluorovinyl-1,2,3-triazoles with fluorinated second-generation Julia-Kocienski reagents.

PubMed

Kumar, Rakesh; Singh, Govindra; Todaro, Louis J; Yang, Lijia; Zajc, Barbara

2015-02-07

A highly modular approach to N-substituted 4-(1-fluorovinyl)triazoles is described. In situ desilylation and Cu-catalyzed ligation reaction of TMS-protected α-fluoropropargyl benzothiazole sulfone with aryl, alkyl, and metallocenyl azides furnished second-generation Julia-Kocienski reagents in good to excellent yields. Condensation reactions of these reagents with aldehydes can be tuned to yield E or Z-alkenes selectively. Under mild conditions with DBU as the base, reactions of aldehydes furnished E-alkenes as the major isomer. On the other hand, in condensation reactions with LHMDS as the base and in appropriate solvents, both aldehydes and ketones reacted to yield fluoroalkenes with Z-selectivity. Stereochemical assignment of E/Z olefins obtained in the reaction of a ketone with two Julia reagents was performed via X-ray crystallographic analysis and comparisons of NMR data. The method allows efficient and ready diversification of the N1-substituent and substituents at the double bond.

E- or Z-selective synthesis of 4-fluorovinyl-1,2,3-triazoles with fluorinated second-generation Julia-Kocienski reagents

PubMed Central

Kumar, Rakesh; Singh, Govindra; Todaro, Louis J.; Yang, Lijia; Zajc, Barbara

2016-01-01

A highly modular approach to N-substituted 4-(1-fluorovinyl)triazoles is described. In situ desilylation and Cu-catalyzed ligation reaction of TMS-protected α-fluoropropargyl benzothiazole sulfone with aryl, alkyl, and metallocenyl azides furnished second-generation Julia-Kocienski reagents in good to excellent yields. Condensation reactions of these reagents with aldehydes can be tuned to yield E or Z-alkenes selectively. Under mild conditions with DBU as base, reactions of aldehydes furnished E-alkenes as the major isomer. On the other hand, in condensations with LHMDS as base and in appropriate solvents, both aldehydes and ketones reacted to yield fluoroalkenes with Z-selectivity. Stereochemical assignment to E/Z olefins obtained in the reaction of a ketone with two Julia reagents was performed via X-ray crystallographic analysis and comparisons of NMR data. The method allows efficient and ready diversification of N1-substituent and substituents at the double bond. PMID:25491086

Molecular Diversity by Olefin Cross-Metathesis on Solid Support. Generation of Libraries of Biologically Promising β-Lactam Derivatives.

PubMed

Méndez, Luciana; Poeylaut-Palena, Andrés A; Mata, Ernesto G

2018-05-16

The application of the reagent-based diversification strategy for generation of libraries of biologically promising β-lactam derivatives is described. Key features are the versatility of the linker used and the cross-metathesis functionalization at the cleavage step. From an immobilized primary library, diversity was expanded by applying different cleavage conditions, leading to a series of cholesterol absorption inhibitor analogues together with interesting hybrid compounds through incorporation of a chalcone moiety.

Ethene/ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27 and ZIF-8.

PubMed

Böhme, Ulrike; Barth, Benjamin; Paula, Carolin; Kuhnt, Andreas; Schwieger, Wilhelm; Mundstock, Alexander; Caro, Jürgen; Hartmann, Martin

2013-07-09

Two types of metal-organic frameworks (MOFs) have been synthesized and evaluated in the separation of C2 and C3 olefins and paraffins. Whereas Co2(dhtp) (=Co-CPO-27 = Co-MOF-74) and Mg2(dhtp) show an adsorption selectivity for the olefins ethene and propene over the paraffins ethane and propane, the zeolitic imidazolate framework ZIF-8 behaves in the opposite way and preferentially adsorbs the alkane. Consequently, in breakthrough experiments, the olefins or paraffins, respectively, can be separated.

Olefinic Thermoplastic Elastomer Gels: Combining Polymer Crystallization and Microphase Separation in a Selective Solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armstrong, Daniel P.; Mineart, Kenneth P.; Lee, Byeongdu

Since selectively swollen thermoplastic elastomer gels (TPEGs) afford a wide range of beneficial properties that open new doors to developing elastomer-based technologies, in this study we examine the unique structure-property behavior of TPEGs composed of olefinic block copolymers (OBCs). Unlike their styrenic counterparts typically possessing two chemically different blocks, this class of multiblock copolymers consists of linear polyethylene hard blocks and poly(ethylene-co-α-octene) soft blocks, in which case, microphase separation between the hard and the soft blocks is accompanied by crystallization of the hard blocks. We prepare olefinic TPEGs (OTPEGs) through the incorporation of a primarily aliphatic oil that selectively swellsmore » the soft block and investigate the resultant morphological features through the use of polarized light microscopy and small-/wideangle X-ray scattering. These features are correlated with thermal and mechanical property measurements from calorimetry, rheology, and extensiometry to elucidate the roles of crystallization and self-assembly on gel characteristics and establish useful structure-property relationships.« less

Olefinic Thermoplastic Elastomer Gels: Combining Polymer Crystallization and Microphase Separation in a Selective Solvent

DOE PAGES

Armstrong, Daniel P.; Mineart, Kenneth P.; Lee, Byeongdu; ...

2016-11-01

Since selectively swollen thermoplastic elastomer gels (TPEGs) afford a wide range of beneficial properties that open new doors to developing elastomer-based technologies, in this study we examine the unique structure-property behavior of TPEGs composed of olefinic block copolymers (OBCs). Unlike their styrenic counterparts typically possessing two chemically different blocks, this class of multiblock copolymers consists of linear polyethylene hard blocks and poly(ethylene-co-α-octene) soft blocks, in which case, microphase separation between the hard and the soft blocks is accompanied by crystallization of the hard blocks. We prepare olefinic TPEGs (OTPEGs) through the incorporation of a primarily aliphatic oil that selectively swellsmore » the soft block and investigate the resultant morphological features through the use of polarized light microscopy and small-/wideangle X-ray scattering. These features are correlated with thermal and mechanical property measurements from calorimetry, rheology, and extensiometry to elucidate the roles of crystallization and self-assembly on gel characteristics and establish useful structure-property relationships.« less

Prosodically Driven Metathesis in Mutsun

ERIC Educational Resources Information Center

Butler, Lynnika

2013-01-01

Among the many ways in which sounds alternate in the world's languages, changes in the order of sounds (metathesis) are relatively rare. Mutsun, a Southern Costanoan language of California which was documented extensively before the death of its last speaker in 1930, displays three patterns of synchronic consonant-vowel (CV) metathesis. Two of…

Directed evolution of artificial metalloenzymes for in vivo metathesis

NASA Astrophysics Data System (ADS)

Jeschek, Markus; Reuter, Raphael; Heinisch, Tillmann; Trindler, Christian; Klehr, Juliane; Panke, Sven; Ward, Thomas R.

2016-09-01

The field of biocatalysis has advanced from harnessing natural enzymes to using directed evolution to obtain new biocatalysts with tailor-made functions. Several tools have recently been developed to expand the natural enzymatic repertoire with abiotic reactions. For example, artificial metalloenzymes, which combine the versatile reaction scope of transition metals with the beneficial catalytic features of enzymes, offer an attractive means to engineer new reactions. Three complementary strategies exist: repurposing natural metalloenzymes for abiotic transformations; in silico metalloenzyme (re-)design; and incorporation of abiotic cofactors into proteins. The third strategy offers the opportunity to design a wide variety of artificial metalloenzymes for non-natural reactions. However, many metal cofactors are inhibited by cellular components and therefore require purification of the scaffold protein. This limits the throughput of genetic optimization schemes applied to artificial metalloenzymes and their applicability in vivo to expand natural metabolism. Here we report the compartmentalization and in vivo evolution of an artificial metalloenzyme for olefin metathesis, which represents an archetypal organometallic reaction without equivalent in nature. Building on previous work on an artificial metallohydrolase, we exploit the periplasm of Escherichia coli as a reaction compartment for the ‘metathase’ because it offers an auspicious environment for artificial metalloenzymes, mainly owing to low concentrations of inhibitors such as glutathione, which has recently been identified as a major inhibitor. This strategy facilitated the assembly of a functional metathase in vivo and its directed evolution with substantially increased throughput compared to conventional approaches that rely on purified protein variants. The evolved metathase compares favourably with commercial catalysts, shows activity for different metathesis substrates and can be further evolved in

Learning metathesis: Evidence for syllable structure constraints.

PubMed

Finley, Sara

2017-02-01

One of the major questions in the cognitive science of language is whether the perceptual and phonological motivations for the rules and patterns that govern the sounds of language are a part of the psychological reality of grammatical representations. This question is particularly important in the study of phonological patterns - systematic constraints on the representation of sounds, because phonological patterns tend to be grounded in phonetic constraints. This paper focuses on phonological metathesis, which occurs when two adjacent sounds switch positions (e.g., ca st pronounced as ca ts ). While many cases of phonological metathesis appear to be motivated by constraints on syllable structure, it is possible that these metathesis patterns are merely artifacts of historical change, and do not represent the linguistic knowledge of the speaker (Blevins & Garrett, 1998). Participants who were exposed to a metathesis pattern that can be explained in terms of structural or perceptual improvement were less likely to generalize to metathesis patterns that did not show the same improvements. These results support a substantively biased theory in which phonological patterns are encoded in terms of structurally motivated constraints.

Learning metathesis: Evidence for syllable structure constraints

PubMed Central

Finley, Sara

2016-01-01

One of the major questions in the cognitive science of language is whether the perceptual and phonological motivations for the rules and patterns that govern the sounds of language are a part of the psychological reality of grammatical representations. This question is particularly important in the study of phonological patterns – systematic constraints on the representation of sounds, because phonological patterns tend to be grounded in phonetic constraints. This paper focuses on phonological metathesis, which occurs when two adjacent sounds switch positions (e.g., cast pronounced as cats). While many cases of phonological metathesis appear to be motivated by constraints on syllable structure, it is possible that these metathesis patterns are merely artifacts of historical change, and do not represent the linguistic knowledge of the speaker (Blevins & Garrett, 1998). Participants who were exposed to a metathesis pattern that can be explained in terms of structural or perceptual improvement were less likely to generalize to metathesis patterns that did not show the same improvements. These results support a substantively biased theory in which phonological patterns are encoded in terms of structurally motivated constraints. PMID:28082764

Synthesis of (+)-Didemniserinolipid B: Application of a 2-Allyl-4-fluorophenyl Auxiliary for Relay Ring-Closing Metathesis

PubMed Central

Marvin, Christopher C.; Voight, Eric A.; Suh, Judy M.; Paradise, Christopher L.; Burke, Steven D.

2009-01-01

The synthesis of didemniserinolipid B utilizing a ketalization/ring-closing metathesis (K/RCM) strategy is described. In the course of this work, a novel 2-allyl-4-fluorophenyl auxiliary for relay ring-closing metathesis (RRCM) was developed which increased the yield of the RCM. The resulting 6,8-dioxabicyclo[3.2.1]octene core was selectively functionalized by complimentary dihydroxylation and epoxidation routes to install the C10 axial alcohol. This bicyclic ketal core was further functionalized by etherification and an alkene cross metathesis with an unsaturated α-phenylselenyl ester en route to completing the total synthesis. PMID:18811201

Functionalized linear and cyclic polyolefins

DOEpatents

Tuba, Robert; Grubbs, Robert H.

2018-02-13

This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

Selective Oxidation and Ammoxidation of Olefins by Heterogeneous Catalysis.

ERIC Educational Resources Information Center

Grasselli, Robert K.

1986-01-01

Shows how the ammoxidation of olefins can be understood in terms of free radicals and surface bound organometallic intermediates. Also illustrates the close intellectual relationships between heterogeneous catalysis and organometallic chemistry. (JN)

Femtosecond Kerr index of cyclic olefin co/polymers for THz nonlinear optics

NASA Astrophysics Data System (ADS)

Noskovicova, E.; Lorenc, D.; Slusna, L.; Velic, D.

2016-10-01

The second-order nonlinear refractive index n2 (Kerr index) of cyclic olefin copolymer (TOPAS) and cyclic olefin polymers (ZEONEX, ZEONOR) was determined at the wavelength of 800 nm within this work. Bulk samples of ZEONEX, ZEONOR and TOPAS were measured using the single-beam Z-scan technique and the values of their nonlinear refractive index were determined to be approximately 2 × 10-20 m2W-1 for all cases. The obtained values of n2 play a vital role for ultrafast pulse evolution and corresponding phenomena such as nonlinear spectral transformation.

Computational study of productive and non-productive cycles in fluoroalkene metathesis.

PubMed

Rybáčková, Markéta; Hošek, Jan; Šimůnek, Ondřej; Kolaříková, Viola; Kvíčala, Jaroslav

2015-01-01

A detailed DFT study of the mechanism of metathesis of fluoroethene, 1-fluoroethene, 1,1-difluoroethene, cis- and trans-1,2-difluoroethene, tetrafluoroethene and chlorotrifluoroethene catalysed with the Hoveyda-Grubbs 2(nd) generation catalyst was performed. It revealed that a successful metathesis of hydrofluoroethenes is hampered by a high preference for a non-productive catalytic cycle proceeding through a ruthenacyclobutane intermediate bearing fluorines in positions 2 and 4. Moreover, the calculations showed that the cross-metathesis of perfluoro- or perhaloalkenes should be a feasible process and that the metathesis is not very sensitive to stereochemical issues.

Ionic liquids for separation of olefin-paraffin mixtures

DOEpatents

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2013-09-17

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Ionic liquids for separation of olefin-paraffin mixtures

DOEpatents

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2014-07-15

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Terminal Olefin Profiles and Phylogenetic Analyses of Olefin Synthases of Diverse Cyanobacterial Species.

PubMed

Zhu, Tao; Scalvenzi, Thibault; Sassoon, Nathalie; Lu, Xuefeng; Gugger, Muriel

2018-07-01

Cyanobacteria can synthesize alkanes and alkenes, which are considered to be infrastructure-compatible biofuels. In terms of physiological function, cyanobacterial hydrocarbons are thought to be essential for membrane flexibility for cell division, size, and growth. The genetic basis for the biosynthesis of terminal olefins (1-alkenes) is a modular type I polyketide synthase (PKS) termed olefin synthase (Ols). The modular architectures of Ols and structural characteristics of alkenes have been investigated only in a few species of the small percentage (approximately 10%) of cyanobacteria that harbor putative Ols pathways. In this study, investigations of the domains, modular architectures, and phylogenies of Ols in 28 cyanobacterial strains suggested distinctive pathway evolution. Structural feature analyses revealed 1-alkenes with three carbon chain lengths (C 15 , C 17 , and C 19 ). In addition, the total cellular fatty acid profile revealed the diversity of the carbon chain lengths, while the fatty acid feeding assay indicated substrate carbon chain length specificity of cyanobacterial Ols enzymes. Finally, in silico analyses suggested that the N terminus of the modular Ols enzyme exhibited characteristics typical of a fatty acyl-adenylate ligase (FAAL), suggesting a mechanism of fatty acid activation via the formation of acyl-adenylates. Our results shed new light on the diversity of cyanobacterial terminal olefins and a mechanism for substrate activation in the biosynthesis of these olefins. IMPORTANCE Cyanobacterial terminal olefins are hydrocarbons with promising applications as advanced biofuels. Despite the basic understanding of the genetic basis of olefin biosynthesis, the structural diversity and phylogeny of the key modular olefin synthase (Ols) have been poorly explored. An overview of the chemical structural traits of terminal olefins in cyanobacteria is provided in this study. In addition, we demonstrated by in vivo fatty acid feeding assays that

Understanding the desensitizing mechanism of olefin in explosives: shear slide of mixed HMX-olefin systems.

PubMed

Zhang, Chaoyang; Cao, Xia; Xiang, Bin

2012-04-01

We simulated the shear slide behavior of typical mixed HMX-olefin systems and the effect of thickness of olefin layers (4-22 Å) on the behavior at a molecular level by considering two cases: bulk shear and interfacial shear. The results show that: (1) the addition of olefin into HMX can reduce greatly the shear sliding barriers relative to the pure HMX in the two cases, suggesting that the desensitizing mechanism of olefin is controlled dominantly by its good lubricating property; (2) the change of interaction energy in both systoles of shear slide is strongly dominated by van der Waals interaction; and (3) the thickness of olefin layers in the mixed explosives can influence its desensitizing efficiency. That is, the excessive thinness of olefin layers in the mixed explosive systems, for example, several angstroms, can lead to very high sliding barriers.

Poly(aryleneethynylene)s: Properties, Applications and Synthesis Through Alkyne Metathesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortiz, Michael; Yu, Chao; Jin, Yinghua

2017-06-26

Functional polymeric materials have seen their way into every facet of materials chemistry and engineering. In this review article, we focus on a promising class of polymers, poly(aryleneethynylene)s, by covering several of the numerous applications found thus far for these materials. Additionally, we survey the current synthetic strategies used to create these polymers, with a focus on the emerging technique of alkyne metathesis. An overview is presented of the most recent catalytic systems that support alkyne metathesis as well as the more useful alkyne metathesis reaction capable of synthesizing poly(aryleneethynylene)s.

Ethenolysis: A Green Catalytic Tool to Cleave Carbon-Carbon Double Bonds.

PubMed

Bidange, Johan; Fischmeister, Cédric; Bruneau, Christian

2016-08-22

Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross-metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon-carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2006-10-10

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-04-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, and SnR".sub.3 containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2007-01-09

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-Containing Low-Valent Early Transition Metal Olefin Polymerization Catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2004-06-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C-containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-12-30

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Methods for treating a metathesis feedstock with metal alkoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cohen, Steven A.; Anderson, Donde R.; Wang, Zhe

Various methods are provided for treating and reacting a metathesis feedstock. In one embodiment, the method includes providing a feedstock comprising a natural oil, chemically treating the feedstock with a metal alkoxide under conditions sufficient to diminish catalyst poisons in the feedstock, and, following the treating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis

DOE PAGES

Marx, Vanessa M.; Sullivan, Alexandra H.; Melaimi, Mohand; ...

2014-12-17

In this paper, an expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. Finally, this is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, withmore » activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products.« less

Richard Schrock, Robert Grubbs, and Metathesis Method in Organic Synthesis

Science.gov Websites

Organic Synthesis Resources with Additional Information Richard R. Schrock of the Massachusetts Institute Nobel Prize in Chemistry "for the development of the metathesis method in organic synthesis" ] Chauvin, Grubbs and Schrock "for the development of the metathesis method in organic synthesis,"

Methods for synthesis of olefins and derivatives

DOEpatents

Burk, Mark J.; Pharkya, Priti; Van Dien, Stephen J.; Burgard, Anthony P.; Schilling, Christophe H.

2016-06-14

The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

PHENANTHROLINE-STABILIZED PALLADIUM NANOPARTICLES IN POLYETHYLENE GLYCOL—AN ACTIVE AND RECYCLABLE CATALYST SYSTEM FOR THE SELECTIVE HYDROGENATION OF OLEFINS USING MOLECULAR HYDROGEN

EPA Science Inventory

1,10-Phenanthroline-stabilized palladium nanoparticles dispersed in a polyethylene glycol (PEG) matrix is synthesized which is found to be a stable and active catalyst for the selective hydrogenation of olefins using molecular hydrogen under mild reaction conditions. A variety of...

The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters.

PubMed

Zhang, Shihong; Yang, Mingfa; Shao, Jingai; Yang, Haiping; Zeng, Kuo; Chen, Yingquan; Luo, Jun; Agblevor, Foster A; Chen, Hanping

2018-07-01

Light olefins are the key building blocks for the petrochemical industry. In this study, the effects of in-situ and ex-situ process, temperature, Fe loading, catalyst to feed ratio and gas flow rate on the olefins carbon yield and selectivity were explored. The results showed that Fe-modified ZSM-5 catalyst increased the olefins yield significantly, and the ex-situ process was much better than in-situ. With the increasing of temperature, Fe-loading amount, catalyst to feed ratio, and gas flow rate, the carbon yields of light olefins were firstly increased and further decreased. The maximum carbon yield of light olefins (6.98% C-mol) was obtained at the pyrolysis temperature of 600°C, catalyst to feed ratio of 2, gas flow rate of 100ml/min, and 3wt% Fe/ZSM-5 for cellulose. The selectivity of C 2 H 4 was more than 60% for all feedstock, and the total light olefins followed the decreasing order of cellulose, corn stalk, hemicelluloses and lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

2009-01-01

Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

Iron-catalyzed stereospecific activation of olefinic C-H bonds with Grignard reagent for synthesis of substituted olefins.

PubMed

Ilies, Laurean; Asako, Sobi; Nakamura, Eiichi

2011-05-25

The reaction of an aryl Grignard reagent with a cyclic or acyclic olefin possessing a directing group such as pyridine or imine results in the stereospecific substitution of the olefinic C-H bond syn to the directing group. The reaction takes place smoothly and without isomerization of the product olefin in the presence of a mild oxidant (1,2-dichloro-2-methylpropane) and an aromatic cosolvent. Several lines of evidence suggest that the reaction proceeds via iron-catalyzed olefinic C-H bond activation rather than an oxidative Mizoroki-Heck-type reaction.

Methods for the synthesis of olefins and derivatives

DOEpatents

Burk, Mark J; Pharkya, Priti; Van Dien, Stephen J; Burgard, Anthony P; Schilling, Christophe H

2013-06-04

The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

Methods for the synthesis of olefins and derivatives

DOEpatents

Burk, Mark J [San Diego, CA; Pharkya, Priti [San Diego, CA; Van Dien, Stephen J [Encinitas, CA; Burgard, Anthony P [Bellefonte, PA; Schilling, Christophe H [San Diego, CA

2011-09-27

The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

Integrated process and dual-function catalyst for olefin epoxidation

DOEpatents

Zhou, Bing; Rueter, Michael

2003-01-01

The invention discloses a dual-functional catalyst composition and an integrated process for production of olefin epoxides including propylene oxide by catalytic reaction of hydrogen peroxide from hydrogen and oxygen with olefin feeds such as propylene. The epoxides and hydrogen peroxide are preferably produced simultaneously in situ. The dual-functional catalyst comprises noble metal crystallites with dimensions on the nanometer scale (on the order of <1 nm to 10 nm), specially dispersed on titanium silicalite substrate particles. The dual functional catalyst catalyzes both the direct reaction of hydrogen and oxygen to generate hydrogen peroxide intermediate on the noble metal catalyst surface and the reaction of the hydrogen peroxide intermediate with the propylene feed to generate propylene oxide product. Combining both these functions in a single catalyst provides a very efficient integrated process operable below the flammability limits of hydrogen and highly selective for the production of hydrogen peroxide to produce olefin oxides such as propylene oxide without formation of undesired co-products.

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

PubMed Central

2014-01-01

Conspectus One of the most important challenges in catalyst design is the synthesis of stable promoters without compromising their activity. For this reason, it is important to understand the factors leading to decomposition of such catalysts, especially if side-products negatively affect the activity and selectivity of the starting complex. In this context, the understanding of termination and decomposition processes in olefin metathesis is receiving significant attention from the scientific community. For example, the decomposition of ruthenium olefin metathesis precatalysts in alcohol solutions can occur during either the catalyst synthesis or the metathesis process, and such decomposition has been found to be common for Grubbs-type precatalysts. These decomposition products are usually hydridocarbonyl complexes, which are well-known to be active in several transformations such as hydrogenation, terminal alkene isomerization, and C–H activation chemistry. The reactivity of these side products can be unwanted, and it is therefore important to understand how to avoid them and maybe also important to keep an open mind and think of ways to use these in other catalytic reactions. A showcase of these decomposition studies is reported in this Account. These reports analyze the stability of ruthenium phenylindenylidene complexes, highly active olefin metathesis precatalysts, in basic alcohol solutions. Several different decomposition processes can occur under these conditions depending on the starting complex and the alcohol used. These indenylidene-bearing metathesis complexes display a completely different behavior compared with that of other metathesis precatalysts and show an alternative competitive alcoholysis pathway, where rather than forming the expected hydrido carbonyl complexes, the indenylidene fragment is transformed into a η1-indenyl, which then rearranges to its η5-indenyl form. In particular, [RuCl(η5-(3-phenylindenylidene)(PPh3)2] has been found to

Myoglobin-Catalyzed Olefination of Aldehydes.

PubMed

Tyagi, Vikas; Fasan, Rudi

2016-02-12

The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Positive selection drives faster-Z evolution in silkmoths

PubMed Central

Sackton, Timothy B.; Corbett-Detig, Russell B.; Nagaraju, Javaregowda; Vaishna, R. Lakshmi; Arunkumar, Kallare P.; Hartl, Daniel L.

2014-01-01

Genes linked to X or Z chromosomes, which are hemizygous in the heterogametic sex, are predicted to evolve at different rates than those on autosomes. This “faster-X effect” can arise either as a consequence of hemizygosity, which leads to more efficient selection for recessive beneficial mutations in the heterogametic sex, or as a consequence of reduced effective population size of the hemizygous chromosome, which leads to increased fixation of weakly deleterious mutations due to genetic drift. Empirical results to date suggest that, while the overall pattern across taxa is complicated, systems with male-heterogamy show a faster-X effect attributable to more efficient selection, while the faster-Z effect in female-heterogametic taxa is attributable to increased drift. To test the generality of the faster-Z pattern seen in birds and snakes, we sequenced the genome of the Lepidopteran silkmoth Bombyx huttoni. We show that silkmoths experience faster-Z evolution, but unlike in birds and snakes, the faster-Z effect appears to be attributable to more efficient positive selection. These results suggest that female-heterogamy alone is unlikely to explain the reduced efficacy of selection on the bird Z chromosome. It is likely that many factors, including differences in overall effective population size, influence Z chromosome evolution. PMID:24826901

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters† †Electronic supplementary information (ESI) available: Full procedures, computational details and characterization data. See DOI: 10.1039/c7sc04283c

PubMed Central

Thomas, Bryce N.; Moon, Patrick J.; Yin, Shengkang; Brown, Alex

2017-01-01

A well-defined Ir–allyl complex catalyzes the Z-selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E-products typically observed in metal-mediated coupling reactions to enable the synthesis of Z,E-dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir–carbene and Ir–allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E–H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt3. PMID:29629093

Domino-hydroformylation/aldol condensation catalysis: highly selective synthesis of α,β-unsaturated aldehydes from olefins.

PubMed

Fang, Xianjie; Jackstell, Ralf; Franke, Robert; Beller, Matthias

2014-10-06

A general and highly chemo-, regio-, and stereoselective synthesis of α,β-unsaturated aldehydes by a domino hydroformylation/aldol condensation reaction has been developed. A variety of olefins and aromatic aldehydes were efficiently converted into various substituted α,β-unsaturated aldehydes in good to excellent yields in the presence of a rhodium phosphine/acid-base catalyst system. In view of the easy availability of the substrates, the high atom-efficiency, the excellent selectivity, and the mild conditions, this method is expected to complement current methodologies for the preparation of α,β-unsaturated aldehydes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dehydrogenation of n-Alkanes by Solid-Phase Molecular Pincer-Iridium Catalysts. High Yields of α-Olefin Product.

PubMed

Kumar, Akshai; Zhou, Tian; Emge, Thomas J; Mironov, Oleg; Saxton, Robert J; Krogh-Jespersen, Karsten; Goldman, Alan S

2015-08-12

We report the transfer-dehydrogenation of gas-phase alkanes catalyzed by solid-phase, molecular, pincer-ligated iridium catalysts, using ethylene or propene as hydrogen acceptor. Iridium complexes of sterically unhindered pincer ligands such as (iPr4)PCP, in the solid phase, are found to give extremely high rates and turnover numbers for n-alkane dehydrogenation, and yields of terminal dehydrogenation product (α-olefin) that are much higher than those previously reported for solution-phase experiments. These results are explained by mechanistic studies and DFT calculations which jointly lead to the conclusion that olefin isomerization, which limits yields of α-olefin from pincer-Ir catalyzed alkane dehydrogenation, proceeds via two mechanistically distinct pathways in the case of ((iPr4)PCP)Ir. The more conventional pathway involves 2,1-insertion of the α-olefin into an Ir-H bond of ((iPr4)PCP)IrH2, followed by 3,2-β-H elimination. The use of ethylene as hydrogen acceptor, or high pressures of propene, precludes this pathway by rapid hydrogenation of these small olefins by the dihydride. The second isomerization pathway proceeds via α-olefin C-H addition to (pincer)Ir to give an allyl intermediate as was previously reported for ((tBu4)PCP)Ir. The improved understanding of the factors controlling rates and selectivity has led to solution-phase systems that afford improved yields of α-olefin, and provides a framework required for the future development of more active and selective catalytic systems.

Splitting a C-O bond in dialkylethers with bis(1,2,4-tri-t-butylcyclopentadienyl) cerium-hydride does not occur by a sigma-bond metathesis pathway: a combined experimental and DFT computational study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werkema, Evan; Yahia, Ahmed; Maron, Laurent

2010-04-06

Addition of diethylether to [1,2,4(Me3C)3C5H2]2CeH, abbreviated Cp'2CeH, gives Cp'2CeOEt and ethane. Similarly, di-n-propyl- or di-n-butylether gives Cp'2Ce(O-n-Pr) and propane or Cp'2Ce(O-n-Bu) and butane, respectively. Using Cp'2CeD, the propane and butane contain deuterium predominantly in their methyl groups. Mechanisms, formulated on the basis of DFT computational studies, show that the reactions begin by an alpha or beta-CH activation with comparable activation barriers but only the beta-CH activation intermediate evolves into the alkoxide product and an olefin. The olefin then inserts into the Ce-H bond forming the alkyl derivative, Cp'2CeR, that eliminates alkane. The alpha-CH activation intermediate is in equilibrium with themore » starting reagents, Cp'2CeH and the ether, which accounts for the deuterium label in the methyl groups of the alkane. The one-step sigma-bond metathesis mechanism has a much higher activation barrier than either of the two-step mechanisms.« less

Producing alpha-olefins using polyketide synthases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fortman, Jeffrey L.; Katz, Leonard; Steen, Eric J.

2018-01-02

The present invention provides for a polyketide synthase (PKS) capable of synthesizing an .alpha.-olefin, such as 1-hexene or butadiene. The present invention also provides for a host cell comprising the PKS and when cultured produces the .alpha.-olefin.

Metathesis depolymerizable surfactants

DOEpatents

Jamison, Gregory M [Albuquerque, NM; Wheeler, David R [Albuquerque, NM; Loy, Douglas A [Tucson, AZ; Simmons, Blake A [San Francisco, CA; Long, Timothy M [Evanston, IL; McElhanon, James R [Manteca, CA; Rahimian, Kamyar [Albuquerque, NM; Staiger, Chad L [Albuquerque, NM

2008-04-15

A class of surfactant molecules whose structure includes regularly spaced unsaturation in the tail group and thus, can be readily decomposed by ring-closing metathesis, and particularly by the action of a transition metal catalyst, to form small molecule products. These small molecules are designed to have increased volatility and/or enhanced solubility as compared to the original surfactant molecule and are thus easily removed by solvent extraction or vacuum extraction at low temperature. By producing easily removable decomposition products, the surfactant molecules become particularly desirable as template structures for preparing meso- and microstructural materials with tailored properties.

Enantioselective syntheses of cryptocarya triacetate, cryptocaryolone, and cryptocaryolone diacetate.

PubMed

Smith, Catherine M; O'Doherty, George A

2003-05-29

[reaction: see text] The enantioselective syntheses of three natural products from Cryptocarya latifolia have been achieved in 13-15 steps from ethyl sorbate. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to establish the absolute stereochemistry. The route also relies upon a highly (E)-selective olefin cross-metathesis reaction to form trans-delta-hydroxy-1-enoates. The resulting delta-hydroxy-1-enoates were subsequently converted into cryptocarya triacetate, cryptocaryolone, and cryptocaryolone diacetate.

Catalytic pyrolysis of model compounds and waste cooking oil for production of light olefins over La/ZSM-5 catalysts

NASA Astrophysics Data System (ADS)

Li, F. W.; Ding, S. L.; Li, L.; Gao, C.; Zhong, Z.; Wang, S. X.; Li, Z. X.

2016-08-01

Waste cooking oil (WCO) and its model compounds (oleic acid and methyl laurate) are catalytically pyrolyzed in a fixed-bed reactor over La modified ZSM-5 catalysts (La/ZSM-5) aiming for production of C2-C4 light olefins. The LaO content in catalysts was set at 0, 2, 6, 10 and 14 wt%. The gas and liquid products are analyzed. The La/ZSM-5 catalyst with 6% LaO showed higher selectivity to light olefins when WCO and methyl laurate were pyrolyzed, and olefin content was 26% for WCO and 21% for methyl laurate. The catalyst with 10% LaO showed high selectivity to light olefins (28.5%) when oleic acid was pyrolyzed. The liquid products from WCO and model compounds mainly contain esters and aromatic hydrocarbons. More esters were observed in liquid products from methyl laurate and WCO pyrolysis, indicating that it is more difficult to pyrolyze esters and WCO than oleic acid. The coked catalysts were analyzed by temperature-programmed oxidation. The result shows that graphite is the main component of coke. The conversion of WCO to light olefins potentially provides an alternative and sustainable route for production of the key petrochemicals.

Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

PubMed

Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

2013-03-06

A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, R.

1985-04-09

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Total synthesis of (+)-antroquinonol and (+)-antroquinonol D.

PubMed

Sulake, Rohidas S; Chen, Chinpiao

2015-03-06

The first total synthesis of (+)-antroquinonol and (+)-antroquinonol D, two structurally unique quinonols with a sesquiterpene side chain, is described. The route features an iridium-catalyzed olefin isomerization-Claisen rearrangement reaction (ICR), lactonization, and Grubbs olefin metathesis. The requisite α,β-unsaturation was achieved via the selenylation/oxidation protocol and elimination of β-methoxy group to provide two natural products from a common intermediate.

Chromium-catalysed ethene trimerisation and tetramerisation--breaking the rules in olefin oligomerisation.

PubMed

Wass, Duncan F

2007-02-28

The discovery of a new generation of highly active and selective ethene trimerisation and tetramerisation catalysts has radically changed the field of olefin oligomerisation. This Frontiers article gives an overview of these recent advances.

Recovery of olefin monomers

DOEpatents

Golden, Timothy Christoph; Weist, Jr., Edward Landis; Johnson, Charles Henry

2004-03-16

In a process for the production of a polyolefin, an olefin monomer is polymerised said polyolefin and residual monomer is recovered. A gas stream comprising the monomer and nitrogen is subjected to a PSA process in which said monomer is adsorbed on a periodically regenerated silica gel or alumina adsorbent to recover a purified gas stream containing said olefin and a nitrogen rich stream containing no less than 99% nitrogen and containing no less than 50% of the nitrogen content of the gas feed to the PSA process.

A new efficient iron catalyst for olefin epoxidation with hydrogen peroxide.

PubMed

Mikhalyova, Elena A; Makhlynets, Olga V; Palluccio, Taryn D; Filatov, Alexander S; Rybak-Akimova, Elena V

2012-01-18

A new aminopyridine ligand derived from bipiperidine (the product of full reduction of bipyridine, bipy) coordinates to iron(II) in a cis-α fashion, yielding a new selective catalyst for olefin epoxidation with H(2)O(2) under limiting substrate conditions.

Toward chemical propulsion: synthesis of ROMP-propelled nanocars.

PubMed

Godoy, Jazmin; Vives, Guillaume; Tour, James M

2011-01-25

The synthesis and ring-opening metathesis polymerization (ROMP) activity of two nanocars functionalized with an olefin metathesis catalyst is reported. The nanocars were attached to a Hoveyda-Grubbs first- or second-generation metathesis catalyst via a benzylidene moiety. The catalytic activity of these nanocars toward ROMP of 1,5-cyclooctadiene was similar to that of their parent catalysts. The activity of the Hoveyda-Grubbs first-generation catalyst-functionalized nanocar was further tested with polymerization of norbornene. Hence, the prospect is heightened for a ROMP process to propel nanocars across a surface by providing the translational force.

Fe-Catalyzed C–C Bond Construction from Olefins via Radicals

PubMed Central

2017-01-01

This Article details the development of the iron-catalyzed conversion of olefins to radicals and their subsequent use in the construction of C–C bonds. Optimization of a reductive diene cyclization led to the development of an intermolecular cross-coupling of electronically-differentiated donor and acceptor olefins. Although the substitution on the donor olefins was initially limited to alkyl and aryl groups, additional efforts culminated in the expansion of the scope of the substitution to various heteroatom-based functionalities, providing a unified olefin reactivity. A vinyl sulfone acceptor olefin was developed, which allowed for the efficient synthesis of sulfone adducts that could be used as branch points for further diversification. Moreover, this reactivity was extended into an olefin-based Minisci reaction to functionalize heterocyclic scaffolds. Finally, mechanistic studies resulted in a more thorough understanding of the reaction, giving rise to the development of a more efficient second-generation set of olefin cross-coupling conditions. PMID:28094980

Tandem ring-closing metathesis/transfer hydrogenation: practical chemoselective hydrogenation of alkenes.

PubMed

Connolly, Timothy; Wang, Zhongyu; Walker, Michael A; McDonald, Ivar M; Peese, Kevin M

2014-09-05

An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.

40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium salt...

40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

Activation of olefins via asymmetric Bronsted acid catalysis

DOE PAGES

Tsuji, Nobuya; Kennemur, Jennifer L.; Buyck, Thomas; ...

2018-03-30

The activation of olefins for asymmetric chemical synthesis traditionally relies on transition metal catalysts. In contrast, biological enzymes with Bronsted acidic sites of appropriate strength can protonate olefins and thereby generate carbocations that ultimately react to form natural products. Although chemists have recently designed chiral Bronsted acid catalysts to activate imines and carbonyl compounds, mimicking these enzymes to protonate simple olefins that then engage in asymmetric catalytic reactions has remained a substantial synthetic challenge. Here, we show that a class of confined and strong chiral Bronsted acids enables the catalytic asymmetric intramolecular hydroalkoxylation of unbiased olefins. In conclusion, the methodologymore » gives rapid access to biologically active 1,1-disubstituted tetrahydrofurans, including (–)-Boivinianin A.« less

Activation of olefins via asymmetric Bronsted acid catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsuji, Nobuya; Kennemur, Jennifer L.; Buyck, Thomas

The activation of olefins for asymmetric chemical synthesis traditionally relies on transition metal catalysts. In contrast, biological enzymes with Bronsted acidic sites of appropriate strength can protonate olefins and thereby generate carbocations that ultimately react to form natural products. Although chemists have recently designed chiral Bronsted acid catalysts to activate imines and carbonyl compounds, mimicking these enzymes to protonate simple olefins that then engage in asymmetric catalytic reactions has remained a substantial synthetic challenge. Here, we show that a class of confined and strong chiral Bronsted acids enables the catalytic asymmetric intramolecular hydroalkoxylation of unbiased olefins. In conclusion, the methodologymore » gives rapid access to biologically active 1,1-disubstituted tetrahydrofurans, including (–)-Boivinianin A.« less

21 CFR 177.1520 - Olefin polymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Olefin polymers. 177.1520 Section 177.1520 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1520 Olefin polymers. The olefi...

Stereospecific olefin polymerization catalysts

DOEpatents

Bercaw, John E.; Herzog, Timothy A.

1998-01-01

A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

Stereospecific olefin polymerization catalysts

DOEpatents

Bercaw, J.E.; Herzog, T.A.

1998-01-13

A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

PubMed

Pyl, Steven P; Dijkmans, Thomas; Antonykutty, Jinto M; Reyniers, Marie-Françoise; Harlin, Ali; Van Geem, Kevin M; Marin, Guy B

2012-12-01

Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers. Steam cracking of HDO-TOFA in a pilot plant revealed that high light olefin yields can be obtained, with 35.4 wt.% of ethene and 18.2 wt.% of propene at a coil outlet pressure (COP) of 1.7 bara, a dilution of 0.45 kg(steam)/kg(HDO-TOFA) and a coil outlet temperature (COT) of 820 °C. A pilot plant coking experiment indicated that cracking of HDO-TOFA at a COT of 850 °C results in limited fouling in the reactor. Co-cracking of HDO tall oil fractions with a typical fossil-based naphtha showed improved selectivity to desired light olefins, further demonstrating the potential of large scale olefin production from hydrotreated tall oil fractions in conventional crackers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Ruthenium-catalyzed metathesis reactions of ortho- and meta-dialkenyl-carboranes: efficient ring-closing and acyclic diene polymerization reactions.

PubMed

Guron, Marta; Wei, Xiaolan; Carroll, Patrick J; Sneddon, Larry G

2010-07-05

The ruthenium-catalyzed metathesis reactions of dialkenyl-substituted ortho- and meta-carboranes provide excellent routes to both cyclic-substituted o-carboranes and new types of main-chain m-carborane polymers. The adjacent positions of the two olefins in the 1,2-(alkenyl)(2)-o-carboranes strongly favor the formation of ring-closed (RCM) products with the reactions of 1,2-(CH(2)=CHCH(2))(2)-1,2-C(2)B(10)H(10) (1), 1,2-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,2-C(2)B(10)H(10) (2), 1,2-(CH(2)=CHSiMe(2))(2)-1,2-C(2)B(10)H(10) (3), 1,2-(CH(2)=CHCH(2)SiMe(2))(2)-1,2-C(2)B(10)H(10) (4), and 1,2-[CH(2)=CH(CH(2))(4)SiMe(2)](2)-1,2-C(2)B(10)H(10) (5) affording 1,2-(-CH(2)CH=CHCH(2)-)-C(2)B(10)H(10) (10), 1,2-[-CH(2)(CH(2))(3)CH=CH(CH(2))(3)CH(2)-]-1,2-C(2)B(10)H(10) (11), 1,2-[-SiMe(2)CH=CHSiMe(2)-]-1,2-C(2)B(10)H(10) (12), 1,2-[-SiMe(2)CH(2)CH=CHCH(2)SMe(2)-]-C(2)B(10)H(10) (13), and 1,2-[-SiMe(2)(CH(2))(4)CH=CH(CH(2))(4)SiMe(2)-]-C(2)B(10)H(10) (14), respectively, in 72-97% yields. On the other hand, the reaction of 1,2-(CH(2)-CHCH(2)OC(=O))(2)-1,2-C(2)B(10)H(10) (6) gave cyclo-[1,2-(1',8'-C(=O)OCH(2)CH=CHCH(2)OC(=O))-1,2-C(2)B(10)H(10)](2) (15a) and polymer 15b resulting from intermolecular metathesis reactions. The nonadjacent positions of the alkenyl groups in the 1,7-(alkenyl)(2)-m-carboranes, 1,7-(CH(2)=CHCH(2))(2)-1,7-C(2)B(10)H(10) (7), 1,7-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,7-C(2)B(10)H(10) (8), and 1,7-(CH(2)=CHCH(2)SiMe(2))(2)-1,7-C(2)B(10)H(10) (9), disfavor the formation of RCM products, and in these cases, acyclic diene metathesis polymerizations (ADMET) produced new types of main chain m-carborane polymers. The structures of 3, 9, 11, 12, 13, and 15a were crystallographically confirmed.

Positive Selection Underlies Faster-Z Evolution of Gene Expression in Birds.

PubMed

Dean, Rebecca; Harrison, Peter W; Wright, Alison E; Zimmer, Fabian; Mank, Judith E

2015-10-01

The elevated rate of evolution for genes on sex chromosomes compared with autosomes (Fast-X or Fast-Z evolution) can result either from positive selection in the heterogametic sex or from nonadaptive consequences of reduced relative effective population size. Recent work in birds suggests that Fast-Z of coding sequence is primarily due to relaxed purifying selection resulting from reduced relative effective population size. However, gene sequence and gene expression are often subject to distinct evolutionary pressures; therefore, we tested for Fast-Z in gene expression using next-generation RNA-sequencing data from multiple avian species. Similar to studies of Fast-Z in coding sequence, we recover clear signatures of Fast-Z in gene expression; however, in contrast to coding sequence, our data indicate that Fast-Z in expression is due to positive selection acting primarily in females. In the soma, where gene expression is highly correlated between the sexes, we detected Fast-Z in both sexes, although at a higher rate in females, suggesting that many positively selected expression changes in females are also expressed in males. In the gonad, where intersexual correlations in expression are much lower, we detected Fast-Z for female gene expression, but crucially, not males. This suggests that a large amount of expression variation is sex-specific in its effects within the gonad. Taken together, our results indicate that Fast-Z evolution of gene expression is the product of positive selection acting on recessive beneficial alleles in the heterogametic sex. More broadly, our analysis suggests that the adaptive potential of Z chromosome gene expression may be much greater than that of gene sequence, results which have important implications for the role of sex chromosomes in speciation and sexual selection. © The Author 2015. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Positive Selection Underlies Faster-Z Evolution of Gene Expression in Birds

PubMed Central

Dean, Rebecca; Harrison, Peter W.; Wright, Alison E.; Zimmer, Fabian; Mank, Judith E.

2015-01-01

The elevated rate of evolution for genes on sex chromosomes compared with autosomes (Fast-X or Fast-Z evolution) can result either from positive selection in the heterogametic sex or from nonadaptive consequences of reduced relative effective population size. Recent work in birds suggests that Fast-Z of coding sequence is primarily due to relaxed purifying selection resulting from reduced relative effective population size. However, gene sequence and gene expression are often subject to distinct evolutionary pressures; therefore, we tested for Fast-Z in gene expression using next-generation RNA-sequencing data from multiple avian species. Similar to studies of Fast-Z in coding sequence, we recover clear signatures of Fast-Z in gene expression; however, in contrast to coding sequence, our data indicate that Fast-Z in expression is due to positive selection acting primarily in females. In the soma, where gene expression is highly correlated between the sexes, we detected Fast-Z in both sexes, although at a higher rate in females, suggesting that many positively selected expression changes in females are also expressed in males. In the gonad, where intersexual correlations in expression are much lower, we detected Fast-Z for female gene expression, but crucially, not males. This suggests that a large amount of expression variation is sex-specific in its effects within the gonad. Taken together, our results indicate that Fast-Z evolution of gene expression is the product of positive selection acting on recessive beneficial alleles in the heterogametic sex. More broadly, our analysis suggests that the adaptive potential of Z chromosome gene expression may be much greater than that of gene sequence, results which have important implications for the role of sex chromosomes in speciation and sexual selection. PMID:26067773

A general approach to medium ring alkynes by using metathesis of cobalt hexacarbonyl containing dienes.

PubMed

Young, David G J; Burlison, Joseph A; Peters, Ulf

2003-05-02

The assembly of medium sized rings (7-9) was achieved by using the metathesis of dienes linked by a cobalt hexacarbonyl complexed alkyne with either Grubbs' or Schrock's catalysts. The products of metathesis were subjected to transformations involving the dicobalt hexacarbonyl complexes, for example, decomplexation to liberate cyclic alkynes or Pauson-Khand reaction.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Baumann, Robert

1999-01-01

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, R.R.; Baumann, R.

1999-03-30

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Baumann, Robert

2003-08-26

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Bauman, Robert

2006-11-14

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Separation of Olefin/Paraffin Mixtures with Carrier Facilitated Membrane Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merkel, T.C.; Blanc, R.; Zeid, J.

2007-03-12

This document describes the results of a DOE funded joint effort of Membrane Technology and Research Inc. (MTR), SRI International (SRI), and ABB Lummus (ABB) to develop facilitated transport membranes for olefin/paraffin separations. Currently, olefin/paraffin separation is done by distillation—an extremely energy-intensive process because of the low relative volatilities of olefins and paraffins. If facilitated transport membranes could be successfully commercialized, the potential energy savings achievable with this membrane technology are estimated to be 48 trillion Btu per year by the year 2020. We discovered in this work that silver salt-based facilitated transport membranes are not stable even in themore » presence of ideal olefin/paraffin mixtures. This decline in membrane performance appears to be caused by a previously unrecognized phenomenon that we have named olefin conditioning. As the name implies, this mechanism of performance degradation becomes operative once a membrane starts permeating olefins. This project is the first study to identify olefin conditioning as a significant factor impacting the performance of facilitated olefin transport membranes. To date, we have not identified an effective strategy to mitigate the impact of olefin conditioning. other than running at low temperatures or with low olefin feed pressures. In our opinion, this issue must be addressed before further development of facilitated olefin transport membranes can proceed. In addition to olefin conditioning, traditional carrier poisoning challenges must also be overcome. Light, hydrogen, hydrogen sulfide, and acetylene exposure adversely affect membrane performance through unwanted reaction with silver ions. Harsh poisoning tests with these species showed useful membrane lifetimes of only one week. These tests demonstrate a need to improve the stability of the olefin complexing agent to develop membranes with lifetimes satisfactory for commercial application. A

Increased functionality of methyl oleate using alkene metathesis

USDA-ARS?s Scientific Manuscript database

A series of alkene cross metathesis reactions were performed using a homogeneous ruthenium based catalyst. Using this technology, a variety of functional groups can be incorporated into the biobased starting material, methyl oleate. Trans-stilbene, styrene, methyl cinnamate and hexen-3-ol were all s...

Cobalt carbide nanoprisms for direct production of lower olefins from syngas

NASA Astrophysics Data System (ADS)

Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

2016-10-01

Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

PubMed

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel-Catalyzed, Carbonyl-Ene-Type Reactions: Selective for Alpha Olefins and More Efficient with Electron-Rich Aldehydes

PubMed Central

Ho, Chun-Yu; Ng, Sze-Sze; Jamison, Timothy F.

2011-01-01

Described are several classes of unusual or unprecedented carbonyl-ene-type reactions, including those between alpha olefins and aromatic aldehydes. Catalyzed by nickel, these processes complement existing Lewis acid-catalyzed methods in several respects. Not only are monosubstituted alkenes, aromatic aldehydes, and tert-alkyl aldehydes effective substrates, but monosubstituted olefins also react faster than those that are more substituted, and large or electron-rich aldehydes are more effective than small or electron-poor ones. Conceptually, in the presence of a nickel-phosphine catalyst, the combination of off-the-shelf alkenes, silyl triflates, and triethylamine functions as a replacement for an allylmetal reagent. PMID:16620106

Selecting a Z39.50 Client or Web Gateway.

ERIC Educational Resources Information Center

Turner, Fay

1998-01-01

Provides a brief description of the Z39.50 information retrieval standard and reviews evaluation criteria and questions that should be asked when selecting a Z39.50 client. Areas for consideration include whether to buy or build a Z39.50 client, the end-user's requirements, connecting to a remote server, searching, managing the search response,…

An efficient, second-generation synthesis of the signature dioxabicyclo[3.2.1]octane core of (+)-sorangicin A and elaboration of the (Z,Z,E)-triene acid system.

PubMed

Smith, Amos B; Dong, Shuzhi

2009-03-05

An efficient, second-generation synthesis of the signature dioxabicyclo[3.2.1]octane core of (+)-sorangicin A (1), in conjunction with an effective, stereocontrolled protocol to arrive at the requisite (Z,Z,E)-triene acid system has been developed. Highlights of the core construction entail a three-component union, a KHMDS-promoted epoxide ring formation-ring opening cascade, a Takai olefination, and a chemoselective Sharpless dihydroxylation. Assembly of the triene acid system was then achieved via Stille cross-coupling with the ethyl ester of (Z,Z)-5-tributylstannyl-2,4-pentadienoic acid, followed by mild hydrolysis preserving the triene configuration.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, R.

1985-04-02

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Process for the synthesis of unsaturated alcohols

DOEpatents

Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

2007-02-13

A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

The Production and Recovery of C2-C4 Olefins from Syngas.

ERIC Educational Resources Information Center

Murchison, C. B.; And Others

1986-01-01

Discusses reacting coal-derived hydrogen and carbon monoxide (syngas) at relatively high selectivity to ethylene, propylene, and butenes over novel catalysts. In addition, data are given which illustrate a unique ethylene removal step which is compatible with operating the olefin synthesis at low conversion. (JN)

Supported organometallic catalysts for hydrogenation and Olefin Polymerization

DOEpatents

Marks, Tobin J.; Ahn, Hongsang

2001-01-01

Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, Robert J.; Gao, Hanrong

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

Multinuclear group 4 catalysis: olefin polymerization pathways modified by strong metal-metal cooperative effects.

PubMed

McInnis, Jennifer P; Delferro, Massimiliano; Marks, Tobin J

2014-08-19

Polyolefins are produced today catalytically on a vast scale, and the manufactured polymers find use in everything from artificial limbs and food/medical packaging to automotive and electrical components and lubricants. Although polyolefin monomers are typically cheap (e.g., ethylene, propylene, α-olefins), the resulting polymer properties can be dramatically tuned by the particular polymerization catalyst employed, and reflect a rich interplay of macromolecular chemistry, materials science, and physics. For example, linear low-density polyethylene (LLDPE), produced by copolymerization of ethylene with linear α-olefin comonomers such as 1-butene, 1-hexene, or 1-octene, has small but significant levels of short alkyl branches (C2, C4, C6) along the polyethylene backbone, and is an important technology material due to outstanding rheological and mechanical properties. In 2013, the total world polyolefin production was approximately 211 million metric tons, of which about 11% was LLDPE. Historically, polyolefins were produced using ill-defined but highly active heterogeneous catalysts composed of supported groups 4 or 6 species (usually halides) activated by aluminum alkyls. In 1963, Karl Ziegler and Giulio Natta received the Nobel Prize for these discoveries. Beginning in the late 1980s, a new generation of group 4 molecule-based homogeneous olefin polymerization catalysts emerged from discoveries by Walter Kaminsky, a team led by James Stevens at The Dow Chemical Company, this Laboratory at Northwestern University, and a host of talented groups in Germany, Italy, Japan, the United Kingdom, and the United States. These new "single-site" catalysts and their activating cocatalysts were far better defined and more rationally tunable in terms of structure, mechanism, thermodynamics, and catalyst activity and selectivity than ever before possible. An explosion of research advances led to new catalysts, cocatalysts, deeper mechanistic understanding of both the

Theoretical study of photoinduced epoxidation of olefins catalyzed by ruthenium porphyrin.

PubMed

Ishikawa, Atsushi; Sakaki, Shigeyoshi

2011-05-12

Epoxidation of olefin by [Ru(TMP)(CO)(O)](-) (TMP = tetramesitylporphine), which is a key step of the photocatalyzed epoxidation of olefin by [Ru(TMP)(CO)], is studied mainly with the density functional theory (DFT) method, where [Ru(Por)(CO)] is employed as a model complex (Por = unsubstituted porphyrin). The CASSCF method was also used to investigate the electronic structure of important species in the catalytic cycle. In all of the ruthenium porphyrin species involved in the catalytic cycle, the weight of the main configuration of the CASSCF wave function is larger than 85%, suggesting that the static correlation is not very large. Also, unrestricted-DFT-calculated natural orbitals are essentially the same as CASSCF-calculated ones, here. On the basis of these results, we employed the DFT method in this work. Present computational results show characteristic features of this reaction, as follows: (i) The epoxidation reaction occurs via carboradical-type transition state. Neither carbocation-type nor concerted oxene-insertion-type character is observed in the transition state. (ii) Electron and spin populations transfer from the olefin moiety to the porphyrin ring in the step of the C-O bond formation. (iii) Electron and spin populations of the olefin and porphyrin moieties considerably change around the transition state. (iv) The atomic and spin populations of Ru change little in the reaction, indicating that the Ru center keeps the +II oxidation state in the whole catalytic cycle. (v) The stability of the olefin adduct [Ru(Por)(CO)(O)(olefin)](-) considerably depends on the kind of olefin, such as ethylene, n-hexene, and styrene. In particular, styrene forms a stable olefin adduct. And, (vi) interestingly, the difference in the activation barrier among these olefins is small in the quantitative level (within 5 kcal/mol), indicating that this catalyst can be applied to various substrates. This is because the stabilities and electronic structures of both the

A chameleon catalyst for nonheme iron-promoted olefin oxidation.

PubMed

Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence

2014-11-18

We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

Electrochemistry for biofuel generation: transformation of fatty acids and triglycerides to diesel-like olefin/ether mixtures and olefins.

PubMed

dos Santos, Tatiane R; Harnisch, Falk; Nilges, Peter; Schröder, Uwe

2015-03-01

Electroorganic synthesis can be exploited for the production of biofuels from fatty acids and triglycerides. With Coulomb efficiencies (CE) of up to 50 %, the electrochemical decarboxylation of fatty acids in methanolic and ethanolic solutions leads to the formation of diesel-like olefin/ether mixtures. Triglycerides can be directly converted in aqueous solutions by using sonoelectrochemistry, with olefins as the main products (with a CE of more than 20 %). The latter reaction, however, is terminated at around 50 % substrate conversion by the produced side-product glycerol. An energy analysis shows that the electrochemical olefin synthesis can be an energetically competitive, sustainable, and--in comparison with established processes--economically feasible alternative for the exploitation of fats and oils for biofuel production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Cyclic Porphyrin Trimers through Alkyne Metathesis Cyclooligomerization and Their Host–Guest Binding Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Chao; Long, Hai; Jin, Yinghua

2016-06-17

Cyclic porphyrin trimers were synthesized through one-step cyclooligomerization via alkyne metathesis from diyne monomers. These macrocycles show interesting host-guest binding interactions with fullerenes, selectively binding C70 (6 x 103 M-1) over C60 and C84 (no binding observed). The fullerene-encapsulated host-guest complex can undergo guest or host exchange in the presence of another guest (2,4,6-tri(4-pyridyl)-1,3,5-triazine) or host (cage COP5) molecule with higher binding affinity.

Revealing the Influence of Silver in Ni-Ag Catalysts on the Selectivity of Higher Olefin Synthesis from Stearic Acid

NASA Astrophysics Data System (ADS)

Danyushevsky, V. Ya.; Murzin, V. Yu.; Kuznetsov, P. S.; Shamsiev, R. S.; Katsman, E. A.; Khramov, E. V.; Zubavichus, Y. V.; Berenblyum, A. S.

2018-01-01

Results on the conversion of stearic acid to olefins over Ni-Ag/γ-Al2O3 catalysts are presented. XANES and EXAFS experiments in situ and DFT calculations were applied to reveal the structure of active sites therein. It is shown that the introduction of Ag to Ni catalysts leads to an increase in the olefin yield. After a reduction in hydrogen (350°C, 3 h) alumina-supported nanoparticles of nickel sulfides and metallic Ag are formed. The role of metal hydrides formed during the reaction is extensively discussed.

Co-Aromatization of Methane with Olefins: The Role of Inner Pore and External Surface Catalytic Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, Matthew M; He, Peng; Jarvis, Jack

The co-aromatization of methane with olefins is investigated using Ag-Ga/HZSM-5 as the catalyst at 400 degrees C. The presence of methane has a pronounced effect on the product distribution in terms of increased average carbon number and substitution index and decreased aromatic carbon fraction compared with its N2 environment counterpart. The participation of methane during the co-aromatization over the Ag-Ga/HZSM-5 catalyst diminishes as the co-fed olefin feedstock molecule becomes larger, from 1-hexene to 1-octene and 1-decene, in diameter. The effect of suppressed methane participation with larger olefinic molecules is not as significant when Ag-Ga/HY is employed as the catalyst, whichmore » might be attributed to the larger pore size of HY that gives more room to hold olefin and methane molecules within the inner pores and reduces the diffusion limitation of olefin molecules. The effect of olefin feedstock on the methane participation during the co-aromatization over Ag-Ga/HZSM-5 is experimentally evidenced by 13C and 2D NMR. The incorporation of the methane carbon atoms into the phenyl ring of product molecules is reduced significantly with larger co-fed olefins, whereas its incorporation into the substitution groups of the formed aromatic molecules is not notably affected, suggesting that the methane participation in the phenyl ring formation might preferably occur within inner pores, while its incorporation into substitution groups may mainly take place on external catalytic sites. This hypothesis is well supported by the product selectivity obtained over Ag-Ga/HZSM-5 catalysts prepared using conventional ZSM-5, ZSM-5 with the external catalytic sites deactivated, nanosize ZSM-5, ZSM-5 with a micro/meso pore structure and ZSM-5 with the inner pores blocked, and further confirmed by the isotopic labeling studies.« less

Tandem enyne metathesis-Diels-Alder reaction for construction of natural product frameworks.

PubMed

Rosillo, Marta; Domínguez, Gema; Casarrubios, Luis; Amador, Ulises; Pérez-Castells, Javier

2004-03-19

Enynes connected through aromatic rings are used as substrates for metathesis reactions. The reactivity of three ruthenium carbene complexes is compared. The resulting 1,3-dienes are suitable precursors of polycyclic structures via a Diels-Alder process. Some domino RCM-Diels-Alder reactions are performed, suggesting a possible beneficial effect of the ruthenium catalyst in the cycloaddition process. Other examples require Lewis acid cocatalyst. When applied to aromatic ynamines or enamines, a new synthesis of vinylindoles is achieved. Monitorization of several metathesis reactions with NMR shows the different behavior for ruthenium catalysts. New carbenic species are detected in some reactions with an important dependence on the solvent used.

Infrared Color Selection of Massive Galaxies at z > 3

NASA Astrophysics Data System (ADS)

Wang, T.; Elbaz, D.; Schreiber, C.; Pannella, M.; Shu, X.; Willner, S. P.; Ashby, M. L. N.; Huang, J.-S.; Fontana, A.; Dekel, A.; Daddi, E.; Ferguson, H. C.; Dunlop, J.; Ciesla, L.; Koekemoer, A. M.; Giavalisco, M.; Boutsia, K.; Finkelstein, S.; Juneau, S.; Barro, G.; Koo, D. C.; Michałowski, M. J.; Orellana, G.; Lu, Y.; Castellano, M.; Bourne, N.; Buitrago, F.; Santini, P.; Faber, S. M.; Hathi, N.; Lucas, R. A.; Pérez-González, P. G.

2016-01-01

We introduce a new color selection technique to identify high-redshift, massive galaxies that are systematically missed by Lyman-break selection. The new selection is based on the H160 (H) and Infrared Array Camera (IRAC) 4.5 μm bands, specifically H-[4.5]\\gt 2.25 mag. These galaxies, called “HIEROs,” include two major populations that can be separated with an additional J - H color. The populations are massive and dusty star-forming galaxies at z\\gt 3 ({JH}-{blue}) and extremely dusty galaxies at z≲ 3 ({JH}-{red}). The 350 arcmin2 of the GOODS-North and GOODS-South fields with the deepest Hubble Space Telescope (HST)/Wide Field Camera 3 (WFC3) near-infrared and IRAC data contain as many as 285 HIEROs down to [4.5]\\lt 24 mag. Inclusion of the most extreme HIEROs, not even detected in the H band, makes this selection particularly complete for the identification of massive high-redshift galaxies. We focus here primarily on {JH}-{blue} (z\\gt 3) HIEROs, which have a median photometric redshift < z> ˜ 4.4 and stellar mass {M}*˜ {10}10.6 {M}⊙ and are much fainter in the rest-frame UV than similarly massive Lyman-break galaxies (LBGs). Their star formation rates (SFRs), derived from their stacked infrared spectral energy distributions (SEDs), reach ˜240 {M}⊙ yr-1, leading to a specific SFR, {{sSFR}}\\equiv {{SFR}}/{M}*˜ 4.2 Gyr-1, suggesting that the sSFRs for massive galaxies continue to grow at z\\gt 2 but at a lower growth rate than from z = 0 to z = 2. With a median half-light radius of 2 kpc, including ˜ 20% as compact as quiescent (QS) galaxies at similar redshifts, {JH}-{blue} HIEROs represent perfect star-forming progenitors of the most massive ({M}*≳ {10}11.2 {M}⊙ ) compact QS galaxies at z˜ 3 and have the right number density. HIEROs make up ˜ 60% of all galaxies with {M}*\\gt {10}10.5 {M}⊙ identified at z\\gt 3 from their photometric redshifts. This is five times more than LBGs with nearly no overlap between the two populations

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, R.J.; Gao, H.

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

Dynamic Modification of Pore Opening of SAPO-34 by Adsorbed Surface Methoxy Species during Induction of Catalytic Methanol-to-Olefins Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lo, Benedict T W.; Ye, Lin; Change, G.G. Z.

Here, we report that the pore opening of SAPO-34 can be significantly modified by an adsorbed surface methoxy species during induction of the catalytic methanol-to-olefins process, which offers molecular sieving properties due to physical obstacle of the methoxy group and its adsorption modification to other hydrocarbons. X-ray powder diffraction and Rietveld refinement clearly reveal that the adsorbed single carbon atom as the methoxy group is dynamically created from methanol dehydration on a Brønsted acid site in close proximity to the pore windows. As a result, industrial desirable smaller olefins such as ethylene and propylene can be favourably made at themore » expenses of higher olefins. The structures and fundamental understanding in alteration in the olefins selectivity during induction may allow rational optimisation in catalytic performance under the complex fluidisation conditions.« less

Obscured AGN at z ~ 1 from the zCOSMOS-Bright Survey. I. Selection and optical properties of a [Ne v]-selected sample

NASA Astrophysics Data System (ADS)

Mignoli, M.; Vignali, C.; Gilli, R.; Comastri, A.; Zamorani, G.; Bolzonella, M.; Bongiorno, A.; Lamareille, F.; Nair, P.; Pozzetti, L.; Lilly, S. J.; Carollo, C. M.; Contini, T.; Kneib, J.-P.; Le Fèvre, O.; Mainieri, V.; Renzini, A.; Scodeggio, M.; Bardelli, S.; Caputi, K.; Cucciati, O.; de la Torre, S.; de Ravel, L.; Franzetti, P.; Garilli, B.; Iovino, A.; Kampczyk, P.; Knobel, C.; Kovač, K.; Le Borgne, J.-F.; Le Brun, V.; Maier, C.; Pellò, R.; Peng, Y.; Perez Montero, E.; Presotto, V.; Silverman, J. D.; Tanaka, M.; Tasca, L.; Tresse, L.; Vergani, D.; Zucca, E.; Bordoloi, R.; Cappi, A.; Cimatti, A.; Koekemoer, A. M.; McCracken, H. J.; Moresco, M.; Welikala, N.

2013-08-01

Aims: The application of multi-wavelength selection techniques is essential for obtaining a complete and unbiased census of active galactic nuclei (AGN). We present here a method for selecting z ~ 1 obscured AGN from optical spectroscopic surveys. Methods: A sample of 94 narrow-line AGN with 0.65 < z < 1.20 was selected from the 20k-Bright zCOSMOS galaxy sample by detection of the high-ionization [Ne v] λ3426 line. The presence of this emission line in a galaxy spectrum is indicative of nuclear activity, although the selection is biased toward low absorbing column densities on narrow-line region or galactic scales. A similar sample of unobscured (type 1 AGN) was collected applying the same analysis to zCOSMOS broad-line objects. This paper presents and compares the optical spectral properties of the two AGN samples. Taking advantage of the large amount of data available in the COSMOS field, the properties of the [Ne v]-selected type 2 AGN were investigated, focusing on their host galaxies, X-ray emission, and optical line-flux ratios. Finally, a previously developed diagnostic, based on the X-ray-to-[Ne v] luminosity ratio, was exploited to search for the more heavily obscured AGN. Results: We found that [Ne v]-selected narrow-line AGN have Seyfert 2-like optical spectra, although their emission line ratios are diluted by a star-forming component. The ACS morphologies and stellar component in the optical spectra indicate a preference for our type 2 AGN to be hosted in early-type spirals with stellar masses greater than 109.5 - 10 M⊙, on average higher than those of the galaxy parent sample. The fraction of galaxies hosting [Ne v]-selected obscured AGN increases with the stellar mass, reaching a maximum of about 3% at ≈2 × 1011 M⊙. A comparison with other selection techniques at z ~ 1, namely the line-ratio diagnostics and X-ray detections, shows that the detection of the [Ne v] λ3426 line is an effective method for selecting AGN in the optical band, in

Recent advances in the development of alkyne metathesis catalysts

PubMed Central

Wu, Xian

2011-01-01

Summary The number of well-defined molybdenum and tungsten alkylidyne complexes that are able to catalyze alkyne metathesis reactions efficiently has been significantly expanded in recent years.The latest developments in this field featuring highly active imidazolin-2-iminato- and silanolate–alkylidyne complexes are outlined in this review. PMID:21286398

Enhanced catalytic performance for light-olefins production from chloromethane over hierarchical porous ZSM-5 zeolite synthesized by a growth-inhibition strategy

NASA Astrophysics Data System (ADS)

Liu, Qing; Wen, Dafen; Yang, Yanran; Fei, Zhaoyang; Zhang, Zhuxiu; Chen, Xian; Tang, Jihai; Cui, Mifen; Qiao, Xu

2018-03-01

Hierarchical porous ZSM-5 (HP-ZSM-5) zeolites were synthesized by hydrothermal crystallization method adding triethoxyvinylsilane as the growth-inhibitor at different hydrothermal crystallized temperatures. The properties of the obtained samples were characterized by XRD, SEM, N2-sorption, uptake of ethylene, 27Al MAS NMR, NH3-TPD, and Py-IR. It was found that the mesopore was introduced and the acidity was adjusted over HP-ZSM-5 samples successfully. The hydrothermal crystallized temperature had an important influence on the porous structure and surface properties. The catalytic performance for chloromethane to light-olefins (CMTO) were also investigated. Compared with ZSM-5 samples, HP-ZSM-5 samples exhibited enhanced stability and increased selectivity of light-olefins for CMTO reaction because of the introduction of the abundant mesopore and appropriate acidity. The lifetime (the duration of chloromethane conversion >98%) and selectivity of light-olefins reached 115 h and 69.3%, respectively.

Homogeneous catalysts for stereoregular olefin polymerization

DOEpatents

Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.

1995-01-01

The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R"'.sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R"', and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

Homogeneous catalysts for stereoregular olefin polymerization

DOEpatents

Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.

1994-01-01

The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

EXPOXIDATION OF OLEFINS AND α,β-UNSATURATED KEYTONES OVER SONOCHEMICALLY PREPARED HYDROXYAPATITES USING HYDROGEN PEROXIDE

EPA Science Inventory

An effective and environmentally friendly protocol for the epoxidation of olefins and α,β-unsaturated ketones in the presence of hydroxyapatite as catalyst using hydrogen peroxide is described. The catalyst is active and reusable for the selective epoxidation of a variety...

Formation of polycyclic lactones through a ruthenium-catalyzed ring-closing metathesis/hetero-Pauson-Khand reaction sequence.

PubMed

Finnegan, David F; Snapper, Marc L

2011-05-20

Processes that form multiple carbon-carbon bonds in one operation can generate molecular complexity quickly and therefore be used to shorten syntheses of desirable molecules. We selected the hetero-Pauson-Khand (HPK) cycloaddition and ring-closing metathesis (RCM) as two unique carbon-carbon bond-forming reactions that could be united in a tandem ruthenium-catalyzed process. In doing so, complex polycyclic products can be obtained in one reaction vessel from acyclic precursors using a single ruthenium additive that can catalyze sequentially two mechanistically distinct transformations.

Hemizygosity Enhances Purifying Selection: Lack of Fast-Z Evolution in Two Satyrine Butterflies.

PubMed

Rousselle, Marjolaine; Faivre, Nicolas; Ballenghien, Marion; Galtier, Nicolas; Nabholz, Benoit

2016-10-23

The fixation probability of a recessive beneficial mutation is increased on the X or Z chromosome, relative to autosomes, because recessive alleles carried by X or Z are exposed to selection in the heterogametic sex. This leads to an increased dN/dS ratio on sex chromosomes relative to autosomes, a pattern called the "fast-X" or "fast-Z" effect. Besides positive selection, the strength of genetic drift and the efficacy of purifying selection, which affect the rate of molecular evolution, might differ between sex chromosomes and autosomes. Disentangling the complex effects of these distinct forces requires the genome-wide analysis of polymorphism, divergence and gene expression data in a variety of taxa. Here we study the influence of hemizygosity of the Z chromosome in Maniola jurtina and Pyronia tithonus, two species of butterflies (Lepidoptera, Nymphalidae, Satyrinae). Using transcriptome data, we compare the strength of positive and negative selection between Z and autosomes accounting for sex-specific gene expression. We show that M. jurtina and P. tithonus do not experience a faster, but rather a slightly slower evolutionary rate on the Z than on autosomes. Our analysis failed to detect a significant difference in adaptive evolutionary rate between Z and autosomes, but comparison of male-biased, unbiased and female-biased Z-linked genes revealed an increased efficacy of purifying selection against recessive deleterious mutations in female-biased Z-linked genes. This probably contributes to the lack of fast-Z evolution of satyrines. We suggest that the effect of hemizygosity on the fate of recessive deleterious mutations should be taken into account when interpreting patterns of molecular evolution in sex chromosomes vs. autosomes. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Direct observation of OH production from the ozonolysis of olefins

NASA Astrophysics Data System (ADS)

Donahue, Neil M.; Kroll, Jesse H.; Anderson, James G.; Demerjian, Kenneth L.

Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans-2-butene and 2,3 dimethyl-2-butene) in 4-6 torr of nitrogen. Using LIF to directly observe the steady-state of OH produced by the initial ozone-olefin reaction and subsequently destroyed by the OH-olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab-initio potential energy surface for the O3-ethene reaction, extending from the reactants to available products.

ULTRASOUND-ASSISTED EPOXIDATION OF OLEFINS AND A,B-UNSATURATED KETONES OVER HYDROTALCITES USING HYDROGEN PEROXIDE

EPA Science Inventory

An efficient ultrasound-assisted epoxidation of olefins and a,B-unsaturated ketones over hydrotacite catalysts in the presence of hydrogen peroxide and acetonitrile is described. This general and selective protocol is relatively fast and is applicable to a wide variety of substra...

Decarboxylative alkenylation

NASA Astrophysics Data System (ADS)

Edwards, Jacob T.; Merchant, Rohan R.; McClymont, Kyle S.; Knouse, Kyle W.; Qin, Tian; Malins, Lara R.; Vokits, Benjamin; Shaw, Scott A.; Bao, Deng-Hui; Wei, Fu-Liang; Zhou, Ting; Eastgate, Martin D.; Baran, Phil S.

2017-04-01

Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis being the most recent addition. Here we describe a simple method of accessing olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The activating principles used in amide-bond synthesis can therefore be used, with nickel- or iron-based catalysis, to extract carbon dioxide from a carboxylic acid and economically replace it with an organozinc-derived olefin on a molar scale. We prepare more than 60 olefins across a range of substrate classes, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of 16 different natural products across 10 different families.

Pharmacophore mapping in the laulimalide series: total synthesis of a vinylogue for a late-stage metathesis diversification strategy.

PubMed

Wender, Paul A; Hilinski, Michael K; Skaanderup, Philip R; Soldermann, Nicolas G; Mooberry, Susan L

2006-08-31

An efficient synthesis of the macrocyclic core of laulimalide with a pendant vinyl group at C20 is described, allowing for late-stage introduction of various side chains through a selective and efficient cross metathesis diversification step. Representative analogues reported herein are the first to contain modifications to only the side chain dihydropyran of laulimalide and des-epoxy laulimalide. This step-economical strategy enables the rapid synthesis of new analogues using alkenes as an inexpensive, abundantly available diversification feedstock.

Homogeneous catalysts for stereoregular olefin polymerization

DOEpatents

Marks, T.J.; Eisen, M.S.; Giardello, M.A.

1995-10-03

The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C{sub 5}R{prime}{sub 4{minus}x}R*{sub x})A(C{sub 5}R{double_prime}{sub 4{minus}y}R{double_prime}{prime}{sub y})MQ{sub p}, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R{prime}, R{double_prime}, R{double_prime}{prime}, and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3{>=}p{>=}0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form ``cation-like`` species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other {alpha}-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.

Homogeneous catalysts for stereoregular olefin polymerization

DOEpatents

Marks, T.J.; Eisen, M.S.; Giardello, M.A.

1994-07-19

The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C[sub 5]R[prime][sub 4[minus]x]R*[sub x])-A-(C[sub 5]R[double prime][sub 4[minus]y]R[prime][double prime][sub y])-M-Q[sub p], where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R[prime], R[double prime], R[prime][double prime], and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3 [<=] p [<=] 0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form cation-like'' species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other [alpha]-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.

Catalytic metathesis of carbon dioxide with heterocumulenes mediated by titanium isopropoxide.

PubMed

Ghosh, Rajshekhar; Samuelson, Ashoka G

2005-04-21

The insertion of an isopropoxide ligand of titanium isopropoxide into heterocumulenes gives a product that carries out metathesis at elevated temperatures by undergoing insertion of a second heterocumulene in a head to head fashion, followed by an extrusion reaction.

Catalytic epoxidation activity of keplerate polyoxomolybdate nanoball toward aqueous suspension of olefins under mild aerobic conditions.

PubMed

Rezaeifard, Abdolreza; Haddad, Reza; Jafarpour, Maasoumeh; Hakimi, Mohammad

2013-07-10

Catalytic efficiency of a sphere-shaped nanosized polyoxomolybdate {Mo132} in the aerobic epoxidation of olefins in water at ambient temperature and pressure in the absence of reducing agent is exploited which resulted good-to-high yields and desired selectivity.

Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

PubMed

Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

2018-03-26

Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

DOEpatents

Rathke, J.W.; Klingler, R.J.

1993-03-30

A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

DOEpatents

Rathke, Jerome W.; Klingler, Robert J.

1993-01-01

A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

Xe/Kr Selectivity Measurements using AgZ-PAN at Various Temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garn, Troy Gerry; Greenhalgh, Mitchell Randy; Watson, Tony Leroy

2015-05-01

In preparation for planned FY-15 Xe/Kr multi-column testing, a series of experiments were performed to determine the selectivity of Xe over Kr using the silver converted mordenite-polyacrylonitrile (AgZ-PAN) sorbent. Results from these experiments will be used for parameter selection guidelines to define test conditions for Kr gas capture purity evaluations later this year. The currently configured experimental test bed was modified by installing a new cooling apparatus to permit future multi-column testing with independent column temperature control. The modified test bed will allow for multi-column testing to facilitate a Xe separation followed by a Kr separation using engineered form sorbents.more » Selectivity experiments were run at temperatures of 295, 250 and 220 K. Two feed gas compositions of 1000 ppmv Xe, 150 ppmv Kr in either a He or an air balance were used. AgZ-PAN sorbent selectivity was calculated using Xe and Kr capacity determinations. AgZ-PAN sorbent selectivities for Xe over Kr of 72 were calculated at room temperature (295 K) using the feed gas with a He balance and 34 using the feed gas with an air balance. As the test temperatures were decreased the selectivity of Xe over Kr also decreased due to an increase in both Xe and Kr capacities. At 220 K, the sorbent selectivities for Xe over Kr were 22 using the feed gas with a He balance and 28 using the feed gas with an air balance. The selectivity results indicate that AgZ-PAN used in the first column of a multi-column configuration will provide adequate partitioning of Xe from Kr in the tested temperature range to produce a more pure Kr end product for collection.« less

Photometric Selection of a Massive Galaxy Catalog with z ≥ 0.55

NASA Astrophysics Data System (ADS)

Núñez, Carolina; Spergel, David N.; Ho, Shirley

2017-02-01

We present the development of a photometrically selected massive galaxy catalog, targeting Luminous Red Galaxies (LRGs) and massive blue galaxies at redshifts of z≥slant 0.55. Massive galaxy candidates are selected using infrared/optical color-color cuts, with optical data from the Sloan Digital Sky Survey (SDSS) and infrared data from “unWISE” forced photometry derived from the Wide-field Infrared Survey Explorer (WISE). The selection method is based on previously developed techniques to select LRGs with z> 0.5, and is optimized using receiver operating characteristic curves. The catalog contains 16,191,145 objects, selected over the full SDSS DR10 footprint. The redshift distribution of the resulting catalog is estimated using spectroscopic redshifts from the DEEP2 Galaxy Redshift Survey and photometric redshifts from COSMOS. Restframe U - B colors from DEEP2 are used to estimate LRG selection efficiency. Using DEEP2, the resulting catalog has an average redshift of z = 0.65, with a standard deviation of σ =2.0, and an average restframe of U-B=1.0, with a standard deviation of σ =0.27. Using COSMOS, the resulting catalog has an average redshift of z = 0.60, with a standard deviation of σ =1.8. We estimate 34 % of the catalog to be blue galaxies with z≥slant 0.55. An estimated 9.6 % of selected objects are blue sources with redshift z< 0.55. Stellar contamination is estimated to be 1.8%.

Improved synthesis of (3E,6Z,9Z)-1,3,6,9-nonadecatetraene, attraction inhibitor of bruce spanworm, Operophtera bruceata, to pheromone traps for monitoring winter moth, Operophtera brumata.

PubMed

Khrimian, Ashot; Lance, David R; Mastro, Victor C; Elkinton, Joseph S

2010-02-10

The winter moth, Operophtera brumata (Lepidoptera: Geometridae), is an early-season defoliator that attacks a wide variety of hardwoods and, in some cases, conifers. The insect is native to Europe but has become established in at least three areas of North America including southeastern New England. The female-produced sex attractant pheromone of the winter moth was identified as (3Z,6Z,9Z)-1,3,6,9-nonadecatetraene (1), which also attracts a native congener, the Bruce spanworm, Operophtera bruceata . Dissection, or (for certainty) DNA molecular testing, is required to differentiate between males of the two species. Thus, a trapping method that is selective for winter moth would be desirable. A geometric isomer of the pheromone, (3E,6Z,9Z)-1,3,6,9-nonadecatetraene (2), can reportedly inhibit attraction of Bruce spanworm to traps without affecting winter moth catch, but use of the pheromone and inhibitor together has not been optimized, nor has the synthesis of the inhibitor. This paper presents two new syntheses of the inhibitor (3E,6Z,9Z)-1,3,6,9-nonadecatetraene based on the intermediate (3Z,6Z)-3,6-hexadecadien-1-ol (4), which has also been utilized in the synthesis of the pheromone. The syntheses combine traditional acetylenic chemistry and Wittig olefination reactions. In one approach, 2 was synthesized in 80% purity (20% being pheromone 1), and in the second, tetraene 2 of 96% purity (and free of 1) was produced in 25% overall yield from dienol 4. The last method benefitted from a refined TEMPO-mediated PhI(OAc)(2) oxidation of 4 and a two-carbon homologation of the corresponding aldehyde 7.

A detachable ester bond enables perfect Z-alkylations of olefins for the synthesis of tri- and tetrasubstituted alkenes.

PubMed

Nishikata, Takashi; Nakamura, Kimiaki; Inoue, Yuki; Ishikawa, Shingo

2015-06-25

2-Vinyl-substituted phenol and an alpha-bromoester undergo a tandem esterification-alkylation reaction in the presence of a Cu-amine catalyst system to produce benzene-fused lactone. Z-Alkylated styrene is obtained after hydrolysis of the lactone with perfect selectivity. The simple protocol developed in this work opens a new avenue in the multi-substitution chemistry of alkenes.

Ruthenium-catalyzed intramolecular metathesis of dienes and its application in the synthesis of bridged and spiro azabicycles

NASA Astrophysics Data System (ADS)

Kuznetsov, N. Yu; Bubnov, Yu N.

2015-07-01

The review presents a historical excursion into catalytic alkene metathesis, covering the problems of history of the discovery of this process, as well as investigations on the properties, structure and reactivity of the most popular ruthenium catalysts for metathesis, mechanism of their action and decomposition. The main part covers studies devoted to the syntheses of bridged azabicyclic and 1-azaspirocyclic compounds comprising the intramolecular metathesis of dienes as the key step. The formation of a bicyclic skeleton of a series of natural bridged (cocaine, ferruginine, calystegines, and anatoxin-a) and spiro (pinnaic acids, halichlorine, hystrionicotoxin, and cephalotaxine) azabicycles, as well as their analogues and compounds with larger rings is demonstrated. The methods for the synthesis of diene precursors and the conditions for final assembling of the bicyclic compounds are considered in detail. The generalization of the literature data allows one to efficiently carry out the mentioned process taking into account the most important features. The bibliography includes 129 references.

Mechanism of olefin epoxidation in the presence of a titanium-containing zeolite

NASA Astrophysics Data System (ADS)

Danov, S. M.; Krasnov, V. L.; Sulimov, A. V.; Ovcharova, A. V.

2013-11-01

The effect of the nature of a solvent on the liquid-phase epoxidation of olefins with an aqueous solution of hydrogen peroxide over a titanium-containing zeolite is studied. Butanol-1, butanol-2, propanol-1, isopropanol, methanol, ethanol, water, acetone, methyl ethyl ketone, isobutanol, and tert-butanol are examined as solvents. A mechanism of olefin epoxidation with hydrogen peroxide in an alcohol medium over a titanium-containing zeolite is proposed. Epoxidation reactions involving hydrogen peroxide and different olefins are studied experimentally.

Palladium-Catalyzed Allylic C-H Bond Functionalization of Olefins

NASA Astrophysics Data System (ADS)

Liu, Guosheng; Wu, Yichen

Transition metal-mediated carbon-hydrogen bond cleavage and functionalization is a mechanistically interesting and synthetically attractive process. One of the important cases is the removal of a allylic hydrogen from an olefin by a PdII salt to yield a π-allylpalladium complex, followed by nucleophilic attack to efficient produce allylic derivatives. In contrast to the well-known allylic acetoxylation of cyclohexene, the reaction of open-chain olefins is fairly poor until recent several years. Some palladium catalytic systems have been reported to achieve allylic C-H functionalization, including acetoxylation, amination and alkylation of terminal alkenes. In the most of cases, ligand is crucial to the success of the transformation. This review surveys the recent development of palladium-catalyzed allylic C-H functionalziation of alkenes. These results promise a significant increase in the scope of olefin transformation.

Gum formation tendencies of olefinic structures in gasoline and synergistic effect of sulphur compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagpal, J.M.; Joshi, G.C.; Aswal, D.S.

1995-04-01

The high octane gasoline pool contains varying amounts of cracked naphthas as an important ingredient in formulating high octane lead free gasoline. The cracked naphthas are largely from Fluidized Catalytic Cracking (FCC) units and to lesser extend from thermal cracking units. While the role of olefinic unsaturation in gum formation during storage of gasoline has been extensively studied, there is little published work on contribution of individual olefin types in storage stability and gum formation tendency of gasoline containing these compound types. In the present work we report our results on storage stability and gum formation tendency of different olefinmore » types present in cracked naphthas through model compound matrix. It is found that cyclic olefins and cyclic diolefins are the most prolific gum formers. We have also studied the role of sulfur compounds present in the gasolines on gum formation tendency of olefins. While thiols enhance gum formation from all olefinic types, sulfides and disulfides interact depending on the structure of olefins. These can have either an accelerating, or inhibiting effect on gum formation.« less

Improving olefin tolerance and production in E. coli using native and evolved AcrB

DOE PAGES

Mingardon, Florence; Clement, Camille; Hirano, Kathleen; ...

2015-01-20

Microorganisms can be engineered for the production of chemicals utilized in the polymer industry. However many such target compounds inhibit microbial growth and might correspondingly limit production levels. Here, we focus on compounds that are precursors to bioplastics, specifically styrene and representative alpha-olefins; 1-hexene, 1-octene, and 1-nonene. We evaluated the role of the Escherichia coli efflux pump, AcrAB-TolC, in enhancing tolerance towards these olefin compounds. AcrAB-TolC is involved in the tolerance towards all four compounds in E. coli. Both styrene and 1-hexene are highly toxic to E. coli. Styrene is a model plastics precursor with an established route for productionmore » in E. coli (McKenna and Nielsen, 2011). Though our data indicates that AcrAB-TolC is important for its optimal production, we observed a strong negative selection against the production of styrene in E. coli. Thus we used 1-hexene as a model compound to implement a directed evolution strategy to further improve the tolerance phenotype towards this alpha-olefin. We focused on optimization of AcrB, the inner membrane domain known to be responsible for substrate binding, and found several mutations (A279T, Q584R, F617L, L822P, F927S, and F1033Y) that resulted in improved tolerance. Several of these mutations could also be combined in a synergistic manner. Our study shows efflux pumps to be an important mechanism in host engineering for olefins, and one that can be further improved using strategies such as directed evolution, to increase tolerance and potentially production.« less

Synthesis of 5/7-, 5/8- and 5/9-bicyclic lactam templates as constraints for external beta-turns.

PubMed

Duggan, Heather M E; Hitchcock, Peter B; Young, Douglas W

2005-06-21

The 5/7-, 5/8- and 5/9-bicyclic lactams 3, 17, 5 and 6 have been synthesised as single diastereoisomers by a route involving ring closing olefin metathesis. The X-ray crystal structure of the amino acid hydrochloride has been carried out and compared to that of the saturated external beta-turn constraint 18.

Design of highly selective ethanol dehydration nanocatalysts for ethylene production.

PubMed

Austin, Natalie; Kostetskyy, Pavlo; Mpourmpakis, Giannis

2018-02-22

Rational design of catalysts for selective conversion of alcohols to olefins is key since product selectivity remains an issue due to competing etherification reactions. Using first principles calculations and chemical rules, we designed novel metal-oxide-protected metal nanoclusters (M 13 X 4 O 12 , with M = Cu, Ag, and Au and X = Al, Ga, and In) exhibiting strong Lewis acid sites on their surface, active for the selective formation of olefins from alcohols. These symmetrical nanocatalysts, due to their curvature, show unfavorable etherification chemistries, while favoring the olefin production. Furthermore, we determined that water removal and regeneration of the nanocatalysts is more feasible compared to the equivalent strong acid sites on solid acids used for alcohol dehydration. Our results demonstrate an exceptional stability of these new nanostructures with the most energetically favorable being Cu-based. Thus, the high selectivity and stability of these in-silico-predicted novel nanoclusters (e.g. Cu 13 Al 4 O 12 ) make them attractive catalysts for the selective dehydration of alcohols to olefins.

Copper(I)-induced amplification of a [2]catenane in a virtual dynamic library of macrocyclic alkenes.

PubMed

Berrocal, José Augusto; Nieuwenhuizen, Marko M L; Mandolini, Luigi; Meijer, E W; Di Stefano, Stefano

2014-08-28

Olefin cross-metathesis of diluted dichloromethane solutions (≤0.15 M) of the 28-membered macrocyclic alkene C1, featuring a 1,10-phenanthroline moiety in the backbone, as well as of catenand 1, composed of two identical interlocked C1 units, generates families of noninterlocked oligomers Ci. The composition of the libraries is strongly dependent on the monomer concentration, but independent of whether C1 or 1 is used as feedstock, as expected for truly equilibrated systems. Accordingly, the limiting value 0.022 M approached by the equilibrium concentration of C1 when the total monomer concentration approaches the critical value, as predicted by the Jacobson-Stockmayer theory, provides a reliable estimate of the thermodynamically effective molarity. Catenand 1 behaves as a virtual component of the dynamic libraries, in that there is no detectable trace of its presence in the equilibrated mixtures, but becomes the major component - in the form of its copper(I) complex - when olefin cross-metathesis is carried out in the presence of a copper(I) salt.

In Situ Generated Ruthenium-Arene Catalyst for Photoactivated Ring-Opening Metathesis Polymerization through Photolatent N-Heterocyclic Carbene Ligand.

PubMed

Pinaud, Julien; Trinh, Thi Kim Hoang; Sauvanier, David; Placet, Emeline; Songsee, Sriprapai; Lacroix-Desmazes, Patrick; Becht, Jean-Michel; Tarablsi, Bassam; Lalevée, Jacques; Pichavant, Loïc; Héroguez, Valérie; Chemtob, Abraham

2018-01-09

1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH + BPh 4 - ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl 2 (p-cymene)] 2 precatalyst, the highly active RuCl 2 (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature. To the best of our knowledge, this is the first example of a photogenerated NHC. Its exploitation in photoROMP has resulted in a simplified process compared to current photocatalysts, because only stable commercial or easily synthesized reagents are required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of the carbocyclic core of the cornexistins by ring-closing metathesis.

PubMed

Clark, J Stephen; Marlin, Frederic; Nay, Bastien; Wilson, Claire

2003-01-09

An advanced intermediate in the synthesis of the phytotoxins cornexistin and hydroxycornexistin has been synthesized. Sequential palladium-mediated sp(2)-sp(3) fragment coupling and ring-closing diene metathesis have been used to construct the nine-membered carbocyclic core found in the natural products. [reaction--see text

Iron-catalyzed, directed oxidative arylation of olefins with organozinc and Grignard reagents.

PubMed

Ilies, Laurean; Okabe, Jun; Yoshikai, Naohiko; Nakamura, Eiichi

2010-06-18

Chelation-controlled arylation of olefins with organozinc or Grignard reagents proceeds in the presence of an iron catalyst, under mild conditions and typically without the need of external ligands, to afford substituted olefins in high yield and with complete regio- and stereocontrol.

Computational Elucidation of Selectivities and Mechanisms Performed by Organometallic and Bioinorganic Catalysts

NASA Astrophysics Data System (ADS)

Grandner, Jessica Marie

Computational methods were used to determine the mechanisms and selectivities of organometallic-catalyzed reactions. The first half of the dissertation focuses on the study of metathesis catalysts in collaboration with the Grubbs group at CalTech. Chapter 1 describes the studies of the decomposition modes of several ruthenium-based metathesis catalysts. These studies were performed to better understand the decomposition of such catalysts in order to prevent decomposition (Chapter 1.2) or utilize decomposed catalysts for alternative reactions (Chapter 1.1). Chapter 2.1 describes the computational investigation of the origins of stereoretentive metathesis with ruthenium-based metathesis catalysts. These findings were then used to computationally design E-selective metathesis catalysts (Chapter 2.2). While the first half of the dissertation was centered around ruthenium catalysts, the second half of the dissertation pertains to iron-catalyzed reaction, in particular, iron-catalyzed reactions by P450 enzymes. The elements of Chapter 3 concentrate on the stereo- and chemo-selectivity of P450-catalyzed C-H hydroxylations. By combining multiple computational methods, the inherent activity of the iron-oxo catalyst and the influence of the active site on such reactions were illuminated. These discoveries allow for the engineering of new substrates and mutant enzymes for tailored C-H hydroxylation. While the mechanism of C-H hydroxylations catalyzed by P450 enzymes has been well studied, there are several P450-catalyzed transformations for which the mechanism is unknown. The components of Chapter 4 describe the use of computations to determine the mechanisms of complex, multi-step reactions catalyzed by P450s. The determination of these mechanisms elucidates how these enzymes react with various functional groups and substrate architectures and allows for a better understanding of how drug-like compounds may be broken down by human P450s.

Variation in promiscuity and sexual selection drives avian rate of Faster-Z evolution.

PubMed

Wright, Alison E; Harrison, Peter W; Zimmer, Fabian; Montgomery, Stephen H; Pointer, Marie A; Mank, Judith E

2015-03-01

Higher rates of coding sequence evolution have been observed on the Z chromosome relative to the autosomes across a wide range of species. However, despite a considerable body of theory, we lack empirical evidence explaining variation in the strength of the Faster-Z Effect. To assess the magnitude and drivers of Faster-Z Evolution, we assembled six de novo transcriptomes, spanning 90 million years of avian evolution. Our analysis combines expression, sequence and polymorphism data with measures of sperm competition and promiscuity. In doing so, we present the first empirical evidence demonstrating the positive relationship between Faster-Z Effect and measures of promiscuity, and therefore variance in male mating success. Our results from multiple lines of evidence indicate that selection is less effective on the Z chromosome, particularly in promiscuous species, and that Faster-Z Evolution in birds is due primarily to genetic drift. Our results reveal the power of mating system and sexual selection in shaping broad patterns in genome evolution. © 2015 John Wiley & Sons Ltd.

In vivo and in vitro olefin cyclopropanation catalyzed by heme enzymes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coelho, Pedro S.; Brustad, Eric M.; Arnold, Frances H.

The present invention provides methods for catalyzing the conversion of an olefin to any compound containing one or more cyclopropane functional groups using heme enzymes. In certain aspects, the present invention provides a method for producing a cyclopropanation product comprising providing an olefinic substrate, a diazo reagent, and a heme enzyme; and admixing the components in a reaction for a time sufficient to produce a cyclopropanation product. In other aspects, the present invention provides heme enzymes including variants and fragments thereof that are capable of carrying out in vivo and in vitro olefin cyclopropanation reactions. Expression vectors and host cellsmore » expressing the heme enzymes are also provided by the present invention.« less

Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds

NASA Astrophysics Data System (ADS)

Koledina, K. F.; Gubaidullin, I. M.

2016-05-01

The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.

Zwitterionic Group VIII transition metal initiators supported by olefin ligands

DOEpatents

Bazan, Guillermo C [Goleta, CA; Chen, Yaofeng [Shanghai, CN

2011-10-25

A zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that catalyzes the formation of polypropylene and high molecular weight polyethylene. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct. The present invention also provides methods of polymerizing olefin monomers using zwitterionic catalysts, particularly polypropylene and high molecular weight polyethylene.

Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

PubMed

Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

2013-07-19

A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

Hydrogenation catalysts were derived from Mo(Co)/sub 6//alumina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman, R.G.

1979-01-01

Alumina hydrogenation catalysts were derived from mo(CO)/sub 6//alumina with characteristics dependent upon the activation temperature, degree of alumina hydroxylation, and carrier gas used. Decomposition of Mo(CO)/sub 6/ at 100/sup 0/C on partially hydroxylated alumina in helium or hydrogen yielded Mo(CO)/sub 3//alumina, which catalyzed olefin metathesis in helium carrier and both metathesis and hydrogenation in hydrogen carrier. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina at 100/sup 0/C in helium and in hydrogen resulted in complete decarbonylation and partial oxidation of molybdenum; this catalyst was 10 times as active as Mo(CO)/sub 3//alumina for hydrogenation. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina atmore » 500/sup 0/C in helium gave essentially Mo(0)/alumina, which catalyzed hydrogenation, methanation, and hydrogenolysis in hydrogen. Catalysts activated on dehydroxylated alumina were ten times more active for methanation at 300/sup 0/C than catalyst activated on partially hydroxylated alumina and showed differences in selectivity for cyclopropane hydrogenolysis at 100/sup 0/C.« less

Conversion of olefins to liquid motor fuels

DOEpatents

Rabo, Jule A.; Coughlin, Peter K.

1988-01-01

Linear and/or branched claim C.sub.2 to C.sub.12 olefins are converted to hydrocarbon mixtures suitable for use as liquid motor fuels by contact with a catalyst capable of ensuring the production of desirable products with only a relatively minor amount of heavy products boiling beyond the diesel oil range. The catalyst having desirable stability during continuous production operations, comprises a steam stabilized zeolite Y catalyst of hydrophobic character, desirably in aluminum-extracted form. The olefins such as propylene, may be diluted with inerts, such as paraffins or with water, the latter serving to moderate the acidity of the catalyst, or to further moderate the activity of the aluminum-extracted catalyst, so as to increase the effective life of the catalyst.

Influence of the Reaction Temperature on the Nature of the Active and Deactivating Species During Methanol-to-Olefins Conversion over H-SAPO-34

PubMed Central

2017-01-01

The selectivity toward lower olefins during the methanol-to-olefins conversion over H-SAPO-34 at reaction temperatures between 573 and 773 K has been studied with a combination of operando UV–vis diffuse reflectance spectroscopy and online gas chromatography. It was found that the selectivity toward propylene increases in the temperature range of 573–623 K, while it decreases in the temperature range of 623–773 K. The high degree of incorporation of olefins, mainly propylene, into the hydrocarbon pool affects the product selectivity at lower reaction temperatures. The nature and dynamics of the active and deactivating hydrocarbon species with increasing reaction temperature were revealed by a non-negative matrix factorization of the time-resolved operando UV–vis diffuse reflectance spectra. The active hydrocarbon pool species consist of mainly highly methylated benzene carbocations at temperatures between 573 and 598 K, of both highly methylated benzene carbocations and methylated naphthalene carbocations at 623 K, and of only methylated naphthalene carbocations at temperatures between 673 and 773 K. The operando spectroscopy results suggest that the nature of the active species also influences the olefin selectivity. In fact, monoenylic and highly methylated benzene carbocations are more selective to the formation of propylene, whereas the formation of the group of low methylated benzene carbocations and methylated naphthalene carbocations at higher reaction temperatures (i.e., 673 and 773 K) favors the formation of ethylene. At reaction temperatures between 573 and 623 K, catalyst deactivation is caused by the gradual filling of the micropores with methylated naphthalene carbocations, while between 623 and 773 K the formation of neutral poly aromatics and phenanthrene/anthracene carbocations are mainly responsible for catalyst deactivation, their respective contribution increasing with increasing reaction temperature. Methanol pulse experiments at

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, Michael S.; Saunders, Randall

1997-01-01

Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

Ring-Closing Metathesis: An Advanced Guided-Inquiry Experiment for the Organic Laboratory

ERIC Educational Resources Information Center

Schepmann, Hala G.; Mynderse, Michelle

2010-01-01

The design and implementation of an advanced guided-inquiry experiment for the organic laboratory is described. Grubbs's second-generation catalyst is used to effect the ring-closing metathesis of diethyl diallylmalonate. The reaction is carried out under an inert atmosphere at room temperature and monitored by argentic TLC. The crude reaction is…

Process and catalyst for carbonylating olefins

DOEpatents

Zoeller, Joseph Robert

1998-06-02

Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents

PubMed Central

2016-01-01

Alkene metathesis is a widely and increasingly used reaction in academia and industry because of its efficiency in terms of atom economy and its wide applicability. This reaction is notably responsible for the production of several million tons of propene annually. Such industrial processes rely on inexpensive silica-supported tungsten oxide catalysts, which operate at high temperatures (>350 °C), in contrast with the mild room temperature reaction conditions typically used with the corresponding molecular alkene metathesis homogeneous catalysts. This large difference in the temperature requirements is generally thought to arise from the difficulty in generating active sites (carbenes or metallacyclobutanes) in the classical metal oxide catalysts and prevents broader applicability, notably with functionalized substrates. We report here a low temperature activation process of well-defined metal oxo surface species using organosilicon reductants, which generate a large amount of active species at only 70 °C (0.6 active sites/W). This high activity at low temperature broadens the scope of these catalysts to functionalized substrates. This activation process can also be applied to classical industrial catalysts. We provide evidence for the formation of a metallacyclopentane intermediate and propose how the active species are formed. PMID:27610418

Alternative Test Method for Olefins in Gasoline

EPA Pesticide Factsheets

This action proposes to allow for an additional alternative test method for olefins in gasoline, ASTM D6550-05. The allowance of this additional alternative test method will provide more flexibility to the regulated industry.

Survival of aerosolized bacteriophage phi X174 in air containing ozone--olefin mixtures.

PubMed Central

Mik, G.; de Groot, I.; Gerbrandy, J. L.

1977-01-01

The effects of ozone and ozonized olefins on aerosol survival of bacteriophage phiX174 were studied. The ozone concentrations used were between 0 and 110 parts/10(9), giving decay rates up to 0-03 min-1. The olefins used were trans-2-butene and cyclohexene in concentrations of 500 parts/10(9) and 2-4 parts/10(6), respectively. Olefins alone have no effect, whereas in combination with ozone, decay rates of 0-1 min-1 and higher were obtained. The results are discussed in relation to the viricidal effect of open air. PMID:265341

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, M.S.; Saunders, R.

1997-02-18

Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

Labelling Polymers and Micellar Nanoparticles via Initiation, Propagation and Termination with ROMP

PubMed Central

Thompson, Matthew P.; Randolph, Lyndsay M.; James, Carrie R.; Davalos, Ashley N.; Hahn, Michael E.

2014-01-01

In this paper we compare and contrast three approaches for labelling polymers with functional groups via ring-opening metathesis polymerization (ROMP). We explored the incorporation of functionality via initiation, termination and propagation employing an array of novel initiators, termination agents and monomers. The goal was to allow the generation of selectively labelled and well-defined polymers that would in turn lead to the formation of labelled nanomaterials. Norbornene analogues, prepared as functionalized monomers for ROMP, included fluorescent dyes (rhodamine, fluorescein, EDANS, and coumarin), quenchers (DABCYL), conjugatable moieties (NHS esters, pentafluorophenyl esters), and protected amines. In addition, a set of symmetrical olefins for terminally labelling polymers, and for the generation of initiators in situ is described. PMID:24855496

Conversion of Syngas-Derived C2+ Mixed Oxygenates to C3-C5 Olefins over ZnxZryOz Mixed Oxides Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Colin D.; Lebarbier, Vanessa M.; Flake, Matthew D.

2016-04-01

In this study we report on a ZnxZryOz mixed oxide type catalyst capable of converting a syngas-derived C2+ mixed oxygenate feedstock to isobutene-rich olefins. Aqueous model feed comprising of ethanol, acetaldehyde, acetic acid, ethyl acetate, methanol, and propanol was used as representative liquid product derived from a Rh-based mixed oxygenate synthesis catalyst. Greater than 50% carbon yield to C3-C5 mixed olefins was demonstrated when operating at 400-450oC and 1 atm. In order to rationalize formation of the products observed feed components were individually evaluated. Major constituents of the feed mixture (ethanol, acetaldehyde, acetic acid, and ethyl acetate) were found tomore » produce isobutene-rich olefins. C-C coupling was also demonstrated for propanol feedstock - a minor constituent of the mixed oxygenate feed - producing branched C6 olefins, revealing scalability to alcohols higher than ethanol following an analogous reaction pathway. Using ethanol and propanol feed mixtures, cross-coupling reactions produced mixtures of C4, C5, and C6 branched olefins. The presence of H2 in the feed was found to facilitate hydrogenation of the ketone intermediates, thus producing straight chain olefins as byproducts. While activity loss from coking is observed complete catalyst regeneration is achieved by employing mild oxidation. For conversion of the mixed oxygenate feed a Zr/Zn ratio of 2.5 and a reaction temperature of 450oC provides the best balance of stability, activity, and selectivity. X-ray diffraction and scanning transmission electron microscopy analysis reveals the presence of primarily cubic phase ZrO2 and a minor amount of the monoclinic phase, with ZnO being highly dispersed in the lattice. The presence of ZnO appears to stabilize the cubic phase resulting in less monoclinic phase as the ZnO concentration increases. Infrared spectroscopy shows the mixed oxide acid sites are characterized as primarily Lewis type acidity. The direct relationship

Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process.

PubMed

Gusev, Andrey A; Psarras, Antonios C; Triantafyllidis, Konstantinos S; Lappas, Angelos A; Diddams, Paul A

2017-10-21

ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC) process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam), FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives) are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated) activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n -Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C 12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F) ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas) olefins as the nature (Brønsted-to-Lewis ratio) of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at higher

Novel polymeric materials from vegetable oils and vinyl monomers: preparation, properties, and applications.

PubMed

Lu, Yongshang; Larock, Richard C

2009-01-01

Veggie-based products: Vegetable-oil-based polymeric materials, prepared by free radical, cationic, and olefin metathesis polymerizations, range from soft rubbers to ductile or rigid plastics, and to high-performance biocomposites and nanocomposites. They display a wide range of thermophysical and mechanical properties and may find promising applications as alternatives to petroleum-based polymers.Vegetable oils are considered to be among the most promising renewable raw materials for polymers, because of their ready availability, inherent biodegradability, and their many versatile applications. Research on and development of vegetable oil based polymeric materials, including thermosetting resins, biocomposites, and nanocomposites, have attracted increasing attention in recent years. This Minireview focuses on the latest developments in the preparation, properties, and applications of vegetable oil based polymeric materials obtained by free radical, cationic, and olefin metathesis polymerizations. The novel vegetable oil based polymeric materials obtained range from soft rubbery materials to ductile or rigid plastics and to high-performance biocomposites and nanocomposites. These vegetable oil based polymeric materials display a wide range of thermophysical and mechanical properties and should find useful applications as alternatives to their petroleum-based counterparts.

An adaptive self-healing ionic liquid nanocomposite membrane for olefin-paraffin separations.

PubMed

Pitsch, Fee; Krull, Florian F; Agel, Friederike; Schulz, Peter; Wasserscheid, Peter; Melin, Thomas; Wessling, Matthias

2012-08-16

An adaptive self-healing ionic liquid nanocomposite membrane comprising a multi-layer support structure hosting the ionic salt [Ag](+) [Tf(2) N](-) is used for the separation of the olefin propylene and the paraffin propane. The ionic salt renders liquid like upon complexation with propylene, resulting in facilitated transport of propylene over propane at benchmark-setting selectivity and permeance levels. The contacting with acetylene causes the ionic salt to liquefy without showing evidence of forming explosive silver acetylide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chloromethane to olefins over H-SAPO-34: Probing the hydrocarbon pool mechanism

DOE PAGES

Fickel, Dustin W.; Sabnis, Kaiwalya D.; Li, Luanyi; ...

2016-09-09

In this paper, by means of in situ FTIR and ex situ 13C NMR studies, the initial periods of the chloromethane-to-olefins (CTO) reaction over SAPO-34 were probed in order to investigate the activation period of the reaction and to elucidate the formation of the catalyst active site. A methylated benzene species has been observed to form during the initial activation period of the reaction, and a direct positive correlation was constructed between the formation of this species and the catalytic activity. The data thus indicate that these methylated benzene species contribute to the formation of active sites within SAPO-34 formore » the CTO reaction. This is the first known report identifying a direct semi-quantitative correlation between the catalyst activity and growth of a methylated benzene active species, during the activation period of the chloromethane to olefins reaction. Finally, the findings here in correspond well to those reported for the methanol to olefins reaction, suggesting that a similar ‘hydrocarbon pool’ mechanism may be responsible for the formation of light olefins in CTO chemistry as well.« less

Ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts.

PubMed

Vincent, Guillaume; Kouklovsky, Cyrille

2011-03-01

Strained nitroso Diels-Alder bicyclo[2.2.1] or [2.2.2] adducts functionalized with alkene side chains of diverse length undergo a ring-rearrangement metathesis process with external alkenes and Grubbs II or Hoveyda-Grubbs II ruthenium catalysts, under microwave irradiation or classical heating, to deliver cis-fused bicycles of various ring sizes, which contain a N-O bond. These scaffolds are of synthetic relevance for the generation of molecular diversity and to the total synthesis of alkaloids. The observation of unexpected reactions, such as epimerization or one-carbon homologation of the alkene side chain, is also reported. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic Covalent Synthesis of Aryleneethynylene Cages through Alkyne Metathesis: Dimer, Tetramer, or Interlocked Complex?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qi; Yu, Chao; Zhang, Chenxi

A dynamic covalent approach towards rigid aryleneethynylene covalent organic polyhedrons (COPs) was explored. Our study on the relationship of the COP structures and the geometry of their building blocks reveals that the topology of aryleneethynylene COPs strongly depends on the size of the building blocks. A tetramer (D2h symmetric), dimer, or interlocked complex can be formed from monomers with the same face-to-edge angle but in different sizes. As alkyne metathesis is a self-exchange reaction and non-directional, the cyclooligomerization of multi-alkyne monomers involves both intramolecular cyclization and intermolecular metathesis reaction, resulting in complicated thermodynamic process disturbed by kinetic competition. Although amore » tetrahedron-shaped tetramer (Td symmetric) has comparable thermodynamic stability to a D2h symmetric tetramer, its formation is kinetically disfavored and was not observed experimentally. Aryleneethynylene COPs consist of purely unsaturated carbon backbones and exhibit large internal cavities, which would have interesting applications in host-guest chemistry and development of porous materials.« less

Tuning selectivity in catalysis by controlling particle shape

NASA Astrophysics Data System (ADS)

Lee, Ilkeun; Delbecq, Françoise; Morales, Ricardo; Albiter, Manuel A.; Zaera, Francisco

2009-02-01

A catalytic process for the selective formation of cis olefins would help minimize the production of unhealthy trans fats during the partial hydrogenation of edible oils. Here we report on the design of such a process on the basis of studies with model systems. Temperature programmed desorption data on single crystals showed that the isomerization of trans olefins to their cis counterparts is promoted by (111) facets of platinum, and that such selectivity is reversed on more open surfaces. Quantum mechanics calculations suggested that the extra stability of cis olefins seen on hydrogen-saturated Pt(111) surfaces may be due to a lesser degree of surface reconstruction, a factor found to be significant in the adsorption on close-packed platinum surfaces. Kinetic data using catalysts made out of dispersed tetrahedral Pt nanoparticles corroborated the selective promotion of the trans-to-cis isomerization on the (111) facets of the metal. Our work provides an example for how catalytic selectivity may be controlled by controlling the shape of the catalytic particles.

Selection biases in empirical p(z) methods for weak lensing

DOE PAGES

Gruen, D.; Brimioulle, F.

2017-02-23

To measure the mass of foreground objects with weak gravitational lensing, one needs to estimate the redshift distribution of lensed background sources. This is commonly done in an empirical fashion, i.e. with a reference sample of galaxies of known spectroscopic redshift, matched to the source population. In this paper, we develop a simple decision tree framework that, under the ideal conditions of a large, purely magnitude-limited reference sample, allows an unbiased recovery of the source redshift probability density function p(z), as a function of magnitude and colour. We use this framework to quantify biases in empirically estimated p(z) caused bymore » selection effects present in realistic reference and weak lensing source catalogues, namely (1) complex selection of reference objects by the targeting strategy and success rate of existing spectroscopic surveys and (2) selection of background sources by the success of object detection and shape measurement at low signal to noise. For intermediate-to-high redshift clusters, and for depths and filter combinations appropriate for ongoing lensing surveys, we find that (1) spectroscopic selection can cause biases above the 10 per cent level, which can be reduced to ≈5 per cent by optimal lensing weighting, while (2) selection effects in the shape catalogue bias mass estimates at or below the 2 per cent level. Finally, this illustrates the importance of completeness of the reference catalogues for empirical redshift estimation.« less

α-Fluorovinyl Weinreb Amides and α- Fluoroenones from a Common Fluorinated Building Block

PubMed Central

Ghosh, Arun K.; Banerjee, Shaibal; Sinha, Saikat; Kang, Soon Bang; Zajc, Barbara

2009-01-01

Synthesis and reactivity of N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfonyl)fluoroacetamide, a building block for Julia olefination, is reported. This reagent undergoes condensation reactions with aldehydes and cyclic ketones, to give α-fluorovinyl Weinreb amides. Olefination reactions proceed under mild, DBU-mediated conditions, or in the presence of NaH. DBU-mediated condensations proceed with either E or Z-selectivity, depending upon reaction conditions, whereas NaH-mediated reactions are ≥98% Z-stereoselective. Conversion of the Weinreb amide moiety in N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfanyl)fluoroacetamide to ketones, followed by oxidation, resulted in another set of olefination reagents, namely (1,3-benzothiazol-2-ylsulfonyl)fluoromethyl phenyl and propyl ketones. In the presence of DBU, these compounds react with aldehydes tested to give α-fluoroenones with high Z-selectivity. The use of N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfanyl)fluoroacetamide as a common fluorinated intermediate in the synthesis of α-fluorovinyl Weinreb amides and α-fluoroenones has been demonstrated. Application of the Weinreb amide to α-fluoro allyl amine synthesis is also shown. PMID:19361189

Ozone impact minimization through coordinated scheduling of turnaround operations from multiple olefin plants in an ozone nonattainment area

NASA Astrophysics Data System (ADS)

Ge, Sijie; Wang, Sujing; Xu, Qiang; Ho, Thomas

2018-03-01

Turnaround operations (start-up and shutdown) are critical operations in olefin plants, which emit large quantities of VOCs, NOx and CO. The emission has great potentials to impact the ozone level in ozone nonattainment areas. This study demonstrates a novel practice to minimize the ozone impact through coordinated scheduling of turnaround operations from multiple olefin plants located in Houston, Texas, an ozone nonattainment area. The study considered two olefin plants scheduled to conduct turnaround operations: one start-up and one shutdown, simultaneously on the same day within a five-hour window. Through dynamic simulations of the turnaround operations using ASPEN Plus Dynamics and air quality simulations using CAMx, the study predicts the ozone impact from the combined effect of the two turnaround operations under different starting-time scenarios. The simulations predict that the ozone impact from planned turnaround operations ranges from a maximum of 11.4 ppb to a minimum of 1.4 ppb. Hence, a reduction of up to 10.0 ppb can be achieved on a single day based on the selected two simulation days. This study demonstrates a cost-effective and environmentally benign ozone control practice for relevant stakeholders, including environmental agencies, regional plant operators, and local communities.

A stereoselective synthesis of (+)-physoperuvine using a tandem aza-Claisen rearrangement and ring closing metathesis reaction.

PubMed

Zaed, Ahmed M; Swift, Michael D; Sutherland, Andrew

2009-07-07

A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

Solution-Phase Dynamic Assembly of Permanently Interlocked Aryleneethynylene Cages through Alkyne Metathesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qi; Yu, Chao; Long, Hai

2015-05-08

Highly stable permanently interlocked aryleneethynylene molecular cages were synthesized from simple triyne monomers using dynamic alkyne metathesis. The interlocked complexes are predominantly formed in the reaction solution in the absence of any recognition motif and were isolated in a pure form using column chromatography. This study is the first example of the thermodynamically controlled solution-phase synthesis of interlocked organic cages with high stability.

Structural identification of Zn xZr yO z catalysts for Cascade aldolization and self-deoxygenation reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor

Complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH3/CO2 temperature programmed desorption (NH3/CO2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn2+more » and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO2, caused by steam reforming. The incorporation of atomic Zn2+ into the ZrO2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., ). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C3=-C6=) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Photosensitized cleavage of some olefins as potential linkers to be used in drug delivery

NASA Astrophysics Data System (ADS)

Dinache, Andra; Smarandache, Adriana; Simon, Agota; Nastasa, Viorel; Tozar, Tatiana; Pascu, Alexandru; Enescu, Mironel; Khatyr, Abderrahim; Sima, Felix; Pascu, Mihail-Lucian; Staicu, Angela

2017-09-01

A study of photosensitized cleavage of different olefins as potential linkers for drug carrier complexes is reported. The role of singlet oxygen and the kinetic rates for light induced reactions were estimated by time-resolved measurements of singlet oxygen phosphorescence (at 1270 nm) obtained via 532 nm pulse laser excitation of a photosensitizer. The mixture of each studied olefin with verteporfin (used as photosensitizer) were exposed to low energy visible radiation. The rate constants for singlet oxygen quenching by studied olefins were determined. The irradiated solutions were investigated by FTIR spectroscopy and potential photoproducts were suggested. The experimental results were compared with simulations made by DFT method.

Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

DOEpatents

Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.; Beltran, Leslie V.; Kunz, Linda A.; Pals, Tessa M.; Quinn, Jordan R; Behrends, Jr., Raymond T.; Bernhardt, Randal J.

2016-07-05

Methods are provided for refining natural oil feedstocks and producing isomerized esters and acids. The methods comprise providing a C4-C18 unsaturated fatty ester or acid, and isomerizing the fatty acid ester or acid in the presence of heat or an isomerization catalyst to form an isomerized fatty ester or acid. In some embodiments, the methods comprise forming a dibasic ester or dibasic acid prior to the isomerizing step. In certain embodiments, the methods further comprise hydrolyzing the dibasic ester to form a dibasic acid. In certain embodiments, the olefin is formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having unsaturated esters.

The Acquisition of Consonant Feature Sequences: Harmony, Metathesis, and Deletion Patterns in Phonological Development

ERIC Educational Resources Information Center

Gerlach, Sharon Ruth

2010-01-01

This dissertation examines three processes affecting consonants in child speech: harmony (long-distance assimilation) involving major place features as in "coat" [kouk]; long-distance metathesis as in "cup" [p[wedge]k]; and initial consonant deletion as in "fish" [is]. These processes are unattested in adult phonology, leading to proposals for…

Contra-Thermodynamic, Photocatalytic E→Z Isomerization of Styrenyl Boron Species: Vectors to Facilitate Exploration of Two-Dimensional Chemical Space.

PubMed

Molloy, John J; Metternich, Jan B; Daniliuc, Constantin G; Watson, Allan J B; Gilmour, Ryan

2018-03-12

Designing strategies to access stereodefined olefinic organoboron species is an important synthetic challenge. Despite significant advances, there is a striking paucity of routes to Z-α-substituted styrenyl organoborons. Herein, this strategic imbalance is redressed by exploiting the polarity of the C(sp 2 )-B bond to activate the neighboring π system, thus enabling a mild, traceless photocatalytic isomerization of readily accessible E-α-substituted styrenyl BPins to generate the corresponding Z-isomers with high fidelity. Preliminary validation of this contra-thermodynamic E→Z isomerization is demonstrated in a series of stereoretentive transformations to generate Z-configured trisubstituted alkenes, as well as in a concise synthesis of the anti-tumor agent Combretastatin A4. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemical preparation of olefin addition catalysts

NASA Technical Reports Server (NTRS)

Gray, Harry B. (Inventor); Rembaum, Alan (Inventor); Gupta, Amitava (Inventor)

1978-01-01

Novel polymer supported catalysts are prepared by photo-irradiation of low valent transition metal compounds such as Co.sub.2 (CO).sub.8, Rh.sub.4 (CO).sub.12 or Ru.sub.3 (CO).sub.12 in the presence of solid polymers containing amine ligands such as polyvinyl pyridine. Hydroformylation of olefins to aldehydes at ambient conditions has been demonstrated.

On the selection of high-z quasars using LOFAR observations

NASA Astrophysics Data System (ADS)

Retana-Montenegro, Edwin; Röttgering, Huub

2018-03-01

We present a method to identify candidate quasars which combines optical/infrared color selection with radio detections from the Low Frequency ARray (LOFAR) at 150MHz. We apply this {method} in a region of 9 square degrees located in the Boötes field, with a wealth of multi-wavelength data. Our LOFAR imaging in the central region reaches a rms noise of ˜50μJy with a resolution of 5''. This is so deep that we also routinely, `radio-quiet' quasars. We use quasar spectroscopy from the literature to calculate the completeness and efficiency of our selection method. We conduct our analysis in two redshift intervals, 1<z<2 and 2<z<3. For objects at 1.0<z<2.0, we identify 51% of the spectroscopic quasars, and 80% of our candidates are in the spectroscopic sample; while for objects at 2.0<z<3.0 these numbers are 62% and 30%, respectively. We investigate the effect of the radio spectral index distribution on our selection of candidate quasars. For this purpose, we calculate the spectral index between 1400MHz and 150MHz, by combining our LOFAR-Boötes data with 1.4GHz imaging of the Boötes field obtained with the Westerbork Synthesis Radio Telescope (WSRT), which has a rms noise of σ˜28μJy with a resolution of 13''×27''. We find that 27% of the candidate quasars are detected at 1400 MHz, and that these detected objects have a spectral index distribution with a median value of α=-0.73±0.07. Using a flux density threshold of S_{150MHz}=1.50mJy, so that all the α>-1.0 sources can be detected in the WSRT-Boötes map, we find that the spectral index distribution of the 21 quasars in the resulting sample is steeper than the general LOFAR-WSRT spectral index distribution with a median of α=-0.80±0.06. As the upcoming LOFAR wide area surveys are much deeper than the traditional 1.4GHz surveys like NVSS and FIRST, this indicates that LOFAR in combination with optical and infrared will be an excellent fishing ground to obtain large samples of quasars.

Mechanistic insights into the rhenium-catalyzed alcohol-to-olefin dehydration reaction.

PubMed

Korstanje, Ties J; Jastrzebski, Johann T B H; Klein Gebbink, Robertus J M

2013-09-23

Rhenium-based complexes are powerful catalysts for the dehydration of various alcohols to the corresponding olefins. Here, we report on both experimental and theoretical (DFT) studies into the mechanism of the rhenium-catalyzed dehydration of alcohols to olefins in general, and the methyltrioxorhenium-catalyzed dehydration of 1-phenylethanol to styrene in particular. The experimental and theoretical studies are in good agreement, both showing the involvement of several proton transfers, and of a carbenium ion intermediate in the catalytic cycle. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-particle spectroscopy on large SAPO-34 crystals at work: methanol-to-olefin versus ethanol-to-olefin processes.

PubMed

Qian, Qingyun; Ruiz-Martínez, Javier; Mokhtar, Mohamed; Asiri, Abdullah M; Al-Thabaiti, Shaeel A; Basahel, Suliman N; van der Bij, Hendrik E; Kornatowski, Jan; Weckhuysen, Bert M

2013-08-19

The formation of hydrocarbon pool (HCP) species during methanol-to-olefin (MTO) and ethanol-to-olefin (ETO) processes have been studied on individual micron-sized SAPO-34 crystals with a combination of in situ UV/Vis, confocal fluorescence, and synchrotron-based IR microspectroscopic techniques. With in situ UV/Vis microspectroscopy, the intensity changes of the λ=400 nm absorption band, ascribed to polyalkylated benzene (PAB) carbocations, have been monitored and fitted with a first-order kinetics at low reaction temperatures. The calculated activation energy (Ea ) for MTO, approximately 98 kJ mol(-1) , shows a strong correlation with the theoretical values for the methylation of aromatics. This provides evidence that methylation reactions are the rate-determining steps for the formation of PAB. In contrast for ETO, the Ea value is approximately 60 kJ mol(-1) , which is comparable to the Ea values for the condensation of light olefins into aromatics. Confocal fluorescence microscopy demonstrates that during MTO the formation of the initial HCP species are concentrated in the outer rim of the SAPO-34 crystal when the reaction temperature is at 600 K or lower, whereas larger HCP species are gradually formed inwards the crystal at higher temperatures. In the case of ETO, the observed egg-white distribution of HCP at 509 K suggests that the ETO process is kinetically controlled, whereas the square-shaped HCP distribution at 650 K is indicative of a diffusion-controlled process. Finally, synchrotron-based IR microspectroscopy revealed a higher degree of alkylation for aromatics for MTO as compared to ETO, whereas high reaction temperatures favor dealkylation processes for both the MTO and ETO processes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

PubMed Central

Borguet, Yannick; Sauvage, Xavier; Zaragoza, Guillermo; Demonceau, Albert

2010-01-01

Summary The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymene)Ru(μ-Cl)3RuCl(3-phenyl-1-indenylidene)(PCy3)] (1) to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)–Ru(III) mixed-valence compound [(p-cymene)Ru(μ-Cl)3RuCl2(PCy3)], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions. PMID:21160564

Old Yellow Enzyme: Stepwise reduction of nitro-olefins and catalysis of aci-nitro tautomerization

PubMed Central

Meah, Younus; Massey, Vincent

2000-01-01

The Old Yellow Enzyme has been shown to catalyze efficiently the NADPH-linked reduction of nitro-olefins. The reduction of the nitro-olefin proceeds in a stepwise fashion, with formation of a nitronate intermediate that is freely dissociable from the enzyme. The first step involves hydride transfer from the enzyme-reduced flavin to carbon 2 of the nitro-olefin. The protonation of the nitronate at carbon 1 to form the final nitroalkane product also is catalyzed by the enzyme and involves Tyr-196 as an active site acid/base. This residue also is involved in aci-nitro tautomerization of nitroalkanes, the first example of a nonredox reaction catalyzed by the enzyme. PMID:10995477

Footprint, weathering, and persistence of synthetic-base drilling mud olefins in deep-sea sediments following the Deepwater Horizon disaster.

PubMed

Stout, Scott A; Payne, James R

2017-05-15

Olefin-based synthetic-based drilling mud (SBM) was released into the Gulf of Mexico as a result of the Deepwater Horizon (DWH) disaster in 2010. We studied the composition of neat SBM and, using conventional GC-FID, the extent, concentration, and chemical character of SBM-derived olefins in >3600 seafloor sediments collected in 2010/2011 and 2014. SBM-derived (C 14 -C 20 ) olefins occurred (up to 10cm deep) within a 6.5km 2 "footprint" around the well. The olefin concentration in most sediments decreased an order of magnitude between 2010/2011 and 2014, at least in part due to biodegradation, evidenced by the preferential loss C 16 and C 18 linear (α- and internal) versus branched olefins. Based on their persistence for 4-years in sediments around the Macondo well, and 13-years near a former unrelated drill site (~62km away), weathered SBM-derived olefins released during the DWH disaster are anticipated to persist in deep-sea sediment for (at least) a comparable duration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

NASA Technical Reports Server (NTRS)

Rodriguez, Marc (Inventor); Kaner, Richard B. (Inventor); Bux, Sabah K. (Inventor); Fleurial, Jean-Pierre (Inventor)

2014-01-01

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

Selecting and designing with the right thermoplastic polymer for your microfluidic chip: a close look into cyclo-olefin polymer

NASA Astrophysics Data System (ADS)

Nevitt, Mark

2013-03-01

Engineers who are developing microfluidic devices and bioMEMs for life science applications have many aspects to consider when selecting the proper base materials for constructing a device. While glass and polydimethylsiloxane (PDMS) are the staple materials for proof-of-concept and prototype chip fabrication, they are not a feasible solution for commercial production due to their slow, labor-intensive production rate. Alternatively, a molded or extruded thermoplastic solution can deliver the precision, consistency, and high volume capability required for commercial scale production. Traditional thermoplastics, such as polymethylmethacrylate (PMMA), polycarbonate (PC), and polystyrene (PS), are well known by development engineers in the bioscience community; however, cyclo-olefin polymer (COP), a relative newcomer in the world of plastics, is gaining increasing attention for use in microfluidic devices due to its unique balance of key properties compared to conventional thermoplastics. In this paper, we provide a comprehensive look at the properties which make COP an excellent candidate for providing the flow cell support and reagent storage functions in microfluidic assays. We also explore the processing attributes and capabilities of COP resin and film which are crucial for manufacturing high-performance microfluidic devices.

THE zCOSMOS-SINFONI PROJECT. I. SAMPLE SELECTION AND NATURAL-SEEING OBSERVATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mancini, C.; Renzini, A.; Foerster Schreiber, N. M.

2011-12-10

The zCOSMOS-SINFONI project is aimed at studying the physical and kinematical properties of a sample of massive z {approx} 1.4-2.5 star-forming galaxies, through SINFONI near-infrared integral field spectroscopy (IFS), combined with the multiwavelength information from the zCOSMOS (COSMOS) survey. The project is based on one hour of natural-seeing observations per target, and adaptive optics (AO) follow-up for a major part of the sample, which includes 30 galaxies selected from the zCOSMOS/VIMOS spectroscopic survey. This first paper presents the sample selection, and the global physical characterization of the target galaxies from multicolor photometry, i.e., star formation rate (SFR), stellar mass, age,more » etc. The H{alpha} integrated properties, such as, flux, velocity dispersion, and size, are derived from the natural-seeing observations, while the follow-up AO observations will be presented in the next paper of this series. Our sample appears to be well representative of star-forming galaxies at z {approx} 2, covering a wide range in mass and SFR. The H{alpha} integrated properties of the 25 H{alpha} detected galaxies are similar to those of other IFS samples at the same redshifts. Good agreement is found among the SFRs derived from H{alpha} luminosity and other diagnostic methods, provided the extinction affecting the H{alpha} luminosity is about twice that affecting the continuum. A preliminary kinematic analysis, based on the maximum observed velocity difference across the source and on the integrated velocity dispersion, indicates that the sample splits nearly 50-50 into rotation-dominated and velocity-dispersion-dominated galaxies, in good agreement with previous surveys.« less

(Electro)Mechanical Properties of Olefinic Block Copolymers

NASA Astrophysics Data System (ADS)

Spontak, Richard

2014-03-01

Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

Thermal cracking of poly α-olefin aviation lubricating base oil

NASA Astrophysics Data System (ADS)

Fei, Yiwei; Wu, Nan; Ma, Jun; Hao, Jingtuan

2018-02-01

Thermal cracking of poly α-olefin (PAO) was conducted under different temperatures among 190 °C to 300 °C. The reacted mixtures were sequentially detected by gas chromatography-mass spectrometer (GC/MS). A series of small molecular normal alkanes, branched alkanes and olefins were identified. PAO perfect structure of aligned comb-likely side-chains has been seriously cracked under high temperatures. Property changes about kinematic viscosity and pour point of PAO samples reacted under high temperatures were also investigated. The appearance of small molecular compounds weakened the thermal stability, viscosity temperature performance and low temperature fluidity of PAO samples. Property of PAO samples was deteriorated due to thermal cracking under high temperatures.

Olefins and chemical regulation in Europe: REACH.

PubMed

Penman, Mike; Banton, Marcy; Erler, Steffen; Moore, Nigel; Semmler, Klaus

2015-11-05

REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is the European Union's chemical regulation for the management of risk to human health and the environment (European Chemicals Agency, 2006). This regulation entered into force in June 2007 and required manufacturers and importers to register substances produced in annual quantities of 1000 tonnes or more by December 2010, with further deadlines for lower tonnages in 2013 and 2018. Depending on the type of registration, required information included the substance's identification, the hazards of the substance, the potential exposure arising from the manufacture or import, the identified uses of the substance, and the operational conditions and risk management measures applied or recommended to downstream users. Among the content developed to support this information were Derived No-Effect Levels or Derived Minimal Effect Levels (DNELs/DMELs) for human health hazard assessment, Predicted No Effect Concentrations (PNECs) for environmental hazard assessment, and exposure scenarios for exposure and risk assessment. Once registered, substances may undergo evaluation by the European Chemicals Agency (ECHA) or Member State authorities and be subject to requests for additional information or testing as well as additional risk reduction measures. To manage the REACH registration and related activities for the European olefins and aromatics industry, the Lower Olefins and Aromatics REACH Consortium was formed in 2008 with administrative and technical support provided by Penman Consulting. A total of 135 substances are managed by this group including 26 individual chemical registrations (e.g. benzene, 1,3-butadiene) and 13 categories consisting of 5-26 substances. This presentation will describe the content of selected registrations prepared for 2010 in addition to the significant post-2010 activities. Beyond REACH, content of the registrations may also be relevant to other European activities, for

76 FR 5319 - Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-31

... Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline AGENCY: Environmental... proposing to allow refiners and laboratories to use an alternative test method for olefin content in... test method for compliance measurement while maintaining environmental benefits achieved from our fuels...

76 FR 65382 - Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-21

... Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline AGENCY: Environmental... gasoline. This final rule will provide flexibility to the regulated community by allowing an additional... Method for Olefins in Gasoline III. Statutory and Executive Order Reviews A. Executive Order 12866...

Asymmetric Synthesis of Apratoxin E.

PubMed

Mao, Zhuo-Ya; Si, Chang-Mei; Liu, Yi-Wen; Dong, Han-Qing; Wei, Bang-Guo; Lin, Guo-Qiang

2016-10-21

An efficient method for asymmetric synthesis of apratoxin E 2 is described in this report. The chiral lactone 8, recycled from the degradation of saponin glycosides, was utilized to prepare the non-peptide fragment 6. In addition to this "from nature to nature" strategy, olefin cross-metathesis (CM) was applied as an alternative approach for the formation of the double bond. Moreover, pentafluorophenyl diphenylphosphinate was found to be an efficient condensation reagent for the macrocyclization.

The Munich Near-Infrared Cluster Survey - IX. Galaxy evolution to z ~ 2 from optically selected catalogues†‡

NASA Astrophysics Data System (ADS)

Feulner, Georg; Goranova, Yuliana; Hopp, Ulrich; Gabasch, Armin; Bender, Ralf; Botzler, Christine S.; Drory, Niv

2007-06-01

We present B-, R- and I-band-selected galaxy catalogues based on the Munich Near-Infrared Cluster Survey (MUNICS) which, together with the previously used K-selected sample, serve as an important probe of galaxy evolution in the redshift range 0 <~ z <~ 2. Furthermore, used in comparison they are ideally suited to study selection effects in extragalactic astronomy. The construction of the B-, R- and I-selected photometric catalogues, containing ~9000, ~9000 and ~6000 galaxies, respectively, is described in detail. The catalogues reach 50 per cent completeness limits for point sources of B ~= 24.5 mag, R ~= 23.5 mag and I ~= 22.5 mag and cover an area of about 0.3deg2. Photometric redshifts are derived for all galaxies with an accuracy of δz/(1 + z) ~= 0.057, very similar to the K-selected sample. Galaxy number counts in the B, V, R, I, J and K bands demonstrate the quality of the data set. The rest-frame colour distributions of galaxies at different selection bands and redshifts suggest that the most-massive galaxies have formed the bulk of their stellar population at earlier times and are essentially in place at redshift unity. We investigate the influence of selection band and environment on the specific star formation rate (SSFR). We find that K-band selection indeed comes close to selection in stellar mass, while B-band selection purely selects galaxies in SFR. We use a galaxy group catalogue constructed on the K-band-selected MUNICS sample to study possible differences of the SSFR between the field and the group environment, finding a marginally lower average SSFR in groups as compared to the field, especially at lower redshifts. The field-galaxy luminosity function in the B and R band as derived from the R-selected sample evolves out to z ~= 2 in the sense that the characteristic luminosity increases but the number density decreases. This effect is smaller at longer rest-frame wavelengths and gets more pronounced at shorter wavelengths. Parametrizing the

Request for Symposia Support: Advances in Olefin Polymerization Catalysis

DTIC Science & Technology

2014-11-24

States Polyolefins, including polyethylene ( HDPE and LLDPE) ad polypropylene (PP), represent half of commercial polymers produced in the world...i.e. HDPE vs. UHMWPE) by simply changing the catalyst. Despite this success, the development of novel transition metal olefin polymerization

ULTRASOUND-ASSISTED ORGANIC SYNTHESIS: ALCOHOL OXIDATION AND OLEFIN EPOXIDATION

EPA Science Inventory

Ultrasound-assisted Organic Synthesis: Alcohol Oxidation and Olefin Epoxidation

Unnikrishnan R Pillai, Endalkachew Sahle-Demessie , Vasudevan Namboodiri, Quiming Zhao, Juluis Enriquez
U.S. EPA , 26 W. Martin Luther King Dr. , Cincinnati, OH 45268
Phone: 513-569-773...

Sterically shielded diboron-containing metallocene olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Ja, Li; Yang, Xinmin

1995-09-05

A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula ##STR1## where R is branched lower alkyl, such as t-butyl.

Shale Gas Implications for C2-C3 Olefin Production: Incumbent and Future Technology.

PubMed

Stangland, Eric E

2018-06-07

Substantial natural gas liquids recovery from tight shale formations has produced a significant boon for the US chemical industry. As fracking technology improves, shale liquids may represent the same for other geographies. As with any major industry disruption, the advent of shale resources permits both the chemical industry and the community an excellent opportunity to have open, foundational discussions on how both public and private institutions should research, develop, and utilize these resources most sustainably. This review summarizes current chemical industry processes that use ethane and propane from shale gas liquids to produce the two primary chemical olefins of the industry: ethylene and propylene. It also discusses simplified techno-economics related to olefins production from an industry perspective, attempting to provide a mutually beneficial context in which to discuss the next generation of sustainable olefin process development.

Versatile Tandem Ring-Opening/Ring-Closing Metathesis Polymerization: Strategies for Successful Polymerization of Challenging Monomers and Their Mechanistic Studies.

PubMed

Park, Hyeon; Kang, Eun-Hye; Müller, Laura; Choi, Tae-Lim

2016-02-24

Tandem ring-opening/ring-closing metathesis (RO/RCM) results in extremely fast living polymerization; however, according to previous reports, only monomers containing certain combinations of cycloalkenes, terminal alkynes, and nitrogen linkers successfully underwent tandem polymerization. After examining the polymerization pathways, we proposed that the relatively slow intramolecular cyclization might lead to competing side reactions such as intermolecular cross metathesis reactions to form inactive propagating species. Thus, we developed two strategies to enhance tandem polymerization efficiency. First, we modified monomer structures to accelerate tandem RO/RCM cyclization by enhancing the Thorpe-Ingold effect. This strategy increased the polymerization rate and suppressed the chain transfer reaction to achieve controlled polymerization, even for challenging syntheses of dendronized polymers. Alternatively, reducing the reaction concentration facilitated tandem polymerization, suggesting that the slow tandem RO/RCM cyclization step was the main reason for the previous failure. To broaden the monomer scope, we used monomers containing internal alkynes and observed that two different polymer units with different ring sizes were produced as a result of nonselective α-addition and β-addition on the internal alkynes. Thorough experiments with various monomers with internal alkynes suggested that steric and electronic effects of the alkyne substituents influenced alkyne addition selectivity and the polymerization reactivity. Further polymerization kinetics studies revealed that the rate-determining step of monomers containing certain internal alkynes was the six-membered cyclization step via β-addition, whereas that for other monomers was the conventional intermolecular propagation step, as observed in other chain-growth polymerizations. This conclusion agrees well with all those polymerization results and thus validates our strategies.

Synthesis gas and olefins from the catalytic autothermal reforming of volatile and non-volatile liquids

NASA Astrophysics Data System (ADS)

Dreyer, Bradon Justin

2007-12-01

of NOx traps and hydrogen into diesel engines has shown potential in reducing NOx emissions into the environment. Both concepts are dependent on synthesis gas generated from portable, compact fuel reformers, such as CPO reactors. Chapter 1 also reviews previous research in CPO, along with several important experimental parameters, and outlines the remaining research directions in the remaining chapters. In Chapter 2, steam addition to the CPO of higher hydrocarbons was explored over rhodium-coated ceramic foam supports at millisecond contact times. Steam addition to the CPO of n-decane and n-hexadecane in air produced considerably higher H2 and CO2 and lower olefin and CO selectivities than traditional CPO. For steam to carbon feed ratios from 0.0 to 4.0, the reactor operated autothermally, and the H2 to CO product ratio increased from ˜1.0 to ˜4.0, which is essentially the equilibrium product composition near synthesis gas stoichiometry (C/O ˜1) at contact times of ˜7 milliseconds. In fuel-rich feeds exceeding the synthesis gas ratio (C/O > 1), steam addition suppressed olefins, promoted synthesis gas and water-gas shift products, and reduced catalyst surface carbon. Furthermore, steam addition to the CPO of the military fuel JP-8 was performed successfully, also increasing H2 and suppressing olefins. (Abstract shortened by UMI.)

Experimental evidence of {alpha}-olefin readsorption in Fischer-Tropsch synthesis on ruthenium-supported ETS-10 titanium silicate catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bianchi, C.L.; Ragaini, V.

1997-05-01

Fischer-Tropsch synthesis seems to develop the following two consecutive paths: a primary process that involves the formation of {alpha}-olefin products and a secondary process leading to the production of branched isomers and paraffins and requiring the readsorption of primary {alpha}-olefin products. It was already shown by Iglesia et al. that such readsorption steps are of fundamental importance for Ru catalysts and that they occur due to the slow diffusive removal of {alpha}-olefins when the molecular size increases, this resulting in a long intraparticle residence time. In the present paper {alpha}-olefins readsorption was enhanced by changing the metal distribution inside themore » pores of a titanium silicate (ETS-10), modified by ion exchange with alkali metal ions, used as a support for Ru-based catalysts. 24 refs., 5 figs., 3 tabs.« less

Keck Deep Fields. I. Observations, Reductions, and the Selection of Faint Star-forming Galaxies at Redshifts z ~ 4, 3, and 2

NASA Astrophysics Data System (ADS)

Sawicki, Marcin; Thompson, David

2005-12-01

We introduce a very deep, Rlim~27, multicolor imaging survey of very faint star-forming galaxies at z~4, 3, 2.2, and 1.7. This survey, carried out on the Keck I telescope, uses the very same UnGRI filter system that is employed by the Steidel team to select galaxies at these redshifts and thus allows us to construct identically selected but much fainter samples. However, our survey reaches ~1.5 mag deeper than the work of Steidel and his group, letting us probe substantially below the characteristic luminosity L* and thus study the properties and redshift evolution of the faint component of the high-z galaxy population. The survey covers 169 arcmin2 in three spatially independent patches on the sky and-to R<=27-contains 427 GRI-selected z~4 Lyman break galaxies, 1481 UnGR-selected z~3 Lyman break galaxies, 2417 UnGR-selected z~2.2 star-forming galaxies, and 2043 UnGR-selected z~1.7 star-forming galaxies. In this paper, the first in a series, we introduce the survey, describe our observing and data reduction strategies, and outline the selection of our z~4, 3, 2.2, and 1.7 samples. Based on data obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

DOEpatents

Sen, Ayusman; Jiang, Zhaozhong

1996-01-01

The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

DOEpatents

Sen, A.; Jiang, Z.

1996-05-28

The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

Structural Identification of Zn xZr yO z Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH 3/CO 2 temperature programmed desorption (NH 3/CO 2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO 2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn 2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO 2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn 2+ and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO 2, caused by steam reforming. The incorporation of atomic Zn 2+ into the ZrO 2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO 2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—omore » $$\\curvearrowleft\\atop{e\\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C 3 =-C 6 =) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Structural Identification of Zn xZr yO z Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

DOE PAGES

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor; ...

2018-04-22

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH 3/CO 2 temperature programmed desorption (NH 3/CO 2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO 2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn 2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO 2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn 2+ and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO 2, caused by steam reforming. The incorporation of atomic Zn 2+ into the ZrO 2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO 2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—omore » $$\\curvearrowleft\\atop{e\\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C 3 =-C 6 =) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Improved olefinic fat suppression in skeletal muscle DTI using a magnitude-based dixon method.

PubMed

Burakiewicz, Jedrzej; Hooijmans, Melissa T; Webb, Andrew G; Verschuuren, Jan J G M; Niks, Erik H; Kan, Hermien E

2018-01-01

To develop a method of suppressing the multi-resonance fat signal in diffusion-weighted imaging of skeletal muscle. This is particularly important when imaging patients with muscular dystrophies, a group of diseases which cause gradual replacement of muscle tissue by fat. The signal from the olefinic fat peak at 5.3 ppm can significantly confound diffusion-tensor imaging measurements. Dixon olefinic fat suppression (DOFS), a magnitude-based chemical-shift-based method of suppressing the olefinic peak, is proposed. It is verified in vivo by performing diffusion tensor imaging (DTI)-based quantification in the lower leg of seven healthy volunteers, and compared to two previously described fat-suppression techniques in regions with and without fat contamination. In the region without fat contamination, DOFS produces similar results to existing techniques, whereas in muscle contaminated by subcutaneous fat signal moved due to the chemical shift artefact, it consistently showed significantly higher (P = 0.018) mean diffusivity (MD). Because fat presence lowers MD, this suggests improved fat suppression. DOFS offers superior fat suppression and enhances quantitative measurements in the muscle in the presence of fat. DOFS is an alternative to spectral olefinic fat suppression. Magn Reson Med 79:152-159, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

PubMed

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Direct, enantioselective α-alkylation of aldehydes using simple olefins

NASA Astrophysics Data System (ADS)

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Key product development based on cyclo olefin polymer for LCD-TV

NASA Astrophysics Data System (ADS)

Konishi, Yuichiro; Kobayashi, Masahi; Arakawa, Kouhei

2006-09-01

Cyclo Olefin Polymer (COP), which was developed by Zeon Corporation, is well known and used as an optical plastic in optical markets, having unique properties such as high light transmission, low water absorption, low birefringence etc. Optes Inc, who is ZEON CORPORATION's affiliate optical parts manufacturer, has succeeded in the development of high performance optical base films. These are used for retardation and polarizing films in LCD's (Liquid Crystal Displays), made from Cyclo Olefin Polymer with own film extrusion technologies. The Optical base film developed by Optes Inc has superior properties compared with those of existing products such as polycarbonate (PC), polyethylene terephthalate (PET) and Triacetate Cellulose (TAC) base in terms of low birefringence, high optical isotropy and high dimensional stability under high humidity and temperature conditions.

Distributions of imidacloprid, imidacloprid-olefin and imidacloprid-urea in green plant tissues and roots of rapeseed (Brassica napus) from artificially contaminated potting soil.

PubMed

Seifrtova, Marcela; Halesova, Tatana; Sulcova, Klara; Riddellova, Katerina; Erban, Tomas

2017-05-01

Imidacloprid-urea is the primary imidacloprid soil metabolite, whereas imidacloprid-olefin is the main plant-relevant metabolite and is more toxic to insects than imidacloprid. We artificially contaminated potting soil and used quantitative UHPLC-QqQ-MS/MS to determine the imidacloprid, imidacloprid-olefin and imidacloprid-urea distributions in rapeseed green plant tissues and roots after 4 weeks of exposure. In soil, the imidacloprid/imidacloprid-urea molar ratios decreased similarly after the 250 and 2500 µg kg -1 imidacloprid treatments. The imidacloprid/imidacloprid-urea molar ratios in the root and soil were similar, whereas in the green plant tissue, imidacloprid-urea increased more than twofold compared with the root. Although imidacloprid-olefin was prevalent in the green plant tissues, with imidacloprid/imidacloprid-olefin molar ratios of 2.24 and 1.47 for the 250 and 2500 µg kg -1 treatments respectively, it was not detected in the root. However, imidacloprid-olefin was detected in the soil after the 2500 µg kg -1 imidacloprid treatment. Significant proportions of imidacloprid-olefin and imidacloprid-urea in green plant tissues were demonstrated. The greater imidacloprid supply increased the imidacloprid-olefin/imidacloprid molar ratio in the green plant tissues. The absence of imidacloprid-olefin in the root excluded its retransport from leaves. The similar imidacloprid/imidacloprid-urea ratios in the soil and root indicated that the root serves primarily for transporting these substances. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

The antimicrobial peptide nisin Z induces selective toxicity and apoptotic cell death in cultured melanoma cells.

PubMed

Lewies, Angélique; Wentzel, Johannes Frederik; Miller, Hayley Christy; Du Plessis, Lissinda Hester

2018-01-01

Reprogramming of cellular metabolism is now considered one of the hallmarks of cancer. Most malignant cells present with altered energy metabolism which is associated with elevated reactive oxygen species (ROS) generation. This is also evident for melanoma, the leading cause of skin cancer related deaths. Altered mechanisms affecting mitochondrial bioenergetics pose attractive targets for novel anticancer therapies. Antimicrobial peptides have been shown to exhibit selective anticancer activities. In this study, the anti-melanoma potential of the antimicrobial peptide, nisin Z, was evaluated in vitro. Nisin Z was shown to induce selective toxicity in melanoma cells compared to non-malignant keratinocytes. Furthermore, nisin Z was shown to negatively affect the energy metabolism (glycolysis and mitochondrial respiration) of melanoma cells, increase reactive oxygen species generation and cause apoptosis. Results also indicate that nisin Z can decrease the invasion and proliferation of melanoma cells demonstrating its potential use against metastasis associated with melanoma. As nisin Z seems to place a considerable extra burden on the energy metabolism of melanoma cells, combination therapies with known anti-melanoma agents may be effective treatment options. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

40 CFR Appendix 8 to Subpart A of... - Reference C16-C18 Internal Olefin Drilling Fluid Formulation

Code of Federal Regulations, 2014 CFR

2014-07-01

... Drilling Fluid Formulation 8 Appendix 8 to Subpart A of Part 435 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) OIL AND GAS EXTRACTION POINT...—Reference C16-C18 Internal Olefin Drilling Fluid Formulation The reference C16-C18 internal olefin drilling...

40 CFR Appendix 8 to Subpart A of... - Reference C16-C18 Internal Olefin Drilling Fluid Formulation

Code of Federal Regulations, 2012 CFR

2012-07-01

... Drilling Fluid Formulation 8 Appendix 8 to Subpart A of Part 435 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) OIL AND GAS EXTRACTION POINT...—Reference C16-C18 Internal Olefin Drilling Fluid Formulation The reference C16-C18 internal olefin drilling...

40 CFR Appendix 8 to Subpart A of... - Reference C16-C18 Internal Olefin Drilling Fluid Formulation

Code of Federal Regulations, 2013 CFR

2013-07-01

... Drilling Fluid Formulation 8 Appendix 8 to Subpart A of Part 435 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) OIL AND GAS EXTRACTION POINT...—Reference C16-C18 Internal Olefin Drilling Fluid Formulation The reference C16-C18 internal olefin drilling...

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis

NASA Astrophysics Data System (ADS)

Röttger, Max; Domenech, Trystan; van der Weegen, Rob; Breuillac, Antoine; Nicolaÿ, Renaud; Leibler, Ludwik

2017-04-01

Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

Layered transition metal carboxylates: efficient reusable heterogeneous catalyst for epoxidation of olefins.

PubMed

Sen, Rupam; Bhunia, Susmita; Mal, Dasarath; Koner, Subratanath; Miyashita, Yoshitaro; Okamoto, Ken-Ichi

2009-12-01

Layered metal carboxylates [M(malonato)(H(2)O)(2)](n) (M = Ni(II) and Mn(II)) that have a claylike structure have been synthesized hydrothermally and characterized. The interlayer separation in these layered carboxylates is comparable to that of the intercalation distance of the naturally occurring clay materials or layered double hydroxides (LDHs). In this study, we have demonstrated that, instead of intercalating the metal complex into layers of the clay or LDH, layered transition metal carboxylates, [M(malonato)(H(2)O)(2)](n), as such can be used as a recyclable heterogeneous catalyst in olefin epoxidation reaction. Metal carboxylates [M(malonato)(H(2)O)(2)](n) exhibit excellent catalytic performance in olefin epoxidation reaction.

First Principles Simulations of Hydrocarbon Conversion Processes in Functionalized Zeolitic Materials

NASA Astrophysics Data System (ADS)

Mazar, Mark Nickolaus

With increasing demand for chemicals and fuels, and finite traditional crude oil resources, there is a growing need to invent, establish, or optimize chemical processes that convert gasifiable carbon-based feedstocks (e.g., coal, natural gas, oil sands, or biomass) into the needed final products. Catalysis is central to almost every industrial chemical process, including alkane metathesis (AM) and the methanol-to-hydrocarbons (MTH) process, which represent final steps in a sequence of hydrocarbon conversion reactions. An in depth understanding of AM and MTH is essential to the selective production of the desired end products. In this dissertation, ab initio density functional theory simulations provide unique mechanistic and thermodynamic insight of specific elementary steps involved in AM and MTH as performed on zeolite supports. Zeolites have been employed throughout the petroleum industry because of their ability to perform acid-catalyzed reactions (e.g., cracking or MTH). The crystalline structure of zeolites imparts regular microporous networks and, in turn, the selective passage of molecules based on shape and functionality. Many different elements can be grafted onto or substituted into zeolites, resulting in a broad range of catalytic behavior. However, due to the variety of competing and secondary reactions that occur at experimental conditions, it is often difficult to extract quantitative information regarding individual elementary steps. ab initio calculations can be particularly useful for this purpose. Alkane metathesis (i.e., the molecular redistribution or chain length averaging of alkanes) is typically performed by transition metal hydrides on amorphous alumina or silica supports. In Chapter 3, the feasibility of AM in zeolites is assessed by using a grafted Ta-hydride complex to explore the full catalytic cycle in the self-metathesis of ethane. The decomposition of a Ta-metallacyclobutane reaction intermediate that forms during olefin metathesis

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

DOEpatents

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Deinking selectivity (Z-factor) : a new parameter to evaluate the performance of flotation deinking process

Treesearch

J.Y.: Tan Zhu; K.L. Scallon; Y.L. Zhao; Y. Deng

2005-01-01

This study proposes a deinking selectivity concept that considers both ink removal and fiber yield in determining the performance of deinking operations. The defined deinking selectivity. or Z -factor, is expressed by the ratio of ink removal expressed by the International Standards Organization (ISO) brightness gain or the reduction in relative effective residual ink...

Direct, enantioselective α-alkylation of aldehydes using simple olefins

PubMed Central

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-01-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

Developing new methods for the mono-end functionalization of living ring opening metathesis polymers.

PubMed

Kilbinger, Andreas F M

2012-01-01

In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer-protein conjugates are two examples for the former and polymer-β-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

Synthesis of Side-Chain Oxysterols and their Enantiomers through Cross-Metathesis Reactions of Δ22 Steroids

PubMed Central

Brownholland, David P.

2017-01-01

A synthetic route that utilizes a cross-metathesis reaction with Δ22 steroids has been developed to prepare sterols with varying C-27 side-chains. Natural sterols containing hydroxyl groups at the 25 and (25R)-26 positions were prepared. Enantiomers of cholesterol and (3β,25R)-26-hydroxycholesterol (27-hydroxycholesterol) trideuterated at C-19 were prepared for future biological studies. PMID:28300584

Deinking selectivity (Z-factor) : a new parameter to evaluate the performance of flotation deinking process

Treesearch

J.Y. Zhu; F. Tan; K.L. Scallon; Y. Zhao; Y. Deng

2004-01-01

Reducing fiber loss is also important to conserve resources and reduce the cost of secondary fibers. This study proposes a deinking selectivity concept that considers both ink removal and fiber yield in determining the performance of deinking operations. The defined deinking selectivity, or Z-factor, is expressed by the ratio of ink removal expressed by the...

Catalyst–Controlled C–O versus C–N Allylic Functionalization of Terminal Olefins

PubMed Central

Strambeanu, Iulia I.; White, M. Christina

2014-01-01

The divergent synthesis of syn-1, 2-aminoalcohol or syn-1,2-diamine precursors from a common terminal olefin has been accomplished using a combination of palladium(II) catalysis with Lewis acid co-catalysis. Palladium(II)/bis-sulfoxide catalysis with a silver triflate co-catalyst leads for the first time to anti-2-aminooxazolines (C—O) in good to excellent yields. Simple removal of the bis-sulfoxide ligand from this reaction results in a complete switch in reactivity to afford anti-imidazolidinone products (C—N) in good yields and excellent diastereoselectivities. Mechanistic studies suggest the divergent C—O versus C—N reactivity from a common ambident nucleophile arises due to a switch in mechanism from allylic C—H cleavage/functionalization to olefin isomerization/oxidative amination. PMID:23855956

Clustering properties of g -selected galaxies at z ~ 0.8

DOE PAGES

Favole, Ginevra; Comparat, Johan; Prada, Francisco; ...

2016-06-21

In current and future large redshift surveys, as the Sloan Digital Sky Survey IV extended Baryon Oscillation Spectroscopic Survey (SDSS-IV/eBOSS) or the Dark Energy Spectroscopic Instrument (DESI), we will use emission-line galaxies (ELGs) to probe cosmological models by mapping the large-scale structure of the Universe in the redshift range 0.6 < z < 1.7. We explore the halo-galaxy connection, with current data and by measuring three clustering properties of g-selected ELGs as matter tracers in the redshift range 0.6 < z < 1: (i) the redshift-space two-point correlation function using spectroscopic redshifts from the BOSS ELG sample and VIPERS; (ii)more » the angular two-point correlation function on the footprint of the CFHT-LS; (iii) the galaxy-galaxy lensing signal around the ELGs using the CFHTLenS. Furthermore, we interpret these observations by mapping them on to the latest high-resolution MultiDark Planck N-body simulation, using a novel (Sub)Halo-Abundance Matching technique that accounts for the ELG incompleteness. ELGs at z ~ 0.8 live in haloes of (1 ± 0.5) × 10 12 h -1 M⊙ and 22.5 ± 2.5 per cent of them are satellites belonging to a larger halo. The halo occupation distribution of ELGs indicates that we are sampling the galaxies in which stars form in the most efficient way, according to their stellar-to-halo mass ratio.« less

Fourier-transform i.r. gas chromatography—mass spectrometry study of varying light olefin reactivity on dealuminated ZSM-5

NASA Astrophysics Data System (ADS)

Sayed, Moein B.

Olefin oligomerization and alkylation (by methanol) of ethene, propene, and isobutene on HZSM-5 have been studied in typical conditions of the catalytic Mobil methanol to gasoline (MTG) process. This has been to identify the most likely light olefin involved as a key intermediate and the most likely mechanism by which such a light olefin propagates to gasoline in the MTG process. Reactions involving bulky intermediates are restricted within the narrow channels of ZSM-5. The oligomerization of ethene and isobutene appears to be an example of such restricted reactions. Zeolite dealumination seems to assist in overcoming the steric barrier by increasing both the zeolite pore volume and the population of the site (silanol) hosting the adsorbate. Spectral i.r. evidence reveals a role of zeolite Lewis acidity as a precursor in initiating olefin protonation by the zeolite Brønsted acidity. Both i.r. and GC—MS data consistently reveal a product distribution similar to that obtained in the MTG process, which suggests a dominant oligomerization and/or alkylation to be the mechanism leading to gasoline in the MTG process. However, the higher reactivity detected for olefin alkylation indicates alkylation to be the favoured mechanism. Propene is more likely to be a key intermediate, whereas isobutene contributes with a role being increasingly dominant over the more dealuminated ZSM-5 surfaces. Ethene, in contrast, shows poor reactivity, which can be enhanced by the zeolite dealumination.

Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

DTIC Science & Technology

2006-08-01

aryl iodide to the Grignard reagent . Treatment of the magnesium compound with allyl bromide and CuCN·2LiCl afforded benzoate 4-11, which was then...cyclization of a linear peptide by conventional coupling agents to form a new amide bond (Scheme 1-12)36,44 Some common reagents are...dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), and expensive reagents such as HATU or PyBroP, which are more efficient.44 Racemization of the chiral

Dismantlable Thermosetting Adhesives Composed of a Cross-Linkable Poly(olefin sulfone) with a Photobase Generator.

PubMed

Sasaki, Takeo; Hashimoto, Shouta; Nogami, Nana; Sugiyama, Yuichi; Mori, Madoka; Naka, Yumiko; Le, Khoa V

2016-03-02

A novel photodetachable adhesive was prepared using a photodepolymerizable cross-linked poly(olefin sulfone). A mixture of a cross-linkable poly(olefin sulfone), a cross-linking reagent, and a photobase generator functioned as a thermosetting adhesive and exhibited high adhesive strength on quartz plates comparable to that obtained for commercially available epoxy adhesives. The cured resin was stable in the absence of UV light irradiation but completely lost its adhesive strength upon exposure of glued quartz plates to UV light in conjunction with heating to 100 °C.

Cobalt Fischer-Tropsch catalysts having improved selectivity

DOEpatents

Miller, James G.; Rabo, Jule A.

1989-01-01

The promoter(s) Mn oxide or Mn oxide and Zr oxide are added to a cobalt Fischer-Tropsch catalyst combined with the molecular sieve TC-103 or TC-123 such that the resultant catalyst demonstrates improved product selectivity, stability and catalyst life. The improved selectivity is evidenced by lower methane production, higher C5+ yield and increased olefin production.

Synthesis of side-chain oxysterols and their enantiomers through cross-metathesis reactions of Δ22 steroids.

PubMed

Brownholland, David P; Covey, Douglas F

2017-05-01

A synthetic route that utilizes a cross-metathesis reaction with Δ 22 steroids has been developed to prepare sterols with varying C-27 side-chains. Natural sterols containing hydroxyl groups at the 25 and (25R)-26 positions were prepared. Enantiomers of cholesterol and (3β,25R)-26-hydroxycholesterol (27-hydroxycholesterol) trideuterated at C-19 were prepared for future biological studies. Copyright © 2017 Elsevier Inc. All rights reserved.

Hydrocarbon-stapled lipopeptides exhibit selective antimicrobial activity.

PubMed

Jenner, Zachary B; Crittenden, Christopher M; Gonzalez, Martín; Brodbelt, Jennifer S; Bruns, Kerry A

2017-05-01

Antimicrobial peptides (AMPs) occur widely in nature and have been studied for their therapeutic potential. AMPs are of interest due to the large number of possible chemical structural combinations using natural and unnatural amino acids, with varying effects on their biological activities. Using physicochemical properties from known naturally occurring amphipathic cationic AMPs, several hydrocarbon-stapled lipopeptides (HSLPs) were designed, synthesized, and tested for antimicrobial properties. Peptides were chemically modified by N-terminal acylation, C-terminal amidation, and some were hydrocarbon stapled by intramolecular olefin metathesis. The effects of peptide length, amphipathic character, and stapling on antimicrobial activity were tested against Escherichia coli, three species of Gram-positive bacteria (Staphylococcus aureus, Bacillus megaterium, and Enterococcus faecalis), and two strains of Candida albicans. Peptides were shown to disrupt liposomes of different phospholipid composition, as measured by leakage of a fluorescent compound from vesicles. Peptides with (S)-2-(4'-pentenyl)-alanine substituted for l-alanine in a reference peptide showed a marked increase in antimicrobial activity, hemolysis, and membrane disruption. Stapled peptides exhibited slightly higher antimicrobial potency; those with greatest hydrophobic character showed the greatest hemolysis and liposome leakage, but lower antimicrobial activity. The results support a model of HSLPs as membrane-disruptive AMPs with potent antimicrobial activity and relatively low hemolytic potential at biologically active peptide concentrations. © 2017 Wiley Periodicals, Inc.

Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aghamohammadi, Sogand; Reactor and Catalysis Research Center; Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir

2014-02-01

Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion.more » - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH{sub 3}-TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH{sub 3}-TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A

A DFT Study of Tungsten-Methylidene Formation on a W/ZSM-5 Zeolite: The Metathesis Active Site.

PubMed

Maihom, Thana; Probst, Michael; Limtrakul, Jumras

2015-10-26

Tungsten-methylidene formation from ethene on either the W(IV) , W(V) , or W(VI) active sites of a W/ZSM-5 zeolite is investigated by using the M06-L functional. The reaction is assumed to proceed in two steps; the first step is the [2+2] cycloaddition between ethene and the W-O active site to form an oxametallacycle intermediate. The intermediate is then decomposed to produce the W-methylidene active site from the metathesis reaction. The overall activation barrier of the reaction on W(VI) (27.3 kcal mol(-1) ) is considerably lower than the ones for W(IV) and W(V) (69.4 and 37.1 kcal mol(-1) , respectively). Moreover, the reaction involving the W(VI) site also stabilizes intermediates and products to a larger extent than the ones on the W(IV) and W(V) sites. As a result, we have demonstrated that the reaction of the W-methylidene metathesis active site is both kinetically and thermodynamically favored to occur on the W(VI) active site of the zeolite. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microchannel fabrication on cyclic olefin polymer substrates via 1064 nm Nd:YAG laser ablation

NASA Astrophysics Data System (ADS)

McCann, Ronán; Bagga, Komal; Groarke, Robert; Stalcup, Apryll; Vázquez, Mercedes; Brabazon, Dermot

2016-11-01

This paper presents a method for fabrication of microchannels on cyclic olefin polymer films that have application in the field of microfluidics and chemical sensing. Continuous microchannels were fabricated on 188-μm-thick cyclic olefin polymer substrates using a picosecond pulsed 1064 nm Nd:YAG laser. The effect of laser fluence on the microchannel morphology and dimensions was analysed via scanning electron microscopy and optical profilometry. Single laser passes were found to produce v-shaped microchannels with depths ranging from 12 μm to 47 μm and widths from 44 μm to 154 μm. The ablation rate during processing was lower than predicted theoretically. Multiple laser passes were applied to examine the ability for finer control over microchannel morphology with channel depths ranging from 22 μm to 77 μm and channel widths from 59 μm to 155 μm. For up to five repeat passes, acceptable reproducibility was found in the produced microchannel morphology. Infrared spectroscopy revealed oxidation and dehydrogenation of the polymer surface following laser ablation. These results were compared to other work conducted on cyclic olefin polymers.

A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal

NASA Astrophysics Data System (ADS)

Solowey, Douglas P.; Mane, Manoj V.; Kurogi, Takashi; Carroll, Patrick J.; Manor, Brian C.; Baik, Mu-Hyun; Mindiola, Daniel J.

2017-11-01

Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community. Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CHtBu(CH3) (PNP=N[2-P(CHMe2)2-4-methylphenyl]2-), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C4 to C8 to terminal olefins under mild conditions. This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst. We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.

A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal.

PubMed

Solowey, Douglas P; Mane, Manoj V; Kurogi, Takashi; Carroll, Patrick J; Manor, Brian C; Baik, Mu-Hyun; Mindiola, Daniel J

2017-11-01

Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community. Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CH t Bu(CH 3 ) (PNP=N[2-P(CHMe 2 ) 2 -4-methylphenyl] 2 - ), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C 4 to C 8 to terminal olefins under mild conditions. This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst. We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.

Quick and selective extraction of Z-ligustilide from Angelica sinensis using magnetic multiwalled carbon nanotubes.

PubMed

Zeng, Qiong; Jia, Yan-Wei; Xu, Pei-Li; Xiao, Meng-Wei; Liu, Yi-Ming; Peng, Shu-Lin; Liao, Xun

2015-12-01

A facile and highly efficient magnetic solid-phase extraction method has been developed for Z-ligustilide, the major therapeutic agent in Angelica sinensis. The solid-phase adsorbent material used was prepared by conjugating carbon nanotubes with magnetic Fe3 O4 nanoparticles via a hydrothermal reaction. The magnetic material showed a high affinity toward Z-ligustilide due to the π-π stacking interaction between the carbon nanotubes and Z-ligustilide, allowing a quick and selective exaction of Z-ligustilide from complex sample matrices. Factors influencing the magnetic solid-phase extraction such as the amount of the added adsorbent, adsorption and desorption time, and desorption solvent, were investigated. Due to its high extraction efficiency, this method was proved highly useful for sample cleanup/enrichment in quantitative high-performance liquid chromatography analysis. The proposed method had a linear calibration curve (R(2) = 0.9983) over the concentration between 4 ng/mL and 200 μg/mL Z-ligustilide. The accuracy of the method was determined by the recovery, which was from 92.07 to 104.02%, with the relative standard deviations >4.51%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper(II) acetate promoted intramolecular diamination of unactivated olefins.

PubMed

Zabawa, Thomas P; Kasi, Dhanalakshmi; Chemler, Sherry R

2005-08-17

A concise method for the synthesis of cyclic sulfamides and vicinal diamines is presented. This method is enabled by Cu(OAc)2 and demonstrates a new transformation for this metal. Both five- and six-membered vicinal diamine-containing heterocycles have been synthesized in good to excellent yields, and substrate-based asymmetric induction has been achieved. This is the first reported example of intramolecular diamination of olefins.

Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

PubMed

Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

2015-08-18

-site catalysts. This Account is intended to give an overview of our recent studies on organo rare-earth catalysis, in particular the synthesis and application of half-sandwich rare-earth alkyl complexes bearing monocyclopentadienyl ligands for olefin polymerization, carbometalation, and hydroarylation. Treatment of half-sandwich rare-earth dialkyl complexes having the general formula CpMR2 with an equimolar amount of an appropriate borate compound such as [Ph3C][B(C6F5)4] can generate the corresponding cationic monoalkyl species, which serve as excellent single-site catalysts for the polymerization and copolymerization of a wide range of olefin monomers such as ethylene, 1-hexene, styrene, conjugated and nonconjugated dienes, and cyclic olefins. The cationic half-sandwich rare-earth alkyl complexes can also catalyze the regio- and stereoselective alkylative alumination of alkenes and alkynes through insertion of the unsaturated C-C bond into the metal-alkyl bond followed by transmetalation between the resulting new alkyl or alkenyl species and an alkylaluminum compound. Moreover, a combination of deprotonative C-H bond activation of appropriate organic compounds such as anisoles and pyridines by the rare-earth alkyl species and insertion of alkenes into the resulting new metal-carbon bond can lead to catalytic C-H bond alkylation of the organic substrates. Most of these transformations are unique to the rare-earth catalysts with selectivity and functional group tolerance different from those of late-transition-metal catalysts.

Metal catalyzed synthesis of hyperbranched ethylene and/or .alpha.-olefin polymers

DOEpatents

Sen, Ayusman; Kim, Jang Sub; Pawlow, James H.; Murtuza, Shahid; Kacker, Smita; Wojcinski, III, Louis M.

2001-01-01

Oily hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin, and a method for their synthesis, are disclosed. The polymers have non-regular microstructures and are characterized by a ratio ({character pullout})of methyl hydrogens centered around 0.85 ppm on the 1H-NMR spectra of the polymers relative to total aliphatic hydrogens of from about 0.40 to about 0.65 for polymers derived from ethylene or butene, and a ratio ({character pullout})of from greater than 0.50 to about 0.65 for polymers derived from propylene. A method for grafting hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin onto aromatic rings in organic molecules and polymers, and the resulting grafted materials, are also disclosed. The hyperbranched polymers and grafted materials are useful, for example, as lubricants and lubricant additives.

THE SUBARU HIGH-z QUASAR SURVEY: DISCOVERY OF FAINT z ∼ 6 QUASARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kashikawa, Nobunari; Furusawa, Hisanori; Niino, Yuu

2015-01-01

We present the discovery of one or two extremely faint z ∼ 6 quasars in 6.5 deg{sup 2} utilizing a unique capability of the wide-field imaging of the Subaru/Suprime-Cam. The quasar selection was made in (i'-z{sub B} ) and (z{sub B} -z{sub R} ) colors, where z{sub B} and z{sub R} are bandpasses with central wavelengths of 8842 Å and 9841 Å, respectively. The color selection can effectively isolate quasars at z ∼ 6 from M/L/T dwarfs without the J-band photometry down to z{sub R} < 24.0, which is 3.5 mag deeper than the Sloan Digital Sky Survey (SDSS). Wemore » have selected 17 promising quasar candidates. The follow-up spectroscopy for seven targets identified one apparent quasar at z = 6.156 with M {sub 1450} = –23.10. We also identified one possible quasar at z = 6.041 with a faint continuum of M {sub 1450} = –22.58 and a narrow Lyα emission with HWHM =427 km s{sup –1}, which cannot be distinguished from Lyman α emitters. We derive the quasar luminosity function at z ∼ 6 by combining our faint quasar sample with the bright quasar samples by SDSS and CFHQS. Including our data points invokes a higher number density in the faintest bin of the quasar luminosity function than the previous estimate employed. This suggests a steeper faint-end slope than lower z, though it is yet uncertain based on a small number of spectroscopically identified faint quasars, and several quasar candidates still remain to be diagnosed. The steepening of the quasar luminosity function at the faint end does increase the expected emission rate of the ionizing photon; however, it only changes by a factor of approximately two to six. This was found to still be insufficient for the required photon budget of reionization at z ∼ 6.« less

Cobalt Fischer-Tropsch catalysts having improved selectivity

DOEpatents

Miller, James G.; Rabo, Jule A.

1989-01-01

A cobalt Fischer-Tropsch catalyst having an improved steam treated, acid extracted LZ-210 support is taught. The new catalyst system demonstrates improved product selectivity at Fischer-Tropsch reaction conditions evidenced by lower methane production, higher C.sub.5.sup.+ yield and increased olefin production.

Application of Ring-Closing Metathesis to Grb2 SH3 Domain-Binding Peptides | Center for Cancer Research

Cancer.gov

In silico-generated hypothetical interactions of a ring-closing metathesis-macrocylized peptide bound to the amino terminal SH3 domain of the growth factor receptor bound protein 2 (Grb2). The complex was derived from the NMR solution structure of the bound parent peptide, Ac-V-P-P-P-V-P-P-R-R-R-amide (Protein Data Bank: 3GBQ). The protein surface is shown as electrostatic

Thermoplastic Adhesives based on polyolefin and olefinic copolymers

NASA Astrophysics Data System (ADS)

Paul, Rituparna

2014-03-01

H.B. Fuller has been a leading global industrial adhesive manufacturer for over 125 years. It is a company with a rich history of consistently delivering adhesive innovations for enhancing product performance in the market place. H.B. Fuller technologies/products find application in several markets including packaging, personal hygiene and nonwovens, durable assembly and electronics. In this presentation, H. B. Fuller's technology innovation journey will be shared with emphasis on groundbreaking technologies/products based on polyolefin and olefin copolymers.

Catalog of candidates for quasars at 3 < z < 5.5 selected among X-Ray sources from the 3XMM-DR4 survey of the XMM-Newton observatory

NASA Astrophysics Data System (ADS)

Khorunzhev, G. A.; Burenin, R. A.; Meshcheryakov, A. V.; Sazonov, S. Yu.

2016-05-01

We have compiled a catalog of 903 candidates for type 1 quasars at redshifts 3 < z < 5.5 selected among the X-ray sources of the "serendipitous" XMM-Newton survey presented in the 3XMMDR4 catalog (the median X-ray flux is ≈5 × 10-15 erg s-1 cm-2 in the 0.5-2 keV energy band) and located at high Galactic latitudes | b| > 20° in Sloan Digital Sky Survey (SDSS) fields with a total area of about 300 deg2. Photometric SDSS data as well infrared 2MASS and WISE data were used to select the objects. We selected the point sources from the photometric SDSS catalog with a magnitude error δ mz' < 0.2 and a color i' - z' < 0.6 (to first eliminate the M-type stars). For the selected sources, we have calculated the dependences χ2( z) for various spectral templates from the library that we compiled for these purposes using the EAZY software. Based on these data, we have rejected the objects whose spectral energy distributions are better described by the templates of stars at z = 0 and obtained a sample of quasars with photometric redshift estimates 2.75 < z phot < 5.5. The selection completeness of known quasars at z spec > 3 in the investigated fields is shown to be about 80%. The normalized median absolute deviation (Δ z = | z spec - z phot|) is σ Δ z /(1+ z spec) = 0.07, while the outlier fraction is η = 9% when Δ z/(1 + z cпek.) > 0.2. The number of objects per unit area in our sample exceeds the number of quasars in the spectroscopic SDSS sample at the same redshifts approximately by a factor of 1.5. The subsequent spectroscopic testing of the redshifts of our selected candidates for quasars at 3 < z < 5.5 will allow the purity of this sample to be estimated more accurately.

Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions.

PubMed

Jia, Xiangqing; Qin, Chuan; Friedberger, Tobias; Guan, Zhibin; Huang, Zheng

2016-06-01

Polyethylene (PE) is the largest-volume synthetic polymer, and its chemical inertness makes its degradation by low-energy processes a challenging problem. We report a tandem catalytic cross alkane metathesis method for highly efficient degradation of polyethylenes under mild conditions. With the use of widely available, low-value, short alkanes (for example, petroleum ethers) as cross metathesis partners, different types of polyethylenes with various molecular weights undergo complete conversion into useful liquid fuels and waxes. This method shows excellent selectivity for linear alkane formation, and the degradation product distribution (liquid fuels versus waxes) can be controlled by the catalyst structure and reaction time. In addition, the catalysts are compatible with various polyolefin additives; therefore, common plastic wastes, such as postconsumer polyethylene bottles, bags, and films could be converted into valuable chemical feedstocks without any pretreatment.

EVIDENCE FOR THE UNIVERSALITY OF PROPERTIES OF RED-SEQUENCE GALAXIES IN X-RAY- AND RED-SEQUENCE-SELECTED CLUSTERS AT z ∼ 1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foltz, R.; Wilson, G.; DeGroot, A.

We study the slope, intercept, and scatter of the color–magnitude and color–mass relations for a sample of 10 infrared red-sequence-selected clusters at z ∼ 1. The quiescent galaxies in these clusters formed the bulk of their stars above z ≳ 3 with an age spread Δt ≳ 1 Gyr. We compare UVJ color–color and spectroscopic-based galaxy selection techniques, and find a 15% difference in the galaxy populations classified as quiescent by these methods. We compare the color–magnitude relations from our red-sequence selected sample with X-ray- and photometric-redshift-selected cluster samples of similar mass and redshift. Within uncertainties, we are unable tomore » detect any difference in the ages and star formation histories of quiescent cluster members in clusters selected by different methods, suggesting that the dominant quenching mechanism is insensitive to cluster baryon partitioning at z ∼ 1.« less

Organo-Lewis acid as cocatalyst for cationic homogenous metallocene Ziegler-Natta olefin polymerizations

DOEpatents

Marks, Tobin J.; Chen, You-Xian

2000-01-01

The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

Process for selective monoaddition to silanes containing two silicon-hydrogen bonds and products thereof

NASA Technical Reports Server (NTRS)

Crivello, James V. (Inventor)

1996-01-01

A process for the selective monoadditon of an olefin or acetylene to a siloxane which contains two reactive Si--H bonds to produce a product in which only one of the two Si--H functions has added across the olefin or acetylene is disclosed. A process for making unsymmetrical siloxanes from symmetrical dihydrosiloxanes and products of both of these processes are also disclosed. Products are represented by the formula I in which R.sup.1 and R.sup.4 are different: ##STR1##.

Design of direct-vision cyclo-olefin-polymer double Amici prism for spectral imaging.

PubMed

Wang, Lei; Shao, Zhengzheng; Tang, Wusheng; Liu, Jiying; Nie, Qianwen; Jia, Hui; Dai, Suian; Zhu, Jubo; Li, Xiujian

2017-10-20

A direct-vision Amici prism is a desired dispersion element in the value of spectrometers and spectral imaging systems. In this paper, we focus on designing a direct-vision cyclo-olefin-polymer double Amici prism for spectral imaging systems. We illustrate a designed structure: E48R/N-SF4/E48R, from which we obtain 13 deg dispersion across the visible spectrum, which is equivalent to 700 line pairs/mm grating. We construct a simulative spectral imaging system with the designed direct-vision cyclo-olefin-polymer double Amici prism in optical design software and compare its imaging performance to a glass double Amici prism in the same system. The results of spot-size RMS demonstrate that the plastic prism can serve as well as their glass competitors and have better spectral resolution.

Determination of aromatics and olefins in wide-boiling petroleum fractions

NASA Technical Reports Server (NTRS)

Spakowski, A E; Evans, A; Hibbard, R R

1950-01-01

A chromatographic method is described herein for the analysis of aromatics and olefins in wide boiling petroleum fractions. The fuel is split into four fractions: nonaromatic, intermediate, pure aromatic, and wash. The analysis, which need be run only on the intermediate cut to determine aromatics in the fuel, is based on specific dispersion. With analysis times of less than 8 hours, accuracies of 1 percent were attained.

Coupling of exothermic and endothermic reactions in oxidative conversion of natural gas into ethylene/olefins over diluted SrO/La{sub 2}O{sub 3}/SA5205 catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, V.R.; Mulla, S.A.R.

1997-09-01

In the oxidative conversion of natural gas to ethylene/lower olefins over SrO (17.3 wt.%)/La{sub 2}O{sub 3} (17.9 wt.%)/SA5205 catalyst diluted with inert solid particles (inerts/catalyst(w/w) = 2.0) in the presence of limited O{sub 2}, the exothermic oxidative conversion reactions of natural gas are coupled with the endothermic C{sub 2+} hydrocarbon thermal cracking reactions for avoiding hot spot formation and eliminating heat removal problems. Because of this, the process is operated in the most energy-efficient and safe manner. The influence of various process variables (viz. temperature, NG/O{sub 2} and steam/NG ratios in feed, and space velocity) on the conversion of carbonmore » and also of the individual hydrocarbons in natural gas, the selectivity for C{sub 2}-C{sub 4} olefins, and also on the net heat of reactions in the process has been thoroughly investigated. By carrying out the process at 800--850 C in the presence of steam (H{sub 2}O/NG {le} 0.2) and using limited O{sub 2} in the feed (NG/O{sub 2} = 12--18), high selectivity for ethylene (about 60%) or C{sub 2}-C{sub 4} olefins (above 80%) at the carbon conversion (>15%) of practical interest could be achieved at high space velocity ({ge}34,000 cm{sup 3}/g (catalyst) h), requiring no external energy and also without forming coke or tar-like products. The net heat of reactions can be controlled and the process can be made mildly exothermic or even close to thermoneutral by manipulating the O{sub 2} concentration in the feed.« less

Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions

PubMed Central

Jia, Xiangqing; Qin, Chuan; Friedberger, Tobias; Guan, Zhibin; Huang, Zheng

2016-01-01

Polyethylene (PE) is the largest-volume synthetic polymer, and its chemical inertness makes its degradation by low-energy processes a challenging problem. We report a tandem catalytic cross alkane metathesis method for highly efficient degradation of polyethylenes under mild conditions. With the use of widely available, low-value, short alkanes (for example, petroleum ethers) as cross metathesis partners, different types of polyethylenes with various molecular weights undergo complete conversion into useful liquid fuels and waxes. This method shows excellent selectivity for linear alkane formation, and the degradation product distribution (liquid fuels versus waxes) can be controlled by the catalyst structure and reaction time. In addition, the catalysts are compatible with various polyolefin additives; therefore, common plastic wastes, such as postconsumer polyethylene bottles, bags, and films could be converted into valuable chemical feedstocks without any pretreatment. PMID:27386559

An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4.

PubMed

Nicolaou, K C; Adsool, Vikrant A; Hale, Christopher R H

2010-04-02

PhI(OAc)(2) in the presence of OsO(4) (cat.) and 2,6-lutidine cleaves olefinic bonds to yield the corresponding carbonyl compounds, albeit, in some cases, with alpha-hydroxy ketones as byproduct. A more practical and clean protocol to effect oxidative cleavage of olefinic bonds involves NMO, OsO(4) (cat.), 2,6-lutidine, and PhI(OAc)(2).

Evolution of dosage compensation under sexual selection differs between X and Z chromosomes

PubMed Central

Mullon, Charles; Wright, Alison E.; Reuter, Max; Pomiankowski, Andrew; Mank, Judith E.

2015-01-01

Complete sex chromosome dosage compensation has more often been observed in XY than ZW species. In this study, using a population genetic model and the chicken transcriptome, we assess whether sexual conflict can account for this difference. Sexual conflict over expression is inevitable when mutation effects are correlated across the sexes, as compensatory mutations in the heterogametic sex lead to hyperexpression in the homogametic sex. Coupled with stronger selection and greater reproductive variance in males, this results in slower and less complete evolution of Z compared with X dosage compensation. Using expression variance as a measure of selection strength, we find that, as predicted by the model, dosage compensation in the chicken is most pronounced in genes that are under strong selection biased towards females. Our study explains the pattern of weak dosage compensation in ZW systems, and suggests that sexual selection plays a major role in shaping sex chromosome dosage compensation. PMID:26212613

Development of a ruthenium/phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide.

PubMed

Liu, Qiang; Wu, Lipeng; Fleischer, Ivana; Selent, Detlef; Franke, Robert; Jackstell, Ralf; Beller, Matthias

2014-06-02

An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-Methylpyrrolidone Hydroperoxide/Cs2 CO3 as an Excellent Reagent System for the Hydroxy-Directed Diastereoselective Epoxidation of Electron-Deficient Olefins.

PubMed

Victor, Napoleon John; Gana, Janardhanan; Muraleedharan, Kannoth Manheri

2015-10-12

This report introduces N-methylpyrrolidone hydroperoxide (NMPOOH)/base as an excellent reagent system for hydroxy-directed syn selective epoxidation of electron-deficient olefins, characterized by high diastereoselectivity, short reaction times and remarkable chemoselectivity, especially in presence of oxidatively labile nitrogen or sulfur atoms. NMPOOH also proves efficient in the oxidation of electron-deficient aromatic aldehydes, in the removal of oxazolidinone chiral auxiliary, and in the functionalization of alkenes and alkynes, showing wide application potential. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strategy Toward the Total Synthesis of Epothilones A and B

DTIC Science & Technology

1999-07-01

2-(iV-morpholino)ethanesulfonic acid ). 1 mM EGTA(1.2-di(2-aminoethoxy)ethane-/V..V..V’.Af’-tetraaceticacid). 0.5 mM MgCl2, 1 mM GTP. and 3 M... acid ), 1 mM EGTA. 0.5 nM MgCU. ImM GTP and 3M glyceropH £6- Tta concentration of tubulin in MTP was estimated to be about 85%. Assembly was...fragment projected for the olefin metathesis step. For this purpose, it would be appropriate to reach a carboxylic acid (cf. 28, Scheme 4) for

Asymmetric Total Synthesis of (-)-(3 R)-Inthomycin C.

PubMed

Balcells, Sandra; Haughey, Maxwell B; Walker, Johannes C L; Josa-Culleré, Laia; Towers, Christopher; Donohoe, Timothy J

2018-06-04

A short (10 step) and efficient (15% overall yield) synthesis of the natural product (-)-(3 R)-inthomycin C is reported. The key steps comprise three C-C bond-forming reactions: (i) a vinylogous Mukaiyama aldol, (ii) an olefin cross-metathesis reaction, and (iii) an asymmetric Mukaiyama-Kiyooka aldol. This route is notable for its brevity and has the advantage of lacking stoichiometric tin-promoted cross-coupling reactions present in previous approaches. Initial investigations on the biological activity of (-)-(3 R)-inthomycin C and structural analogues on human cancer cell lines are also described for the first time.

The Synthesis of Fragrant Natural Products from Santalum album L.: (+)-(Z)-α-Santalol and (-)-(Z)-β-Santalol.

PubMed

Birkbeck, Anthony A

2017-12-01

The synthetic challenges associated with the selective synthesis of α-Santalene (1), (Z)-α-Santalol (2), β-Santalene (3), and most importantly (Z)-β-Santalol (4) have interested the world's synthetic chemists for decades. These molecules, lovely examples of nature's exquisite creations, have been isolated from East Indian Sandalwood Oil (Santalum album L.) and have stimulated chemists to develop new and efficient methodologies to synthesize them. The synthesis and evolution of various approaches to the [2.2.1]bicycloheptane ring system present in β-Santalene (3) and the even more challenging selective synthesis of the (Z)-allylic alcohol sidechain present in both (Z)-α-Santalol (2) and ((Z)-β-Santalol (4) will be covered in this review.

An Expedient Procedure for the Oxidative Cleavage of Olefinic Bonds with PhI(OAc)2, NMO, and Catalytic OsO4

PubMed Central

Nicolaou, K. C.; Adsool, Vikrant A.; Hale, Christopher R. H.

2010-01-01

PhI(OAc)2 in the presence of OsO4 (cat.) and 2,6-lutidine cleaves olefinic bonds to yield the corresponding carbonyl compounds, albeit, in some cases, with α-hydroxy ketones as by-products. A more practical and clean protocol to effect oxidative cleavage of olefinic bonds involves NMO, OsO4 (cat.), 2,6-lutidine, and PhI(OAc)2. PMID:20192259

Nanodispersed Suspensions of Zeolite Catalysts for Converting Dimethyl Ether into Olefins

NASA Astrophysics Data System (ADS)

Kolesnichenko, N. V.; Yashina, O. V.; Ezhova, N. N.; Bondarenko, G. N.; Khadzhiev, S. N.

2018-01-01

Nanodispersed suspensions that are effective in DME conversion and stable in the reaction zone in a three-phase system (slurry reactor) are obtained from MFI zeolite commercial samples (TsVM, IK-17-1, and CBV) in liquid media via ultrasonic treatment (UST). It is found that the dispersion medium, in which ultrasound affects zeolite commercial sample, has a large influence on particle size in the suspension. UST in the aqueous medium produces zeolite nanoparticles smaller than 50 nm, while larger particles of MFI zeolite samples form in silicone or hydrocarbon oils. Spectral and adsorption data show that when zeolites undergo UST in an aqueous medium, the acid sites are redistributed on the zeolite surface and the specific surface area of the mesopores increases. Preliminary UST in aqueous media of zeolite commercial samples (TsVM, IK-17-1, and CBV) affects the catalytic properties of MFI zeolite nanodispersed suspensions. The selectivity of samples when paraffins and olefins form is largely due to superacid sites consisting of OH groups of hydroxonium ion H3O+.

OsO(4) in ionic liquid [Bmim]PF(6): a recyclable and reusable catalyst system for olefin dihydroxylation. remarkable effect of DMAP.

PubMed

Yao, Qingwei

2002-06-27

[reaction: see text] The combination of the ionic liquid [bmim]PF(6) and DMAP provides a most simple and practical approach to the immobilization of OsO(4) as catalyst for olefin dihydroxylation. Both the catalyst and the ionic liquid can be repeatedly recycled and reused in the dihydroxylation of a variety of olefins with only a very slight drop in catalyst activity.

Catalysis by cytochrome P-450 of an oxidative reaction in xenobiotic aldehyde metabolism: deformylation with olefin formation.

PubMed Central

Roberts, E S; Vaz, A D; Coon, M J

1991-01-01

As we have briefly described elsewhere, cytochrome P-450 catalyzes the oxidative deformylation of cyclohexane carboxaldehyde to yield cyclohexene and formic acid in a reaction believed to involve a peroxyhemiacetal-like adduct formed between the substrate and molecular oxygen-derived hydrogen peroxide. This reaction is a useful model for the demethylation reactions catalyzed by the steroidogenic P-450s, aromatase, and lanosterol demethylase. In the present study, the cytochrome P-450-catalyzed formation of olefinic products from a series of xenobiotic aldehydes has been demonstrated. Isobutyraldehyde and trimethylacetaldehyde, but not propionaldehyde, are converted to the predicted olefinic products, suggesting a requirement for branching at the alpha carbon. In addition, the four C5 aldehydes of similar hydrophobicity were compared for their ability to undergo the reaction. The straight-chain valeraldehyde gave no olefinic products with five different rabbit liver microsomal P-450 isozymes. However, increasing activity was seen with the other isomers in the order of isovaleraldehyde, 2-methylbutyraldehyde, and trimethylacetaldehyde, with all of the P-450 cytochromes. The catalytic rate with trimethylacetaldehyde is highest with antibiotic-inducible P-450 form 3A6, followed by phenobarbital-inducible form 2B4 and ethanol-inducible form 2E1. Citronellal, a beta-branched aldehyde that is found in many essential oils and is widely used as an odorant and a flavorant, was found to undergo the oxidative deformylation reaction to yield 2,6-dimethyl-1,5-heptadiene, but only with P-450 2B4. The oxidative cleavage reaction with olefin formation appears to be widespread, as judged by the variety of aldehydes that serve as substrates and of P-450 cytochromes that serve as catalysts. PMID:1924356

Ring-Opening Metathesis Polymerization in Aqueous Media using a Macroinitiator Approach.

PubMed

Foster, Jeffery; Varlas, Spyridon; Blackman, Lewis; Arkinstall, Lucy; O'Reilly, Rachel Kerry

2018-06-26

Water-soluble and amphiphilic polymers are of great interest to industry and academia, as they can be used in applications such as biomaterials and drug delivery. Whilst ring-opening metathesis polymerization (ROMP) is a fast and functional group tolerant methodology for the synthesis of a wide range of polymers, its full potential for the synthesis of water-soluble polymers has yet to be realized. To address this we report a general strategy for the synthesis of block copolymers in aqueous milieu using a commercially available ROMP catalyst and a macroinitiator approach. This allows for excellent control in the preparation of block copolymers in water. If the second monomer is chosen such that it forms a water-insoluble polymer, polymerization-induced self-assembly (PISA) occurs and a variety of self-assembled nano-object morphologies can be accessed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Olefin polymerization from single site catalysts confined within porous media

NASA Astrophysics Data System (ADS)

Kasi, Rajeswari M.

Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

Homogeneous dihydroxylation of olefins catalyzed by OsO(4)(2-) immobilized on a dendritic backbone with a tertiary nitrogen at its core position.

PubMed

Fujita, Ken-Ichi; Inoue, Kensuke; Tsuchimoto, Teruhisa; Yasuda, Hiroyuki

2012-01-01

OsO(4)(2-) immobilized on a poly(benzyl ether) dendrimer with a tertiary nitrogen at its core position efficiently catalyzed the homogeneous dihydroxylation of olefins with a low level of osmium leaching. The dendritic osmium catalyst could be applied to the wide range of olefins. Furthermore, the dendritic osmium catalyst was recovered by reprecipitation and then reused up to five times.

Major merging history in CANDELS. I. Evolution of the incidence of massive galaxy-galaxy pairs from z = 3 to z ˜ 0

NASA Astrophysics Data System (ADS)

Mantha, Kameswara Bharadwaj; McIntosh, Daniel H.; Brennan, Ryan; Ferguson, Henry C.; Kodra, Dritan; Newman, Jeffrey A.; Rafelski, Marc; Somerville, Rachel S.; Conselice, Christopher J.; Cook, Joshua S.; Hathi, Nimish P.; Koo, David C.; Lotz, Jennifer M.; Simmons, Brooke D.; Straughn, Amber N.; Snyder, Gregory F.; Wuyts, Stijn; Bell, Eric F.; Dekel, Avishai; Kartaltepe, Jeyhan; Kocevski, Dale D.; Koekemoer, Anton M.; Lee, Seong-Kook; Lucas, Ray A.; Pacifici, Camilla; Peth, Michael A.; Barro, Guillermo; Dahlen, Tomas; Finkelstein, Steven L.; Fontana, Adriano; Galametz, Audrey; Grogin, Norman A.; Guo, Yicheng; Mobasher, Bahram; Nayyeri, Hooshang; Pérez-González, Pablo G.; Pforr, Janine; Santini, Paola; Stefanon, Mauro; Wiklind, Tommy

2018-04-01

The rate of major galaxy-galaxy merging is theoretically predicted to steadily increase with redshift during the peak epoch of massive galaxy development (1 ≤ z ≤ 3). We use close-pair statistics to objectively study the incidence of massive galaxies (stellar M1 > 2 × 1010 M⊙) hosting major companions (1 ≤ M1/M2 ≤ 4; i.e. <4:1) at six epochs spanning 0 < z < 3. We select companions from a nearly complete, mass-limited (≥5 × 109 M⊙) sample of 23 696 galaxies in the five Cosmic Assembly Near-Infrared Deep Extragalactic Legacy Survey fields and the Sloan Digital Sky Survey. Using 5-50 kpc projected separation and close redshift proximity criteria, we find that the major companion fraction fmc(z) based on stellar mass-ratio (MR) selection increases from 6 per cent (z ˜ 0) to 16 per cent (z ˜ 0.8), then turns over at z ˜ 1 and decreases to 7 per cent (z ˜ 3). Instead, if we use a major F160W flux-ratio (FR) selection, we find that fmc(z) increases steadily until z = 3 owing to increasing contamination from minor (MR > 4:1) companions at z > 1. We show that these evolutionary trends are statistically robust to changes in companion proximity. We find disagreements between published results are resolved when selection criteria are closely matched. If we compute merger rates using constant fraction-to-rate conversion factors (Cmerg,pair = 0.6 and Tobs,pair = 0.65 Gyr), we find that MR rates disagree with theoretical predictions at z > 1.5. Instead, if we use an evolving Tobs,pair(z) ∝ (1 + z)-2 from Snyder et al., our MR-based rates agree with theory at 0 < z < 3. Our analysis underscores the need for detailed calibration of Cmerg,pair and Tobs,pair as a function of redshift, mass, and companion selection criteria to better constrain the empirical major merger history.

The Lyman Continuum Escape Fraction of Emission Line-selected z ∼ 2.5 Galaxies Is Less Than 15%

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rutkowski, Michael J.; Hayes, Matthew; Scarlata, Claudia

Recent work suggests that strong emission line, star-forming galaxies (SFGs) may be significant Lyman continuum leakers. We combine archival Hubble Space Telescope broadband ultraviolet and optical imaging (F275W and F606W, respectively) with emission line catalogs derived from WFC3 IR G141 grism spectroscopy to search for escaping Lyman continuum (LyC) emission from homogeneously selected z ∼ 2.5 SFGs. We detect no escaping Lyman continuum from SFGs selected on [O ii] nebular emission ( N = 208) and, within a narrow redshift range, on [O iii]/[O ii]. We measure 1 σ upper limits to the LyC escape fraction relative to the non-ionizingmore » UV continuum from [O ii] emitters, f {sub esc} ≲ 5.6%, and strong [O iii]/[O ii] > 5 ELGs, f {sub esc} ≲ 14.0%. Our observations are not deep enough to detect f {sub esc} ∼ 10% typical of low-redshift Lyman continuum emitters. However, we find that this population represents a small fraction of the star-forming galaxy population at z ∼ 2. Thus, unless the number of extreme emission line galaxies grows substantially to z ≳ 6, such galaxies may be insufficient for reionization. Deeper survey data in the rest-frame ionizing UV will be necessary to determine whether strong line ratios could be useful for pre-selecting LyC leakers at high redshift.« less

High performance optical materials cyclo olefin polymer ZEONEX

NASA Astrophysics Data System (ADS)

Obuchi, Kazuyuki; Komatsu, Masaaki; Minami, Koji

2007-09-01

ZEON CORPORATION developed innovative optical plastic Cyclo Olefin Polymer (COP), ZEONEX (R) with own technology in 1990 then started commercial production of ZEONEX (R) for optical applications with its very unique properties such as high light transmission, low birefringence, low water absorption, and high glass-transition temperature etc. ZEONEX (R) exhibits outstanding optical performance even under high humidity and temperature conditions. In order to meet increasing requirements of optical market, ZEON CORPORATION newly developed ZEONEX (R)F52R which has high glass-transition temperature 156 deg. C and shows the feature of very low focal length change after high-temperature and high-humidity test.

Heteropolytungstate nanoparticles: Microemulsion-mediated preparation and investigation of their catalytic activity in the epoxidation of olefins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com; Ghorbani, M.

2016-04-15

Highlights: • Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles were synthesized by using microemulsion system. • The nanoparticles have uniform size of about 25 nm and spherical morphologies. • The prepared nanoparticles act as reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}. - Abstract: Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles (Q = cetyltrimethylammonium cation) were synthesized in water-in-oil (w/o) microemulsion consisted of water/cetyltrimethylammonium bromide/n-butanol/isooctane. Reaction of Na{sub 2}WO{sub 4}, Na{sub 2}HPO{sub 4} and hydrochloric acid within water containing nanoreactors of reverse micelles resulted in the preparation of Q{sub 3}PW{sub 12}O{sub 40} nanoparticles. The resultant nanoparticles weremore » analyzed by physicochemical methods such as FT-IR spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, thermogravimetric analyses (TGA-DTA), scanning and transmission electron microscopy and atomic force microscopy which show nearly uniform spherical nanoparticles with size of about 15 nm. Finally, catalytic activity of the Q{sub 3}PW{sub 12}O{sub 40} nanoparticles was examined in the epoxidation of olefins with H{sub 2}O{sub 2}. The prepared nanoparticles acted as recoverable and reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}.« less

Coke formation and carbon atom economy of methanol-to-olefins reaction.

PubMed

Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

2012-05-01

The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Titanium compounds as catalysts of higher alpha-olefin-based super-high-molecular polymers synthesis

NASA Astrophysics Data System (ADS)

Konovalov, K. B.; Kazaryan, M. A.; Manzhay, V. N.; Vetrova, O. V.

2016-01-01

The synthesis of polymers of 10 million or more molecular weight is a difficult task even in a chemical lab. Higher α-olefin-based polymer agents of such kind have found a narrow but quite important niche, the reduction of drag in the turbulent flow of hydrocarbon fluids such as oil and oil-products. In its turn, searching for a catalytic system capable to produce molecules of such a high length and to synthesize polymers of a low molecular-mass distribution is part of a global task of obtaining a high-quality product. In this paper we had observed a number of industrial catalysts with respect to their suitability for higher poly-α- olefins synthesis. A number samples representing copolymers of 1-hexene with 1-decene obtained on a previous generation catalyst, a microsphere titanium chloride catalytic agent had been compared to samples synthesized using a titanium-magnesium catalyst both in solution and in a polymer medium.

RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.

EPA Science Inventory

In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

Stereoselective protecting group free synthesis of D,L-gulose ethyl glycoside via multicomponent enyne cross metathesis--hetero Diels-Alder reaction.

PubMed

Castagnolo, Daniele; Botta, Lorenzo; Botta, Maurizio

2009-07-27

An efficient and stereoselective synthesis of D,L-gulose was described. The key step of the synthetic route is represented by a multicomponent enyne cross metathesis-hetero Diels-Alder reaction which allows the formation of the pyran ring from cheap and commercially available substrates in a single synthetic step. The synthesis of D,L-gulose was accomplished without the use of protecting groups making this approach highly desirable also in terms of atom economy.

New synthesis of artepillin C, a prenylated phenol, utilizing lipase-catalyzed regioselective deacetylation as the key step.

PubMed

Yashiro, Kazuki; Hanaya, Kengo; Shoji, Mitsuru; Sugai, Takeshi

2015-01-01

We have synthesized artepillin C, a diprenylated p-hydroxycinnamate originally isolated from Brazilian propolis and exhibiting antioxidant and antitumor activities, from 2,6-diallylphenol. Replacement of the terminal vinyl with 2,2-dimethylvinyl group by olefin cross-metathesis and subsequent transformation yielded 2,6-diprenyl-1,4-hydroquinone diacetate. Candida antarctica lipase B-catalyzed deacetylation in 2-propanol regioselectively removed the less hindered acetyl group to give 2,6-diprenyl-1,4-hydroquinone 1-monoacetate. After triflation of the liberated 4-hydroxy group, a three-carbon side chain was introduced by palladium-mediated alkenylation with methyl acrylate. Final hydrolysis of the esters furnished artepillin C.

A NEW INFRARED COLOR CRITERION FOR THE SELECTION OF 0 < z < 7 AGNs: APPLICATION TO DEEP FIELDS AND IMPLICATIONS FOR JWST SURVEYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Messias, H.; Afonso, J.; Salvato, M.

2012-08-01

It is widely accepted that observations at mid-infrared (mid-IR) wavelengths enable the selection of galaxies with nuclear activity, which may not be revealed even in the deepest X-ray surveys. Many mid-IR color-color criteria have been explored to accomplish this goal and tested thoroughly in the literature. Besides missing many low-luminosity active galactic nuclei (AGNs), one of the main conclusions is that, with increasing redshift, the contamination by non-active galaxies becomes significant (especially at z {approx}> 2.5). This is problematic for the study of the AGN phenomenon in the early universe, the main goal of many of the current and futuremore » deep extragalactic surveys. In this work new near- and mid-IR color diagnostics are explored, aiming for improved efficiency-better completeness and less contamination-in selecting AGNs out to very high redshifts. We restrict our study to the James Webb Space Telescope wavelength range (0.6-27 {mu}m). The criteria are created based on the predictions by state-of-the-art galaxy and AGN templates covering a wide variety of galaxy properties, and tested against control samples with deep multi-wavelength coverage (ranging from the X-rays to radio frequencies). We show that the colors K{sub s} - [4.5], [4.5] - [8.0], and [8.0] - [24] are ideal as AGN/non-AGN diagnostics at, respectively, z {approx}< 1, 1 {approx}< z {approx}< 2.5, and z {approx}> 2.5-3. However, when the source redshift is unknown, these colors should be combined. We thus develop an improved IR criterion (using K{sub s} and IRAC bands, KI) as a new alternative at z {approx}< 2.5. KI does not show improved completeness (50%-60% overall) in comparison to commonly used Infrared Array Camera (IRAC) based AGN criteria, but is less affected by non-AGN contamination (revealing a >50%-90% level of successful AGN selection). We also propose KIM (using K{sub s} , IRAC, and MIPS 24 {mu}m bands, KIM), which aims to select AGN hosts from local distances to as

Prilezhaev dihydroxylation of olefins in a continuous flow process.

PubMed

van den Broek, Bas A M W; Becker, René; Kössl, Florian; Delville, Mariëlle M E; Nieuwland, Pieter J; Koch, Kaspar; Rutjes, Floris P J T

2012-02-13

Epoxidation of both terminal and non-terminal olefins with peroxy acids is a well-established and powerful tool in a wide variety of chemical processes. In an additional step, the epoxide can be readily converted into the corresponding trans-diol. Batch-wise scale-up, however, is often troublesome because of the thermal instability and explosive character of the peroxy acids involved. This article describes the design and semi-automated optimization of a continuous flow process and subsequent scale-up to preparative production volumes in an intrinsically safe manner. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly selective water channel activity measured by voltage clamp: analysis of planar lipid bilayers reconstituted with purified AqpZ.

PubMed

Pohl, P; Saparov, S M; Borgnia, M J; Agre, P

2001-08-14

Aquaporins are membrane channels selectively permeated by water or water plus glycerol. Conflicting reports have described ion conductance associated with some water channels, raising the question of whether ion conductance is a general property of the aquaporin family. To clarify this question, a defined system was developed to simultaneously measure water permeability and ion conductance. The Escherichia coli water channel aquaporin-Z (AqpZ) was studied, because it is a highly stable tetramer. Planar lipid bilayers were formed from unilamellar vesicles containing purified AqpZ. The hydraulic conductivity of bilayers made from the total extract of E. coli lipids increased 3-fold if reconstituted with AqpZ, but electric conductance was unchanged. No channel activity was detected under voltage-clamp conditions, indicating that less than one in 10(9) transport events is electrogenic. Microelectrode measurements were simultaneously undertaken adjacent to the membrane. Changes in sodium concentration profiles accompanying transmembrane water flow permitted calculation of the activation energies: 14 kcal/mol for protein-free lipid bilayers and 4 kcal/mol for lipid bilayers containing AqpZ. Neither the water permeability nor the electric conductivity exhibited voltage dependence. This sensitive system demonstrated that AqpZ is permeated by water but not charged ions and should permit direct analyses of putative electrogenic properties of other aquaporins.

Catalyst for converting synthesis gas to light olefins

DOEpatents

Rao, V. Udaya S.; Gormley, Robert J.

1982-01-01

A catalyst and process for making same useful in the catalytic hydrogenation of carbon monoxide in which a silicalite support substantially free of aluminum is soaked in an aqueous solution of iron and potassium salts wherein the iron and potassium are present in concentrations such that the dried silicalite has iron present in the range of from about 5 to about 25 percent by weight and has potassium present in an amount not less than about 0.2 percent by weight, and thereafter the silicalite is dried and combined with amorphous silica as a binder for pellets, the catalytic pellets are used to convert synthesis gas to C.sub.2 -C.sub.4 olefins.

Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

PubMed

Nash, Aaron; Soheili, Arash; Tambar, Uttam K

2013-09-20

Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

The evolution of the intracluster medium metallicity in Sunyaev Zel'dovich-selected galaxy clusters at 0 < z < 1.5

DOE PAGES

McDonald, M.; Bulbul, E.; Haan, T. de; ...

2016-07-27

Here, we present the results of an X-ray spectral analysis of 153 galaxy clusters observed with the Chandra, XMM-Newton, and Suzaku space telescopes. These clusters, which span 0 < z < 1.5, were drawn from a larger, mass-selected sample of galaxy clusters discovered in the 2500 square degree South Pole Telescope Sunyaev Zel'dovich (SPT-SZ) survey. With a total combined exposure time of 9.1 Ms, these data yield the strongest constraints to date on the evolution of the metal content of the intracluster medium (ICM). We find no evidence for strong evolution in the global (r < R 500) ICM metallicity (dZ/dz = –0.06 ± 0.04 Z ⊙), with a mean value at z = 0.6 ofmore » $$\\langle Z\\rangle =0.23\\pm 0.01$$ Z ⊙ and a scatter of σ Z = 0.08 ± 0.01 Z ⊙. These results imply that the emission-weighted metallicity has not changed by more than 40% since z = 1 (at 95% confidence), consistent with the picture of an early (z > 1) enrichment. We find, in agreement with previous works, a significantly higher mean value for the metallicity in the centers of cool core clusters versus non-cool core clusters. We find weak evidence for evolution in the central metallicity of cool core clusters (dZ/dz = –0.21 ± 0.11 Z ⊙), which is sufficient to account for this enhanced central metallicity over the past ~10 Gyr. We find no evidence for metallicity evolution outside of the core (dZ/dz = –0.03 ± 0.06 Z ⊙), and no significant difference in the core-excised metallicity between cool core and non-cool core clusters. This suggests that strong radio-mode active galactic nucleus feedback does not significantly alter the distribution of metals at $$r\\gt 0.15{R}_{500}$$. Given the limitations of current-generation X-ray telescopes in constraining the ICM metallicity at z > 1, significant improvements on this work will likely require next-generation X-ray missions.« less

Reactivity of the Ni-->B dative sigma-bond in the nickel boratrane compounds [kappa4-B(mimBut)3]NiX (X=Cl, OAc, NCS, N3): synthesis of a series of B-functionalized tris(2-mercapto-1-tert-butylimidazolyl)borato complexes, [YTmBut)]NiZ.

PubMed

Pang, Keliang; Tanski, Joseph M; Parkin, Gerard

2008-02-28

The nickel boratrane complexes [kappa4-B(mimBut))3]Ni(kappa1-OAc), [kappa4-B(mimBut)3]NiNCS and [kappa4-B(mimBut)3]NiN3 are obtained via metathesis of the chloride ligand of [kappa4-B(mimBut)3]NiCl with TlOAc, KSCN and NaN3, respectively; the Ni-->B bond in these complexes is a site of reactivity, thereby providing a means of synthesizing nickel complexes that feature B-functionalized tris(mercaptoimidazolyl)borate derivatives, [YTmBut]NiZ.

Artificial Informational Polymers and Nanomaterials from Ring-Opening Metathesis Polymerization

NASA Astrophysics Data System (ADS)

James, Carrie Rae

Inspired by naturally occurring polymers (DNA, polypeptides, polysaccharides, etc.) that can self-assemble on the nanoscale into complex, information-rich architectures, we have synthesized nucleic acid based polymers using ROMP. These polymers were synthesized using a graft-through strategy, whereby nucleic acids bearing a strained cyclic olefin were directly polymerized. This is the first example of the graft-through polymerization of nucleic acids. Our approach takes advantage of non-charged peptide nucleic acids (PNAs) as elements to incorporate into ROMP polymer backbones. PNA is a synthetic nucleic acid analogue known for its increased affinity and specificity for complementary DNA or RNA. To accomplish the graft-through polymerization of PNA, we conjugated PNA to strained cyclic olefins using solid phase peptide conjugation chemistry. These PNA monomers were then directly polymerized into homo and block copolymers forming brushes, or comb-like arrangements, of information. Block copolymer amphiphiles of these materials, where the PNA brush served as the hydrophilic portion, were capable of self-assembly into spherical nanoparticles (PNA NPs). These PNA NPs were then studied with respect to their ability to hybridize complementary DNA sequences, as well as their ability to undergo cellular internalization. PNA NPs consisting of densely packed brushes of nucleic acids possessed increased thermal stability when mixed with their complementary DNA sequence, indicating a greater DNA binding affinity over their unpolymerized PNA counterparts. In addition, by arranging the PNA into dense brushes at the surface of the nanoparticle, Cy5.5 labeled PNA NPs were able to undergo cellular internalization into HeLa cells without the need for an additional cellular delivery device. Importantly, cellular internalization of PNA has remained a significant challenge in the literature due to the neutrally charged amino-ethyl glycine backbone of PNA. Therefore, this represents a

zCOSMOS: A Large VLT/VIMOS Redshift Survey Covering 0 < z < 3 in the COSMOS Field

NASA Astrophysics Data System (ADS)

Lilly, S. J.; Le Fèvre, O.; Renzini, A.; Zamorani, G.; Scodeggio, M.; Contini, T.; Carollo, C. M.; Hasinger, G.; Kneib, J.-P.; Iovino, A.; Le Brun, V.; Maier, C.; Mainieri, V.; Mignoli, M.; Silverman, J.; Tasca, L. A. M.; Bolzonella, M.; Bongiorno, A.; Bottini, D.; Capak, P.; Caputi, K.; Cimatti, A.; Cucciati, O.; Daddi, E.; Feldmann, R.; Franzetti, P.; Garilli, B.; Guzzo, L.; Ilbert, O.; Kampczyk, P.; Kovac, K.,; Lamareille, F.; Leauthaud, A.; Le Borgne, J.-F.; McCracken, H. J.; Marinoni, C.; Pello, R.; Ricciardelli, E.; Scarlata, C.; Vergani, D.; Sanders, D. B.; Schinnerer, E.; Scoville, N.; Taniguchi, Y.; Arnouts, S.; Aussel, H.; Bardelli, S.; Brusa, M.; Cappi, A.; Ciliegi, P.; Finoguenov, A.; Foucaud, S.; Franceschini, A.; Halliday, C.; Impey, C.; Knobel, C.; Koekemoer, A.; Kurk, J.; Maccagni, D.; Maddox, S.; Marano, B.; Marconi, G.; Meneux, B.; Mobasher, B.; Moreau, C.; Peacock, J. A.; Porciani, C.; Pozzetti, L.; Scaramella, R.; Schiminovich, D.; Shopbell, P.; Smail, I.; Thompson, D.; Tresse, L.; Vettolani, G.; Zanichelli, A.; Zucca, E.

2007-09-01

zCOSMOS is a large-redshift survey that is being undertaken in the COSMOS field using 600 hr of observation with the VIMOS spectrograph on the 8 m VLT. The survey is designed to characterize the environments of COSMOS galaxies from the 100 kpc scales of galaxy groups up to the 100 Mpc scale of the cosmic web and to produce diagnostic information on galaxies and active galactic nuclei. The zCOSMOS survey consists of two parts: (1) zCOSMOS-bright, a magnitude-limited I-band IAB<22.5 sample of about 20,000 galaxies with 0.1<z<1.2 covering the whole 1.7 deg2 COSMOS ACS field, for which the survey parameters at z~0.7 are designed to be directly comparable to those of the 2dFGRS at z~0.1 and (2) zCOSMOS-deep, a survey of approximately 10,000 galaxies selected through color-selection criteria to have 1.4<z<3.0, within the central 1 deg 2. This paper describes the survey design and the construction of the target catalogs and briefly outlines the observational program and the data pipeline. In the first observing season, spectra of 1303 zCOSMOS-bright targets and 977 zCOSMOS-deep targets have been obtained. These are briefly analyzed to demonstrate the characteristics that may be expected from zCOSMOS, and particularly zCOSMOS-bright, when it is finally completed between 2008 and 2009. The power of combining spectroscopic and photometric redshifts is demonstrated, especially in correctly identifying the emission line in single-line spectra and in determining which of the less reliable spectroscopic redshifts are correct and which are incorrect. These techniques bring the overall success rate in the zCOSMOS-bright so far to almost 90% and to above 97% in the 0.5<z<0.8 redshift range. Our zCOSMOS-deep spectra demonstrate the power of our selection techniques to isolate high-redshift galaxies at 1.4<z<3.0 and of VIMOS to measure their redshifts using ultraviolet absorption lines. Based on observations undertaken at the European Southern Observatory (ESO) Very Large Telescope

Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

DOE PAGES

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

2018-01-17

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the presentmore » case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M 3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.« less

Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the presentmore » case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M 3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.« less

Stereochemistry of C18 monounsaturated cork suberin acids determined by spectroscopic techniques including (1) H-NMR multiplet analysis of olefinic protons.

PubMed

Santos, Sara; Graça, José

2014-01-01

Suberin is a biopolyester responsible for the protection of secondary plant tissues, and yet its molecular structure remains unknown. The C18:1 ω-hydroxyacid and the C18:1 α,ω-diacid are major monomers in the suberin structure, but the configuration of the double bond remains to be elucidated. To unequivocally define the configuration of the C18:1 suberin acids. Pure C18:1 ω-hydroxyacid and C18:1 α,ω-diacid, isolated from cork suberin, and two structurally very close C18:1 model compounds of known stereochemistry, methyl oleate and methyl elaidate, were analysed by NMR spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopy, and GC-MS. The GC-MS analysis showed that both acids were present in cork suberin as only one geometric isomer. The analysis of dimethyloxazoline (DMOX) and picolinyl derivatives proved the double bond position to be at C-9. The FTIR spectra were concordant with a cis-configuration for both suberin acids, but their unambiguous stereochemical assignment came from the NMR analysis: (i) the chemical shifts of the allylic (13) C carbons were shielded comparatively to the trans model compound, and (ii) the complex multiplets of the olefinic protons could be simulated only with (3) JHH and long-range (4) JHH coupling constants typical of a cis geometry. The two C18:1 suberin acids in cork are (Z)-18-hydroxyoctadec-9-enoic acid and (Z)-octadec-9-enedoic acid. Copyright © 2013 John Wiley & Sons, Ltd.

The active galactic nucleus population in X-ray-selected galaxy groups at 0.5 < Z < 1.1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oh, Semyeong; Woo, Jong-Hak; Matsuoka, Kenta

2014-07-20

We use Chandra data to study the incidence and properties of active galactic nuclei (AGNs) in 16 intermediate redshift (0.5 < z < 1.1) X-ray-selected galaxy groups in the Chandra Deep Field-South. We measure an AGN fraction of f(L{sub X,H}>10{sup 42};M{sub R}<−20)=8.0{sub −2.3}{sup +3.0}% at z-bar ∼0.74, approximately a factor of two higher than the AGN fraction found for rich clusters at comparable redshift. This extends the trend found at low redshift for groups to have higher AGN fractions than clusters. Our estimate of the AGN fraction is also more than a factor of three higher than that of lowmore » redshift X-ray-selected groups. Using optical spectra from various surveys, we also constrain the properties of emission-line selected AGNs in these groups. In contrast to the large population of X-ray AGNs (N(L{sub X,{sub H}} > 10{sup 41} erg s{sup –1}) = 25), we find only four emission-line AGNs, three of which are also X-ray bright. Furthermore, most of the X-ray AGNs in our groups are optically dull (i.e., lack strong emission-lines), similar to those found in low redshift X-ray groups and clusters of galaxies. This contrasts with the AGN population found in low redshift optically selected groups which are dominated by emission-line AGNs. The differences between the optically and X-ray-selected AGNs populations in groups are consistent with a scenario where most AGNs in the densest environments are currently in a low accretion state.« less

SHARDS: A Global View of the Star Formation Activity at z ~ 0.84 and z ~ 1.23

NASA Astrophysics Data System (ADS)

Cava, Antonio; Pérez-González, Pablo G.; Eliche-Moral, M. Carmen; Ricciardelli, Elena; Vidal-García, Alba; Alcalde Pampliega, Belen; Alonso-Herrero, Almudena; Barro, Guillermo; Cardiel, Nicolas; Cenarro, A. Javier; Charlot, Stephane; Daddi, Emanuele; Dessauges-Zavadsky, Miroslava; Domínguez Sánchez, Helena; Espino-Briones, Nestor; Esquej, Pilar; Gallego, Jesus; Hernán-Caballero, Antonio; Huertas-Company, Marc; Koekemoer, Anton M.; Muñoz-Tunon, Casiana; Rodriguez-Espinosa, Jose M.; Rodríguez-Muñoz, Lucia; Tresse, Laurence; Villar, Victor

2015-10-01

In this paper, we present a comprehensive analysis of star-forming galaxies (SFGs) at intermediate redshifts (z ˜ 1). We combine the ultra-deep optical spectro-photometric data from the Survey for High-z Absorption Red and Dead Sources (SHARDS) with deep UV-to-FIR observations in the GOODS-N field. Exploiting two of the 25 SHARDS medium-band filters, F687W17 and F823W17, we select [O ii] emission line galaxies at z ˜ 0.84 and z ˜ 1.23 and characterize their physical properties. Their rest-frame equivalent widths (EWrf([O ii])), line fluxes, luminosities, star formation rates (SFRs), and dust attenuation properties are investigated. The evolution of EWrf([O ii]) closely follows the SFR density evolution of the universe, with a trend of EWrf([O ii]) \\propto (1 + z)3 up to redshift z ≃ 1, followed by a possible flattening. The SF properties of the galaxies selected on the basis of their [O ii] emission are compared with complementary samples of SFGs selected by their MIR and FIR emission, and also with a general mass-selected sample of galaxies at the same redshifts. We demonstrate observationally that the UVJ diagram (or, similarly, a cut in the specific SFR) is only partially able to distinguish the quiescent galaxies from the SFGs. The SFR-M* relation is investigated for the different samples, yielding a logarithmic slope ˜1, in good agreement with previous results. The dust attenuations derived from different SFR indicators (UV(1600), UV(2800), [O ii], IR) are compared and show clear trends with respect to both the stellar mass and total SFR, with more massive and highly star-forming galaxies being affected by stronger dust attenuation.

(3Z,6Z,9Z,12Z,15Z)-Pentacosapentaene and (Z) -11-Hexadecenyl Acetate: sex attractant blend for Dioryctria amatella (Lepidoptera: Pyralidae).

Treesearch

Daniel Miller; Jocelyn Millar; Alex Mangini; Christopher Crowe; Gary Grant

2010-01-01

In 2006-2008, we tested (3Z,6Z,9Z,12Z,15Z)-pentacosapentaene (pentaene) with the pheromone components (Z)-11-hexadecenyl acetate (Z11-16:Ac) and (Z)-9-tetradecenyl acetate (Z9-14:Ac), as sex attractants for four sympatric species of coneworms, Dioryctria Zeller (Lepidoptera: Pyralidae) in slash (Pinus elliottii Engelm.) and...

Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae.

PubMed

Jongedijk, Esmer; Cankar, Katarina; Ranzijn, Jorn; van der Krol, Sander; Bouwmeester, Harro; Beekwilder, Jules

2015-01-01

Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a (+)-limonene synthase from Citrus limon. Both proteins were expressed either with their native plastid targeting signal or in a truncated form in which the plastidial sorting signal was removed. The yeast host strain for expression was AE9 K197G, which expresses a mutant Erg20 enzyme. This enzyme catalyses the formation of geranyl diphosphate, which is the precursor for monoterpenes. Several methods were tested to capture limonene produced by the yeast. Extraction from the culture medium by pentane, or by the addition of CaCl2 followed by solid-phase micro-extraction, did not lead to detectable limonene, indicating that limonene is rapidly lost from the culture medium. Volatile terpenes such as limonene may also be trapped in a dodecane phase added to the medium during fermentation. This method resulted in recovery of 0.028 mg/l (+)-limonene and 0.060 mg/l (-)-limonene in strains using the truncated Citrus and Perilla synthases, respectively. Trapping the headspace during culture of the limonene synthase-expressing strains resulted in higher titres, at 0.12 mg/l (+)-limonene and 0.49 mg/l (-)-limonene. These results show that the volatile properties of the olefins produced require specific methods for efficient recovery of these molecules from biotechnological production systems. Copyright © 2014 John Wiley & Sons, Ltd.

Exploring the boundary between aromatic and olefinic character: Bad news for second-order perturbation theory and density functional schemes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sulzbach, H.M.; Schaefer, H.F. III; Klopper, W.

1996-04-10

The question whether [10]annulene prefers olefinic structures with alternate single and double bonds or aromatic structures like all other small to medium sized uncharged (4n + 2){pi} electron homologs (e.g. benzene, [14]annulene) has been controversial for more than 20 years. Our new results suggest that only the high-order correlated methods will be able to correctly predict the [10]annulene potential energy surface. The UNO-CAS results and the strong oscillation of the MP series show that nondynamical electron correlation is important. Consequently, reliable results can only be expected at the highest correlated levels like CCSD(T) method, which predicts the olefinic twist structuremore » to be lower in energy by 3-7 kcal/mol. This prediction that the twist structure is lower in energy is supported by (a) the MP2-R12 method, which shows that large basis sets favor the olefinic structure relative to the aromatic, and (b) the fact that both structures are about equally affected by nondynamical electron correlation. We conclude that [10]annulene is a system which cannot be described adequately by either second-order Moller-Plesset perturbation theory or density functional methods. 13 refs., 3 tabs.« less

Electrophilic Pt(II) Complexes: Precision Instruments for the Initiation of Transformations Mediated by the Cation–Olefin Reaction

PubMed Central

2015-01-01

A discontinuity exists between the importance of the cation–olefin reaction as the principal C–C bond forming reaction in terpene biosynthesis and the synthetic tools for mimicking this reaction under catalyst control; that is, having the product identity, stereochemistry, and functionality under the control of a catalyst. The main reason for this deficiency is that the cation–olefin reaction starts with a reactive intermediate (a carbocation) that reacts exothermically with an alkene to reform the reactive intermediate; not to mention that reactive intermediates can also react in nonproductive fashions. In this Account, we detail our efforts to realize catalyst control over this most fundamental of reactions and thereby access steroid like compounds. Our story is organized around our progress in each component of the cascade reaction: the metal controlled electrophilic initiation, the propagation and termination of the cyclization (the cyclase phase), and the turnover deplatinating events. Electrophilic Pt(II) complexes efficiently initiate the cation–olefin reaction by first coordinating to the alkene with selection rules that favor less substituted alkenes over more substituted alkenes. In complex substrates with multiple alkenes, this preference ensures that the least substituted alkene is always the better ligand for the Pt(II) initiator, and consequently the site at which all electrophilic chemistry is initiated. This control element is invariant. With a suitably electron deficient ligand set, the catalyst then activates the coordinated alkene to intramolecular addition by a second alkene, which initiates the cation–olefin reaction cascade and generates an organometallic Pt(II)-alkyl. Deplatination by a range of mechanisms (β-H elimination, single electron oxidation, two-electron oxidation, etc.) provides an additional level of control that ultimately enables A-ring functionalizations that are orthogonal to the cyclase cascade. We particularly

Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift† †Electronic supplementary information (ESI) available: Experimental and computational details, NMR spectra, results of NMR calculations and NCS analysis, graphical representation of shielding tensors, molecular orbital diagrams of selected compounds, optimized structures for all calculated species. See DOI: 10.1039/c7sc05039a

PubMed Central

Gordon, Christopher P.; Yamamoto, Keishi; Searles, Keith; Shirase, Satoru

2018-01-01

Metal alkylidenes, which are key organometallic intermediates in reactions such as olefination or alkene and alkane metathesis, are typically generated from metal dialkyl compounds [M](CH2R)2 that show distinctively deshielded chemical shifts for their α-carbons. Experimental solid-state NMR measurements combined with DFT/ZORA calculations and a chemical shift tensor analysis reveal that this remarkable deshielding originates from an empty metal d-orbital oriented in the M–Cα–Cα′ plane, interacting with the Cα p-orbital lying in the same plane. This π-type interaction inscribes some alkylidene character into Cα that favors alkylidene generation via α-H abstraction. The extent of the deshielding and the anisotropy of the alkyl chemical shift tensors distinguishes [M](CH2R)2 compounds that form alkylidenes from those that do not, relating the reactivity to molecular orbitals of the respective molecules. The α-carbon chemical shifts and tensor orientations thus predict the reactivity of metal alkyl compounds towards alkylidene generation. PMID:29675237

THE STAR FORMATION HISTORIES OF z {approx} 2 DUST-OBSCURED GALAXIES AND SUBMILLIMETER-SELECTED GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bussmann, R. S.; Dey, Arjun; Jannuzi, B. T.

The Spitzer Space Telescope has identified a population of ultraluminous infrared galaxies (ULIRGs) at z {approx} 2 that may play an important role in the evolution of massive galaxies. We measure the stellar masses (M{sub *}) of two populations of Spitzer-selected ULIRGs that have extremely red R - [24] colors (dust-obscured galaxies, or DOGs) and compare our results with submillimeter-selected galaxies (SMGs). One set of 39 DOGs has a local maximum in their mid-infrared (mid-IR) spectral energy distribution (SED) at rest frame 1.6 {mu}m associated with stellar emission ({sup b}ump DOGs{sup )}, while the other set of 51 DOGs havemore » power-law mid-IR SEDs that are typical of obscured active galactic nuclei ({sup p}ower-law DOGs{sup )}. We measure M{sub *} by applying Charlot and Bruzual stellar population synthesis models to broadband photometry in the rest-frame ultraviolet, optical, and near-infrared of each of these populations. Assuming a simple stellar population and a Chabrier initial mass function, we find that power-law DOGs and bump DOGs are on average a factor of 2 and 1.5 more massive than SMGs, respectively (median and inter-quartile M{sub *} values for SMGs, bump DOGs, and power-law DOGs are log(M{sub *}/M{sub Sun }) = 10.42{sup +0.42}{sub -0.36}, 10.62{sup +0.36}{sub -0.32}, and 10.71{sup +0.40}{sub -0.34}, respectively). More realistic star formation histories drawn from two competing theories for the nature of ULIRGs at z {approx} 2 (major merger versus smooth accretion) can increase these mass estimates by up to 0.5 dex. A comparison of our stellar masses with the instantaneous star formation rate (SFR) in these z {approx} 2 ULIRGs provides a preliminary indication supporting high SFRs for a given M{sub *}, a situation that arises more naturally in major mergers than in smooth accretion-powered systems.« less

Palladium-catalyzed stereoretentive olefination of unactivated C(sp3)-H bonds with vinyl iodides at room temperature: synthesis of β-vinyl α-amino acids.

PubMed

Wang, Bo; Lu, Chengxi; Zhang, Shu-Yu; He, Gang; Nack, William A; Chen, Gong

2014-12-05

A method is reported for palladium-catalyzed N-quinolyl carboxamide-directed olefination of the unactivated C(sp(3))-H bonds of phthaloyl alanine with a broad range of vinyl iodides at room temperature. This reaction represents the first example of the stereoretentive installation of multisubstituted terminal and internal olefins onto unactivated C(sp(3))-H bonds. These methods enable access to a wide range of challenging β-vinyl α-amino acid products in a streamlined and controllable fashion, beginning from simple precursors.

Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

USDA-ARS?s Scientific Manuscript database

A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

PubMed Central

Vatansever, Fatma; Hamblin, Michael R.

2016-01-01

Core–shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original trioctylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48–53 nm. PMID:28360819

Galaxies at z~7-8: z850-Dropouts in the Hubble Ultra Deep Field

NASA Astrophysics Data System (ADS)

Bouwens, R. J.; Thompson, R. I.; Illingworth, G. D.; Franx, M.; van Dokkum, P. G.; Fan, X.; Dickinson, M. E.; Eisenstein, D. J.; Rieke, M. J.

2004-12-01

We have detected likely z~7-8 galaxies in the 144''×144'' Near-Infrared Camera and Multi-Object Spectrometer (NICMOS) observations of the Hubble Ultra Deep Field. Objects are required to be >=3 σ detections in both NICMOS bands, J110 and H160. The selection criteria for this sample are (z850-J110)AB>0.8, (z850-J110)AB>0.66(J110-H160)AB+0.8, (J110-H160)AB<1.2 and no detection at less than 8500 Å. The five selected sources have total magnitudes H160,AB~27. Four of the five sources are quite blue compared to typical lower redshift dropout galaxies and are clustered within a 1 arcmin2 region. Because all five sources are near the limit of the NICMOS data, we have carefully evaluated their reality. Each of the candidates is visible in different splits of the data and a median stack. We analyzed several noise images and estimate the number of spurious sources to be 1+/-1. A search using an independent reduction of this same data set clearly revealed three of the five candidates and weakly detected a fourth candidate, suggesting that the contamination could be higher. For comparison with predictions from lower redshift samples, we take a conservative approach and adopt four z~7-8 galaxies as our sample. With the same detection criteria on simulated data sets, assuming no evolution from z~3.8, we predict 10 sources at z~7-8, or 14 if we use a more realistic (1+z)-1 size scaling. We estimate that the rest-frame continuum UV (~1800 Å) luminosity density at z~7.5 (integrated down to 0.3L*z=3) is just 0.20+0.12-0.08 times that found at z~3.8 (or 0.20+0.23-0.12 times this quantity including cosmic variance). Effectively this sets an upper limit on the luminosity density down to 0.3L*z=3 and is consistent with significant evolution at the bright end of the luminosity function from z~7.5 to 3.8. Even with the lower UV luminosity density at z~7.5, it appears that galaxies could still play an important role in reionization at these redshifts, although definitive measurements

New high boron content polyborane precursors to advanced ceramic materials: New syntheses, new applications

NASA Astrophysics Data System (ADS)

Guron, Marta

There is a need for new synthetic routes to high boron content materials for applications as polymeric precursors to ceramics, as well as in neutron shielding and potential medical applications. To this end, new ruthenium-catalyzed olefin metathesis routes have been devised to form new complex polyboranes and polymeric species. Metathesis of di-alkenyl substituted o-carboranes allowed the synthesis of ring-closed products fused to the carborane cage, many of which are new compounds and one that offers a superior synthetic method to one previously published. Acyclic diene metathesis of di-alkenyl substituted m-carboranes resulted in the formation of new main-chain carborane-containing polymers of modest molecular weights. Due to their extremely low char yields, and in order to explore other metathesis routes, ring opening metathesis polymerization (ROMP) was used to generate the first examples of poly(norbornenyl- o-carboranes). Monomer synthesis was achieved via a two-step process, incorporating Ti-catalyzed hydroboration to make 6-(5-norbornenyl)-decaborane, followed by alkyne insertion in ionic liquid media to achieve 1,2-R2 -3-norbornenyl o-carborane species. The monomers were then polymerized using ROMP to afford several examples of poly(norbornenyl- o-carboranes) with relatively high molecular weights. One such polymer, [1-Ph, 3-(=CH2-C5H7-CH2=)-1,2-C 2B10H10]n, had a char yield very close to the theoretical char yield of 44%. Upon random copolymerization with poly(6-(5-norbornenyl) decaborane), char yields significantly increased to 80%, but this number was well above the theoretical value implicating the formation of a boron-carbide/carbon ceramic. Finally, applications of polyboranes were explored via polymer blends toward the synthesis of ceramic composites and the use of polymer precursors as reagents for potential ultra high temperature ceramic applications. Upon pyrolysis, polymer blends of poly(6-(5-norbornenyl)-decaborane) and poly

Toward Green Acylation of (Hetero)arenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones

PubMed Central

2017-01-01

Green Friedel–Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero)arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C–H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel–Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene) as well as of natural products (eugenol and safrole). Furthermore, synthetic applications to drug molecules are showcased. PMID:29392174

Metal- and Reagent-Free Anodic C-C Cross-Coupling of Phenols with Benzofurans leading to a Furan Metathesis.

PubMed

Lips, Sebastian; Frontana-Uribe, Bernardo Antonio; Dörr, Maurice; Schollmeyer, Dieter; Franke, Robert; Waldvogel, Siegfried R

2018-04-20

Heterobiaryls consisting of a phenol and a benzofuran motif are of significant importance for pharmaceutical applications. An attractive sustainable, metal- and reagent-free, electrosynthetic, and highly efficient method, that allows access to (2-hydroxyphenyl)benzofurans is presented. Upon the electrochemical dehydrogenative C-C cross-coupling reaction, a metathesis of the benzo moiety at the benzofuran occurs. This gives rise to a substitution pattern at the hydroxyphenyl moiety which would not be compatible by a direct coupling process. The single-step protocol is easy to conduct in an undivided electrolysis cell, therefore scalable, and inherently safe. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

EDDINGTON RATIO DISTRIBUTION OF X-RAY-SELECTED BROAD-LINE AGNs AT 1.0 < z < 2.2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suh, Hyewon; Hasinger, Günther; Steinhardt, Charles

2015-12-20

We investigate the Eddington ratio distribution of X-ray-selected broad-line active galactic nuclei (AGNs) in the redshift range 1.0 < z < 2.2, where the number density of AGNs peaks. Combining the optical and Subaru/Fiber Multi Object Spectrograph near-infrared spectroscopy, we estimate black hole masses for broad-line AGNs in the Chandra Deep Field South (CDF-S), Extended Chandra Deep Field South (E-CDF-S), and the XMM-Newton Lockman Hole (XMM-LH) surveys. AGNs with similar black hole masses show a broad range of AGN bolometric luminosities, which are calculated from X-ray luminosities, indicating that the accretion rate of black holes is widely distributed. We find a substantial fraction ofmore » massive black holes accreting significantly below the Eddington limit at z ≲ 2, in contrast to what is generally found for luminous AGNs at high redshift. Our analysis of observational selection biases indicates that the “AGN cosmic downsizing” phenomenon can be simply explained by the strong evolution of the comoving number density at the bright end of the AGN luminosity function, together with the corresponding selection effects. However, one might need to consider a correlation between the AGN luminosity and the accretion rate of black holes, in which luminous AGNs have higher Eddington ratios than low-luminosity AGNs, in order to understand the relatively small fraction of low-luminosity AGNs with high accretion rates in this epoch. Therefore, the observed downsizing trend could be interpreted as massive black holes with low accretion rates, which are relatively fainter than less-massive black holes with efficient accretion.« less

The stellar masses of ˜ 40 000 UV selected Galaxies from the WiggleZ survey at 0.3<z<1.0: analogues of Lyman break galaxies?

NASA Astrophysics Data System (ADS)

Banerji, Manda; Glazebrook, Karl; Blake, Chris; Brough, Sarah; Colless, Matthew; Contreras, Carlos; Couch, Warrick; Croton, Darren J.; Croom, Scott; Davis, Tamara M.; Drinkwater, Michael J.; Forster, Karl; Gilbank, David; Gladders, Mike; Jelliffe, Ben; Jurek, Russell J.; Li, I.-hui; Madore, Barry; Martin, D. Christopher; Pimbblet, Kevin; Poole, Gregory B.; Pracy, Michael; Sharp, Rob; Wisnioski, Emily; Woods, David; Wyder, Ted K.; Yee, H. K. C.

2013-05-01

We characterize the stellar masses and star formation rates in a sample of ˜40 000 spectroscopically confirmed UV-luminous galaxies at 0.3 < z < 1.0 selected from within the WiggleZ Dark Energy Survey. In particular, we match this UV bright population to wide-field infrared surveys such as the near-infrared (NIR) UKIDSS Large Area Survey (LAS) and the mid-infrared Wide-Field Infrared Survey Explorer (WISE) All-Sky Survey. We find that ˜30 per cent of the UV-luminous WiggleZ galaxies, corresponding to the brightest and reddest subset, are detected at >5σ in the UKIDSS-LAS at all redshifts. An even more luminous subset of 15 per cent are also detected in the WISE 3.4 and 4.6 μm bands. In addition, 22 of the WiggleZ galaxies are extremely luminous at 12 and 22 μm and have colours consistent with being star formation dominated. We compute stellar masses for this very large sample of extremely blue galaxies and quantify the sensitivity of the stellar mass estimates to various assumptions made during the spectral energy distribution (SED) fitting. The median stellar masses are log10(M*/M⊙) = 9.6 ± 0.7, 10.2 ± 0.5 and 10.4 ± 0.4 for the IR undetected, UKIDSS detected and UKIDSS+WISE detected galaxies, respectively. We demonstrate that the inclusion of NIR photometry can lead to tighter constraints on the stellar masses by bringing down the upper bound on the stellar mass estimate. The mass estimates are found to be most sensitive to the inclusion of secondary bursts of star formation as well as changes in the stellar population synthesis models, both of which can lead to median discrepancies of the order of 0.3 dex in the stellar masses. We conclude that even for these extremely blue galaxies, different SED fitting codes therefore produce extremely robust stellar mass estimates. We find, however, that the best-fitting M/LK is significantly lower than that predicted by simple optical colour-based estimators for many of the WiggleZ galaxies. The simple colour

A census of star-forming galaxies in the z ∼ 9-10 universe based on HST+Spitzer observations over 19 clash clusters: three candidate z ∼ 9-10 galaxies and improved constraints on the star formation rate density at z ∼ 9.2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bouwens, R. J.; Franx, M.; Smit, R.

2014-11-10

We utilize a two-color Lyman-break selection criterion to search for z ∼ 9-10 galaxies over the first 19 clusters in the CLASH program. A systematic search yields three z ∼ 9-10 candidates. While we have already reported the most robust of these candidates, MACS1149-JD, two additional z ∼ 9 candidates are also found and have H {sub 160}-band magnitudes of ∼26.2-26.9. A careful assessment of various sources of contamination suggests ≲1 contaminants for our z ∼ 9-10 selection. To determine the implications of these search results for the luminosity function (LF) and star formation rate density at z ∼ 9,more » we introduce a new differential approach to deriving these quantities in lensing fields. Our procedure is to derive the evolution by comparing the number of z ∼ 9-10 galaxy candidates found in CLASH with the number of galaxies in a slightly lower-redshift sample (after correcting for the differences in selection volumes), here taken to be z ∼ 8. This procedure takes advantage of the fact that the relative volumes available for the z ∼ 8 and z ∼ 9-10 selections behind lensing clusters are not greatly dependent on the details of the lensing models. We find that the normalization of the UV LF at z ∼ 9 is just 0.28{sub −0.20}{sup +0.39}× that at z ∼ 8, which is ∼1.4{sub −0.8}{sup +3.0}× lower than extrapolating z ∼ 4-8 LF results. While consistent with the evolution in the UV LF seen at z ∼ 4-8, these results marginally favor a more rapid evolution at z > 8. Compared to similar evolutionary findings from the HUDF, our result is less insensitive to large-scale structure uncertainties, given our many independent sightlines on the high-redshift universe.« less

Olefin Epoxidation by Methyltrioxorhenium: A Density Functional Study on Energetics and Mechanisms.

PubMed

Gisdakis, Philip; Antonczak, Serge; Köstlmeier, Sibylle; Herrmann, Wolfgang A; Rösch, Notker

1998-09-04

A spiro attack on a peroxo group is calculated to be the preferred reaction pathway for olefin epoxidation with the catalytic system CH 3 ReO 3 /H 2 O 2 (see picture). This finding is supported by density functional calculations on more than ten transition states for the most probable mechanisms. Hydration has significant effects on various reaction species: it stabilizes the intermediates and destabilizes, with one exception, the transition states. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Synthesis, in vitro and in vivo antimalarial assessment of sulfide, sulfone and vinyl amide-substituted 1,2,4-trioxanes prepared via thiol-olefin co-oxygenation (TOCO) of allylic alcohols.

PubMed

Amewu, Richard; Gibbons, Peter; Mukhtar, Amira; Stachulski, Andrew V; Ward, Stephen A; Hall, Charlotte; Rimmer, Karen; Davies, Jill; Vivas, Livia; Bacsa, John; Mercer, Amy E; Nixon, Gemma; Stocks, Paul A; O'Neill, Paul M

2010-05-07

Thiol-Olefin Co-Oxygenation (TOCO) methodology has been applied to the synthesis of a small library of weak base and polar 1,2,4-trioxanes. The 1,2,4-trioxane units synthesised exhibit remarkable stability as they survive base catalysed hydrolysis and mixed anhydride/amine coupling reactions. This unique stability feature has enabled a range of novel substitution patterns to be incorporated within the spiro 1,2,4-trioxane unit. Selected analogues express potent in vitro nM antimalarial activity, low cytotoxicity and oral activity in the Plasmodium berghei mouse model of malaria.

Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiang, Yizhi; Kruse, Norbert

Here, the catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ~97% can be n-aldehydes. While the product slate contains ~60% n-aldehydes at /p CO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson–Schulz–Flory behaviour,more » independent of the /p CO ratio, is found for the sum of C 4+ products. We advocate a synergistic interaction between a Mn 5O 8 oxide and a bulk Co 2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies.« less

Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

DOE PAGES

Xiang, Yizhi; Kruse, Norbert

2016-10-06

Here, the catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ~97% can be n-aldehydes. While the product slate contains ~60% n-aldehydes at /p CO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson–Schulz–Flory behaviour,more » independent of the /p CO ratio, is found for the sum of C 4+ products. We advocate a synergistic interaction between a Mn 5O 8 oxide and a bulk Co 2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies.« less

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

PubMed

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Effect of Feedstock and Catalyst Impurities on the Methanol‐to‐Olefin Reaction over H‐SAPO‐34

PubMed Central

Vogt, Charlotte; Ruiz‐Martínez, Javier

2016-01-01

Abstract Operando UV/Vis spectroscopy with on‐line mass spectrometry was used to study the effect of different types of impurities on the hydrocarbon pool species and the activity of H‐SAPO‐34 as a methanol‐to‐olefins (MTO) catalyst. Successive reaction cycles with different purity feedstocks were studied, with an intermittent regeneration step. The combined study of two distinct impurity types (i.e., feed and internal impurities) leads to new insights into MTO catalyst activation and deactivation mechanisms. In the presence of low amounts of feed impurities, the induction and active periods of the process are prolonged. Feed impurities are thus beneficial in the formation of the initial hydrocarbon pool, but also aid in the unwanted formation of deactivating coke species by a separate, competing mechanism favoring coke species over olefins. Further, feedstock impurities strongly influence the location of coke deposits, and thus influence the deactivation mechanism, whereas a study of the organic impurities retained after calcination reveals that these species are less relevant for catalyst activity and function as “seeds” for coke formation only. PMID:28163792

Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

PubMed

Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

2011-01-04

Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

Iron-catalyzed olefin epoxidation in the presence of acetic acid: insights into the nature of the metal-based oxidant.

PubMed

Mas-Ballesté, Rubén; Que, Lawrence

2007-12-26

The iron complexes [(BPMEN)Fe(OTf)2] (1) and [(TPA)Fe(OTf)2] (2) [BPMEN = N,N'-bis-(2-pyridylmethyl)-N,N'-dimethyl-1,2-ethylenediamine; TPA = tris-(2-pyridylmethyl)amine] catalyze the oxidation of olefins by H2O2 to yield epoxides and cis-diols. The addition of acetic acid inhibits olefin cis-dihydroxylation and enhances epoxidation for both 1 and 2. Reactions carried out at 0 degrees C with 0.5 mol % catalyst and a 1:1.5 olefin/H2O2 ratio in a 1:2 CH3CN/CH3COOH solvent mixture result in nearly quantitative conversions of cyclooctene to epoxide within 1 min. The nature of the active species formed in the presence of acetic acid has been probed at low temperature. For 2, in the absence of substrate, [(TPA)FeIII(OOH)(CH3COOH)]2+ and [(TPA)FeIVO(NCCH3)]2+ intermediates can be observed. However, neither is the active epoxidizing species. In fact, [(TPA)FeIVO(NCCH3)]2+ is shown to form in competition with substrate oxidation. Consequently, it is proposed that epoxidation is mediated by [(TPA)FeV(O)(OOCCH3)]2+, generated from O-O bond heterolysis of the [(TPA)FeIII(OOH)(CH3COOH)]2+ intermediate, which is promoted by the protonation of the terminal oxygen atom of the hydroperoxide by the coordinated carboxylic acid.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

NASA Astrophysics Data System (ADS)

McMillan, Paul F.; Gryko, Jan; Bull, Craig; Arledge, Richard; Kenyon, Anthony J.; Cressey, Barbara A.

2005-03-01

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr 2) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300 °C. Syntheses at higher temperatures gave rise to microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.

Spectroscopic Confirmation of Two Massive Red-sequence-selected Galaxy Clusters at Z Approximately Equal to 1.2 in the Sparcs-North Cluster Survey

NASA Technical Reports Server (NTRS)

Muzzin, Adam; Wilson, Gillian; Yee, H.K.C.; Hoekstra, Henk; Gilbank, David; Surace, Jason; Lacy, Mark; Blindert, Kris; Majumdar, Subhabrata; Demarco, Ricardo;

Rapid solid-state metathesis route to transition-metal doped titanias

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coleman, Nathaniel; Perera, Sujith; Gillan, Edward G., E-mail: edward-gillan@uiowa.edu

2015-12-15

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganesemore » doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.« less

Crystal and electronic structures, luminescence properties of Eu 2+-doped Si 6-zAl zO zN 8-z and M ySi 6-zAl z-yO z+yN 8-z-y ( M=2Li, Mg, Ca, Sr, Ba)

NASA Astrophysics Data System (ADS)

Li, Y. Q.; Hirosaki, N.; Xie, R. J.; Takeda, T.; Mitomo, M.

2008-12-01

The crystal structure, electronic structure, and photoluminescence properties of Eu xSi 6-zAl z-xO z+xN 8-z-x ( x=0-0.1, 0< z<1) and Eu xM ySi 6-zAl z-x-yO z+x+yN 8-z-x-y ( M=2Li, Mg, Ca, Sr, Ba) have been studied. Single-phase Eu xSi 6-zAl z-xO z+xN 8-z-x can be obtained in very narrow ranges of x⩽0.06 ( z=0.15) and z<0.5 ( x=0.3), indicating that limited Eu 2+ ions can be incorporated into nitrogen-rich Si 6-zAl zO zN 8-z. The Eu 2+ ion is found to occupy the 2 b site in a hexagonal unit cell ( P6 3/ m) and directly connected by six adjacent nitrogen/oxygen atoms ranging 2.4850-2.5089 Å. The calculated host band gaps by the relativistic DV-X α method are about 5.55 and 5.45 eV (without Eu 2+ 4 f5 d levels) for x=0 and 0.013 in Eu xSi 6-zAl z-xO z+xN 8-z-x ( z=0.15), in which the top of the 5 d orbitals overlap with the Si-3 s3 p and N-2 p orbitals within the bottom of the conduction band of the host. Eu xSi 6-zAl z-xO z+xN 8-z-x shows a strong green emission with a broad Eu 2+ band centered at about 530 nm under UV to near-UV excitation range. The excitation and emission spectra are hardly modified by Eu concentration and dual-doping ions of Li and other alkaline-earth ions with Eu. Higher Eu concentrations can significantly quench the luminescence of Eu 2+ and decrease the thermal quenching temperature. In addition, the emission spectrum can only be slightly tuned to the longer wavelengths (˜529-545 nm) by increasing z within the solid solution range of z<0.5. Furthermore, the luminescence intensity of Eu xSi 6-zAl z-xO z+xN 8-z-x can be improved by increasing z and the dual-doping of Li and Ba.

Dust-obscured star formation and the contribution of galaxies escaping UV/optical color selections at z ~ 2

NASA Astrophysics Data System (ADS)

Riguccini, L.; Le Floc'h, E.; Ilbert, O.; Aussel, H.; Salvato, M.; Capak, P.; McCracken, H.; Kartaltepe, J.; Sanders, D.; Scoville, N.

2011-10-01

Context. A substantial amount of the stellar mass growth across cosmic time occurred within dust-enshrouded environments. So far, identification of complete samples of distant star-forming galaxies from the short wavelength range has been strongly biased by the effect of dust extinction. Nevertheless, the exact amount of star-forming activity that took place in high-redshift dusty galaxies but that has currently been missed by optical surveys has barely been explored. Aims: Our goal is to determine the number of luminous star-forming galaxies at 1.5 ≲ z ≲ 3 that are potentially missed by the traditional color selection techniques because of dust extinction. We also aim at quantifying the contribution of these sources to the IR luminosity and cosmic star formation density at high redshift. Methods: We based our work on a sample of 24 μm sources brighter than 80 μJy and taken from the Spitzer survey of the COSMOS field. Almost all of these sources have accurate photometric redshifts. We applied to this mid-IR selected sample the BzK and BM/BX criteria, as well as the selections of the IRAC peakers and the Optically-Faint IR-bright (OFIR) galaxies. We analyzed the fraction of sources identified with these techniques. We also computed 8 μm rest-frame luminosity from the 24 μm fluxes of our sources, and considering the relationships between L8 μm and LPaα and between L8 μm and LIR, we derived ρIR and then ρSFR for our MIPS sources. Results: The BzK criterion offers an almost complete (~90%) identification of the 24 μm sources at 1.4 < z < 2.5. In contrast, the BM/BX criterion misses 50% of the MIPS sources. We attribute this bias to the effect of extinction, which reddens the typical colors of galaxies. The contribution of these two selections to the IR luminosity density produced by all the sources brighter than 80 μJy are on the same order. Moreover the criterion based on the presence of a stellar bump in their spectra (IRAC peakers) misses up to 40% of

Platform Chemicals from an Oilseed Biorefinery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tupy, Mike; Schrodi Yann

2006-11-06

The US chemical industry is $460 billion in size where a $150 billion segment of which is non-oxygenated chemicals that is sourced today via petroleum but is addressable by a renewable feedstock if one considers a more chemically reduced feedstock such as vegetable oils. Vegetable oil, due to its chemical functionality, provides a largely untapped opportunity as a renewable chemical source to replace petroleum-derived chemicals and produce platform chemicals unavailable today. This project examined the fertile intersection between the rich building blocks provided by vegetable oils and the enhanced chemical modification capability provided by metathesis chemistry. The technology advanced inmore » this study is the process of ethylene cross-metathesis (referred to as ethenolysis) with vegetable oil and vegetable oil derivatives to manufacture the platform-chemical 9-decenoic acid (or 9DA) and olefin co-products. The project team meet its goals of demonstrating improved catalyst efficiencies of several multiples, deepening the mechanistic understanding of metathesis, synthesis and screening of dozens of new catalysts, designing and modeling commercial processes, and estimating production costs. One demonstrable result of the study was a step change improvement in catalyst turnover number in the ethenolysis of methyl oleate as reported here. We met our key measurable of producing 100 lbs of 9DA at the pilot-scale, which demonstrated ability to scale-up ethenolysis. DOE Project funding had significant positive impact on development of metathetically modified vegetable oils more broadly as the Cargill/Materia partnership, that was able to initiate primarily due to DOE funding, has succeeded in commercializing products, validating metathesis as a platform technology, and expanding a diverse products portfolio in high value and in large volume markets. Opportunities have expanded and business development has gained considerable momentum and enabled further expansion of

Recent advances in heterobimetallic catalysis across a "transition metal-tin" motif.

PubMed

Das, Debjit; Mohapatra, Swapna Sarita; Roy, Sujit

2015-06-07

Heterobimetallic catalysts, bearing a metal-metal bond between a transition metal (TM) and a tin atom, are very promising due to their ability in mediating a wide variety of organic transformations. Indeed the utilization of such catalysts is a challenging and evolving area in the field of homogeneous catalysis. Catalysis across a 'TM-Sn' motif is an emerging area in the broader domain of multimetallic catalysis. The present review apprises the chemists' community of the past, present and future scope of this versatile catalytic motif. The TM-Sn catalyzed reactions presented include, among others, Friedel-Crafts alkylation, carbonylation, polymerization, cyclization, olefin metathesis, Heck coupling, hydroarylation Michael addition and tandem coupling. The mechanistic aspects of the reactions have been highlighted as well.

Kinetics of the addition of olefins to Si-centered radicals: the critical role of dispersion interactions revealed by theory and experiment.

PubMed

Johnson, Erin R; Clarkin, Owen J; Dale, Stephen G; DiLabio, Gino A

2015-06-04

Solution-phase rate constants for the addition of selected olefins to the triethylsilyl and tris(trimethylsilyl)silyl radicals are measured using laser-flash photolysis and competition kinetics. The results are compared with predictions from density functional theory (DFT) calculations, both with and without dispersion corrections obtained from the exchange-hole dipole moment (XDM) model. Without a dispersion correction, the rate constants are consistently underestimated; the errors increase with system size, up to 10(6) s(-1) for the largest system considered. Dispersion interactions preferentially stabilize the transition states relative to the separated reactants and bring the DFT-calculated rate constants into excellent agreement with experiment. Thus, dispersion interactions are found to play a key role in determining the kinetics for addition reactions, particularly those involving sterically bulky functional groups.

Species-specific AFLP markers for identification of Zingiber officinale, Z. montanum and Z. zerumbet (Zingiberaceae).

PubMed

Ghosh, S; Majumder, P B; Sen Mandi, S

2011-02-08

The Zingiber genus, which includes the herbs known as gingers, commonly used in cooking, is well known for its medicinal properties, as described in the Indian pharmacopoeia. Different members of this genus, although somewhat similar in morphology, differ widely in their pharmacological and therapeutic properties. The most important species of this genus, with maximal therapeutic properties, is Zingiber officinale (garden ginger), which is often adulterated with other less-potent Zingiber sp. There is an existing demand in the herbal drug industry for an authentication system for the Zingiber sp in order to facilitate their commercial use as genuine phytoceuticals. To this end, we used amplified fragment length polymorphism (AFLP) to produce DNA fingerprints for three Zingiber species. Sixteen collections (six of Z. officinale, five of Z. montanum, and five of Z. zerumbet) were used in the study. Seven selective primer pairs were found to be useful for all the accessions. A total of 837 fragments were produced by these primer pairs. Species-specific markers were identified for all three Zingiber species (91 for Z. officinale, 82 for Z. montanum, and 55 for Z. zerumbet). The dendogram analysis generated from AFLP patterns showed that Z. montanum and Z. zerumbet are phylogenetically closer to each other than to Z. officinale. The AFLP fingerprints of the Zingiber species could be used to authenticate Zingiber sp-derived drugs and to resolve adulteration-related problems faced by the commercial users of these herbs.

Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

T. Brent Gunnoe

2011-02-17

3}CEt, which has provided a comprehensive understanding of the impact of steric and electronic parameters of 'L' on the catalytic hydroarylation of olefins. (3) We have completed and published a detailed mechanistic study of stoichiometric aromatic C-H activation by TpRu(L)(NCMe)Ph (L = CO or PMe{sub 3}). These efforts have probed the impact of functionality para to the site of C-H activation for benzene substrates and have allowed us to develop a detailed model of the transition state for the C-H activation process. These results have led us to conclude that the C-H bond cleavage occurs by a {sigma}-bond metathesis process in which the C-H transfer is best viewed as an intramolecular proton transfer. (4) We have completed studies of Ru complexes possessing the N-heterocyclic carbene IMes (IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene). One of these systems is a unique four-coordinate Ru(II) complex that catalyzes the oxidative hydrophenylation of ethylene (in low yields) to produce styrene and ethane (utilizing ethylene as the hydrogen acceptor) as well as the hydrogenation of olefins, aldehydes and ketones. These results provide a map for the preparation of catalysts that are selective for oxidative olefin hydroarylation. (5) The ability of TpRu(PMe{sub 3})(NCMe)R systems to activate sp{sup 3} C-H bonds has been demonstrated including extension to subsequent C-C bond forming steps. These results open the door to the development of catalysts for the functionalization of more inert C-H bonds. (6) We have discovered that Pt(II) complexes supported by simple nitrogen-based ligands serve as catalysts for the hydroarylation of olefins. Given the extensive studies of Pt-based catalytic C-H activation, we believe these results will provide an entry point into an array of possible catalysts for hydrocarbon functionalization.« less

Modeling random methyl branching in ethylene/ propylene copolymers using metathesis chemistry: synthesis and thermal behavior.

PubMed

Sworen, John C; Smith, Jason A; Wagener, Kenneth B; Baugh, Lisa S; Rucker, Steven P

2003-02-26

The structure of random ethylene/propylene (EP) copolymers has been modeled using step polymerization chemistry. Six ethylene/propylene model copolymers have been prepared via acyclic diene metathesis (ADMET) polymerization and characterized for primary and higher level structure using in-depth NMR, IR, DSC, WAXD, and GPC analysis. These copolymers possess 1.5, 7.1, 13.6, 25.0, 43.3, and 55.6 methyl branches per 1000 carbons. Examination of these macromolecules by IR and WAXD analysis has demonstrated the first hexagonal phase in EP copolymers containing high ethylene content (90%) without the influence of sample manipulation (temperature, pressure, or radiation). Thermal behavior studies have shown that the melting point and heat of fusion decrease as the branch content increases. Further, comparisons have been made between these random ADMET EP copolymers, random EP copolymers made by typical chain addition techniques, and precisely branched ADMET EP copolymers.

A Cu-Zn nanoparticle promoter for selective carbon dioxide reduction and its application in visible-light-active Z-scheme systems using water as an electron donor.

PubMed

Yin, Ge; Sako, Hiroshi; Gubbala, Ramesh V; Ueda, Shigenori; Yamaguchi, Akira; Abe, Hideki; Miyauchi, Masahiro

2018-04-17

Selective carbon dioxide photoreduction to produce formic acid was achieved under visible light irradiation using water molecules as electron donors, similar to natural plants, based on the construction of a Z-scheme light harvesting system modified with a Cu-Zn alloy nanoparticle co-catalyst. The faradaic efficiency of our Z-scheme system for HCOOH generation was over 50% under visible light irradiation.

Enhanced performance of a structured cyclo olefin copolymer-based amorphous silicon solar cell

NASA Astrophysics Data System (ADS)

Zhan, Xinghua; Chen, Fei; Gao, Mengyu; Tie, Shengnian; Gao, Wei

2017-07-01

The submicron array was fabricated onto a cyclo olefin copolymer (COC) film by a hot embossing method. An amorphous silicon p-i-n junction and transparent conductive layers were then deposited onto it through a plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering. The efficiency of the fabricated COC-based solar cell was measured and the result demonstrated 18.6% increase of the solar cell efficiency when compared to the sample without array structure. The imprinted polymer solar cells with submicron array indeed increase their efficiency.

40 CFR Appendix 8 to Subpart A of... - Reference C16-C18 Internal Olefin Drilling Fluid Formulation

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Reference C16-C18 Internal Olefin Drilling Fluid Formulation 8 Appendix 8 to Subpart A of Part 435 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS OIL AND GAS EXTRACTION POINT SOURCE CATEGORY...

40 CFR Appendix 8 to Subpart A of... - Reference C16-C18 Internal Olefin Drilling Fluid Formulation

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Reference C16-C18 Internal Olefin Drilling Fluid Formulation 8 Appendix 8 to Subpart A of Part 435 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS OIL AND GAS EXTRACTION POINT SOURCE CATEGORY...

The nature of H α-selected galaxies along the large-scale structure at z = 0.4 revealed by Subaru Hyper Suprime-Cam survey

NASA Astrophysics Data System (ADS)

Koyama, Yusei; Hayashi, Masao; Tanaka, Masayuki; Kodama, Tadayuki; Shimakawa, Rhythm; Yamamoto, Moegi; Nakata, Fumiaki; Tanaka, Ichi; Suzuki, Tomoko L.; Tadaki, Ken-ichi; Nishizawa, Atsushi J.; Yabe, Kiyoto; Toba, Yoshiki; Lin, Lihwai; Jian, Hung-Yu; Komiyama, Yutaka

2018-01-01

We present the environmental dependence of color, stellar mass, and star formation (SF) activity in Hα-selected galaxies along the large-scale structure at z = 0.4 hosting twin clusters in the DEEP2-3 field, discovered by the Subaru Strategic Program of Hyper Suprime-Cam (HSC SSP). By combining photo-z-selected galaxies and Hα emitters selected with broadband and narrowband (NB) data from the recent data release of HSC SSP (DR1), we confirm that galaxies in higher-density environments or galaxies in cluster central regions show redder colors. We find that there still remains a possible color-density and color-radius correlation even if we restrict the sample to Hα-selected galaxies, probably due to the presence of massive Hα emitters in denser regions. We also find a hint of increased star formation rates (SFR) amongst Hα emitters toward the highest-density environment, again primarily driven by the excess of red/massive Hα emitters in high-density environments, while their specific SFRs do not significantly change with environment. This work demonstrates the power of the HSC SSP NB data for studying SF galaxies across environments in the distant universe.

HerMES: dust attenuation and star formation activity in ultraviolet-selected samples from z˜ 4 to ˜ 1.5

NASA Astrophysics Data System (ADS)

Heinis, S.; Buat, V.; Béthermin, M.; Bock, J.; Burgarella, D.; Conley, A.; Cooray, A.; Farrah, D.; Ilbert, O.; Magdis, G.; Marsden, G.; Oliver, S. J.; Rigopoulou, D.; Roehlly, Y.; Schulz, B.; Symeonidis, M.; Viero, M.; Xu, C. K.; Zemcov, M.

2014-01-01

We study the link between observed ultraviolet (UV) luminosity, stellar mass and dust attenuation within rest-frame UV-selected samples at z ˜ 4, ˜ 3 and ˜1.5. We measure by stacking at 250, 350 and 500 μm in the Herschel/Spectral and Photometric Imaging Receiver images from the Herschel Multi-Tiered Extragalactic Survey (HerMES) program the average infrared luminosity as a function of stellar mass and UV luminosity. We find that dust attenuation is mostly correlated with stellar mass. There is also a secondary dependence with UV luminosity: at a given UV luminosity, dust attenuation increases with stellar mass, while at a given stellar mass it decreases with UV luminosity. We provide new empirical recipes to correct for dust attenuation given the observed UV luminosity and the stellar mass. Our results also enable us to put new constraints on the average relation between star formation rate (SFR) and stellar mass at z ˜ 4, ˜3 and ˜1.5. The SFR-stellar mass relations are well described by power laws (SFR∝ M_*^{0.7}), with the amplitudes being similar at z ˜ 4 and ˜3, and decreasing by a factor of 4 at z ˜ 1.5 at a given stellar mass. We further investigate the evolution with redshift of the specific SFR. Our results are in the upper range of previous measurements, in particular at z ˜ 3, and are consistent with a plateau at 3 < z < 4. Current model predictions (either analytic, semi-analytic or hydrodynamic) are inconsistent with these values, as they yield lower predictions than the observations in the redshift range we explore. We use these results to discuss the star formation histories of galaxies in the framework of the main sequence of star-forming galaxies. Our results suggest that galaxies at high redshift (2.5 < z < 4) stay around 1 Gyr on the main sequence. With decreasing redshift, this time increases such that z = 1 main-sequence galaxies with 108z = 0.

Discovery of a Color-selected Quasar at z = 5.50.

PubMed

Stern; Spinrad; Eisenhardt; Bunker; Dawson; Stanford; Elston

2000-04-20

We present observations of RD J030117+002025, a quasar at z=5.50 discovered from deep, multicolor, ground-based observations covering 74 arcmin2. This is the most distant quasar or active galaxy currently known. The object was targeted as an R-band dropout, with RAB>26.3 (3 sigma limit in a 3&arcsec; diameter region), IAB=23.8, and zAB=23.4. The Keck/Low-Resolution Imaging Spectrometer spectrum shows broad Lyalpha/N v lambda1240 emission and sharp absorption decrements from the highly redshifted hydrogen forests. The fractional continuum depression due to the Lyalpha forest is DA=0.90. RD J030117+002025 is the least luminous high-redshift quasar known (MB approximately -22.7).

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMillan, Paul F.; Gryko, Jan; Bull, Craig

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr{sub 2}) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300{sup o}C. Syntheses at higher temperatures gave rise tomore » microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.« less

The origin of exo-selectivity in methyl cyanoformate addition onto the C=C bond of norbornene in Pd-catalyzed cyanoesterification.

PubMed

Okuda, Yasuhiro; Szilagyi, Robert K; Mori, Seiji; Nishihara, Yasushi

2014-07-07

A computational investigation has been carried out to elucidate the origin of the exclusive exo-selectivity in the Pd-catalyzed cyanoesterification of strained cyclic olefins, norbornene and norbornadiene. A hybrid density functional was selected for the level of theory with a triple-ζ quality basis set, which was proposed in an earlier study to provide an experimentally sound ground state electronic structure description for palladium(ii) and palladium(iv) complexes from multi-edge X-ray absorption spectroscopic measurements. Given that the product of oxidative addition can be isolated, we focused on the olefin coordination as the earliest possible origin of exo-selectivity. The calculated geometric structure for the trans-Pd(CN)(COOR)(PPh3)2 complex at the BHandHLYP/def2TZVP/PCM(toluene) level is in an excellent agreement with its experimental structure from crystallographic measurements. Upon dissociation of one of its phosphane ligands, the coordinatively unsaturated trans-isomer is only 17 kJ mol(-1) away from the isomerization transition state, leading to the 14-electron cis-isomers that are 17 to 37 kJ mol(-1) lower in energy than the trans-isomers. Regardless of the initial complex for olefin coordination, the exo-isomer for the norbornene complex is at least 8 kJ mol(-1) lower than the corresponding endo-isomer. The origin of this considerable difference in Gibbs free energy can be attributed to the remarkably different steric and agostic hydrogen interactions between the methylene and the ethylene bridges of the norbornene and the adjacent cis-ligands at the Pd(II) center.

Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

PubMed

Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

2009-01-01

One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

Catalytic asymmetric dihydroxylation of olefins with reusable OsO(4)(2-) on ion-exchangers: the scope and reactivity using various cooxidants.

PubMed

Choudary, Boyapati M; Chowdari, Naidu S; Jyothi, Karangula; Kantam, Mannepalli L

2002-05-15

Exchanger-OsO(4) catalysts are prepared by an ion-exchange technique using layered double hydroxides and quaternary ammonium salts covalently bound to resin and silica as ion-exchangers. The ion-exchangers with different characteristics and opposite ion selectivities are specially chosen to produce the best heterogeneous catalyst that can operate using the various cooxidants in the asymmetric dihydroxylation reaction. LDH-OsO(4) catalysts composed of different compositions are evaluated for the asymmetric dihydroxylation of trans-stilbene. Resin-OsO(4) and SiO(2)-OsO(4) designed to overcome the problems associated with LDH-OsO(4) indeed show consistent activity and enantioselectivity in asymmetric dihydroxylation of olefins using K(3)Fe(CN)(6) and molecular oxygen as cooxidants. Compared to the Kobayashi heterogeneous systems, resin-OsO(4) is a very efficient catalyst for the dihydroxylation of a wide variety of aromatic, aliphatic, acyclic, cyclic, mono-, di-, and trisubstituted olefins to afford chiral vicinal diols with high yields and enantioselectivities irrespective of the cooxidant used. Resin-OsO(4) is recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity. The high binding ability of the heterogeneous osmium catalyst enables the use of an equimolar ratio of ligand to osmium to give excellent enantioselectives in asymmetric dihydroxylation in contrast to the homogeneous osmium system in which excess molar quantities of the expensive chiral ligand to osmium are invariably used. The complexation of the chiral ligand (DHQD)(2)PHAL, having very large dimension, a prerequisite to obtain higher ee, is possible only with the OsO(4)(2-) located on the surface of the supports.

On the track to silica-supported tungsten oxo metathesis catalysts: input from 17O solid-state NMR.

PubMed

Merle, Nicolas; Girard, Guillaume; Popoff, Nicolas; De Mallmann, Aimery; Bouhoute, Yassine; Trébosc, Julien; Berrier, Elise; Paul, Jean-François; Nicholas, Christopher P; Del Rosal, Iker; Maron, Laurent; Gauvin, Régis M; Delevoye, Laurent; Taoufik, Mostafa

2013-09-03

The grafting of an oxo chloro trisalkyl tungsten derivative on silica dehydroxylated at 700 °C was studied by several techniques that showed reaction via W-Cl cleavage, to afford a well-defined precatalyst for alkene metathesis. This was further confirmed by DFT calculations on the grafting process. (17)O labeling of the oxo moiety of a series of related molecular and supported tungsten oxo derivatives was achieved, and the corresponding (17)O MAS NMR spectra were recorded. Combined experimental and theoretical NMR studies yielded information on the local structure of the surface species. Assessment of the (17)O NMR parameters also confirmed the nature of the grafting pathway by ruling out other possible grafting schemes, thanks to highly characteristic anisotropic features arising from the quadrupolar and chemical shift interactions.

Synthesis of densely functionalized enantiopure indolizidines by ring-closing metathesis (RCM) of hydroxylamines from carbohydrate-derived nitrones

PubMed Central

Bonanni, Marco; Marradi, Marco; Cardona, Francesca; Cicchi, Stefano; Goti, Andrea

2007-01-01

Background Indolizidine alkaloids widely occur in nature and display interesting biological activity. This is the reason for which their total synthesis as well as the synthesis of non-natural analogues still attracts the attention of many research groups. To establish new straightforward accesses to these molecules is therefore highly desirable. Results The ring closing metathesis (RCM) of enantiopure hydroxylamines bearing suitable unsaturated groups cleanly afforded piperidine derivatives in good yields. Further cyclization and deprotection of the hydroxy groups gave novel highly functionalized indolizidines. The synthesis of a pyrroloazepine analogue is also described. Conclusion We have developed a new straightforward methodology for the synthesis of densely functionalized indolizidines and pyrroloazepine analogues in 6 steps and 30–60% overall yields from enantiopure hydroxylamines obtained straightforwardly from carbohydrate-derived nitrones. PMID:18076753

Stereoselective Formation of Trisubstituted Vinyl Boronate Esters by the Acid-Mediated Elimination of α-Hydroxyboronate Esters

PubMed Central

2015-01-01

The copper-catalyzed diboration of ketones followed by an acid-catalyzed elimination leads to the formation of 1,1-disubstituted and trisubstituted vinyl boronate esters with moderate to good yields and selectivity. Addition of tosic acid to the crude diboration products provides the corresponding vinyl boronate esters upon elimination. The trisubstituted vinyl boronate esters are formed as the (Z)-olefin isomer, which was established by subjecting the products to a Suzuki–Miyaura coupling reaction to obtain alkenes of known geometry. PMID:24915498

Subaru High-z Exploration of Low-luminosity Quasars (SHELLQs). I. Discovery of 15 Quasars and Bright Galaxies at 5.7 < z < 6.9

NASA Astrophysics Data System (ADS)

Matsuoka, Yoshiki; Onoue, Masafusa; Kashikawa, Nobunari; Iwasawa, Kazushi; Strauss, Michael A.; Nagao, Tohru; Imanishi, Masatoshi; Niida, Mana; Toba, Yoshiki; Akiyama, Masayuki; Asami, Naoko; Bosch, James; Foucaud, Sébastien; Furusawa, Hisanori; Goto, Tomotsugu; Gunn, James E.; Harikane, Yuichi; Ikeda, Hiroyuki; Kawaguchi, Toshihiro; Kikuta, Satoshi; Komiyama, Yutaka; Lupton, Robert H.; Minezaki, Takeo; Miyazaki, Satoshi; Morokuma, Tomoki; Murayama, Hitoshi; Nishizawa, Atsushi J.; Ono, Yoshiaki; Ouchi, Masami; Price, Paul A.; Sameshima, Hiroaki; Silverman, John D.; Sugiyama, Naoshi; Tait, Philip J.; Takada, Masahiro; Takata, Tadafumi; Tanaka, Masayuki; Tang, Ji-Jia; Utsumi, Yousuke

2016-09-01

We report the discovery of 15 quasars and bright galaxies at 5.7 < z < 6.9. This is the initial result from the Subaru High-z Exploration of Low-Luminosity Quasars project, which exploits the exquisite multiband imaging data produced by the Subaru Hyper Suprime-Cam (HSC) Strategic Program survey. The candidate selection is performed by combining several photometric approaches including a Bayesian probabilistic algorithm to reject stars and dwarfs. The spectroscopic identification was carried out with the Gran Telescopio Canarias and the Subaru Telescope for the first 80 deg2 of the survey footprint. The success rate of our photometric selection is quite high, approaching 100% at the brighter magnitudes (z AB < 23.5 mag). Our selection also recovered all the known high-z quasars on the HSC images. Among the 15 discovered objects, six are likely quasars, while the other six with interstellar absorption lines and in some cases narrow emission lines are likely bright Lyman-break galaxies. The remaining three objects have weak continua and very strong and narrow Lyα lines, which may be excited by ultraviolet light from both young stars and quasars. These results indicate that we are starting to see the steep rise of the luminosity function of z ≥ 6 galaxies, compared with that of quasars, at magnitudes fainter than M 1450 ˜ -22 mag or z AB ˜ 24 mag. Follow-up studies of the discovered objects as well as further survey observations are ongoing.

Partial synthesis of ganglioside and lysoganglioside lipoforms as internal standards for MS quantification.

PubMed

Gantner, Martin; Schwarzmann, Günter; Sandhoff, Konrad; Kolter, Thomas

2014-12-01

Within recent years, ganglioside patterns have been increasingly analyzed by MS. However, internal standards for calibration are only available for gangliosides GM1, GM2, and GM3. For this reason, we prepared homologous internal standards bearing nonnatural fatty acids of the major mammalian brain gangliosides GM1, GD1a, GD1b, GT1b, and GQ1b, and of the tumor-associated gangliosides GM2 and GD2. The fatty acid moieties were incorporated after selective chemical or enzymatic deacylation of bovine brain gangliosides. For modification of the sphingoid bases, we developed a new synthetic method based on olefin cross metathesis. This method was used for the preparation of a lyso-GM1 and a lyso-GM2 standard. The total yield of this method was 8.7% for the synthesis of d17:1-lyso-GM1 from d20:1/18:0-GM1 in four steps. The title compounds are currently used as calibration substances for MS quantification and are also suitable for functional studies. Copyright © 2014 by the American Society for Biochemistry and Molecular Biology, Inc.

The Host Galaxies Of UV-selected AGNs At z 2-3

NASA Astrophysics Data System (ADS)

Hainline, Kevin; Shapley, A.; Greene, J.; Steidel, C.

2012-01-01

An important goal for studies of galaxy formation consists of tracing a direct evolutionary connection between the growth of supermassive black holes powering active galactic nuclei (AGNs) and the build-up of stellar mass in their host galaxies. In the local universe, AGNs are preferentially found in bulge-dominated galaxies, but the AGN demographics at earlier epochs are not as well understood. We present a rest-frame UV composite spectrum for a sample of 33 z 2-3 AGNs drawn from the UV-selected Lyman Break Galaxy (LBG) survey. This spectrum shows many emission and absorption features, such as HI Lyman-alpha, NV 1240, NIV] 1483, 1486, CIV 1548, 1550, HeII 1640, and CIII] 1907, 1909. Redshifted SiIV 1394 absorption provides evidence for outflowing high-ionization gas in these objects at speeds of 103 km/s. Finally, using optical, near-IR, and mid-IR photometry, which cover the rest-frame UV to near-IR portions of the galaxies' spectral energy distributions, we perform stellar population synthesis modeling of the sample. Based on these results, we explore the relationship in the host galaxy between AGN activity, maturity of the stellar population, and regulation of star formation.

Remote site-selective C–H activation directed by a catalytic bifunctional template

PubMed Central

Zhang, Zhipeng; Tanaka, Keita; Yu, Jin-Quan

2017-01-01

Converting C–H bonds directly into carbon-carbon and carbon-heteroatom bonds can significantly improve step-economy in synthesis by providing alternative disconnections to traditional functional group manipulations. In this context, directed C–H activation reactions have been extensively explored for regioselective functionalization1-5. Though applicability can be severely curtailed by distance from the directing group and the shape of the molecule, a number of approaches have been developed to overcome this limitation6-12. For instance, recognition of the distal and geometric relationship between an existing functional group and multiple C–H bonds has recently been exploited to achieve meta-selective C–H activation by use of a covalently attached U-shaped template13-17. However, stoichiometric installation of the template is not feasible in the absence of an appropriate functional group handle. Here we report the design of a catalytic, bifunctional template that binds heterocyclic substrate via reversible coordination instead of covalent linkage, allowing remote site-selective C–H olefination of heterocycles. The two metal centers coordinated to this template play different roles; anchoring substrates to the proximity of catalyst and cleaving the remote C–H bonds respectively. Using this strategy, we demonstrate remote site-selective C–H olefination of heterocyclic substrates which do not have functional group handles for covalently attaching templates. PMID:28273068

Synthesis of 13(R)-Hydroxy-7Z,10Z,13R,14E,16Z,19Z Docosapentaenoic Acid (13R-HDPA) and Its Biosynthetic Conversion to the 13-Series Resolvins

PubMed Central

2016-01-01

Specialized pro-resolving lipid mediators are biosynthesized during the resolution phase of acute inflammation from n-3 polyunsaturated fatty acids. Recently, the isolation and identification of the four novel mediators denoted 13-series resolvins, namely, RvT1 (1), RvT2 (2), RvT3 (3) and RvT4 (4), were reported, which showed potent bioactions characteristic for specialized pro-resolving lipid mediators. Herein, based on results from LC/MS-MS metabololipidomics and the stereoselective synthesis of 13(R)-hydroxy-7Z,10Z,13R,14E,16Z,19Z docosapentaenoic acid (13R-HDPA, 5), we provide direct evidence that the four novel mediators 1–4 are all biosynthesized from the pivotal intermediate 5. The UV and LC/MS-MS results from synthetic 13R-HDPA (5) matched those from endogenously and biosynthetically produced material obtained from in vivo infectious exudates, endothelial cells, and human recombinant COX-2 enzyme. Stereochemically pure 5 was obtained with the use of a chiral pool starting material that installed the configuration at the C-13 atom as R. Two stereoselective Z-Wittig reactions and two Z-selective reductions of internal alkynes afforded the geometrically pure alkene moieties in 5. Incubation of 5 with isolated human neutrophils gave all four RvTs. The results presented herein provide new knowledge on the biosynthetic pathways and the enzymatic origin of RvTs 1–4. PMID:27704804

Statistical Ring Opening Metathesis Copolymerization of Norbornene and Cyclopentene by Grubbs' 1st-Generation Catalyst.

PubMed

Nikovia, Christiana; Maroudas, Andreas-Philippos; Goulis, Panagiotis; Tzimis, Dionysios; Paraskevopoulou, Patrina; Pitsikalis, Marinos

2015-08-27

Statistical copolymers of norbornene (NBE) with cyclopentene (CP) were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs' catalyst, in the presence or absence of triphenylphosphine, PPh₃. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined.

Alkaline earth metallocenes coordinated with ester pendants: synthesis, structural characterization, and application in metathesis reactions.

PubMed

Li, Heng; Zhang, Wen-Xiong; Xi, Zhenfeng

2013-09-16

A variety of ester-substituted cyclopentadiene derivatives have been synthesized by one-pot reactions of 1,4-dilithio-1,3-butadienes, CO, and acid chlorides. Direct deprotonation of the ester-substituted cyclopentadienes with Ae[N(SiMe3 )2 ]2 (Ae=Ca, Sr, Ba) efficiently generated members of a new class of heavier alkaline earth (Ca, Sr, Ba) metallocenes in good to excellent yields. Single-crystal X-ray structural analysis demonstrated that these heavier alkaline earth metallocenes incorporated two intramolecularly coordinated ester pendants and multiply-substituted cyclopentadienyl ligands. The corresponding transition metal metallocenes, such as ferrocene derivatives and half-sandwich cyclopentadienyl tricarbonylrhenium complexes, could be generated highly efficiently by metathesis reactions. The multiply-substituted cyclopentadiene ligands bearing an ester pendant, and the corresponding heavier alkaline earth and transition-metal metallocenes, may have further applications in coordination chemistry, organometallic chemistry, and organic synthesis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving Olefin Purification Using Metal Organic Frameworks with Open Metal Sites.

PubMed

Luna-Triguero, A; Vicent-Luna, J M; Poursaeidesfahani, A; Vlugt, T J H; Sánchez-de-Armas, R; Gómez-Álvarez, P; Calero, S

2018-05-16

The separation and purification of light hydrocarbons is challenging in the industry. Recently, a ZJNU-30 metal-organic framework (MOF) has been found to have the potential for adsorption-based separation of olefins and diolefins with four carbon atoms [H. M. Liu et al. Chem.-Eur. J. 2016, 22, 14988-14997]. Our study corroborates this finding but reveals Fe-MOF-74 as a more efficient candidate for the separation because of the open metal sites. We performed adsorption-based separation, transient breakthrough curves, and density functional theory calculations. This combination of techniques provides an extensive understanding of the studied system. Using this MOF, we propose a separation scheme to obtain a high-purity product.

Catalytic asymmetric dihydroxylation of olefins using a recoverable and reusable OsO(4)2- in ionic liquid [bmim][PF6].

PubMed

Branco, Luís C; Afonso, Carlos A M

2002-12-21

The use of the solvent systems water/ionic liquid or water/ionic liquid/tert-butanol provides a recoverable, reusable, robust and simple system for the asymmetric dihydroxylation of olefins, based on the immobilization of the osmium-ligand catalyst in the ionic liquid phase.

Spectroscopic Confirmation of a Massive Red-sequence Selected Galaxy Cluster at Z=1.34 in the SpARCS-South Cluster Survey

NASA Technical Reports Server (NTRS)

Wilson, Gillian; Demarco, Ricardo; Muzzin, Adam; Yee, H.K.C.; Lacy, Mark; Surace, Jason; Gilbank, David; Blindert, Kris; Hoekstra, Henk; Majumdar, Subhabrata;

Patterns of gene flow and selection across multiple species of Acrocephalus warblers: footprints of parallel selection on the Z chromosome.

PubMed

Reifová, Radka; Majerová, Veronika; Reif, Jiří; Ahola, Markus; Lindholm, Antero; Procházka, Petr

2016-06-16

Understanding the mechanisms and selective forces leading to adaptive radiations and origin of biodiversity is a major goal of evolutionary biology. Acrocephalus warblers are small passerines that underwent an adaptive radiation in the last approximately 10 million years that gave rise to 37 extant species, many of which still hybridize in nature. Acrocephalus warblers have served as model organisms for a wide variety of ecological and behavioral studies, yet our knowledge of mechanisms and selective forces driving their radiation is limited. Here we studied patterns of interspecific gene flow and selection across three European Acrocephalus warblers to get a first insight into mechanisms of radiation of this avian group. We analyzed nucleotide variation at eight nuclear loci in three hybridizing Acrocephalus species with overlapping breeding ranges in Europe. Using an isolation-with-migration model for multiple populations, we found evidence for unidirectional gene flow from A. scirpaceus to A. palustris and from A. palustris to A. dumetorum. Gene flow was higher between genetically more closely related A. scirpaceus and A. palustris than between ecologically more similar A. palustris and A. dumetorum, suggesting that gradual accumulation of intrinsic barriers rather than divergent ecological selection are more efficient in restricting interspecific gene flow in Acrocephalus warblers. Although levels of genetic differentiation between different species pairs were in general not correlated, we found signatures of apparently independent instances of positive selection at the same two Z-linked loci in multiple species. Our study brings the first evidence that gene flow occurred during Acrocephalus radiation and not only between sister species. Interspecific gene flow could thus be an important source of genetic variation in individual Acrocephalus species and could have accelerated adaptive evolution and speciation rate in this avian group by creating novel genetic

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis.

PubMed

Goblirsch, Brandon R; Jensen, Matthew R; Mohamed, Fatuma A; Wackett, Lawrence P; Wilmot, Carrie M

2016-12-23

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety-unusual for a thiolase-are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys 143 ) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C 12 and C 14 ) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ 117 ) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis*

PubMed Central

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

2016-01-01

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. PMID:27815501

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry aremore » precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation.« less

The properties and evolution of a K-band selected sample of massive galaxies at z ~ 0.4-2 in the Palomar/DEEP2 survey

NASA Astrophysics Data System (ADS)

Conselice, C. J.; Bundy, K.; Trujillo, I.; Coil, A.; Eisenhardt, P.; Ellis, R. S.; Georgakakis, A.; Huang, J.; Lotz, J.; Nandra, K.; Newman, J.; Papovich, C.; Weiner, B.; Willmer, C.

2007-11-01

We present the results of a study on the properties and evolution of massive (M* > 1011Msolar) galaxies at z ~ 0.4-2 utilizing Keck spectroscopy, near-infrared Palomar imaging, and Hubble, Chandra and Spitzer data covering fields targeted by the DEEP2 galaxy spectroscopic survey. Our sample is K-band selected and stellar mass limited, based on wide-area near-infrared imaging from the Palomar Observatory Wide-Field Infrared Survey, which covers 1.53 deg2 to a 5σ depth of Ks,vega ~ 20.5. Our primary goal is to obtain a broad census of massive galaxies through measuring how their number and mass densities, morphology, as well as their star formation and active galactic nucleus content evolve from z ~ 0.4-2. Our major findings include: (i) statistically the mass and number densities of M* > 1011Msolar galaxies show little evolution between z = 0 and 1 and from z ~ 0 to 2 for M* > 1011.5Msolar galaxies. We however find significant evolution within 1 < z < 1.5 for 1011 Msolar < M* < 1011.5Msolar galaxies. (ii) After examining the structures of our galaxies using Hubble ACS imaging, we find that M* > 1011Msolar selected galaxies show a nearly constant elliptical fraction of ~70-90 per cent at all redshifts. The remaining objects tend to be peculiars possibly undergoing mergers at z > 0.8, while spirals dominate the remainder at lower redshifts. A significant fraction (~25 per cent) of these early-types contain minor structural anomalies. (iii) We find that only a fraction (~60 per cent) of massive galaxies with M* > 1011Msolar are on the red sequence at z ~ 1.4, while nearly 100 per cent evolve on to it by z ~ 0.4. (iv) By utilizing Spitzer MIPS imaging and [OII] line fluxes we argue that M* > 1011.5Msolar galaxies have a steeply declining star formation rate (SFR) density ~ (1 + z)6. By examining the contribution of star formation to the evolution of the mass function, as well as the merger history through the CAS parameters, we determine that M* > 1011Msolar galaxies

Ultrashort pulse laser micro-welding of cyclo-olefin copolymers

NASA Astrophysics Data System (ADS)

Roth, Gian-Luca; Rung, Stefan; Hellmann, Ralf

2017-06-01

We report on the joining of transparent thermoplastic polymers using infrared femtosecond laser pulses. Due to nonlinear absorption, the developed micro-welding process for cyclo-olefin copolymers does not require any intermediate absorbing layers or any surface pre-processing of the welding partners. In view of an optimized and stable micro-welding process, the influence of the welding speed and focal position on both, the quality and shear force strength are investigated. We highlight that welding seam widths of down to 65 μm are feasible for welding speeds of up to 75 mm/s. However, a variation of the welding speed affects the required focal position for a successful joining process. The shear force strength of the welding seam is determined to 37 MPa, which corresponds to 64% of the shear strength of the bulk material and is not affected by the welding speed.

Extreme Emission Line Galaxies in CANDELS: Broad-Band Selected, Star-Bursting Dwarf Galaxies at Z greater than 1

NASA Technical Reports Server (NTRS)

VanDerWel, A.; Straughn, A. N.; Rix, H.-W.; Finkelstein, S. L.; Koekemoer, A. M.; Weiner, B. J.; Wuyts, S.; Bell, E. F.; Faber, S. M.; Trump, J. R.;

Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, January--March 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curtis, C.W.

Previous research has suggested that using a more effective hydrogen donor solvent in the low severity coal liquefaction reaction improves coal conversion. In order to understand the results of these methods, both independently and combined, a factorial experiment was designed. Pretreating coal with hydrochloric and sulfurous acid solutions in both water and methanol is compared with pretreating coal using only methanol and with no pretreatment. The effects of these pretreatments on coal liquefaction behavior are contrasted with the ammonium acetate pretreatment. Within each of these, individual reactions are performed with the hydroaromatic 1,2,3,4-tetrahydronaphthalene (tetralin, TET) and the cyclic olefin 1,4,5,8-tetrahydronaphthalenemore » (isotetralin, ISO). The final aspect of the factorial experiment is the comparison of Wyodak subbituminous coal (WY) from the Argonne Premium Sample Bank and Black Thunder subbituminous coal (BT) provided by Amoco. Half of the reactions in the matrix have now been completed. In all but one case, Black Thunder-HCl/H{sub 2}O, the ISO proved to be more reactive than TET. After the other four reactions using this combination are complete, the average conversion may be greater with the cyclic olefin. The second part of this paper describes the current and future work with Fourier transform infrared spectroscopy. The objective of this work is to determine the kinetics of reaction of isotetralin at high temperatures and pressures. This quarter combinations of three products typically produced from isotetralin were used in spectral subtraction.« less

Synthesis of ω-Oxo Amino Acids and trans-5-Substituted Proline Derivatives Using Cross-Metathesis of Unsaturated Amino Acids.

PubMed

Salih, Nabaz; Adams, Harry; Jackson, Richard F W

2016-09-16

A range of 7-oxo, 8-oxo, and 9-oxo amino acids, analogues of 8-oxo-2-aminodecanoic acid, one of the key components of the cyclic tetrapeptide apicidin, have been prepared by a three-step process involving copper-catalyzed allylation of serine-, aspartic acid-, and glutamic acid-derived organozinc reagents, followed by cross-metathesis of the resulting terminal alkenes with unsaturated ketones and hydrogenation. The intermediate 7-oxo-5-enones underwent a highly diastereoselective (dr ≥96:4) acid-catalyzed aza-Michael reaction to give trans-2,5-disubstituted pyrrolidines, 5-substituted proline derivatives. The aza-Michael reaction was first observed when the starting enones were allowed to stand in solution in deuterochloroform but can be efficiently promoted by catalytic amounts of dry HCl.

Catalytical Photocyclization of Arylamines with a-Olefins in the Synthesis of 2-Alkylquinoline

ERIC Educational Resources Information Center

Makhmutov, Aynur; Usmanov, Salavat; Mustafin, Ahat

2016-01-01

The article deals with the results of investigation of the process of catalytical photocyclization of aniline and aniline hydrochloride with a-olefins (hexene-1, heptene-1 and octene-1). The following compounds of d- and f-metals are tested as probable catalysts: CuSO4•5H2O, EuCl3•6H2O, PrCl3•6H2O, TbCl3•6H2O, La2O3, MnO2, NiSO4•6H2O, NiCl2•6H2O,…

VIMOS Ultra-Deep Survey (VUDS): IGM transmission towards galaxies with 2.5 < z < 5.5 and the colour selection of high-redshift galaxies

NASA Astrophysics Data System (ADS)

Thomas, R.; Le Fèvre, O.; Le Brun, V.; Cassata, P.; Garilli, B.; Lemaux, B. C.; Maccagni, D.; Pentericci, L.; Tasca, L. A. M.; Zamorani, G.; Zucca, E.; Amorin, R.; Bardelli, S.; Cassarà, L.; Castellano, M.; Cimatti, A.; Cucciati, O.; Durkalec, A.; Fontana, A.; Giavalisco, M.; Grazian, A.; Hathi, N. P.; Ilbert, O.; Paltani, S.; Pforr, J.; Ribeiro, B.; Schaerer, D.; Scodeggio, M.; Sommariva, V.; Talia, M.; Tresse, L.; Vanzella, E.; Vergani, D.; Capak, P.; Charlot, S.; Contini, T.; Cuby, J. G.; de la Torre, S.; Dunlop, J.; Fotopoulou, S.; Koekemoer, A.; López-Sanjuan, C.; Mellier, Y.; Salvato, M.; Scoville, N.; Taniguchi, Y.; Wang, P. W.

2017-01-01

The observed UV rest-frame spectra of distant galaxies are the result of their intrinsic emission combined with absorption along the line of sight produced by the inter-galactic medium (IGM). Here we analyse the evolution of the mean IGM transmission Tr(Lyα) and its dispersion along the line of sight for 2127 galaxies with 2.5 < z < 5.5 in the VIMOS Ultra Deep Survey (VUDS). We fitted model spectra combined with a range of IGM transmission to the galaxy spectra using the spectral fitting algorithm GOSSIP+. We used these fits to derive the mean IGM transmission towards each galaxy for several redshift slices from z = 2.5 to z = 5.5. We found that the mean IGM transmission defined as Tr(Lyα) = e- τ (with τ as the HI optical depth) is 79%, 69%, 59%, 55%, and 46% at redshifts 2.75, 3.22, 3.70, 4.23, and 4.77, respectively. We compared these results to measurements obtained from quasar lines of sight and found that the IGM transmission towards galaxies is in excellent agreement with quasar values up to redshift z 4. We found tentative evidence for a higher IGM transmission at z ≥ 4 compared to results from QSOs, but a degeneracy between dust extinction and IGM prevents us from firmly concluding whether the internal dust extinction for star-forming galaxies at z > 4 takes a mean value significantly in excess of E(B-V) > 0.15. Most importantly, we found a large dispersion of IGM transmission along the lines of sight towards distant galaxies with 68% of the distribution within 10 to 17% of the median value in δz = 0.5 bins, similar to what is found on the lines of sight towards QSOs. We demonstrate that taking this broad range of IGM transmission into account is important when selecting high-redshift galaxies based on their colour properties (e.g. LBG or photometric redshiftselection) because failing to do so causes a significant incompleteness in selecting high-redshift galaxy populations. We finally discuss the observed IGM properties and speculate that the broad

Functionalized SBA-15 supported nickel (II)–oxime–imine catalysts for liquid phase oxidation of olefins under solvent-free conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul, Luna; Banerjee, Biplab; Bhaumik, Asim, E-mail: msab@iacs.res.in

2016-05-15

A new oxime–imine functionalized highly ordered mesoporous SBA-15 (SBA-15-NH{sub 2}-DAMO) has been synthesized via post-synthesis functionalization of SBA-15 with 3-aminopropyl-triethoxysilane followed by the Schiff base condensation with diacetylmonooxime, which was further reacted with Ni(ClO{sub 4}){sub 2} to yield the functionalized nickel catalyst SBA-15-NH{sub 2}-DAMO-Ni. All the synthesized materials were thoroughly characterized using different characterization techniques. It was found that SBA-15-NH{sub 2}-DAMO-Ni catalyzes the one-pot oxidation of olefins like styrene, cyclohexene, cyclooctene, 1-hexene and 1-octene to the corresponding benzaldehyde, cyclohexene-1-ol and cyclooctene-oxide, respectively under solvent-free conditions by using tert-butylhydroperoxide as oxidant. - Graphical abstract: A new well characterized oxime–imine functionalized highlymore » ordered mesoporous SBA-15-NH{sub 2}-DAMO-Ni complex catalyzes the one-pot oxidation of olefins under solvent free mild conditions.« less

Organocatalytic sequential alpha-amination-Horner-Wadsworth-Emmons olefination of aldehydes: enantioselective synthesis of gamma-amino-alpha,beta-unsaturated esters.

PubMed

Kotkar, Shriram P; Chavan, Vilas B; Sudalai, Arumugam

2007-03-15

A novel and highly enantioselective method for the synthesis of gamma-amino-alpha,beta-unsaturated esters via tandem alpha-amination-Horner-Wadsworth-Emmons (HWE) olefination of aldehydes is described. The one-pot assembly has been demonstrated for the construction of functionalized chiral 2-pyrrolidones, subunits present in several alkaloids. [structure: see text

Chiral imidate-ferrocenylphosphanes: synthesis and application as P,N-ligands in iridium(I)-catalyzed hydrogenation of unfunctionalized and poorly functionalized olefins.

PubMed

Bert, Katrien; Noël, Timothy; Kimpe, Wim; Goeman, Jan L; Van der Eycken, Johan

2012-11-14

A small library of chiral imidate-ferrocenylphosphane ligands was efficiently synthesized (8 examples) and evaluated in the iridium(I)-catalyzed hydrogenation of unfunctionalized and poorly functionalized olefins. These catalysts perform very well in a range of examples (yields and ee's up to 100%).

Ionic-liquid mediated olefin hydroboration and heteroatom insertion reactions, and the development of template routes to non-oxide ceramic nano- and micro-structures

NASA Astrophysics Data System (ADS)

Kusari, Upal

The goal of the work described in this dissertation was two-fold: (1) To use the unique properties of ionic liquids to develop new synthetic routes to boron-containing molecules including substituted decaboranes, ortho-carboranes and chalcogeno-boranes, and (2) to combine newly developed chemical precursors with template routes to fabricate the non-oxide ceramics boron carbide, silicon carbide and boron nitride on the micro- and nano-scales. The first application of ionic liquid and related salt systems to the hydroboration of a variety of olefins with the polyborane cage B10H 14, leading to the syntheses of functionalized decaborane clusters, 6-R-B10H13, was demonstrated. The decaborane olefin-hydroboration reaction was found to proceed with a wide variety of functional olefins, including, alkenyl, halide, phenyl, ether, ester, pinacolborane, ketone and alcohol-containing olefins. These reactions provide a general, simple, one-pot and high-yield alternative route to functional boranes. The functional decaboranes were then converted by another ionic liquid mediated reaction, to its ortho -carborane derivatives 3-R-1,2-Et2C2B 10H9. Experimental and computational studies of the hydroboration mechanism suggest that the ionic liquid induced the formation of the B 10H13- anion which behaved as an electrophile in the olefin-hydroboration reaction. The unique properties of ionic liquids were also found to be useful in mediating the insertion of chalcogen heteroatoms into the borane clusters nido-B10H14, nido-5,6-C2B8H12 and arachno -4-CB8H14 and led to the improved syntheses of the known compounds nido-7-SB10H12, nido-7-SeB10H12, nido-7,9,10-SC 2B8H10, nido-7,9,10-SeC 2B8H10 and arachno-6,9-CSB 8H12, as well as the synthesis of the new 10-vertex selena-monocarbaborane arachno-6,9-CSeB8H12 (˜40% yield). The second part of the thesis demonstrated that newly developed chemical precursors can be used in conjunction with silica bead and diatom frustule templates to generate

The PEP survey: clustering of infrared-selected galaxies and structure formation at z ˜ 2 in GOODS-South

NASA Astrophysics Data System (ADS)

Magliocchetti, M.; Santini, P.; Rodighiero, G.; Grazian, A.; Aussel, H.; Altieri, B.; Andreani, P.; Berta, S.; Cepa, J.; Castañeda, H.; Cimatti, A.; Daddi, E.; Elbaz, D.; Genzel, R.; Gruppioni, C.; Lutz, D.; Magnelli, B.; Maiolino, R.; Popesso, P.; Poglitsch, A.; Pozzi, F.; Sanchez-Portal, M.; Förster Schreiber, N. M.; Sturm, E.; Tacconi, L.; Valtchanov, I.

2011-09-01

This paper presents the first direct estimate of the 3D clustering properties of far-infrared sources up to z˜ 3. This has been possible thanks to the PACS Evolutionary Probe (PEP) survey of the GOODS-South field performed with the PACS instrument on board the Herschel satellite. 550 and 502 sources were detected respectively in the 100- and 160-μm channels down to fluxes ? mJy and ? mJy, cuts that ensure >80 per cent completeness of the two catalogues. More than 65 per cent of these sources have an (either photometric or spectroscopic) redshift determination from the MUSIC catalogue; this percentage rises to ˜95 per cent in the inner portion of GOODS-South which is covered by data at other wavelengths. An analysis of the deprojected two-point correlation function w(θ) over the whole redshift range spanned by the data reports for the (comoving) correlation length, r0˜ 6.3 and ˜6.7 Mpc, respectively at 100 and 160 μm, corresponding to dark matter halo masses M≳ 1012.4 M⊙, in an excellent agreement with previous estimates obtained for mid-IR selected sources in the same field. Objects at z˜ 2 instead seem to be more strongly clustered, with r0˜ 19 and ˜17 Mpc in the two considered PACS channels. This dramatic increase of the correlation length between z˜ 1 and ˜2 is connected with the presence, more visible at 100 μm than in the other band, of a wide (at least 4 Mpc across in projection), M≳ 1014 M⊙, filamentary structure which includes more than 50 per cent of the sources detected at z˜ 2. An investigation of the properties of such sources indicates the possibility of a boosted star-forming activity in those which reside within the overdense environment with respect to more isolated galaxies found in the same redshift range. If confirmed by larger data sets, this result can be explained as due to the combined effect of large reservoirs of gas available at high redshifts in deep potential wells such as those associated with large overdensities

ENVIRONMENTAL EFFECTS ON STAR FORMATION ACTIVITY AT z {approx} 0.9 IN THE COSMOS FIELD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kajisawa, M.; Shioya, Y.; Taniguchi, Y.

2013-05-01

We investigated the fraction of [O II] emitters in galaxies at z {approx} 0.9 as a function of the local galaxy density in the Hubble Space Telescope (HST) COSMOS 2 deg{sup 2} field. [O II] emitters are selected by the narrowband excess technique with the NB711-band imaging data taken with Suprime-Cam on the Subaru telescope. We carefully selected 614 photo-z-selected galaxies with M{sub U3500} < -19.31 at z = 0.901 - 0.920, which includes 195 [O II] emitters, to directly compare the results with our previous study at z {approx} 1.2. We found that the fraction is almost constant atmore » 0.3 Mpc{sup -2} < {Sigma}{sub 10th} < 10 Mpc{sup -2}. We also checked the fraction of galaxies with blue rest-frame colors of NUV - R < 2 in our photo-z-selected sample, and found that the fraction of blue galaxies does not significantly depend on the local density. On the other hand, the semi-analytic model of galaxy formation predicted that the fraction of star-forming galaxies at z {approx} 0.9 decreases with increasing projected galaxy density even if the effects of the projection and the photo-z error in our analysis were taken into account. The fraction of [O II] emitters decreases from {approx}60% at z {approx} 1.2 to {approx}30% at z {approx} 0.9 independent of galaxy environment. The decrease of the [O II] emitter fraction could be explained mainly by the rapid decrease of star formation activity in the universe from z {approx} 1.2 to z {approx} 0.9.« less

Function-oriented synthesis: biological evaluation of laulimalide analogues derived from a last step cross metathesis diversification strategy.

PubMed

Mooberry, Susan L; Hilinski, Michael K; Clark, Erin A; Wender, Paul A

2008-01-01

Laulimalide is a potent microtubule stabilizing agent and a promising anticancer therapeutic lead. The identification of stable, efficacious and accessible analogues is critical to clinically exploiting this novel lead. To determine which structural features of laulimalide are required for beneficial function and thus for accessing superior clinical candidates, a series of side chain analogues were prepared through a last step cross metathesis diversification strategy and their biological activities were evaluated. Five analogues, differing in potency from 233 nM to 7.9 muM, effectively inhibit cancer cell proliferation. Like laulimalide, they retain activity against multidrug resistant cells, stabilize microtubules and cause the formation of aberrant mitotic spindles, mitotic accumulation, Bcl-2 phosphorylation and initiation of apoptosis. Structural modifications in the C 23-C 27 dihydropyran side chain can be made without changing the overall mechanism of action, but it is clear that this subunit has more than a bystander role.

The diverse evolutionary paths of simulated high-z massive, compact galaxies to z = 0

NASA Astrophysics Data System (ADS)

Wellons, Sarah; Torrey, Paul; Ma, Chung-Pei; Rodriguez-Gomez, Vicente; Pillepich, Annalisa; Nelson, Dylan; Genel, Shy; Vogelsberger, Mark; Hernquist, Lars

2016-02-01

Massive quiescent galaxies have much smaller physical sizes at high redshift than today. The strong evolution of galaxy size may be caused by progenitor bias, major and minor mergers, adiabatic expansion, and/or renewed star formation, but it is difficult to test these theories observationally. Herein, we select a sample of 35 massive, compact galaxies (M* = 1-3 × 1011 M⊙, M*/R1.5 > 1010.5 M⊙/kpc1.5) at z = 2 in the cosmological hydrodynamical simulation Illustris and trace them forwards to z = 0 to uncover their evolution and identify their descendants. By z = 0, the original factor of 3 difference in stellar mass spreads to a factor of 20. The dark matter halo masses similarly spread from a factor of 5 to 40. The galaxies' evolutionary paths are diverse: about half acquire an ex situ envelope and are the core of a more massive descendant, a third survive undisturbed and gain very little mass, 15 per cent are consumed in a merger with a more massive galaxy, and a small remainder are thoroughly mixed by major mergers. The galaxies grow in size as well as mass, and only ˜10 per cent remain compact by z = 0. The majority of the size growth is driven by the acquisition of ex situ mass. The most massive galaxies at z = 0 are the most likely to have compact progenitors, but this trend possesses significant dispersion which precludes a direct linkage to compact galaxies at z = 2. The compact galaxies' merger rates are influenced by their z = 2 environments, so that isolated or satellite compact galaxies (which are protected from mergers) are the most likely to survive to the present day.

Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes.

PubMed

Chen, Min; Yang, Bangpei; Chen, Changle

2015-12-14

The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene-bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting "off" and "on" behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochromatography on acrylate-based monolith in cyclic olefin copolymer microchip: an attractive technology.

PubMed

Ladner, Y; Cretier, G; Faure, K

2015-01-01

Electrochromatography (EC) on a porous monolithic stationary phase prepared within the channels of a microsystem is an attractive alternative for on-chip separation. It combines the separation mechanisms of electrophoresis and liquid chromatography. Moreover, the porous polymer monolithic materials have become popular as stationary phase due to the ease and rapidity of fabrication via free radical photopolymerization. Here, we describe a hexyl acrylate (HA)-based porous monolith which is simultaneously in situ synthesized and anchored to the inner walls of the channel of a cyclic olefin copolymer (COC) device in only 2 min. The baseline separation of a mixture of neurotransmitters including six amino acids and two catecholamines is realized.

Conversion of 2,3-butanediol to 2-butanol, olefins and fuels

DOEpatents

Lilga, Michael A.; Lee, Guo-Shuh; Lee, Suh-Jane

2016-12-13

Embodiments of an integrated method for step-wise conversion of 2,3-butanediol to 2-butanol, and optionally to hydrocarbons, are disclosed. The method includes providing an acidic catalyst, exposing a composition comprising aqueous 2,3-butanediol to the acidic catalyst to produce an intermediate composition comprising methyl ethyl ketone, providing a hydrogenation catalyst that is spatially separated from the acidic catalyst, and subsequently exposing the intermediate composition to the hydrogenation catalyst to produce a composition comprising 2-butanol. The method may further include subsequently exposing the composition comprising 2-butanol to a deoxygenation catalyst, and deoxygenating the 2-butanol to form hydrocarbons. In some embodiments, the hydrocarbons comprise olefins, such as butenes, and the method may further include subsequently exposing the hydrocarbons to a hydrogenation catalyst to form saturated hydrocarbons.

Incorporation of Amino Acids with Long-Chain Terminal Olefins into Proteins.

PubMed

Exner, Matthias P; Köhling, Sebastian; Rivollier, Julie; Gosling, Sandrine; Srivastava, Puneet; Palyancheva, Zheni I; Herdewijn, Piet; Heck, Marie-Pierre; Rademann, Jörg; Budisa, Nediljko

2016-02-29

The increasing need for site-specific protein decorations that mimic natural posttranslational modifications requires access to a variety of noncanonical amino acids with moieties enabling bioorthogonal conjugation chemistry. Here we present the incorporation of long-chain olefinic amino acids into model proteins with rational variants of pyrrolysyl-tRNA synthetase (PylRS). Nε-heptenoyl lysine was incorporated for the first time using the known promiscuous variant PylRS(Y306A/Y384F), and Nε-pentenoyl lysine was incorporated in significant yields with the novel variant PylRS(C348A/Y384F). This is the only example of rational modification at position C348 to enlarge the enzyme's binding pocket. Furthermore, we demonstrate the feasibility of our chosen amino acids in the thiol-ene conjugation reaction with a thiolated polysaccharide.

SHARDS: Survey for High-z Absorption Red & Dead Sources

NASA Astrophysics Data System (ADS)

Pérez-González, P. G.; Cava, A.

2013-05-01

SHARDS, an ESO/GTC Large Program, is an ultra-deep (26.5 mag) spectro-photometric survey with GTC/OSIRIS designed to select and study massive passively evolving galaxies at z=1.0-2.3 in the GOODS-N field using a set of 24 medium-band filters (FWHM~17 nm) covering the 500-950 nm spectral range. Our observing strategy has been planned to detect, for z>1 sources, the prominent Mg absorption feature (at rest-frame ~280 nm), a distinctive, necessary, and sufficient feature of evolved stellar populations (older than 0.5 Gyr). These observations are being used to: (1) derive for the first time an unbiased sample of high-z quiescent galaxies, which extends to fainter magnitudes the samples selected with color techniques and spectroscopic surveys; (2) derive accurate ages and stellar masses based on robust measurements of spectral features such as the Mg_UV or D(4000) indices; (3) measure their redshift with an accuracy Δz/(1+z)<0.02; and (4) study emission-line galaxies (starbursts and AGN) up to very high redshifts. The well-sampled optical SEDs provided by SHARDS for all sources in the GOODS-N field are a valuable complement for current and future surveys carried out with other telescopes (e.g., Spitzer, HST, and Herschel).

Pyrrolidine and Piperidine Formation Via Copper(II) Carboxylate Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

PubMed Central

Sherman, Eric S.; Fuller, Peter H.; Kasi, Dhanalakshmi; Chemler, Sherry R.

2008-01-01

An expanded substrate scope and in depth analysis of the reaction mechanism of the copper(II) carboxylate promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic γ- and δ-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring. PMID:17428100

Accuracy of a new ring-opening metathesis elastomeric dental impression material with spray and immersion disinfection.

PubMed

Kronström, Mats H; Johnson, Glen H; Hompesch, Richard W

2010-01-01

A new elastomeric impression material has been formulated with a ring-opening metathesis chemistry. In addition to other properties of clinical significance, the impression accuracy must be confirmed. The purpose of this study was to compare the accuracy of the new elastomeric impression material with vinyl polysiloxane and polyether following both spray and immersion disinfection. Impressions of a modified dentoform with a stainless steel crown preparation in the lower right quadrant were made, and type IV gypsum working casts and dies were formed. Anteroposterior (AP), cross-arch (CA), buccolingual (BL), mesiodistal (MD), occlusogingivobuccal (OGB), and occlusogingivolingual (OGL) dimensions were measured using a microscope. Working cast and die dimensions were compared to those of the master model. The impression materials were a newly formulated, ring-opening metathesis-polymerization impression material (ROMP Cartridge Tray and ROMP Volume Wash), vinyl polysiloxane (VPS, Aquasil Ultra Monophase/LV), and a polyether (PE, Impregum Penta Soft/Permadyne Garant L). Fifteen impressions with each material were made, of which 5 were disinfected by spray for 10 minutes (CaviCide), 5 were disinfected by immersion for 90 minutes (ProCide D), and 5 were not disinfected. There were significant cross-product interactions with a 2-way ANOVA, so a 1-way ANOVA and Dunnett's T3 multiple comparison test were used to compare the dimensional changes of the 3 impression materials, by disinfection status and for each location (alpha=.05). For ROMP, there were no significant differences from the master, for any dimension, when comparing the control and 2 disinfectant conditions. No significant differences were detected among the 3 impression materials for CA, BL, and MD. The working die dimensions of OGB and OGL for VPS with immersion disinfection were significantly shorter than with PE and ROMP (P<.05). Overall, the AP dimension was more accurate than CA, and the BL of working dies

Kinetic Studies of the Thermal Decomposition of Methylperoxynitrate and of Ozone-Olefin Reactions.

NASA Astrophysics Data System (ADS)

Bahta, Abraha

This research concerns the thermal decomposition kinetics of CH(,3)O(,2)NO(,2) and laboratory kinetic measurements of ozone-olefin reactions. In the first system, the thermal decomposition rate of CH(,3)O(,2)NO(,2) was studied in the temperature range of 256-268 K at (TURN)350 torr total pressure and in the pressure range of 50-720 torr at 263 K by the perturbation of the equilibrium: (UNFORMATTED TABLE FOLLOWS). CH(,3)O(,2) + NO(,2) (+M) (DBLARR) CH(,3)O(,2)NO(,2) (+M) (3,-3). with NO. CH(,3)O(,2) + NO (--->) CH(,3)O + NO(,2) (4). (TABLE ENDS). The CH(,3)O(,2)NO(,2) was generated in situ by the photolysis of Cl(,2) in the presence of O(,2), CH(,4) and NO(,2). The decomposition kinetics were monitored in the presence of NO by the change in ultraviolet absorption at 250 nm. The Arrhenius expression obtained for the thermal decomposition is k(,-3) = 6 x 10('15) exp{-(21,000 (+OR-) 1500)/RT} sec('-1) at (TURNEQ)350 torr total pressure (mostly CH(,4)) where R = 1.987 cal/mole('-) K. The uncertainty in the Arrhenius parameters can be greatly reduced by combining this expression with data for k(,3) and thermodynamics data to give k(,-3) = (6 (+OR-) 3) x 10('15) exp{-(21,300 (+OR-) 300)/RT} sec('-1) at (TURNEQ)350 torr total pressure. Computations based on the pressure dependence of the forward reaction give k(,-3)('(INFIN)) = 2.1 x 10('16) exp{-(21,700 (+OR -) 300)/RT} sec('-1) k(,-3)('(DEGREES)) = 3.3 x 10(' -4) exp{-(20,150 x 300)/RT} cm('3) sec('-1). At 263 K the equilibrium constant K(,3,-3){263 K} is determined to be (2.68 (+OR-) 0.26) x 10('-10) cm('3). In the stratosphere the CH(,3)O(,2)NO(,2) lifetime will be controlled by play a role in the NO(,x) budget of the lower stratosphere. In the second part, the kinetics of the reactions of O(,3) with C(,2)H(,4), C(,3)H(,4), 1,3-C(,4)H(,6), and trans-1,3-C(,5)H(,8) were studied with initial olefin-to -ozone ratios (GREATERTHEQ) 4.9, in the presence of excess O(,2), and over the temperature range 232 to 300 K. The

Determination of mineral oil aromatic hydrocarbons in edible oils and fats by online liquid chromatography-gas chromatography-flame ionization detection - Evaluation of automated removal strategies for biogenic olefins.

PubMed

Nestola, Marco; Schmidt, Torsten C

2017-07-07

The determination of mineral oil aromatic hydrocarbons (MOAH) in foodstuffs gained in importance over the last years as carcinogenicity cannot be excluded for certain MOAH. The existence of olefins in foodstuffs, such as edible oils and fats, can be problematic for the determination of MOAH by LC-GC-FID. Removal of these interfering substances by HPLC based on polarity differences is not possible. During gas chromatographic separation heavily overloaded peaks are observed rendering the detection of small mineral oil contaminations almost impossible. Therefore, removal of these olefins is necessary before subjection of the sample to LC-GC-FID. Epoxidation of olefins to increase their polarity proved to be a valuable tool in the past. Precision and trueness of the results as shown in a collaborative trial, however, are relying on exact reaction conditions. Additionally, it is known that certain MOAH are oxidized during epoxidation and therefore get lost. In the scope of this work, hydroboration, bromohydrin reaction, and epoxidation were examined for their potential for derivatization of unsaturated hydrocarbons with increased robustness and higher recovery of MOAH. Epoxidation by meta-chloroperoxybenzoic acid (mCPBA) delivered the best removal of olefins. Factors influencing this reaction were enlightened. Adaption of the reaction conditions and time-controlled automation increased the recovery of polycyclic MOAH. Good precision (RSD r <1.5%) and recovery (95-102%) for MOAH were also observed for sunflower and olive oils spiked with a lubricating mineral oil (at 24.5mg/kg of MOAH). The trueness of the method was verified by analyzing collaborative trial samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of Shear-Thinning Behavior on Film Thickness and Friction Coefficient of Polyalphaolefin Base Fluids With Varying Olefin Copolymer Content

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zolper, Thomas J.; He, Yifeng; Delferro, Massimiliano

2016-08-11

This study investigates the rheological properties, elastohydrodynamic (EHD) film-forming capability, and friction coefficients of low molecular mass poly-alpha-olefin (PAO) base stocks with varying contents of high molecular mass olefin copolymers (OCPs) to assess their shear stability and their potential for energy-efficient lubrication. Several PAO-OCP mixtures were blended in order to examine the relationship between their additive content and tribological performance. Gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy were used to characterize the molecular masses and structures, respectively. Density, viscosity, EHD film thickness, and friction were measured at 303 K, 348 K, and 398 K. Film thickness andmore » friction were studied at entrainment speeds relevant to the boundary, mixed, and full-film lubrication regimes. The PAO-OCP mixtures underwent temporary shear-thinning resulting in decreases in film thickness and hydrodynamic friction. These results demonstrate that the shear characteristics of PAO-OCP mixtures can be tuned with the OCP content and provide insight into the effects of additives on EHD characteristics.« less

Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins

DOEpatents

Pecharsky, Vitalij K.; Balema, Viktor P.; Wiench, Jerzy W.; Pruski, Marek

2004-05-04

The present invention provides a method of preparing a phosphonium salt of the formula [R.sup.1 R.sup.2 R.sup.3 P--CR.sup.4 R.sup.5 R.sup.6 ]X, comprising ball-milling a phosphine of the formula R.sup.1 R.sup.2 R.sup.3 P with a compound of the formula XCR.sup.4 R.sup.5 R.sup.6 ; a method of preparing a phosphorus ylide of the formula R.sup.1 R.sup.2 R.sup.3 P.dbd.CR.sup.4 R.sup.5, comprising ball-milling a phosphonium salt of the formula [R.sup.1 R.sup.2 R.sup.3 P--HCR.sup.4 R.sup.5 ]X in the presence of a base; and a method of preparing an olefin of the formula R.sup.4 R.sup.5 C.dbd.CR.sup.7 H or R.sup.4 R.sup.5 C.dbd.CR.sup.7 R.sup.8, comprising ball-milling a phosphorus ylide of the formula R.sup.1 R.sup.2 R.sup.3 P.dbd.CR.sup.4 R.sup.5 with a compound of the formula R.sup.7 C(O)H or R.sup.7 C(O)R.sup.8. The inventive method produces phosphonium salts and phosphorus ylides by mechanical processing solid reagents under solvent-free conditions. The advantages of the present invention over conventional solution methods, include: (1) extremely high selectivity; (2) high yields; (3) low processing temperatures; (4) simple and scalable reactions using commercially available equipment; and (5) the complete elimination of solvents from the reaction.

Proto-Clusters with Evolved Populations around Radio Galaxies at 2<z<3

NASA Astrophysics Data System (ADS)

Kodama, T.; Tanaka, M.; Tanaka, I.; Kajisawa, M.

2007-12-01

We present an on-going near-infrared survey of proto-clusters around high-z radio-loud galaxies at 2 ≲ z ≲ 3 with a new wide-field instrument MOIRCS on Subaru. Most of these field are known to show a large number of Lyα and/or Hα emitters at the same redshifts of the radio galaxies. We see a clear excess of near-infrared selected galaxies (JHK_s-selected galaxies as well as DRG) in these fields, and they are indeed proto-clusters with not only young emitters but also evolved populations. Spatial distribution of such NIR selected galaxies is filamentary and track similar structures traced by the emitters. There is an hint that the bright-end of the red sequence first appeared between z=3 and 2.

Eight New Luminous z > 6 Quasars Selected via SED Model Fitting of VISTA, WISE and Dark Energy Survey Year 1 Observations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, S.L.; et al.

We present the discovery and spectroscopic confirmation with the ESO NTT and Gemini South telescopes of eight new 6.0 < z < 6.5 quasars with zmore » $$_{AB}$$ < 21.0. These quasars were photometrically selected without any star-galaxy morphological criteria from 1533 deg$$^{2}$$ using SED model fitting to photometric data from the Dark Energy Survey (g, r, i, z, Y), the VISTA Hemisphere Survey (J, H, K) and the Wide-Field Infrared Survey Explorer (W1, W2). The photometric data was fitted with a grid of quasar model SEDs with redshift dependent Lyman-{\\alpha} forest absorption and a range of intrinsic reddening as well as a series of low mass cool star models. Candidates were ranked using on a SED-model based $$\\chi^{2}$$-statistic, which is extendable to other future imaging surveys (e.g. LSST, Euclid). Our spectral confirmation success rate is 100% without the need for follow-up photometric observations as used in other studies of this type. Combined with automatic removal of the main types of non-astrophysical contaminants the method allows large data sets to be processed without human intervention and without being over run by spurious false candidates. We also present a robust parametric redshift estimating technique that gives comparable accuracy to MgII and CO based redshift estimators. We find two z $$\\sim$$ 6.2 quasars with HII near zone sizes < 3 proper Mpc which could indicate that these quasars may be young with ages < 10$^6$ - 10$^7$ years or lie in over dense regions of the IGM. The z = 6.5 quasar VDESJ0224-4711 has J$$_{AB}$$ = 19.75 is the second most luminous quasar known with z > 6.5.« less

Application of thiol-olefin co-oxygenation methodology to a new synthesis of the 1,2,4-trioxane pharmacophore.

PubMed

O'Neill, Paul M; Mukhtar, Amira; Ward, Stephen A; Bickley, Jamie F; Davies, Jill; Bachi, Mario D; Stocks, Paul A

2004-09-02

[reaction: see text] Thiol-olefin co-oxygenation (TOCO) of substituted allylic alcohols generates alpha-hydroxyperoxides that can be condensed in situ with various ketones to afford a series of functionalized 1,2,4-trioxanes in good yields. Manipulation of the phenylsulfenyl group in 4a allows for convenient modification to the spiro-trioxane substituents, and we describe, for the first time, the preparation of a new class of antimalarial prodrug.

A Solomon link through an interwoven molecular grid.

PubMed

Beves, Jonathon E; Danon, Jonathan J; Leigh, David A; Lemonnier, Jean-François; Vitorica-Yrezabal, Iñigo J

2015-06-22

A molecular Solomon link was synthesized through the assembly of an interwoven molecular grid consisting of four bis(benzimidazolepyridyl)benzthiazolo[5,4-d]thiazole ligands and four zinc(II), iron(II), or cobalt(II) cations, followed by ring-closing olefin metathesis. NMR spectroscopy, mass spectrometry, and X-ray crystallography confirmed the doubly interlocked topology, and subsequent demetalation afforded the wholly organic Solomon link. The synthesis, in which each metal ion defines the crossing point of two ligand strands, suggests that interwoven molecular grids should be useful scaffolds for the rational construction of other topologically complex structures. © 2015 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.

Divergent Total Syntheses of (-)-Huperzine Q, (+)-Lycopladine B, (+)-Lycopladine C, and (-)-4-epi-Lycopladine D.

PubMed

Hong, Benke; Hu, Dachao; Wu, Jinbao; Zhang, Jing; Li, Houhua; Pan, Yingming; Lei, Xiaoguang

2017-07-04

We report herein our synthetic efforts towards the divergent syntheses of (-)-huperzine Q (1), (+)-lycopladine B (2), (+)-lycopladine C (3), and (-)-lycopladine D (4). The 10-step total synthesis of (-)-huperzine Q (1) and the first total syntheses of (+)-lycopladines B (2) and C (3) were accomplished through a series of cascade reactions. Our approach involved a Michael addition/aldol/intramolecular C-alkylation sequence to forge the 6/9 spirocycle ring, and this was followed by an ethylene-accelerated carbonyl-olefin metathesis to construct the common 6/5/9 ring system. Finally, late-stage enamine bromofunctionalization enabled us to access (-)-huperzine Q (1), (+)-lycopladine B (2), and (+)-lycopladine C (3), and a tandem C4-epimerization/retro-Claisen condensation furnished (-)-4-epi-lycopladine D (63). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ethylene polymerization on a SiH4-modified Phillips catalyst: detection of in situ produced α-olefins by operando FT-IR spectroscopy.

PubMed

Barzan, Caterina; Groppo, Elena; Quadrelli, Elsje Alessandra; Monteil, Vincent; Bordiga, Silvia

2012-02-21

Ethylene polymerization on a model Cr(II)/SiO(2) Phillips catalyst modified with gas phase SiH(4) leads to a waxy product containing a bimodal MW distribution of α-olefins (M(w) < 3000 g mol(-1)) and a highly branched polyethylene, LLDPE (M(w) ≈ 10(5) g mol(-1), T(m) = 123 °C), contrary to the unmodified catalyst which gives a linear and more dense PE, HDPE (M(w) = 86,000 g mol(-1) (PDI = 7), T(m) = 134 °C). Pressure and temperature resolved FT-IR spectroscopy under operando conditions (T = 130-230 K) allows us to detect α-olefins, and in particular 1-hexene and 1-butene (characteristic IR absorption bands at 3581-3574, 1638 and 1598 cm(-1)) as intermediate species before their incorporation in the polymer chains. The polymerization rate is estimated, using time resolved FT-IR spectroscopy, to be 7 times higher on the SiH(4)-modified Phillips catalyst with respect to the unmodified one.

Olefin unit primary fractionator on-line Petro-Blast Lancing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, W.D.; Rutan, C.R.

1994-12-31

Today`s commodity chemicals market forces companies to find innovative ways to extend unit on line operation between turnarounds such that they will remain economically competitive. At the OxyChem Chocolate Bayou facility the Primary Fractionator, quench oil column, fouling defined the length of the run between Olefin Unit turnarounds. Polymer growth on the valve trays restricted vapor flow through the column. This increased the column pressure drop which resulted in severe flooding. The inability to cool the furnace effluent while separating the fuel oil and gasoline components would cause premature shutdowns. Fouling locations were defined using gamma scan techniques and pressuremore » surveys. Nozzles were welded and hot tapped at strategic locations around the column. A high pressure Petro-Blast Lancing technique, inserted through the nozzles, was then used to clean the trays. The operation has extended the unit run length although the column may require additional Petro-Blast Lancing before the next scheduled plant turnaround. If this schedule holds, a two year extension in the unit run length will be realized.« less

Recent Structural Evolution of Early-Type Galaxies: Size Growth from z = 1 to z = 0

NASA Astrophysics Data System (ADS)

van der Wel, Arjen; Holden, Bradford P.; Zirm, Andrew W.; Franx, Marijn; Rettura, Alessandro; Illingworth, Garth D.; Ford, Holland C.

2008-11-01

Strong size and internal density evolution of early-type galaxies between z ~ 2 and the present has been reported by several authors. Here we analyze samples of nearby and distant (z ~ 1) galaxies with dynamically measured masses in order to confirm the previous, model-dependent results and constrain the uncertainties that may play a role. Velocity dispersion (σ) measurements are taken from the literature for 50 morphologically selected 0.8 < z < 1.2 field and cluster early-type galaxies with typical masses Mdyn = 2 × 1011 M⊙. Sizes (Reff) are determined with Advanced Camera for Surveys imaging. We compare the distant sample with a large sample of nearby (0.04 < z < 0.08) early-type galaxies extracted from the Sloan Digital Sky Survey for which we determine sizes, masses, and densities in a consistent manner, using simulations to quantify systematic differences between the size measurements of nearby and distant galaxies. We find a highly significant difference between the σ - Reff distributions of the nearby and distant samples, regardless of sample selection effects. The implied evolution in Reff at fixed mass between z = 1 and the present is a factor of 1.97 +/- 0.15. This is in qualitative agreement with semianalytic models; however, the observed evolution is much faster than the predicted evolution. Our results reinforce and are quantitatively consistent with previous, photometric studies that found size evolution of up to a factor of 5 since z ~ 2. A combination of structural evolution of individual galaxies through the accretion of companions and the continuous formation of early-type galaxies through increasingly gas-poor mergers is one plausible explanation of the observations. Based on observations with the Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS5-26555, and observations made with the Spitzer Space Telescope, which is operated by the Jet Propulsion Laboratory

Rhodium-catalyzed sequential allylic amination and olefin hydroacylation reactions: enantioselective synthesis of seven-membered nitrogen heterocycles.

PubMed

Arnold, Jeffrey S; Mwenda, Edward T; Nguyen, Hien M

2014-04-01

Dynamic kinetic asymmetric amination of branched allylic acetimidates has been applied to the synthesis of 2-alkyl-dihydrobenzoazepin-5-ones. These seven-membered-ring aza ketones are prepared in good yield with high enantiomeric excess by rhodium-catalyzed allylic substitution with 2-amino aryl aldehydes followed by intramolecular olefin hydroacylation of the resulting alkenals. This two-step procedure is amenable to varied functionality and proves useful for the enantioselective preparation of these ring systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Galaxies in x-ray selected clusters and groups in Dark Energy Survey Data I: Stellar mass growth of bright central galaxies since Z similar to 1.2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Y.; Miller, C.; McKay, T.

2016-01-10

Using the science verification data of the Dark Energy Survey for a new sample of 106 X-ray selected clusters and groups, we study the stellar mass growth of bright central galaxies (BCGs) since redshift z similar to 1.2. Compared with the expectation in a semi-analytical model applied to the Millennium Simulation, the observed BCGs become under-massive/under-luminous with decreasing redshift. We incorporate the uncertainties associated with cluster mass, redshift, and BCG stellar mass measurements into an analysis of a redshift-dependent BCG-cluster mass relation, m(*) proportional to (M-200/1.5 x 10(14)M(circle dot))(0.24 +/- 0.08)(1+z)(-0.19 +/- 0.34), and compare the observed relation to themore » model prediction. We estimate the average growth rate since z = 1.0 for BCGs hosted by clusters of M-200,M-z = 10(13.8)M(circle dot); at z = 1.0: m(*, BCG) appears to have grown by 0.13 +/- 0.11 dex, in tension at the similar to 2.5 sigma significance level with the 0.40 dex growth rate expected from the semi-analytic model. We show that the build-up of extended intracluster light after z = 1.0 may alleviate this tension in BCG growth rates.« less

Stereocontrolled intramolecular iron-mediated diene/olefin cyclocoupling

NASA Astrophysics Data System (ADS)

Dorange, Ismet B.

A methodology for stereocontrol during the intramolecular coupling between cyclohexadiene-Fe(CO)3 complexes and pendant alkenes is presented. Introduction of a methoxy group at the C(3) position of the diene moiety controls pre- and post-cyclization rearrangements of the diene Fe(CO)3 unit, allowing the preparation of spirolactams with defined relative stereochemistry and with a cyclohexenone framework, thus making this reaction a potentially valuable tool for the construction of quaternary carbon centers.* A new methodology for the formation of tricarbonyl(cyclohexadienyl)ketone iron complexes was also developed. This method involves the coupling of a Grignard reagent with an acyl mesylate iron complex, giving rise to ketone derivatives in excellent yields. The possibility of intramolecular coupling between diene-Fe(CO)3 complexes and homoallylic olefin was demonstrated. The stereospecific formation of spiroketones occurred in excellent yields under thermal conditions, but appeared to be limited to the simpler, less substituted pendant alkenes. The control of the stereochemical outcome of these spirocyclization was achieved using the "C(3) substitution method" previously described. The same trends were observed in these series. Also illustrated in these studies is the extension of this spirocoupling to the formation of a spiro[5.5]undecane framework. It is the first time that this framework has been accessed using this intramolecular coupling.* *Please refer to dissertation for diagram.

The Ellipticities of Cluster Early-type Galaxies from z ~ 1 to z ~ 0: No Evolution in the Overall Distribution of Bulge-to-Disk Ratios

NASA Astrophysics Data System (ADS)

Holden, B. P.; Franx, M.; Illingworth, G. D.; Postman, M.; van der Wel, A.; Kelson, D. D.; Blakeslee, J. P.; Ford, H.; Demarco, R.; Mei, S.

2009-03-01

We have compiled a sample of early-type cluster galaxies from 0 < z < 1.3 and measured the evolution of their ellipticity distributions. Our sample contains 487 galaxies in 17 z>0.3 clusters with high-quality space-based imaging and a comparable sample of 210 galaxies in 10 clusters at z < 0.05. We select early-type galaxies (elliptical and S0 galaxies) that fall within the cluster R 200, and which lie on the red-sequence in the magnitude range -19.3>MB > - 21, after correcting for luminosity evolution as measured by the fundamental plane. Our ellipticity measurements are made in a consistent manner over our whole sample. We perform extensive simulations to quantify the systematic and statistical errors, and find that it is crucial to use point-spread function (PSF)-corrected model fits; determinations of the ellipticity from Hubble Space Telescope image data that do not account for the PSF "blurring" are systematically and significantly biased to rounder ellipticities at redshifts z>0.3. We find that neither the median ellipticity, nor the shape of the ellipticity distribution of cluster early-type galaxies evolves with redshift from z ~ 0 to z>1 (i.e., over the last ~8 Gyr). The median ellipticity at z>0.3 is statistically identical with that at z < 0.05, being higher by only 0.01 ± 0.02 or 3 ± 6%, while the distribution of ellipticities at z>0.3 agrees with the shape of the z < 0.05 distribution at the 1-2% level (i.e., the probability that they are drawn from the same distribution is 98-99%). These results are strongly suggestive of an unchanging overall bulge-to-disk ratio distribution for cluster early-type galaxies over the last ~8 Gyr from z ~ 1 to z ~ 0. This result contrasts with that from visual classifications which show that the fraction of morphologically-selected disk-dominated early-type galaxies, or S0s, is significantly lower at z>0.4 than at z ~ 0. We find that the median disk-dominated early-type, or S0, galaxy has a somewhat higher

Super-Eight: The brightest z~8 Galaxies

NASA Astrophysics Data System (ADS)

Holwerda, Benne; Bouwens, R.; Bradley, L.; Calvi, V.; Illingworth, G.; Labbe, I.; Magee, D.; Oesch, P.; Roberts-Borsani, G.; Smit, R.

2016-08-01

What are the properties of the most massive z~8 galaxies ('Super-Eights') and how luminous can these galaxies become at that epoch? Answering these questions is challenging due to the rarity of luminous z~8 galaxies and the large field-to-field variations in their volume densities. Indeed, the full wide-area CANDELS program only shows 3 z~8 galaxy candidates brighter than 25.5 mag and all of these candidates conspicuously lie in the same CANDELS field (EGS). One of our strongest new probes for particularly luminous z~8 galaxies are the WFC3 Pure-Parallel (PP) programs. Particularly intriguing are 8 bright z~8 candidates in these observations. These candidates have similar luminosities as the 3 brightest z~8 candidates from CANDELS (all spectroscopically confirmed). However, the uncertain contamination levels at extreme bright end of z~8 selection mean that follow-up observations are critical. We propose highly-efficient pointed HST and Spitzer/IRAC observations to determine if these candidates are indeed at z~8. We estimate that anywhere from 50 to 100% of the targeted sources will be confirmed to be at z~8 based on our results from CANDELS. The estimate is very uncertain due to very large cosmic variance in the CANDELS result and contamination from rare low-redshift sources. When combined with CANDELS, our observations would provide us the strongest current constraints on the volume density of bright, massive galaxies in the early Universe (serving as a guide to models of their build-up) and also provide valuable targets for future spectroscopy (e.g. with JWST), useful for probing the ionization state of the IGM.

Super-Eight: The brightest z 8 Galaxies

NASA Astrophysics Data System (ADS)

Holwerda, Benne

2016-10-01

What are the properties of the most massive z 8 galaxies (Super-Eights) and how luminous can these galaxies become at that epoch? Answering these questions is challenging due to the rarity of luminous z 8 galaxies and the large field-to-field variations in their volume densities. Indeed, the full wide-area CANDELS program only shows 3 z 8 galaxy candidates brighter than 25.5 mag and all of these candidates conspicuously lie in the same CANDELS field (EGS). One of our strongest new probes for particularly luminous z 8 galaxies are the WFC3 Pure-Parallel (PP) programs. Particularly intriguing are 8 bright z 8 candidates in these observations. These candidates have similar luminosities as the 3 brightest z 8 candidates from CANDELS (all spectroscopically confirmed). However, the uncertain contamination levels at extreme bright end of z 8 selection mean that follow-up observations are critical. We propose highly-efficient pointed HST and Spitzer/IRAC observations to determine if these candidates are indeed at z 8. We estimate that anywhere from 50 to 100% of the targeted sources will be confirmed to be at z 8 based on our results from CANDELS. The estimate is very uncertain due to very large cosmic variance in the CANDELS result and contamination from rare low-redshift sources.When combined with CANDELS, our observations would provide us the strongest current constraints on the volume density of bright, massive galaxies in the early Universe (serving as a guide to models of their build-up) and also provide valuable targets for future spectroscopy (e.g. with JWST), useful for probing the ionization state of the IGM.

SUBARU HIGH- z EXPLORATION OF LOW-LUMINOSITY QUASARS (SHELLQs). I. DISCOVERY OF 15 QUASARS AND BRIGHT GALAXIES AT 5.7 < z < 6.9

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsuoka, Yoshiki; Kashikawa, Nobunari; Imanishi, Masatoshi

We report the discovery of 15 quasars and bright galaxies at 5.7 < z < 6.9. This is the initial result from the Subaru High- z Exploration of Low-Luminosity Quasars project, which exploits the exquisite multiband imaging data produced by the Subaru Hyper Suprime-Cam (HSC) Strategic Program survey. The candidate selection is performed by combining several photometric approaches including a Bayesian probabilistic algorithm to reject stars and dwarfs. The spectroscopic identification was carried out with the Gran Telescopio Canarias and the Subaru Telescope for the first 80 deg{sup 2} of the survey footprint. The success rate of our photometric selectionmore » is quite high, approaching 100% at the brighter magnitudes (z {sub AB} < 23.5 mag). Our selection also recovered all the known high- z quasars on the HSC images. Among the 15 discovered objects, six are likely quasars, while the other six with interstellar absorption lines and in some cases narrow emission lines are likely bright Lyman-break galaxies. The remaining three objects have weak continua and very strong and narrow Ly α lines, which may be excited by ultraviolet light from both young stars and quasars. These results indicate that we are starting to see the steep rise of the luminosity function of z ≥ 6 galaxies, compared with that of quasars, at magnitudes fainter than M {sub 1450} ∼ −22 mag or z {sub AB} ∼ 24 mag. Follow-up studies of the discovered objects as well as further survey observations are ongoing.« less

A Faint Flux-limited Ly α Emitter Sample at z ∼ 0.3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wold, Isak G. B.; Finkelstein, Steven L.; Barger, Amy J.

2017-10-20

We present a flux-limited sample of z ∼ 0.3 Ly α emitters (LAEs) from Galaxy Evolution Explorer ( GALEX ) grism spectroscopic data. The published GALEX z ∼ 0.3 LAE sample is pre-selected from continuum-bright objects and thus is biased against high equivalent width (EW) LAEs. We remove this continuum pre-selection and compute the EW distribution and the luminosity function of the Ly α emission line directly from our sample. We examine the evolution of these quantities from z ∼ 0.3 to 2.2 and find that the EW distribution shows little evidence for evolution over this redshift range. As shownmore » by previous studies, the Ly α luminosity density from star-forming (SF) galaxies declines rapidly with declining redshift. However, we find that the decline in Ly α luminosity density from z = 2.2 to z = 0.3 may simply mirror the decline seen in the H α luminosity density from z = 2.2 to z = 0.4, implying little change in the volumetric Ly α escape fraction. Finally, we show that the observed Ly α luminosity density from AGNs is comparable to the observed Ly α luminosity density from SF galaxies at z = 0.3. We suggest that this significant contribution from AGNs to the total observed Ly α luminosity density persists out to z ∼ 2.2.« less

VizieR Online Data Catalog: z=4.5 and z=5.7 LAEs properties with Spitzer (Finkelstein+, 2015)

NASA Astrophysics Data System (ADS)

Finkelstein, K. D.; Finkelstein, S. L.; Tilvi, V.; Malhotra, S.; Rhoads, J. E.; Grogin, N. A.; Pirzkal, N.; Dey, A.; Jannuzi, B. T.; Mobasher, B.; Pakzad, S.; Salmon, B.; Wang, J.

2017-10-01

The LAEs targeted by the Spitzer survey were discovered by the Large Area Lyman Alpha (LALA) Survey (Rhoads et al. 2000ApJ...545L..85R), which includes the Bootes field and has accompanying deep broadband imaging in B, V, R, I, and z' bands taken with the MOSAIC camera on the 4 m Mayall telescope at the Kitt Peak National Observatory. To select the z=4.5 and 5.7 LAE candidates the following criteria were used: (1) a secure detection (>5σ) in the narrowband filter; (2) a strong narrowband excess, i.e., the flux density in the narrowband should exceed that in the broadband at the 4σ level, this is done by requiring a narrowband-broadband color <-0.75 mag; and (3) no flux at wavelengths shorter than the expected Lyman break. The last condition implies that at z=4.5, sources are undetected in the B-band, while for z=5.7 sources, they are undetected in both the B-band and V-band. (5 data files).

On-chip micropatterning of plastic (cylic olefin copolymer, COC) microfluidic channels for the fabrication of biomolecule microarrays using photografting methods.

PubMed

Pu, Qiaosheng; Oyesanya, Olufemi; Thompson, Bowlin; Liu, Shantang; Alvarez, Julio C

2007-01-30

This paper reports on the surface modification of plastic microfluidic channels to prepare different biomolecule micropatterns using ultraviolet (UV) photografting methods. The linkage chemistry is based upon UV photopolymerization of acryl monomers to generate thin films (0.01-6 microm) chemically linked to the organic backbone of the plastic surface. The commodity thermoplastic, cyclic olefin copolymer (COC) was selected to build microfluidic chips because of its significant UV transparency and easiness for microfabrication by molding techniques. Once the polyacrylic films were grafted on the COC surface using photomasks, micropatterns of proteins, DNA, and biotinlated conjugates were readily obtained by surface chemical reactions in one or two subsequent steps. The thickness of the photografted films can be tuned from several nanometers up to several micrometers, depending on the reaction conditions. The micropatterned films can be prepared inside the microfluidic channel (on-chip) or on open COC surfaces (off-chip) with densities of functional groups about 10(-7) mol/cm2. Characterization of these films was performed by attenuated-total-reflectance IR spectroscopy, fluorescence microscopy, profilometry, atomic force microscopy, and electrokinetic methods.

Iron(II)-catalyzed intermolecular amino-oxygenation of olefins through the N-O bond cleavage of functionalized hydroxylamines.

PubMed

Lu, Deng-Fu; Zhu, Cheng-Liang; Jia, Zhen-Xin; Xu, Hao

2014-09-24

An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N-O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods.

Variable Selection in Logistic Regression.

DTIC Science & Technology

1987-06-01

23 %. AUTIOR(.) S. CONTRACT OR GRANT NUMBE Rf.i %Z. D. Bai, P. R. Krishnaiah and . C. Zhao F49620-85- C-0008 " PERFORMING ORGANIZATION NAME AND AOORESS...d I7 IOK-TK- d 7 -I0 7’ VARIABLE SELECTION IN LOGISTIC REGRESSION Z. D. Bai, P. R. Krishnaiah and L. C. Zhao Center for Multivariate Analysis...University of Pittsburgh Center for Multivariate Analysis University of Pittsburgh Y !I VARIABLE SELECTION IN LOGISTIC REGRESSION Z- 0. Bai, P. R. Krishnaiah

Catalytic coupling of sp2- and sp-hybridized carbon-hydrogen bonds with vinylmetalloid compounds.

PubMed

Marciniec, Bogdan

2007-10-01

In the Account given herein, it has been shown that silylative coupling of olefins, well-recognized as a new catalytic route for the activation of double bond C-H bond of olefins and double bond C-Si bond of vinylsilicon compounds with ethylene elimination, can be extended over both other vinylmetalloid derivatives (double bond C-E) (where E = Ge, B, and others) as well as the activation of triple bond C-H, double bond C aryl-H, and -O-H bond of alcohols and silanols. This general transformation is catalyzed by transition-metal complexes (mainly Ru and Rh) containing or initiating TM-H and/or TM-E bonds (inorganometallics). This new general catalytic route for the activation of double bond C-H and triple bond C-H as well as double bond C-E bonds called metallative coupling or trans-metalation (cross-coupling, ring-closing, and polycondensation) constitutes an efficient method (complementary to metathesis) for stereo- and regioselective synthesis of a variety of molecular and macromolecular compounds of vinyl-E (E = Si, B, and Ge) and ethynyl-E (E = Si and Ge) functionality, also potent organometallic reagents for efficient synthesis of highly pi-conjugated organic compounds. The mechanisms of the catalysis of this deethenative metalation have been supported by equimolar reactions of TM-H and/or TM-E with initial substances and reactions with deuterium-labeled reagents.

Clustering of moderate luminosity X-ray-selected type 1 and type 2 AGNs at z ∼ 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allevato, V.; Finoguenov, A.; Civano, F.

2014-11-20

We investigate, for the first time at z ∼ 3, the clustering properties of 189 Type 1 and 157 Type 2 X-ray active galactic nuclei (AGNs) of moderate luminosity ((L {sub bol}) = 10{sup 45.3} erg s{sup –1}), with photometric or spectroscopic redshifts in the range 2.2 < z < 6.8. These samples are based on Chandra and XMM-Newton data in COSMOS. We find that Type 1 and Type 2 COSMOS AGNs at z ∼ 3 inhabit DMHs with typical mass of log M{sub h} = 12.84{sub −0.11}{sup +0.10} and 11.73{sub −0.45}{sup +0.39} h {sup –1} M {sub ☉}, respectively.more » This result requires a drop in the halo masses of Type 1 and 2 COSMOS AGNs at z ∼ 3 compared to z ≲ 2 XMM-COSMOS AGNs with similar luminosities. Additionally, we infer that unobscured COSMOS AGNs at z ∼ 3 reside in 10 times more massive halos compared to obscured COSMOS AGNs, at the 2.6σ level. This result extends to z ∼ 3 the results found in COSMOS at z ≲ 2, and rules out the picture in which obscuration is purely an orientation effect. A model which assumes that the AGNs activity is triggered by major mergers is quite successful in predicting both the low halo mass of COSMOS AGNs and the typical mass of luminous SDSS quasars at z ∼ 3, with the latter inhabiting more massive halos respect to moderate luminosity AGNs. Alternatively we can argue, at least for Type 1 COSMOS AGNs, that they are possibly representative of an early phase of fast (i.e., Eddington limited) BH growth induced by cosmic cold flows or disk instabilities. Given the moderate luminosity, these new fast growing BHs have masses of ∼10{sup 7-8} M {sub ☉} at z ∼ 3 which might evolve into ∼10{sup 8.5-9} M {sub ☉} mass BHs at z = 0. Following our clustering measurements, we argue that this fast BH growth at z ∼ 3 in AGNs with moderate luminosity occurs in DMHs with typical mass of ∼ 6× 10{sup 12} h {sup –1} M {sub ☉}.« less

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

PubMed

Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

2015-02-21

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

Extreme Emission Line Galaxies in CANDELS: Broad-Band Selected, Star-Bursting Dwarf Galaxies at Z greater than 1

NASA Technical Reports Server (NTRS)

vanderWel, A.; Straughn, A. N.; Rix, H.-W.; Finkelstein, S. L.; Koekemoer, A. M.; Weiner, B. J.; Wuyts, S.; Bell, E. F.; Faber, S. M.; Trump, J. R.;

When Ethyl Isocyanoacetate Meets Isatins: A 1,3-Dipolar/Inverse 1,3-Dipolar/Olefination Reaction for Access to 3-Ylideneoxindoles.

PubMed

Yuan, Wen-Kui; Cui, Tao; Liu, Wei; Wen, Li-Rong; Li, Ming

2018-03-16

A new CuI/1,10-phen-catalyzed reaction for the synthesis of 3-ylideneoxindoles from readily available isatins and ethyl isocyanoacetate, in which ethyl isocyanoacetate acts as a latent two-carbon donor like the Wittig reagent, is reported. A tandem procedure including 1,3-dipolar cycloaddition/inverse 1,3-dipolar ring opening/olefination allows the preparation of 3-ylideneoxindoles with broad functional group tolerance.

Diastereoselective Carbocyclization of 1,6-Heptadienes Triggered by Rhodium-Catalyzed Activation of an Olefinic C=H Bond**

PubMed Central

Aïssa, Christophe; Ho, Kelvin Y T; Tetlow, Daniel J; Pin-Nó, María

2014-01-01

The use of α,ω-dienes as functionalization reagents for olefinic carbon–hydrogen bonds has been rarely studied. Reported herein is the rhodium(I)-catalyzed rearrangement of prochiral 1,6-heptadienes into [2,2,1]-cycloheptane derivatives with concomitant creation of at least three stereogenic centers and complete diastereocontrol. Deuterium-labeling studies and the isolation of a key intermediate are consistent with a group-directed C=H bond activation, followed by two consecutive migratory insertions, with only the latter step being diastereoselective. PMID:24634225

The Remarkable Similarity of Massive Galaxy Clusters from z ~ 0 to z ~ 1.9

DOE PAGES

McDonald, M.; Allen, S. W.; Bayliss, M.; ...

2017-06-28

We present the results of a Chandra X-ray survey of the 8 most massive galaxy clusters at z>1.2 in the South Pole Telescope 2500 deg^2 survey. We combine this sample with previously-published Chandra observations of 49 massive X-ray-selected clusters at 00.2R500 scaling like E(z)^2. In the centers of clusters (r<0.1R500), we find significant deviations from self similarity (n_e ~ E(z)^{0.1+/-0.5}), consistent with no redshift dependence. When we isolate clusters with over-dense cores (i.e., cool cores), we find that the average over-density profile has not evolved with redshift -- that is, cool cores have not changed in size, density, or totalmore » mass over the past ~9-10 Gyr. We show that the evolving "cuspiness" of clusters in the X-ray, reported by several previous studies, can be understood in the context of a cool core with fixed properties embedded in a self similarly-evolving cluster. We find no measurable evolution in the X-ray morphology of massive clusters, seemingly in tension with the rapidly-rising (with redshift) rate of major mergers predicted by cosmological simulations. We show that these two results can be brought into agreement if we assume that the relaxation time after a merger is proportional to the crossing time, since the latter is proportional to H(z)^(-1).« less

THE STELLAR POPULATION AND STAR FORMATION RATES OF z Almost-Equal-To 1.5-1.6 [O II]-EMITTING GALAXIES SELECTED FROM NARROWBAND EMISSION-LINE SURVEYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ly, Chun; Malkan, Matthew A.; Ross, Nathaniel R.

We present the first detailed study of the stellar populations of star-forming galaxies at z {approx} 1.5, which are selected by their [O II] emission line, detected in narrowband surveys. We identified {approx}1300 [O II] emitters at z = 1.47 and z = 1.62 in the Subaru Deep Field with rest-frame equivalent widths (EWs) above 13 A. Optical and near-infrared spectroscopic observations for Almost-Equal-To 10% of our samples show that our separation of [O II] from [O III] emission-line galaxies in two-color space is 99% successful. We analyze the multi-wavelength properties of a subset of {approx}1200 galaxies with the bestmore » photometry. They have average rest-frame EW of 45 A, stellar mass of 3 Multiplication-Sign 10{sup 9} M{sub Sun }, and stellar age of 100 Myr. In addition, our spectral energy distribution (SED) fitting and broadband colors indicate that [O II] emitters span the full range of galaxy populations at z {approx} 1.5. We also find that 80% of [O II] emitters are also photometrically classified as 'BX/BM' (UV) galaxies and/or the star-forming 'BzK' (near-IR) galaxies. Our [O II] emission line survey produces a far more complete and somewhat deeper sample of z {approx} 1.5 galaxies than either the BX/BM or sBzK selection alone. We constructed average SEDs and find that higher [O II] EW galaxies have somewhat bluer continua. SED model-fitting shows that they have on average half the stellar mass of galaxies with lower [O II] EW. The observed [O II] luminosity is well correlated with the far-UV continuum with a logarithmic slope of 0.89 {+-} 0.22. The scatter of the [O II] luminosity against the far-UV continuum suggests that [O II] can be used as a star formation rate indicator with a reliability of 0.23 dex.« less

Spectroscopy of Luminous z > 7 Galaxy Candidates and Sources of Contamination in z > 7 Galaxy Searches

NASA Astrophysics Data System (ADS)

Capak, P.; Mobasher, B.; Scoville, N. Z.; McCracken, H.; Ilbert, O.; Salvato, M.; Menéndez-Delmestre, K.; Aussel, H.; Carilli, C.; Civano, F.; Elvis, M.; Giavalisco, M.; Jullo, E.; Kartaltepe, J.; Leauthaud, A.; Koekemoer, A. M.; Kneib, J.-P.; LeFloch, E.; Sanders, D. B.; Schinnerer, E.; Shioya, Y.; Shopbell, P.; Tanaguchi, Y.; Thompson, D.; Willott, C. J.

2011-04-01

We present three bright z +-dropout candidates selected from deep near-infrared (NIR) imaging of the COSMOS 2 deg2 field. All three objects match the 0.8-8 μm colors of other published z > 7 candidates but are 3 mag brighter, facilitating further study. Deep spectroscopy of two of the candidates covering 0.64-1.02 μm with Keck-DEIMOS and all three covering 0.94-1.10 μm and 1.52-1.80 μm with Keck-NIRSPEC detects weak spectral features tentatively identified as Lyα at z = 6.95 and z = 7.69 in two of the objects. The third object is placed at z ~ 1.6 based on a 24 μm and weak optical detection. A comparison with the spectral energy distributions of known z < 7 galaxies, including objects with strong spectral lines, large extinction, and large systematic uncertainties in the photometry, yields no objects with similar colors. However, the λ > 1 μm properties of all three objects can be matched to optically detected sources with photometric redshifts at z ~ 1.8, so the non-detection in the i + and z + bands is the primary factor which favors a z > 7 solution. If any of these objects are at z ~ 7, the bright end of the luminosity function is significantly higher at z > 7 than suggested by previous studies, but consistent within the statistical uncertainty and the dark matter halo distribution. If these objects are at low redshift, the Lyman break selection must be contaminated by a previously unknown population of low-redshift objects with very strong breaks in their broadband spectral energy distributions and blue NIR colors. The implications of this result on luminosity function evolution at high redshift are discussed. We show that the primary limitation of z > 7 galaxy searches with broad filters is the depth of the available optical data. Based on observations with the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and the National Aeronautics and Space

The Complete Z-diagram of LMC X-2

NASA Technical Reports Server (NTRS)

White, Nicholas E. (Technical Monitor); Smale, A. P.; Homan, J.; Kuulkers, E.

2003-01-01

We present results from four Rossi X-ray Timing Explorer (RXTE) observations of the bright low mass X-ray binary LMC X-2. During these observations, which span a year and include over 160 hrs of data, the source exhibits clear evolution through three branches on its hardness-intensity and color-color diagrams, consistent with the flaring, normal, and horizontal branches (FB, NB, HB) of a Z-source, and remarkably similar to Z-tracks derived for GX 17+2, Sco X-1 and GX 349+2. LMC X-2 was observed in the FB, NB, and HB for roughly 30%, 40%, and 30% respectively of the total time covered. The source traces out the full extent of the Z in approximately 1 day, and the Z-track shows evidence for secular shifts on a timescale in excess of a few days. Although the count rate of LMC X-2 is low compared with the other known 2-sources due to its greater distance, the power density spectra selected by branch show very-low-frequency noise characteristics at least consistent with those from other Z-sources. We thus confirm the identification of LMC X-2 as a Z-source, the first identified outside our Galaxy.

A well-defined Pd hybrid material for the Z-selective semihydrogenation of alkynes characterized at the molecular level by DNP SENS.

PubMed

Conley, Matthew P; Drost, Ruben M; Baffert, Mathieu; Gajan, David; Elsevier, Cornelis; Franks, W Trent; Oschkinat, Hartmut; Veyre, Laurent; Zagdoun, Alexandre; Rossini, Aaron; Lelli, Moreno; Lesage, Anne; Casano, Gilles; Ouari, Olivier; Tordo, Paul; Emsley, Lyndon; Copéret, Christophe; Thieuleux, Chloé

2013-09-09

Direct evidence of the conformation of a Pd-N heterocyclic carbene (NHC) moiety imbedded in a hybrid material and of the Pd-NHC bond were obtained by dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) at natural abundance in short experimental times (hours). Overall, this silica-based hybrid material containing well-defined Pd-NHC sites in a uniform environment displays high activity and selectivity in the semihydrogenation of alkynes into Z-alkenes (see figure). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature- and Pressure-Dependent Kinetics Studies of Atomic Chlorine Reactions with Some Fluorinated Olefins and Ethers

NASA Astrophysics Data System (ADS)

Nicovich, J. M.; Wine, P. H.; Mazumder, S.; Hatzis, G. P.; Jiang, M.

2016-12-01

Laser flash photolysis of Cl2CO/N2/CO2/X mixtures (X = CF3CH=CH2, E-CF3CH=CHCl, E-CF3CH=CHF, (CF3)2CHOCH3, and CF3CF2CH2OCH3), has been coupled with time-resolved detection of Cl atoms by atomic resonance fluorescence spectroscopy to study the kinetics of Cl + X reactions as a function of temperature (T) and pressure (P). The Cl + X reactions were chosen for study because (1) the compounds X are potentially useful substitutes for ozone depleting substances in practical applications, (2) literature results demonstrate that Cl + X reactions are 60-120 times faster than the corresponding OH + X reactions at ambient T and P, suggesting that reaction with Cl is a significant atmospheric loss process for the compounds X, and (3) to our knowledge, Cl + X kinetics have not previously been studied as functions of T and P. For the Cl + olefin reactions, falloff curves are measured over the approximate T ranges 220-300 K. At elevated temperatures, equilibrium constants are determined for Cl + olefin association/dissociation, thus allowing C-Cl bond strengths in the product haloalkyl radicals to be evaluated. Arrhenius expressions are determined for the (P-independent) Cl + ether reactions over the approximate range of T 200-500K. The Cl + CF3CF2CH2OCH3 reaction is quite fast and its rate coefficient is nearly independent of T. The Cl + (CF3)2CHOCH3 reaction is somewhat slower and has a non-Arrhenius T dependence.

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

DOE PAGES

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.; ...

2017-09-27

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Relationship between soil type and N₂O reductase genotype (nosZ) of indigenous soybean bradyrhizobia: nosZ-minus populations are dominant in Andosols.

PubMed

Shiina, Yoko; Itakura, Manabu; Choi, Hyunseok; Saeki, Yuichi; Hayatsu, Masahito; Minamisawa, Kiwamu

2014-01-01

Bradyrhizobium japonicum strains that have the nosZ gene, which encodes N2O reductase, are able to mitigate N2O emissions from soils (15). To examine the distribution of nosZ genotypes among Japanese indigenous soybean bradyrhizobia, we isolated bradyrhizobia from the root nodules of soybean plants inoculated with 32 different soils and analyzed their nosZ and nodC genotypes. The 1556 resultant isolates were classified into the nosZ+/nodC+ genotype (855 isolates) and nosZ-/nodC+ genotype (701 isolates). The 11 soil samples in which nosZ- isolates significantly dominated (P < 0.05; the χ(2) test) were all Andosols (a volcanic ash soil prevalent in agricultural fields in Japan), whereas the 17 soil samples in which nosZ+ isolates significantly dominated were mainly alluvial soils (non-volcanic ash soils). This result was supported by a principal component analysis of environmental factors: the dominance of the nosZ- genotype was positively correlated with total N, total C, and the phosphate absorption coefficient in the soils, which are soil properties typical of Andosols. Internal transcribed spacer sequencing of representative isolates showed that the nosZ+ and nosZ- isolates of B. japonicum fell mainly into the USDA110 (BJ1) and USDA6 (BJ2) groups, respectively. These results demonstrated that the group lacking nosZ was dominant in Andosols, which can be a target soil type for an N2O mitigation strategy in soybean fields. We herein discussed how the nosZ genotypes of soybean bradyrhizobia depended on soil types in terms of N2O respiration selection and genomic determinants for soil adaptation.

Activation energies of diffusion of organic migrants in cyclo olefin polymer.

PubMed

Welle, Frank

2014-10-01

Cyclo olefin polymer (COP) is an amorphous polymer with good optical transparency and barrier properties, which is increasingly used for pharmaceutical packaging applications like pre-filled syringes, plastic vials, nutrition bags and blisters as well as for micro-well plates. For regulatory purposes, it is important to know the amount and quantity of compounds which migrate from the polymer into the pharmaceutical product. Within the study, diffusion coefficients of organic (model) compounds in COP at various temperatures were determined and the activation energies of diffusion were calculated according to the Arrhenius approach. Correlations were established between the molecular volume V of the migrating compound and the activation energy of diffusion EA as well as between the pre-exponential factor in the Arrhenius equation D0 and EA. From these correlations a prediction model was established for the migration of organic compounds in COP. This might be a useful tool supporting the evaluation process of COP packed pharmaceutical products. Copyright © 2014 Elsevier B.V. All rights reserved.

Assignment of Pre-edge Features in the Ru K-edge X-ray Absorption Spectra of Organometallic Ruthenium Complexes

PubMed Central

Getty, Kendra; Delgado-Jaime, Mario Ulises

2010-01-01

The nature of the lowest energy bound-state transition in the Ru K-edge X-ray Absorption Spectra for a series of Grubbs-type ruthenium complexes was investigated. The pre-edge feature was unambiguously assigned as resulting from formally electric dipole forbidden Ru 4d←1s transitions. The intensities of these transitions are extremely sensitive to the ligand environment and the symmetry of the metal centre. In centrosymmetric complexes the pre-edge is very weak since it is limited by the weak electric quadrupole intensity mechanism. By contrast, upon breaking centrosymmetry, Ru 5p-4d mixing allows for introduction of electric dipole allowed character resulting in a dramatic increase in the pre-edge intensity. The information content of this approach is explored as it relates to complexes of importance in olefin metathesis and its relevance as a tool for the study of reactive intermediates. PMID:20151030

Some current problems in oxidation kinetics

NASA Technical Reports Server (NTRS)

Benson, S. W.

1972-01-01

Experimental data in low temperature and high temperature oxidations are examined from the point of view of reported quantitative inconsistencies. Activation energies for tBuO2 metathesis reactions with alkanes appear to be 7 kcal/mole higher than for comparable reactions of HO2. Related isomerization reactions are examined in the light of these differences without reaching any simple conclusions. The Russell mechanism for a 6-membered, cyclic, transition state for termination of primary and secondary alkyl peroxy radicals is shown to be either inconsistent with thermochemical data, or else unique to solution reactions. Addition reactions of O3 with olefins and acetylenes are shown thermochemically to have the possibility of following concerted and biradical pathways, respectively. Recent data showing strong inhibition by PbO coated surfaces of both oxidation and pyrolysis of i-C4H10 are examined in terms of mechanism.

ALMA Spectroscopic Survey in the Hubble Ultra Deep Field: The Infrared Excess of UV-Selected z = 2-10 Galaxies as a Function of UV-Continuum Slope and Stellar Mass

NASA Astrophysics Data System (ADS)

Bouwens, Rychard J.; Aravena, Manuel; Decarli, Roberto; Walter, Fabian; da Cunha, Elisabete; Labbé, Ivo; Bauer, Franz E.; Bertoldi, Frank; Carilli, Chris; Chapman, Scott; Daddi, Emanuele; Hodge, Jacqueline; Ivison, Rob J.; Karim, Alex; Le Fevre, Olivier; Magnelli, Benjamin; Ota, Kazuaki; Riechers, Dominik; Smail, Ian R.; van der Werf, Paul; Weiss, Axel; Cox, Pierre; Elbaz, David; Gonzalez-Lopez, Jorge; Infante, Leopoldo; Oesch, Pascal; Wagg, Jeff; Wilkins, Steve

2016-12-01

We make use of deep 1.2 mm continuum observations (12.7 μJy beam-1 rms) of a 1 arcmin2 region in the Hubble Ultra Deep Field to probe dust-enshrouded star formation from 330 Lyman-break galaxies spanning the redshift range z = 2-10 (to ˜2-3 M ⊙ yr-1 at 1σ over the entire range). Given the depth and area of ASPECS, we would expect to tentatively detect 35 galaxies, extrapolating the Meurer z ˜ 0 IRX-β relation to z ≥ 2 (assuming dust temperature T d ˜ 35 K). However, only six tentative detections are found at z ≳ 2 in ASPECS, with just three at >3σ. Subdividing our z = 2-10 galaxy samples according to stellar mass, UV luminosity, and UV-continuum slope and stacking the results, we find a significant detection only in the most massive (>109.75 M ⊙) subsample, with an infrared excess (IRX = L IR/L UV) consistent with previous z ˜ 2 results. However, the infrared excess we measure from our large selection of sub-L ∗ (<109.75 M ⊙) galaxies is {0.11}-0.42+0.32 ± 0.34 (bootstrap and formal uncertainties) and {0.14}-0.14+0.15 ± 0.18 at z = 2-3 and z = 4-10, respectively, lying below even an IRX-β relation for the Small Magellanic Cloud (95% confidence). These results demonstrate the relevance of stellar mass for predicting the IR luminosity of z ≳ 2 galaxies. We find that the evolution of the IRX-stellar mass relationship depends on the evolution of the dust temperature. If the dust temperature increases monotonically with redshift (\\propto {(1+z)}0.32) such that T d ˜ 44-50 K at z ≥ 4, current results are suggestive of little evolution in this relationship to z ˜ 6. We use these results to revisit recent estimates of the z ≥ 3 star formation rate density.

The Structure of Massive Quiescent Galaxies at Z ~ 3 in the CANDELS-COSMOS Field

NASA Astrophysics Data System (ADS)

Fan, Lulu; Fang, Guanwen; Chen, Yang; Pan, Zhizheng; Lv, Xuanyi; Li, Jinrong; Lin, Lin; Kong, Xu

2013-07-01

In this Letter, we use a two-color (J - L) versus (V - J) selection criterion to search massive quiescent galaxy (QG) candidates at 2.5 <= z <= 4.0 in the CANDELS-COSMOS field. We construct an H F160W-selected catalog and complement it with public auxiliary data. We finally obtain 19 passive VJL-selected (hereafter pVJL) galaxies as the possible massive QG candidates at z ~ 3 by several constrains. We find the sizes of our pVJL galaxies are on average three to four times smaller than those of local early-type galaxies (ETGs) with analogous stellar mass. The compact size of these z ~ 3 galaxies can be modeled by assuming their formation at z form ~ 4-6 according to the dissipative collapse of baryons. Up to z < 4, the mass-normalized size evolution can be described by re vprop(1 + z)-1.0. Low Sérsic index and axis ratio, with median values n ~1.5 and b/a ~ 0.65, respectively, indicate that most of the pVJL galaxies are disk-dominated. Despite large uncertainty, the inner region of the median mass profile of our pVJL galaxies is similar to those of QGs at 0.5 < z < 2.5 and local ETGs. It indicates that local massive ETGs have been formed according to an inside-out scenario: the compact galaxies at high redshift make up the cores of local massive ETGs and then build up the outskirts according to dissipationless minor mergers.

Gold-catalysed oxyarylation of styrenes and mono- and gem-disubstituted olefins facilitated by an iodine(III) oxidant.

PubMed

Ball, Liam T; Lloyd-Jones, Guy C; Russell, Christopher A

2012-03-05

1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subaru High-z Exploration of Low-Luminosity Quasars (SHELLQs): New z > 6 Quasar Survey with Subaru/HSC

NASA Astrophysics Data System (ADS)