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

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.

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.

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.

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.

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

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

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.

Metathesis of alkanes and related reactions.

PubMed

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

2010-02-16

The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

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

Concise Syntheses of Insect Pheromones Using Z-Selective Cross Metathesis**

PubMed Central

Herbert, Myles B.; Marx, Vanessa M.; Pederson, Richard L.; Grubbs, Robert H.

2013-01-01

The shortest synthetic routes to nine cis-pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported. These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z-olefins. Important insight into the mechanism of Z-selective metathesis was uncovered during experimentation and subsequently explored. PMID:23055437

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.

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

Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

PubMed Central

Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

2016-01-01

Olefin metathesis has made a significant impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is very limited. In this manuscript, we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of an in situ-generated catalyst with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents and proceed to high conversion at ambient temperature within four hours. Many alkenyl chlorides, bromides and fluorides can be obtained in up to 91 percent yield and complete Z selectivity. This method can be used to easily synthesize biologically active compounds and to perform the site- and stereoselective fluorination of other organic compounds. PMID:27008965

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

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%).

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.

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

Kinetically E-selective macrocyclic ring-closing metathesis

NASA Astrophysics Data System (ADS)

Shen, Xiao; Nguyen, Thach T.; Koh, Ming Joo; Xu, Dongmin; Speed, Alexander W. H.; Schrock, Richard R.; Hoveyda, Amir H.

2017-01-01

Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: the potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization—a particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl-B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib—a potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis—was prepared by RCM carried out at a

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.

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.

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.

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.

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.

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.

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.

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

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.

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).

Organocatalytic atroposelective synthesis of axially chiral styrenes

NASA Astrophysics Data System (ADS)

Zheng, Sheng-Cai; Wu, San; Zhou, Qinghai; Chung, Lung Wa; Ye, Liu; Tan, Bin

2017-05-01

Axially chiral compounds are widespread in biologically active compounds and are useful chiral ligands or organocatalysts in asymmetric catalysis. It is well-known that styrenes are one of the most abundant and principal feedstocks and thus represent excellent prospective building blocks for chemical synthesis. Driven by the development of atroposelective synthesis of axially chiral styrene derivatives, we discovered herein the asymmetric organocatalytic approach via direct Michael addition reaction of substituted diones/ketone esters/malononitrile to alkynals. The axially chiral styrene compounds were produced with good chemical yields, enantioselectivities and almost complete E/Z-selectivities through a secondary amine-catalysed iminium activation strategy under mild conditions. Such structural motifs are important precursors for further transformations into biologically active compounds and synthetic useful intermediates and may have potential applications in asymmetric synthesis as olefin ligands or organocatalysts.

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.

Construction of axial chirality by rhodium-catalyzed asymmetric dehydrogenative Heck coupling of biaryl compounds with alkenes.

PubMed

Zheng, Jun; You, Shu-Li

2014-11-24

Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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

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.

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.

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…

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.

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.

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.

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

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.

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

Rhodium-catalyzed asymmetric tandem cyclization for efficient and rapid access to underexplored heterocyclic tertiary allylic alcohols containing a tetrasubstituted olefin.

PubMed

Li, Yi; Xu, Ming-Hua

2014-05-16

The first Rh-catalyzed asymmetric tandem cyclization of nitrogen- or oxygen-bridged 5-alkynones with arylboronic acids was achieved. The simple catalytic system involving a rhodium(I) complex with readily available chiral BINAP ligand promotes the reaction to proceed in a highly stereocontrolled manner. This protocol provides a very reliable and practical access to a variety of chiral heterocyclic tertiary allylic alcohols possessing a tetrasubstituted carbon stereocenter and an all-carbon tetrasubstituted olefin functionality in good yields with great enantioselectivities up to 99% ee.

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.

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

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.

Chiral allene-containing phosphines in asymmetric catalysis

PubMed Central

Cai, Feng; Pu, Xiaotao; Qi, Xiangbing; Lynch, Vincent; Radha, Akella; Ready, Joseph M.

2011-01-01

Traditionally, ligands used in asymmetric catalysis have contained either stereogenic atoms or hindered single bonds (atropisomerism), or both. Here we demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of aryl boronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals generating bi- and tri-dentate ligands. PMID:21972824

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.

Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

PubMed Central

Rubina, Marina; Sherrill, William M; Barkov, Alexey Yu

2014-01-01

Summary A novel class of chiral phosphanyl-oxazoline (PHOX) ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands. PMID:25161709

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.

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,"

Asymmetric Baylis-Hillman reactions promoted by chiral imidazolines.

PubMed

Xu, Junye; Guan, Yanyi; Yang, Shihui; Ng, Yurui; Peh, Guangrong; Tan, Choon-Hong

2006-11-20

The coupling of electrophiles with activated alkenes by using tertiary amines or phosphines is generally known as the Baylis-Hillman reaction. It is a useful and atom-economical carbon-carbon bond-forming reaction that generates multifunctionalized products. This reaction is notoriously slow; yields are often low and substrate-dependent. The asymmetric reaction is still limited especially for unactivated olefins such as acrylates. Imidazolines have been developed as ligands in metal-catalyzed reactions and have also been used as privileged structures in diversity-oriented synthesis. A series of novel chiral imidazolines were prepared and used to develop asymmetric Baylis-Hillman reactions. These imidazolines promote the reactions of various aromatic aldehydes with unactivated acrylates. Enantiomeric excesses of up to 60% and high yields were obtained by using stoichiometric amounts of the promoter. Furthermore, the imidazolines are also suitable promoters for the reactions between aromatic aldehydes and alkyl vinyl ketones. Enantiomeric excesses of up to 78% and high yields were obtained with 50 mol % of an imidazoline with a chiral methylnaphthyl group. These chiral imidazolines are easily prepared from commercially available amino alcohols and can be easily recovered for reuse without loss of product enantioselectivity.

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.

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.

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.

Asymmetric synthesis of diacceptor cyclopropylphosphonates catalyzed by chiral Ru(II)-Pheox complexes

NASA Astrophysics Data System (ADS)

Chi, Le Thi Loan; Chanthamath, Soda; Shibatomi, Kazutaka; Iwasa, Seiji

2018-04-01

The first Ru(II)-catalyzed asymmetric cyclopropanation of diacceptor diazophosphonates with olefins is reported. The Ru(II)-Pheox complex 7e was found to be an efficient catalyst for the asymmetric cyclopropanation of α-cyano diazophosp honate with styrene under mild conditions to give the corresponding chiral diacceptor cyclopropylphosphonate products in high yields (up to 99%) with excellent diastereoselectivities (up to 99/1 dr). However, the enantioselectivity was difficult to control by the C1-symmetric catalyst (up to 68% ee).

An enantioselective approach to the preparation of chiral sulfones by Ir-catalyzed asymmetric hydrogenation.

PubMed

Peters, Byron K; Zhou, Taigang; Rujirawanich, Janjira; Cadu, Alban; Singh, Thishana; Rabten, Wangchuk; Kerdphon, Sutthichat; Andersson, Pher G

2014-11-26

Several chiral sulfonyl compounds were prepared using the iridium catalyzed asymmetric hydrogenation reaction. Vinylic, allylic and homoallylic sulfone substitutions were investigated, and high enantioselectivity is maintained regardless of the location of the olefin with respect to the sulfone. Impressive stereoselectivity was obtained for dialkyl substitutions, which typically are challenging substrates in the hydrogenation. As expected, the more bulky Z-substrates were hydrogenated slower than the corresponding E isomers, and in slightly lower enantioselectivity.

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.

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

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.

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.

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.

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.

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.

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.

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.

Chiral biphenyl diphosphines for asymmetric catalysis: Stereoelectronic design and industrial perspectives

PubMed Central

Jeulin, Séverine; de Paule, Sébastien Duprat; Ratovelomanana-Vidal, Virginie; Genêt, Jean-Pierre; Champion, Nicolas; Dellis, Philippe

2004-01-01

Two original chiral diphosphines, SYNPHOS and DIFLUORPHOS, have been synthesized on multigram scales. Their steric and electronic profiles have been established in comparison with the commonly used 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and 6,6′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-biphenyl ligands. A screening study of the four ligands in RuII-catalyzed asymmetric hydrogenation of prochiral ketones and olefins has been performed. It revealed that the stereoelectronic features of the ligand and the substrate deeply influenced the enantioselectivities obtained in asymmetric hydrogenation, SYNPHOS and DIFLUORPHOS being fully complementary in terms of enantioselectivity for this reaction. PMID:15031423

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...

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...

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.

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.

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...

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.

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.

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.

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

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

C-Glycosyl Analogs of Oligosaccharides

NASA Astrophysics Data System (ADS)

Vauzeilles, Boris; Urban, Dominique; Doisneau, Gilles; Beau, Jean-Marie

This chapter covers the synthesis of a large collection of "C-oligosaccharides ", synthetic analogs of naturally occurring oligosaccharides in which a carbon atom replaces the anomeric, interglycosidic oxygen atom. These non-natural constructs are stable to chemical and enzymatic degradation, and are primarily devised to probe carbohydrate-based biological processes. These mainly target carbohydrate-protein interactions such as the modulation of glycoenzyme (glycosylhydrolases and transferases) activities or the design of ligands for lectin Carbohydrate Recognition Domains. The discussion is based on the key carbon-carbon bond assembling steps on carbohydrate templates: ionic (anionic and cationic chemistries, sigmatropic rearrangements) or radical assemblage, and olefin metathesis. Synthetic schemes in which at least one of the monosaccharide units is constructed by total synthesis or by cyclization of acyclic chiral chains are presented separately in a "partial de novo synthesis" section. The review also provides comments, when they are known, on the conformational and binding properties of these synthetic analogs, as well as their biological behavior when tested.

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.

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.

Asymmetric catalytic hydrogenation. Design of new Ru catalysts and chiral ligands: from laboratory to industrial applications.

PubMed

Genet, Jean-Pierre

2003-12-01

This Account covers the design of Ru catalysts and ligands. Two classes of chiral phosphine ligands are prepared: the electron-rich trans-2,4-substituted phosphetanes, readily available from optically pure 1,3-diol cyclic sulfates, and atropoisomeric ligands (SYNPHOS, MeO-NAPhePHOS, bearing heterotopic biaryl moieties, and a chiral water-soluble diguanidinium binaphthyl diphosphine, Digm-BINAP). Applications of these ligands to rhodium- and ruthenium-mediated hydrogenation of ketones and olefins have been reported with high enantioselectivities. The recognition abilities of Ru-SYNPHOS for a wide range of ketones is superior to those observed with BINAP, MeO-NAPhePHOS, and MeO-BIPHEP. Several biologically active compounds have been prepared through dynamic kinetic resolution. This work gives access to a number of highly active catalysts of the type [Ru(biphosphane)(H)(eta(6)-cot)]BF(4). These catalysts have demonstrated their utility in the enantioselective hydrogenation of the tetrasubstituted cyclopentenone "dehydrodione", which leads to the commercially important perfume component Paradisone (Firmenich).

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.

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

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.

Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality.

PubMed

Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

2017-11-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction-mediated chirality induction and the intrinsic stereogenic center-controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, ( S )-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction-mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly.

Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality

PubMed Central

Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

2017-01-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction–mediated chirality induction and the intrinsic stereogenic center–controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, (S)-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction–mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly. PMID:29119137

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

PubMed

Zeng, Chenjie; Jin, Rongchao

2017-08-04

Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au n (SR) m ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au n (SR) m structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au 133 (SR) 52 and Au 246 (SR) 80 nanoclusters. Overall, the origins of chirality discovered in Au n (SR) m nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Gelation induced supramolecular chirality: chirality transfer, amplification and application.

PubMed

Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

2014-08-14

Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

A computational study on the role of chiral N-oxides in enantioselective Pauson-Khand reactions.

PubMed

Fjermestad, Torstein; Pericàs, Miquel A; Maseras, Feliu

2011-08-29

Density functional calculations were carried out to ascertain the origin of enantioselectivity in the brucine N-oxide (BNO)-assisted enantioselective Pauson-Khand reaction (PKR) of norbornene with 2-methyl-3-butyn-2-ol. The computed ee value in acetone is 68 % (R), which compares well to the previously reported experimental value of 58 % (R). In DME the computed ee value of 76 % (R) is in excellent agreement with the experimentally determined value of 78 % (R). The mechanism of enantioselectivity consists of several steps. First, the dicobalt complex is activated by BNO with chirality transfer from enantiopure BNO to the dicobalt complex. Second, competition occurs between a racemization process and complexation with the olefin reagent, which leads to the products. The lower ee value in acetone is due to the lower energy barrier of the racemization process. Calculations show that replacement of BNO by a hypothetical more enantioselective chiral N-oxide will hardly increase the ee value beyond 90 %. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

Chiral Separations

NASA Astrophysics Data System (ADS)

Stalcup, A. M.

2010-07-01

The main goal of this review is to provide a brief overview of chiral separations to researchers who are versed in the area of analytical separations but unfamiliar with chiral separations. To researchers who are not familiar with this area, there is currently a bewildering array of commercially available chiral columns, chiral derivatizing reagents, and chiral selectors for approaches that span the range of analytical separation platforms (e.g., high-performance liquid chromatography, gas chromatography, supercritical-fluid chromatography, and capillary electrophoresis). This review begins with a brief discussion of chirality before examining the general strategies and commonalities among all of the chiral separation techniques. Rather than exhaustively listing all the chiral selectors and applications, this review highlights significant issues and differences between chiral and achiral separations, providing salient examples from specific classes of chiral selectors where appropriate.

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.

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.

Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

NASA Astrophysics Data System (ADS)

Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

2017-07-01

The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

NASA Astrophysics Data System (ADS)

Jiang, Jinghua; Yang, Deng-Ke

2017-01-01

Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

Chiral signs of TPPS co-assemblies with chiral gelators: role of molecular and supramolecular chirality.

PubMed

Wang, Qiuling; Zhang, Li; Yang, Dong; Li, Tiesheng; Liu, Minghua

2016-10-13

A dianionic tetrakis(4-sulfonatophenyl)porphyrin (TPPS) self-assembled into J-aggregates when it co-assembled with a chiral cationic amphiphile via supramolecular gelation. The chiral signs of TPPS J aggregates followed the supramolecular chirality of amphiphilic assemblies rather than the molecular chirality of the amphiphile.

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

Chiral superconductors.

PubMed

Kallin, Catherine; Berlinsky, John

2016-05-01

Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed.

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.

Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

PubMed

Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

2018-05-16

Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral magnetic effect without chirality source in asymmetric Weyl semimetals

NASA Astrophysics Data System (ADS)

Kharzeev, Dmitri E.; Kikuchi, Yuta; Meyer, René

2018-05-01

We describe a new type of the chiral magnetic effect (CME) that should occur in Weyl semimetals (WSMs) with an asymmetry in the dispersion relations of the left- and right-handed (LH and RH) chiral Weyl fermions. In such materials, time-dependent pumping of electrons from a non-chiral external source can generate a non-vanishing chiral chemical potential. This is due to the different capacities of the LH and RH chiral Weyl cones arising from the difference in the density of states in the LH and RH cones. The chiral chemical potential then generates, via the chiral anomaly, a current along the direction of an applied magnetic field even in the absence of an external electric field. The source of chirality imbalance in this new setup is thus due to the band structure of the system and the presence of (non-chiral) electron source, and not due to the parallel electric and magnetic fields. We illustrate the effect by an argument based on the effective field theory, and by the chiral kinetic theory calculation for a rotationally invariant WSM with different Fermi velocities in the left and right chiral Weyl cones; we also consider the case of a WSM with Weyl nodes at different energies. We argue that this effect is generically present in WSMs with different dispersion relations for LH and RH chiral Weyl cones, such as SrSi2 recently predicted as a WSM with broken inversion and mirror symmetries, as long as the chiral relaxation time is much longer than the transport scattering time.

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.

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

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.

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.

Chiral geometry in multiple chiral doublet bands

NASA Astrophysics Data System (ADS)

Zhang, Hao; Chen, Qibo

2016-02-01

The chiral geometry of multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters γ in the particle rotor model with . The energy spectra, electromagnetic transition probabilities B(M1) and B(E2), angular momenta, and K-distributions are studied. It is demonstrated that the chirality still remains not only in the yrast and yrare bands, but also in the two higher excited bands when γ deviates from 30°. The chiral geometry relies significantly on γ, and the chiral geometry of the two higher excited partner bands is not as good as that of the yrast and yrare doublet bands. Supported by Plan Project of Beijing College Students’ Scientific Research and Entrepreneurial Action, Major State 973 Program of China (2013CB834400), National Natural Science Foundation of China (11175002, 11335002, 11375015, 11461141002), National Fund for Fostering Talents of Basic Science (NFFTBS) (J1103206), Research Fund for Doctoral Program of Higher Education (20110001110087) and China Postdoctoral Science Foundation (2015M580007)

Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

PubMed Central

Jiang, Wenge; Pacella, Michael S.; Athanasiadou, Dimitra; Nelea, Valentin; Vali, Hojatollah; Hazen, Robert M.; Gray, Jeffrey J.; McKee, Marc D.

2017-01-01

Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a ‘right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas ‘left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a ‘mother' subunit nanoparticle spawns a slightly tilted, consequential ‘daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures. PMID:28406143

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.

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…

Chiral Cliffs: Investigating the Influence of Chirality on Binding Affinity.

PubMed

Schneider, Nadine; Lewis, Richard A; Fechner, Nikolas; Ertl, Peter

2018-05-11

Chirality is understood by many as a binary concept: a molecule is either chiral or it is not. In terms of the action of a structure on polarized light, this is indeed true. When examined through the prism of molecular recognition, the answer becomes more nuanced. In this work, we investigated chiral behavior on protein-ligand binding: when does chirality make a difference in binding activity? Chirality is a property of the 3D structure, so recognition also requires an appreciation of the conformation. In many situations, the bioactive conformation is undefined. We set out to address this by defining and using several novel 2D descriptors to capture general characteristic features of the chiral center. Using machine-learning methods, we built different predictive models to estimate if a chiral pair (a set of two enantiomers) might exhibit a chiral cliff in a binding assay. A set of about 3800 chiral pairs extracted from the ChEMBL23 database was used to train and test our models. By achieving an accuracy of up to 75 %, our models provide good performance in discriminating chiral cliffs from non-cliffs. More importantly, we were able to derive some simple guidelines for when one can reasonably use a racemate and when an enantiopure compound is needed in an assay. We critically discuss our results and show detailed examples of using our guidelines. Along with this publication we provide our dataset, our novel descriptors, and the Python code to rebuild the predictive models. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electric line source illumination of a chiral cylinder placed in another chiral background medium

NASA Astrophysics Data System (ADS)

Aslam, M.; Saleem, A.; Awan, Z. A.

2018-05-01

An electric line source illumination of a chiral cylinder embedded in a chiral background medium is considered. The field expressions inside and outside of a chiral cylinder have been derived using the wave field decomposition approach. The effects of various chiral cylinders, chiral background media and source locations upon the scattering gain pattern have been investigated. It is observed that the chiral background reduces the backward scattering gain as compared to the free space background for a dielectric cylinder. It is also studied that by moving a line source away from a cylinder reduces the backward scattering gain for a chiral cylinder placed in a chiral background under some specific conditions. A unique phenomenon of reduced scattering gain has been observed at a specific observation angle for a chiral cylinder placed in a chiral background having an electric line source location of unity free space wavelength. An isotropic scattering gain pattern is observed for a chiral nihility background provided that if cylinder is chiral or chiral nihility type. It is also observed that this isotropic behaviour is independent of background and cylinder chirality.

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.

Active chiral fluids.

PubMed

Fürthauer, S; Strempel, M; Grill, S W; Jülicher, F

2012-09-01

Active processes in biological systems often exhibit chiral asymmetries. Examples are the chirality of cytoskeletal filaments which interact with motor proteins, the chirality of the beat of cilia and flagella as well as the helical trajectories of many biological microswimmers. Here, we derive constitutive material equations for active fluids which account for the effects of active chiral processes. We identify active contributions to the antisymmetric part of the stress as well as active angular momentum fluxes. We discuss four types of elementary chiral motors and their effects on a surrounding fluid. We show that large-scale chiral flows can result from the collective behavior of such motors even in cases where isolated motors do not create a hydrodynamic far field.

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.

Chiral magnetic effect in lattice QCD with a chiral chemical potential.

PubMed

Yamamoto, Arata

2011-07-15

We perform a first lattice QCD simulation including a two-flavor dynamical fermion with a chiral chemical potential. Because the chiral chemical potential gives rise to no sign problem, we can exactly analyze a chirally imbalanced QCD matter by Monte Carlo simulation. By applying an external magnetic field to this system, we obtain a finite induced current along the magnetic field, which corresponds to the chiral magnetic effect. The obtained induced current is proportional to the magnetic field and to the chiral chemical potential, which is consistent with an analytical prediction.

Acylation of Chiral Alcohols: A Simple Procedure for Chiral GC Analysis.

PubMed

Oromí-Farrús, Mireia; Torres, Mercè; Canela, Ramon

2012-01-01

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

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.

Chiral Polymers.

DTIC Science & Technology

1984-10-01

regardless of the method of polymerization. The styrene-bead copolymers were packed in HPLC columns, but none were especiall, effective in separating...enantiomers in a racemic mixture. The chiral butyrolactone polymer was coated on silica, but this material did not effect resolution of racemic mixtures in an...been effected utilizing chiral oxazolines3 prompted the initial efforts to synthesize various chiral 2-vinyl- oxazoline monomers for incorporation

Can a Non-Chiral Object Be Made of Two Identical Chiral Moieties?

ERIC Educational Resources Information Center

LeMarechal, Jean Francois

2008-01-01

Several pedagogical objects can be used to discuss chirality. Here, we use the cut of an apple to show that the association of identical chiral moieties can form a non-chiral object. Octahedral chirality is used to find situations equivalent to the cut of the apple. (Contains 5 figures.)

Enhanced Chiral Discriminatory van der Waals Interactions Mediated by Chiral Surfaces

NASA Astrophysics Data System (ADS)

Barcellona, Pablo; Safari, Hassan; Salam, A.; Buhmann, Stefan Yoshi

2017-05-01

We predict a discriminatory interaction between a chiral molecule and an achiral molecule which is mediated by a chiral body. To achieve this, we generalize the van der Waals interaction potential between two ground-state molecules with electric, magnetic, and chiral response to nontrivial environments. The force is evaluated using second-order perturbation theory with an effective Hamiltonian. Chiral media enhance or reduce the free interaction via many-body interactions, making it possible to measure the chiral contributions to the van der Waals force with current technology. The van der Waals interaction is discriminatory with respect to enantiomers of different handedness and could be used to separate enantiomers. We also suggest a specific geometric configuration where the electric contribution to the van der Waals interaction is zero, making the chiral component the dominant effect.

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.

Chiral plasmonics

PubMed Central

Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

2017-01-01

We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes. PMID:28560336

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

Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

NASA Astrophysics Data System (ADS)

Guo, Zhen; Du, Yu; Liu, Xianbin; Ng, Siu-Choon; Chen, Yuan; Yang, Yanhui

2010-04-01

Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

Thermal chiral vortical and magnetic waves: New excitation modes in chiral fluids

DOE PAGES

Kalaydzhyan, Tigran; Murchikova, Elena

2017-03-24

In certain circumstances, chiral (parity-violating) medium can be described hydrodynamically as a chiral fluid with microscopic quantum anomalies. Possible examples of such systems include strongly coupled quark–gluon plasma, liquid helium 3He-A, neutron stars and the Early Universe. Here, we study first-order hy-drodynamics of a chiral fluid on a vortex background and in an external magnetic field. We show that there are two previously undiscovered modes describing heat waves propagating along the vortex and magnetic field. We call them the Thermal Chiral Vortical Wave and Thermal Chiral Magnetic Wave. We also identify known gapless excitations of density (chiral vortical and chiralmore » magnetic waves) and transverse velocity (chiral Alfvén wave). We also demonstrate that the velocity of the chiral vortical wave is zero, when the full hydrodynamic framework is applied, and hence the wave is absent and the excitation reduces to the charge diffusion mode. We also comment on the frame-dependent contributions to the obtained propagation velocities.« 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.

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.

Chiral supramolecular organization from a sheet-like achiral gel: a study of chiral photoinduction.

PubMed

Royes, Jorge; Polo, Víctor; Uriel, Santiago; Oriol, Luis; Piñol, Milagros; Tejedor, Rosa M

2017-05-31

Chiral photoinduction in a photoresponsive gel based on an achiral 2D architecture with high geometric anisotropy and low roughness has been investigated. Circularly polarized light (CPL) was used as a chiral source and an azobenzene chromophore was employed as a chiral trigger. The chiral photoinduction was studied by evaluating the preferential excitation of enantiomeric conformers of the azobenzene units. Crystallographic data and density functional theory (DFT) calculations show how chirality is transferred to the achiral azomaterials as a result of the combination of chiral photochemistry and supramolecular interactions. This procedure could be applied to predict and estimate chirality transfer from a chiral physical source to a supramolecular organization using different light-responsive units.

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

Characterizing optical chirality

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

Bliokh, Konstantin Y.; Advanced Science Institute, RIKEN, Wako-shi, Saitama 351-0198; Nori, Franco

We examine the recently introduced measure of chirality of a monochromatic optical field [Y. Tang and A. E. Cohen, Phys. Rev. Lett. 104, 163901 (2010)] using the momentum (plane-wave) representation and helicity basis. Our analysis clarifies the physical meaning of the measure of chirality and unveils its close relation to the polarization helicity, spin angular momentum, energy density, and Poynting energy flow. We derive the operators of the optical chirality and of the corresponding chiral momentum, which acquire remarkably simple forms in the helicity representation.

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.

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.

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…

Effect of molecular structure of tartrates on chiral recognition of tartrate-boric acid complex chiral selectors in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shao-Qiang; Chen, Yong-Lei; Zhu, Hua-Dong; Shi, Hai-Jun; Yan, Na; Chen, Xing-Guo

2010-08-20

Eight l-tartrates and a d-tartrate with different alcohol moieties were used as chiral oils to prepare chiral microemulsions, which were utilized in conjunction with borate buffer to separate the enantiomers of beta-blockers or structurally related compounds by the chiral microemulsion electrokinetic chromatography (MEEKC) method. Among them, six were found to have a relatively good chiral separation performance and their chiral recognition effect in terms of both enantioselectivity and resolution increases linearly with the number of carbon atoms in the alkyl group of alcohol moiety. The tartrates containing alkyl groups of different structures but the same number of carbon atoms, i.e. one of straight chain and one of branched chain, provide similar enantioseparations. The trend was elucidated according to the changes in the difference of the steric matching between the molecules of two enantiomers and chiral selector. Furthermore, it was demonstrated for the first time that a water insoluble solid compound, di-i-butyl l-tartrate (mp. 73.5 degrees C), can be used as an oil to prepare a stable microemulsion to be used in the chiral MEEKC successfully. And a critical effect of the microemulsion for chiral separation, which has never been reported before, was found in this experiment, namely providing a hydrophobic environment to strengthen the interactions between the chiral selector and enantiomers. Copyright 2010 Elsevier B.V. All rights reserved.

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.

Silver Films with Hierarchical Chirality.

PubMed

Ma, Liguo; Cao, Yuanyuan; Duan, Yingying; Han, Lu; Che, Shunai

2017-07-17

Physical fabrication of chiral metallic films usually results in singular or large-sized chirality, restricting the optical asymmetric responses to long electromagnetic wavelengths. The chiral molecule-induced formation of silver films prepared chemically on a copper substrate through a redox reaction is presented. Three levels of chirality were identified: primary twisted nanoflakes with atomic crystal lattices, secondary helical stacking of these nanoflakes to form nanoplates, and tertiary micrometer-sized circinates consisting of chiral arranged nanoplates. The chiral Ag films exhibited multiple plasmonic absorption- and scattering-based optical activities at UV/Vis wavelengths based on their hierarchical chirality. The Ag films showed chiral selectivity for amino acids in catalytic electrochemical reactions, which originated from their primary atomic crystal lattices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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

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

Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures.

PubMed

Purcell-Milton, Finn; McKenna, Robert; Brennan, Lorcan J; Cullen, Conor P; Guillemeney, Lilian; Tepliakov, Nikita V; Baimuratov, Anvar S; Rukhlenko, Ivan D; Perova, Tatiana S; Duesberg, Georg S; Baranov, Alexander V; Fedorov, Anatoly V; Gun'ko, Yurii K

2018-02-27

Two-dimensional (2D) nanomaterials have been intensively investigated due to their interesting properties and range of potential applications. Although most research has focused on graphene, atomic layered transition metal dichalcogenides (TMDs) and particularly MoS 2 have gathered much deserved attention recently. Here, we report the induction of chirality into 2D chiral nanomaterials by carrying out liquid exfoliation of MoS 2 in the presence of chiral ligands (cysteine and penicillamine) in water. This processing resulted in exfoliated chiral 2D MoS 2 nanosheets showing strong circular dichroism signals, which were far past the onset of the original chiral ligand signals. Using theoretical modeling, we demonstrated that the chiral nature of MoS 2 nanosheets is related to the presence of chiral ligands causing preferential folding of the MoS 2 sheets. There was an excellent match between the theoretically calculated and experimental spectra. We believe that, due to their high aspect ratio planar morphology, chiral 2D nanomaterials could offer great opportunities for the development of chiroptical sensors, materials, and devices for valleytronics and other potential applications. In addition, chirality plays a key role in many chemical and biological systems, with chiral molecules and materials critical for the further development of biopharmaceuticals and fine chemicals, and this research therefore should have a strong impact on relevant areas of science and technology such as nanobiotechnology, nanomedicine, and nanotoxicology.

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.

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)

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.

Periodic chiral structures

NASA Technical Reports Server (NTRS)

Jaggard, Dwight L.; Engheta, Nader; Pelet, Philippe; Liu, John C.; Kowarz, Marek W.; Kim, Yunjin

1989-01-01

The electromagnetic properties of a structure that is both chiral and periodic are investigated using coupled-mode equations. The periodicity is described by a sinusoidal perturbation of the permittivity, permeability, and chiral admittance. The coupled-mode equations are derived from physical considerations and used to examine bandgap structure and reflected and transmitted fields. Chirality is observed predominantly in transmission, whereas periodicity is present in both reflection and transmission.

Chirality in adsorption on solid surfaces.

PubMed

Zaera, Francisco

2017-12-07

In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral

Chirality in molecular collision dynamics

NASA Astrophysics Data System (ADS)

Lombardi, Andrea; Palazzetti, Federico

2018-02-01

Chirality is a phenomenon that permeates the natural world, with implications for atomic and molecular physics, for fundamental forces and for the mechanisms at the origin of the early evolution of life and biomolecular homochirality. The manifestations of chirality in chemistry and biochemistry are numerous, the striking ones being chiral recognition and asymmetric synthesis with important applications in molecular sciences and in industrial and pharmaceutical chemistry. Chiral discrimination phenomena, due to the existence of two enantiomeric forms, very well known in the case of interaction with light, but still nearly disregarded in molecular collision studies. Here we review some ideas and recent advances about the role of chirality in molecular collisions, designing and illustrating molecular beam experiments for the demonstration of chiral effects and suggesting a scenario for a stereo-directional origin of chiral selection.

Chiral Magnetic Effect in Condensed Matters

NASA Astrophysics Data System (ADS)

Li, Qiang

The chiral magnetic effect is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum chiral anomaly in systems possessing charged chiral fermions. In quark-gluon plasma containing nearly massless quarks, the chirality imbalance is sourced by the topological transitions. In condensed matter systems, the chiral quasiparticles emerge in the 3D Dirac and Weyl semimetals having a linear dispersion relation. Recently, the chiral magnetic effect was discovered in a 3D Dirac semimetal - zirconium pentatelluride, ZrTe5, in which a large negative magnetoresistance is observed when magnetic field is parallel with the current. It is now reported in more than a dozen Dirac and Weyl semimetals. Broadly speaking, the chiral magnetic effect can exist in a variety of condensed matters. In some cases, a material may be transformed into a Weyl semimetal by magnetic field, exhibiting the chiral magnetic effect. In other cases, the chiral magnetic current may be generated in magnetic Dirac semimetals without external magnetic field, or in asymmetric Weyl semimetals without electric field where only a magnetic field and the source of chiral quasipartiles would be necessary. In the limit of conserved quasiparticle chirality, charge transport by the chiral magnetic current is non-dissipative. The powerful notion of chirality, originally discovered in high-energy and nuclear physics, holds promise in new ways of transmitting and processing information and energy. At the same time, chiral materials have opened a fascinating possibility to study the quantum dynamics of relativistic field theory in condensed matter experiments.

Photoremovable chiral auxiliary.

PubMed

Kammath, Viju Balachandran; Sebej, Peter; Slanina, Tomáš; Kříž, Zdeněk; Klán, Petr

2012-03-01

A new concept of a photoremovable chiral auxiliary (PCA), based on the chiral benzoin chromophore, is introduced. This moiety can control the asymmetric formation of a Diels-Alder adduct, and then be removed in a subsequent photochemical step in high chemical and quantum yields. Selective formation of the products at up to 96% ee was observed in the presence of a Lewis acid catalyst in the case of a 2-methoxybenzoinyl chiral auxiliary.

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.

Synthesis and characterization of novel chiral ionic liquids and investigation of their enantiomeric recognition properties.

PubMed

Bwambok, David K; Marwani, Hadi M; Fernand, Vivian E; Fakayode, Sayo O; Lowry, Mark; Negulescu, Ioan; Strongin, Robert M; Warner, Isiah M

2008-02-01

We report the synthesis and characterization of amino acid ester based chiral ionic liquids, derived from L- and D-alanine tert butyl ester chloride. The synthesis was accomplished via an anion metathesis reaction between commercially available L- and D-alanine tert butyl ester chloride using a variety of counterions such as lithium bis (trifluoromethane) sulfonimide, silver nitrate, silver lactate, and silver tetrafluoroborate. Both enantiomeric forms were obtained as confirmed by bands of opposite sign in the circular dichroism spectra. The L- and D-alanine tert butyl ester bis (trifluoromethane) sulfonimide were obtained as liquids at room temperature and intriguingly exhibited the highest thermal stability (up to 263 degrees C). In addition, the ionic liquids demonstrated enantiomeric recognition ability as evidenced by splitting of racemic Mosher's sodium salt signal using a liquid state (19)F nuclear magnetic resonance (NMR) and fluorescence spectroscopy. The L- and D-alanine tert butyl ester chloride resulted in solid salts with nitrate, lactate, and tetrafluoroborate anions. This illustrates the previously observed tunability of ionic liquid synthesis, resulting in ionic liquids of varying properties as a function of varying the anion.

Photoexcitation circular dichroism in chiral molecules

NASA Astrophysics Data System (ADS)

Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

2018-05-01

Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

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...

Maltodextrins as chiral selectors in CE: molecular structure effect of basic chiral compounds on the enantioseparation.

PubMed

Tabani, Hadi; Fakhari, Ali Reza; Nojavan, Saeed

2014-10-01

Prediction of chiral separation for a compound using a chiral selector is an interesting and debatable work. For this purpose, in this study 23 chiral basic drugs with different chemical structures were selected as model solutes and the influence of their chemical structures on the enantioseparation in the presence of maltodextrin (MD) as chiral selector was investigated. For chiral separation, a 100-mM phosphate buffer solution (pH 3.0) containing 10% (w/v) MD with dextrose equivalent (DE) of 4-7 as chiral selector at the temperature of 25°C and voltage of 20 kV was used. Under this condition, baseline separation was achieved for nine chiral compounds and partial separation was obtained for another six chiral compounds while no enantioseparation was obtained for the remaining eight compounds. The results showed that the existence of at least two aromatic rings or cycloalkanes and an oxygen or nitrogen atom or -CN group directly bonded to the chiral center are necessary for baseline separation. With the obtained results in this study, chiral separation of a chiral compound can be estimated with MD-modified capillary electrophoresis before analysis. This prediction will minimize the number of preliminary experiments required to resolve enantiomers and will save time and cost. © 2014 Wiley Periodicals, Inc.

Observation of chiral phonons

NASA Astrophysics Data System (ADS)

Zhu, Hanyu; Yi, Jun; Li, Ming-Yang; Xiao, Jun; Zhang, Lifa; Yang, Chih-Wen; Kaindl, Robert A.; Li, Lain-Jong; Wang, Yuan; Zhang, Xiang

2018-02-01

Chirality reveals symmetry breaking of the fundamental interaction of elementary particles. In condensed matter, for example, the chirality of electrons governs many unconventional transport phenomena such as the quantum Hall effect. Here we show that phonons can exhibit intrinsic chirality in monolayer tungsten diselenide. The broken inversion symmetry of the lattice lifts the degeneracy of clockwise and counterclockwise phonon modes at the corners of the Brillouin zone. We identified the phonons by the intervalley transfer of holes through hole-phonon interactions during the indirect infrared absorption, and we confirmed their chirality by the infrared circular dichroism arising from pseudoangular momentum conservation. The chiral phonons are important for electron-phonon coupling in solids, phonon-driven topological states, and energy-efficient information processing.

Meta-Chirality: Fundamentals, Construction and Applications

PubMed Central

Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Guo, Yinghui; Gao, Ping; Luo, Xiangang

2017-01-01

Chiral metamaterials represent a special type of artificial structures that cannot be superposed to their mirror images. Due to the lack of mirror symmetry, cross-coupling between electric and magnetic fields exist in chiral mediums and present unique electromagnetic characters of circular dichroism and optical activity, which provide a new opportunity to tune polarization and realize negative refractive index. Chiral metamaterials have attracted great attentions in recent years and have given rise to a series of applications in polarization manipulation, imaging, chemical and biological detection, and nonlinear optics. Here we review the fundamental theory of chiral media and analyze the construction principles of some typical chiral metamaterials. Then, the progress in extrinsic chiral metamaterials, absorbing chiral metamaterials, and reconfigurable chiral metamaterials are summarized. In the last section, future trends in chiral metamaterials and application in nonlinear optics are introduced. PMID:28513560

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.

Chirality-controlled crystallization via screw dislocations.

PubMed

Sung, Baeckkyoung; de la Cotte, Alexis; Grelet, Eric

2018-04-11

Chirality plays an important role in science from enantiomeric separation in chemistry to chiral plasmonics in nanotechnology. However, the understanding of chirality amplification from chiral building blocks to ordered helical superstructures remains a challenge. Here, we demonstrate that topological defects, such as screw dislocations, can drive the chirality transfer from particle to supramolecular structure level during the crystallization process. By using a model system of chiral particles, which enables direct imaging of single particle incorporation into growing crystals, we show that the crystallization kinetic pathway is the key parameter for monitoring, via the defects, the chirality amplification of the crystalline structures from racemic to predominantly homohelical. We provide an explanation based on the interplay between geometrical frustration, racemization induced by thermal fluctuations, and particle chirality. Our results demonstrate that screw dislocations not only promote the growth, but also control the chiral morphology and therefore the functionality of crystalline states.

Spin Chirality of Cu3 and V3 Nanomagnets. 1. Rotation Behavior of Vector Chirality, Scalar Chirality, and Magnetization in the Rotating Magnetic Field, Magnetochiral Correlations.

PubMed

Belinsky, Moisey I

2016-05-02

The rotation behavior of the vector chirality κ, scalar chirality χ, and magnetization M in the rotating magnetic field H1 is considered for the V3 and Cu3 nanomagnets, in which the Dzialoshinsky-Moriya coupling is active. The polar rotation of the field H1 of the given strength H1 results in the energy spectrum characterized by different vector and scalar chiralities in the ground and excited states. The magnetochiral correlations between the vector and scalar chiralities, energy, and magnetization in the rotating field were considered. Under the uniform polar rotation of the field H1, the ground-state chirality vector κI performs sawtooth oscillations and the magnetization vector MI performs the sawtooth oscillating rotation that is accompanied by the correlated transformation of the scalar chirality χI. This demonstrates the magnetochiral effect of the joint rotation behavior and simultaneous frustrations of the spin chiralities and magnetization in the rotating field, which are governed by the correlation between the chiralities and magnetization.

Synthesis of (±)-Tetrapetalone A-Me Aglycon**

PubMed Central

Carlsen, Peter N.; Mann, Tyler J.; Hoveyda, Amir H.

2014-01-01

The first synthesis of (±)-tetrapetalone A-Me aglycon is described. Key bond-forming reactions include Nazarov cyclization, a ring-closing metathesis (RCM) promoted with complete diastereoselectivity by a chiral Mo-based complex, tandem conjugate reduction-intramolecular aldol cyclization, and oxidative dearomatization. PMID:25045072

Chirality and protein biosynthesis.

PubMed

Banik, Sindrila Dutta; Nandi, Nilashis

2013-01-01

Chirality is present at all levels of structural hierarchy of protein and plays a significant role in protein biosynthesis. The macromolecules involved in protein biosynthesis such as aminoacyl tRNA synthetase and ribosome have chiral subunits. Despite the omnipresence of chirality in the biosynthetic pathway, its origin, role in current pathway, and importance is far from understood. In this review we first present an introduction to biochirality and its relevance to protein biosynthesis. Major propositions about the prebiotic origin of biomolecules are presented with particular reference to proteins and nucleic acids. The problem of the origin of homochirality is unresolved at present. The chiral discrimination by enzymes involved in protein synthesis is essential for keeping the life process going. However, questions remained pertaining to the mechanism of chiral discrimination and concomitant retention of biochirality. We discuss the experimental evidence which shows that it is virtually impossible to incorporate D-amino acids in protein structures in present biosynthetic pathways via any of the two major steps of protein synthesis, namely aminoacylation and peptide bond formation reactions. Molecular level explanations of the stringent chiral specificity in each step are extended based on computational analysis. A detailed account of the current state of understanding of the mechanism of chiral discrimination during aminoacylation in the active site of aminoacyl tRNA synthetase and peptide bond formation in ribosomal peptidyl transferase center is presented. Finally, it is pointed out that the understanding of the mechanism of retention of enantiopurity has implications in developing novel enzyme mimetic systems and biocatalysts and might be useful in chiral drug design.

Role of Achiral Nucleobases in Multicomponent Chiral Self-Assembly: Purine-Triggered Helix and Chirality Transfer.

PubMed

Deng, Ming; Zhang, Li; Jiang, Yuqian; Liu, Minghua

2016-11-21

Chiral self-assembly is a basic process in biological systems, where many chiral biomolecules such as amino acids and sugars play important roles. Achiral nucleobases usually covalently bond to saccharides and play a significant role in the formation of the double helix structure. However, it remains unclear how the achiral nucleobases can function in chiral self-assembly without the sugar modification. Herein, we have clarified that purine nucleobases could trigger N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to self-assemble into helical nanostructures. Moreover, the helical nanostructure could serve as a matrix and transfer the chirality to an achiral fluorescence probe, thioflavin T (ThT). Upon chirality transfer, the ThT showed not only supramolecular chirality but also circular polarized fluorescence (CPL). Without the nucleobase, the self-assembly processes cannot happen, thus providing an example where achiral molecules played an essential role in the expression and transfer of the chirality. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

2017-12-01

Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

2018-06-01

Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

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.

Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

PubMed

Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

2016-02-24

Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Chiral Anomalous Dispersion

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

Sadofyev, Andrey; Sen, Srimoyee

The linearized Einstein equation describing graviton propagation through a chiral medium appears to be helicity dependent. We analyze features of the corresponding spectrum in a collision-less regime above a flat background. In the long wave-length limit, circularly polarized metric perturbations travel with a helicity dependent group velocity that can turn negative giving rise to a new type of an anomalous dispersion. We further show that this chiral anomalous dispersion is a general feature of polarized modes propagating through chiral plasmas extending our result to the electromagnetic sector.

Chiral Anomalous Dispersion

DOE PAGES

Sadofyev, Andrey; Sen, Srimoyee

2018-02-16

The linearized Einstein equation describing graviton propagation through a chiral medium appears to be helicity dependent. We analyze features of the corresponding spectrum in a collision-less regime above a flat background. In the long wave-length limit, circularly polarized metric perturbations travel with a helicity dependent group velocity that can turn negative giving rise to a new type of an anomalous dispersion. We further show that this chiral anomalous dispersion is a general feature of polarized modes propagating through chiral plasmas extending our result to the electromagnetic sector.

Chiral Responsive Liquid Quantum Dots.

PubMed

Zhang, Jin; Ma, Junkai; Shi, Fangdan; Tian, Demei; Li, Haibing

2017-08-01

How to convert the weak chiral-interaction into the macroscopic properties of materials remains a huge challenge. Here, this study develops highly fluorescent, selectively chiral-responsive liquid quantum dots (liquid QDs) based on the hydrophobic interaction between the chiral chains and the oleic acid-stabilized QDs, which have been designated as (S)-1810-QDs. The fluorescence spectrum and liquidity of thermal control demonstrate the fluorescence properties and the fluidic behavior of (S)-1810-QDs in the solvent-free state. Especially, (S)-1810-QDs exhibit a highly chiral-selective response toward (1R, 2S)-2-amino-1,2-diphenyl ethanol. It is anticipated that this study will facilitate the construction of smart chiral fluidic sensors. More importantly, (S)-1810-QDs can become an attractive material for chiral separation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of chiral phonons.

PubMed

Zhu, Hanyu; Yi, Jun; Li, Ming-Yang; Xiao, Jun; Zhang, Lifa; Yang, Chih-Wen; Kaindl, Robert A; Li, Lain-Jong; Wang, Yuan; Zhang, Xiang

2018-02-02

Chirality reveals symmetry breaking of the fundamental interaction of elementary particles. In condensed matter, for example, the chirality of electrons governs many unconventional transport phenomena such as the quantum Hall effect. Here we show that phonons can exhibit intrinsic chirality in monolayer tungsten diselenide. The broken inversion symmetry of the lattice lifts the degeneracy of clockwise and counterclockwise phonon modes at the corners of the Brillouin zone. We identified the phonons by the intervalley transfer of holes through hole-phonon interactions during the indirect infrared absorption, and we confirmed their chirality by the infrared circular dichroism arising from pseudoangular momentum conservation. The chiral phonons are important for electron-phonon coupling in solids, phonon-driven topological states, and energy-efficient information processing. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Mass-Selective Chiral Analysis

NASA Astrophysics Data System (ADS)

Boesl, Ulrich; Kartouzian, Aras

2016-06-01

Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

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

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.

Increments to chiral recognition facilitating enantiomer separations of chiral acids, bases, and ampholytes using Cinchona-based zwitterion exchanger chiral stationary phases.

PubMed

Wernisch, Stefanie; Pell, Reinhard; Lindner, Wolfgang

2012-07-01

The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral liquid crystal colloids

NASA Astrophysics Data System (ADS)

Yuan, Ye; Martinez, Angel; Senyuk, Bohdan; Tasinkevych, Mykola; Smalyukh, Ivan I.

2018-01-01

Colloidal particles disturb the alignment of rod-like molecules of liquid crystals, giving rise to long-range interactions that minimize the free energy of distorted regions. Particle shape and topology are known to guide this self-assembly process. However, how chirality of colloidal inclusions affects these long-range interactions is unclear. Here we study the effects of distortions caused by chiral springs and helices on the colloidal self-organization in a nematic liquid crystal using laser tweezers, particle tracking and optical imaging. We show that chirality of colloidal particles interacts with the nematic elasticity to predefine chiral or racemic colloidal superstructures in nematic colloids. These findings are consistent with numerical modelling based on the minimization of Landau-de Gennes free energy. Our study uncovers the role of chirality in defining the mesoscopic order of liquid crystal colloids, suggesting that this feature may be a potential tool to modulate the global orientated self-organization of these systems.

Cell Chirality Drives Left-Right Asymmetric Morphogenesis.

PubMed

Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

2018-01-01

Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila , we discovered that cells can have an intrinsic chirality to their structure, and that this "cell chirality" is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF ( Myo31DF ), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans , chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine.

Pure chiral optical fibres.

PubMed

Poladian, L; Straton, M; Docherty, A; Argyros, A

2011-01-17

We investigate the properties of optical fibres made from chiral materials, in which a contrast in optical activity forms the waveguide, rather than a contrast in the refractive index; we refer to such structures as pure chiral fibres. We present a mathematical formulation for solving the modes of circularly symmetric examples of such fibres and examine the guidance and polarisation properties of pure chiral step-index, Bragg and photonic crystal fibre designs. Their behaviour is shown to differ for left- and right-hand circular polarisation, allowing circular polarisations to be isolated and/or guided by different mechanisms, as well as differing from equivalent non-chiral fibres. The strength of optical activity required in each case is quantified.

Chiral quantum dot based materials

NASA Astrophysics Data System (ADS)

Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii

2014-05-01

Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their application in biotechnology, sensing and asymmetric synthesis.

Micropatterning of cells reveals chiral morphogenesis

PubMed Central

2013-01-01

Invariant left-right (LR) patterning or chirality is critical for embryonic development. The loss or reversal of LR asymmetry is often associated with malformations and disease. Although several theories have been proposed, the exact mechanism of the initiation of the LR symmetry has not yet been fully elucidated. Recently, chirality has been detected within single cells as well as multicellular structures using several in vitro approaches. These studies demonstrated the universality of cell chirality, its dependence on cell phenotype, and the role of physical boundaries. In this review, we discuss the theories for developmental LR asymmetry, compare various in vitro cell chirality model systems, and highlight possible roles of cell chirality in stem cell differentiation. We emphasize that the in vitro cell chirality systems have great promise for helping unveil the nature of chiral morphogenesis in development. PMID:23672821

Chiral magnetic effect of light

NASA Astrophysics Data System (ADS)

Hayata, Tomoya

2018-05-01

We study a photonic analog of the chiral magnetic (vortical) effect. We discuss that the vector component of magnetoelectric tensors plays a role of "vector potential," and its rotation is understood as "magnetic field" of a light. Using the geometrical optics approximation, we show that "magnetic fields" cause an anomalous shift of a wave packet of a light through an interplay with the Berry curvature of photons. The mechanism is the same as that of the chiral magnetic (vortical) effect of a chiral fermion, so that we term the anomalous shift "chiral magnetic effect of a light." We further study the chiral magnetic effect of a light beyond geometric optics by directly solving the transmission problem of a wave packet at a surface of a magnetoelectric material. We show that the experimental signal of the chiral magnetic effect of a light is the nonvanishing of transverse displacements for the beam normally incident to a magnetoelectric material.

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.

Enantioselective α-Vinylation of Aldehydes Via the Synergistic Combination of Copper and Amine Catalysis

PubMed Central

Skucas, Eduardas; MacMillan, David W. C.

2012-01-01

The enantioselective α-vinylation of aldehydes using vinyl iodonium triflate salts has been accomplished via the synergistic combination of copper and chiral amine catalysis. These mild catalytic conditions provide a direct route for the enantioselective construction of enolizable α-formyl vinylic stereocenters without racemization or olefin transposition. These high-value coupling adducts are readily converted into a variety of useful olefin synthons. PMID:22616631

Chirality-dependent cellular uptake of chiral nanocarriers and intracellular delivery of different amounts of guest molecules

NASA Astrophysics Data System (ADS)

Kehr, Nermin Seda; Jose, Joachim

2017-12-01

We demonstrate the organic molecules loaded and chiral polymers coated periodic mesoporous organosilica (PMO) to generate chiral nanocarriers that we used to study chirality-dependent cellular uptake in serum and serum-free media and the subsequent delivery of different amounts of organic molecules into cells. Our results show that the amount of internalized PMO and thus the transported amount of organic molecules by nanocarrier PMO into cells was chirality dependent and controlled by hard/soft protein corona formation on the PMO surfaces. Therefore, this study demonstrate that chiral porous nanocarriers could potentially be used as advanced drug delivery systems which are able to use the specific chiral surface-protein interactions to influence/control the amount of (bio)active molecules delivered to cells in drug delivery and/or imaging applications.

Quark structure of chiral solitons

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

Dmitri Diakonov

2004-05-01

There is a prejudice that the chiral soliton model of baryons is something orthogonal to the good old constituent quark models. In fact, it is the opposite: the spontaneous chiral symmetry breaking in strong interactions explains the appearance of massive constituent quarks of small size thus justifying the constituent quark models, in the first place. Chiral symmetry ensures that constituent quarks interact very strongly with the pseudoscalar fields. The ''chiral soliton'' is another word for the chiral field binding constituent quarks. We show how the old SU(6) quark wave functions follow from the ''soliton'', however, with computable relativistic corrections andmore » additional quark-antiquark pairs. We also find the 5-quark wave function of the exotic baryon Theta+.« less

Cell Chirality Drives Left-Right Asymmetric Morphogenesis

PubMed Central

Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

2018-01-01

Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila, we discovered that cells can have an intrinsic chirality to their structure, and that this “cell chirality” is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF (Myo31DF), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans, chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine. PMID:29666795

Chiral electroweak currents in nuclei

DOE PAGES

Riska, D. O.; Schiavilla, R.

2017-01-10

Here, the development of the chiral dynamics based description of nuclear electroweak currents is reviewed. Gerald E. (Gerry) Brown’s role in basing theoretical nuclear physics on chiral Lagrangians is emphasized. Illustrative examples of the successful description of electroweak observables of light nuclei obtained from chiral effective field theory are presented.

Five chiral Cd(II) complexes with dual chiral components: Effect of positional isomerism, luminescence and SHG response

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

Cheng, Lin, E-mail: lcheng@seu.edu.cn; Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189; Wang, Jun

2015-01-15

Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of (1R,2R)–N{sup 1},N{sup 2}-bis(pyridinylmethyl)cyclohexane-1,2-diamine ligands with different N-positions of pyridyl rings and Cd(NO{sub 3}){sub 2}. The circular dichroism (CD) spectra and second-harmonic generation (SHG) efficiency measurements confirmed that they are of structural chirality in the bulk samples. The luminescent properties indicated that they may have potential applications as optical materials. The formation of discrete mononuclear and binuclear complexes, and one-dimensional chains may be attributed to positional isomerism of the ligands. - Graphical abstract: Five chiral Cd(II) complexes with dual chiral components have been synthesized bymore » using a series of chiral ligands with different N-positions of pyridyl rings. - Highlights: • Five chiral Cd(II) complexes with dual chiral components have been synthesized. • CD spectra and SHG efficiency of the bulk samples have been measured. • The complexes display luminescent properties.« less

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.

Nanoscale chirality in metal and semiconductor nanoparticles

PubMed Central

Thomas, K. George

2016-01-01

The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided. PMID:27752651

Nanoscale chirality in metal and semiconductor nanoparticles.

PubMed

Kumar, Jatish; Thomas, K George; Liz-Marzán, Luis M

2016-10-18

The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided.

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.

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.

Enantiomeric separation of six chiral pesticides that contain chiral sulfur/phosphorus atoms by supercritical fluid chromatography.

PubMed

Zhang, Lijun; Miao, Yelong; Lin, Chunmian

2018-03-01

Six chiral pesticides containing chiral sulfur/phosphorus atoms were separated by supercritical fluid chromatography with supercritical CO 2 as the main mobile phase component. The effect of the chiral stationary phase, different type and concentration of modifiers, column temperature, and backpressure on the separation efficiency was investigated to obtain the appropriate separation condition. Five chiral pesticides (isofenphos-methyl, isocarbophos, flufiprole, fipronil, and ethiprole) were baseline separated under experimental conditions, while isofenphos only obtained partial separation. The Chiralpak AD-3 column showed a better chiral separation ability than others for chiral pesticides containing chiral sulfur/phosphorus atoms. When different modifiers at the same concentration were used, the retention factor of pesticides except flufiprole decreased in the order of isopropanol, ethanol, methanol; meanwhile, the retention factor of flufiprole increased in the order of isopropanol, ethanol, methanol. For a given modifier, the retention factor and resolution decreased on the whole with the increase of its concentration. The enantiomer separation of five chiral pesticides was an "enthalpy-driven" process, and the separation factor decreased as the temperature increased. The backpressure of the mobile phase had little effect on the separation factor and resolution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Broadband reflection of polymer-stabilized chiral nematic liquid crystals induced by a chiral azobenzene compound.

PubMed

Chen, Xingwu; Wang, Ling; Chen, Yinjie; Li, Chenyue; Hou, Guoyan; Liu, Xin; Zhang, Xiaoguang; He, Wanli; Yang, Huai

2014-01-21

A chiral nematic liquid crystal-photopolymerizable monomer-chiral azobenzene compound composite was prepared and then polymerized under UV irradiation. The reflection wavelength of the composite can be extended to cover the 1000-2400 nm range and also be adjusted to the visible light region by controlling the concentration of chiral compounds.

Chiral amplification and sensing of chirality with lyotropic chromonic liquid crystals

NASA Astrophysics Data System (ADS)

Srinivasarao, Mohan; Park, Jung Ok; Fu, Jinxin; Nayani, Karthik; Chang, Rui

Due to the anisotropic elastic properties of lyotropic chromonic liquid crystals (LCLCs), a spontaneously twisted chiral structure has been reported in the achiral LCLCs system under cylindrical confinement. It is found that the handedness of chirality could be biased with a minute amount of a chiral additive. The entire system becomes ``homochiral'' and takes on the handedness of the additive. When 1% by weight of L-glutamic acid was added to LCLCs in a cylinder, the LCLC sbecomes homochiral and possesses giant optical rotation. We explore the mechanism for this based on the ``sergeants-and-soldiers'' and the ``majority-rule'' principles known for organic molecular systems.

Macdonald index and chiral algebra

NASA Astrophysics Data System (ADS)

Song, Jaewon

2017-08-01

For any 4d N = 2 SCFT, there is a subsector described by a 2d chiral algebra. The vacuum character of the chiral algebra reproduces the Schur index of the corresponding 4d theory. The Macdonald index counts the same set of operators as the Schur index, but the former has one more fugacity than the latter. We conjecture a prescription to obtain the Macdonald index from the chiral algebra. The vacuum module admits a filtration, from which we construct an associated graded vector space. From this grading, we conjecture a notion of refined character for the vacuum module of a chiral algebra, which reproduces the Macdonald index. We test this prescription for the Argyres-Douglas theories of type ( A 1 , A 2 n ) and ( A 1 , D 2 n+1) where the chiral algebras are given by Virasoro and \\widehat{su}(2) affine Kac-Moody algebra. When the chiral algebra has more than one family of generators, our prescription requires a knowledge of the generators from the 4d.

Macdonald index and chiral algebra

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

Song, Jaewon

For any 4dN = 2 SCFT, there is a subsector described by a 2d chiral algebra. The vacuum character of the chiral algebra reproduces the Schur index of the corresponding 4d theory. The Macdonald index counts the same set of operators as the Schur index, but the former has one more fugacity than the latter. Here, we conjecture a prescription to obtain the Macdonald index from the chiral algebra. The vacuum module admits a filtration, from which we construct an associated graded vector space. From this grading, we conjecture a notion of refined character for the vacuum module of a chiral algebra, which reproduces the Macdonald index. We test this prescription for the Argyres-Douglas theories of type (A 1, A 2n) and (A 1, D 2n+1) where the chiral algebras are given by Virasoro andmore » $$ˆ\\atop{su}$$(2) affine Kac-Moody algebra. When the chiral algebra has more than one family of generators, our prescription requires a knowledge of the generators from the 4d.« less

Macdonald index and chiral algebra

DOE PAGES

Song, Jaewon

2017-08-10

For any 4dN = 2 SCFT, there is a subsector described by a 2d chiral algebra. The vacuum character of the chiral algebra reproduces the Schur index of the corresponding 4d theory. The Macdonald index counts the same set of operators as the Schur index, but the former has one more fugacity than the latter. Here, we conjecture a prescription to obtain the Macdonald index from the chiral algebra. The vacuum module admits a filtration, from which we construct an associated graded vector space. From this grading, we conjecture a notion of refined character for the vacuum module of a chiral algebra, which reproduces the Macdonald index. We test this prescription for the Argyres-Douglas theories of type (A 1, A 2n) and (A 1, D 2n+1) where the chiral algebras are given by Virasoro andmore » $$ˆ\\atop{su}$$(2) affine Kac-Moody algebra. When the chiral algebra has more than one family of generators, our prescription requires a knowledge of the generators from the 4d.« less

Electromagnetic wave propagation through a dielectric-chiral interface and through a chiral slab

NASA Technical Reports Server (NTRS)

Bassiri, S.; Papas, C. H.; Engheta, N.

1988-01-01

The reflection from and transmission through a semiinfinite chiral medium are analyzed by obtaining the Fresnel equations in terms of parallel- and perpendicular-polarized modes, and a comparison is made with results reported previously. The chiral medium is described electromagnetically by the constitutive relations D = (epsilon)E+i(gamma)B and H = i(gamma)E+(1/mu)B. The constants epsilon, mu and gamma are real and have values that are fixed by the size, the shape, and the spatial distribution of the elements that collectively compose the medium. The conditions are obtained for the total internal reflection of the incident wave from the interface and for the existence of the Brewster angle. The effects of the chirality on the polarization and the intensity of the reflected wave from the chiral half-space are discussed and illustrated by using the Stokes parameters. The propagation of electromagnetic wave through an infinite slab of chiral medium is formulated for oblique incidence and solved analytically for the case of normal incidence.

Out-of-equilibrium chiral magnetic effect from chiral kinetic theory

NASA Astrophysics Data System (ADS)

Huang, Anping; Jiang, Yin; Shi, Shuzhe; Liao, Jinfeng; Zhuang, Pengfei

2018-02-01

Recently there has been significant interest in the macroscopic manifestation of chiral anomaly in many-body systems of chiral fermions. A notable example is the Chiral Magnetic Effect (CME). Enthusiastic efforts have been made to search for the CME in the quark-gluon plasma created in heavy ion collisions. A crucial challenge is that the extremely strong magnetic field in such collisions may last only for a brief moment and the CME current may have to occur at so early a stage that the quark-gluon matter is still far from thermal equilibrium. This thus requires modeling of the CME in an out-of-equilibrium setting. With the recently developed theoretical tool of chiral kinetic theory, we make a first phenomenological study of the CME-induced charge separation during the pre-thermal stage in heavy ion collisions. The effect is found to be very sensitive to the time dependence of the magnetic field and also influenced by the initial quark momentum spectrum as well as the relaxation time of the system evolution toward thermal equilibrium. Within the present approach, such pre-thermal charge separation is found to be modest.

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.

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation

PubMed Central

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-01-01

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3, 5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. PMID:23891368

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation.

PubMed

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-08-30

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3,5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. Copyright © 2013 Elsevier B.V. All rights reserved.

The chiral magnetic effect and chiral symmetry breaking in SU(3) quenched lattice gauge theory

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

Braguta, V. V., E-mail: braguta@mail.ru; Buividovich, P. V., E-mail: buividovich@itep.ru; Kalaydzhyan, T., E-mail: tigran.kalaydzhyan@desy.de

2012-04-15

We study some properties of the non-Abelian vacuum induced by strong external magnetic field. We perform calculations in the quenched SU(3) lattice gauge theory with tadpole-improved Luescher-Weisz action and chirally invariant lattice Dirac operator. The following results are obtained: The chiral symmetry breaking is enhanced by the magnetic field. The chiral condensate depends on the strength of the applied field as a power function with exponent {nu} = 1.6 {+-} 0.2. There is a paramagnetic polarization of the vacuum. The corresponding susceptibility and other magnetic properties are calculated and compared with the theoretical estimations. There are nonzero local fluctuations ofmore » the chirality and electromagnetic current, which grow with the magnetic field strength. These fluctuations can be a manifestation of the Chiral Magnetic Effect.« less

Chiral nanoparticles in singular light fields

NASA Astrophysics Data System (ADS)

Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

2017-04-01

The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre-Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams.

Controlling Chirality of Entropic Crystals.

PubMed

Damasceno, Pablo F; Karas, Andrew S; Schultz, Benjamin A; Engel, Michael; Glotzer, Sharon C

2015-10-09

Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

Controlling Chirality of Entropic Crystals

NASA Astrophysics Data System (ADS)

Damasceno, Pablo F.; Karas, Andrew S.; Schultz, Benjamin A.; Engel, Michael; Glotzer, Sharon C.

2015-10-01

Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

Novel electrochemical method for the characterization of the degree of chirality in chiral polyaniline.

PubMed

Feng, Zhang; Li, Ma; Yan, Yang; Jihai, Tang; Xiao, Li; Wanglin, Li

2013-01-01

A novel method to indicate the degree of chirality in polyaniline (PANI) was developed. The (D-camphorsulfonic acid)- and (HCl)-PANI-based electrodes exhibited significantly different electrochemical performances in D- and L-Alanine (Ala) aqueous solution, respectively, which can be used for the characterization the optical activity of chiral PANI. Cyclic voltammogram, tafel, and open circuit potential of PANI-based electrodes were measured within D- and L-Ala electrolyte solution, respectively. The open circuit potentials under different reacting conditions were analyzed by Doblhofer model formula, in which [C(+)](poly1)/[C(+)](poly2) was used as a parameter to characterize the degree of chirality in chiral PANI. The results showed that [C(+)](poly1)/[C(+)](poly2) can be increased with increasing concentrations of (1S)-(+)- and (1R)-(-)-10-camphorsulfonic acid. In addition, we detected that appropriate response time and lower temperature are necessary to improve the degree of chirality. Copyright © 2012 Wiley Periodicals, Inc.

Molecular-Level Design of Heterogeneous Chiral Catalysis

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

Francisco Zaera

2012-03-21

The following is a proposal to continue our multi-institutional research on heterogeneous chiral catalysis. Our team combines the use of surface-sensitive analytical techniques for the characterization of model systems with quantum and statistical mechanical calculations to interpret experimental data and guide the design of future research. Our investigation focuses on the interrelation among the three main mechanisms by which enantioselectivity can be bestowed to heterogeneous catalysts, namely: (1) by templating chirality via the adsorption of chiral supramolecular assemblies, (2) by using chiral modifiers capable of forming chiral complexes with the reactant and force enantioselective surface reactions, and (3) by formingmore » naturally chiral surfaces using imprinting chiral agents. Individually, the members of our team are leaders in these various aspects of chiral catalysis, but the present program provides the vehicle to generate and exploit the synergies necessary to address the problem in a comprehensive manner. Our initial work has advanced the methodology needed for these studies, including an enantioselective titration procedure to identify surface chiral sites, infrared spectroscopy in situ at the interface between gases or liquids and solids to mimic realistic catalytic conditions, and DFT and Monte Carlo algorithms to simulate and understand chirality on surfaces. The next step, to be funded by the monies requested in this proposal, is to apply those methods to specific problems in chiral catalysis, including the identification of the requirements for the formation of supramolecular surface structures with enantioselective behavior, the search for better molecules to probe the chiral nature of the modified surfaces, the exploration of the transition from supramolecular to one-to-one chiral modification, the correlation of the adsorption characteristics of one-to-one chiral modifiers with their physical properties, in particular with their

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.

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.

Spin chirality and polarised neutron scattering

NASA Astrophysics Data System (ADS)

Plakhty, V. P.; Maleyev, S. V.; Kulda, J.; Visser, E. D.; Wosnitza, J.; Moskvin, E. V.; Brückel, Th.; Kremer, R. K.

2001-03-01

Possibilities of polarised neutrons in studies of chiral criticality are discussed. The critical exponents β C of the average chirality below TN, as well as φ C=β C+γ C and, therefore, γ C of the chiral susceptibility above TN are determined for a XY triangular lattice antiferromagnet (TLA) CsMnBr3: β C=0.44(2) , γ C=0.84(7) . The critical behaviour of the chirality that orders at TN with a relative precision of 5×10 -4 proves that the phase transition belongs to a new chiral universality class. For the TLA CsNiCl 3 ( S=1) we found in the XY region ( B=3 T) φ C=1.24(7) in agreement with the Monte-Carlo value φ C=1.22(6) for the chiral universality class. In the easy-axis region at B=1 T, φ C=0.54(4) , and the Haldane excitations are observed in the polarisation-dependent inelastic cross section above TN. The helimagnet holmium exhibits a different chiral criticality with φ C=1.56(5) , essentially higher than for TLAs.

Chirality-induced magnon transport in AA-stacked bilayer honeycomb chiral magnets.

PubMed

Owerre, S A

2016-11-30

In this Letter, we study the magnetic transport in AA-stacked bilayer honeycomb chiral magnets coupled either ferromagnetically or antiferromagnetically. For both couplings, we observe chirality-induced gaps, chiral protected edge states, magnon Hall and magnon spin Nernst effects of magnetic spin excitations. For ferromagnetically coupled layers, thermal Hall and spin Nernst conductivities do not change sign as function of magnetic field or temperature similar to single-layer honeycomb ferromagnetic insulator. In contrast, for antiferromagnetically coupled layers, we observe a sign change in the thermal Hall and spin Nernst conductivities as the magnetic field is reversed. We discuss possible experimental accessible honeycomb bilayer quantum materials in which these effects can be observed.

Chiral Graphene Quantum Dots

DOE PAGES

Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; ...

2016-01-15

Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the “crowded” edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210–220 and 250–265 nm that changed their signs formore » different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210–220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250–265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to l/d-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than l-GQDs. Finally, emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials.« less

Chiral nanoparticles in singular light fields

PubMed Central

Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

2017-01-01

The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre–Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams. PMID:28378842

Asymmetric synthesis using chiral-encoded metal

NASA Astrophysics Data System (ADS)

Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

2016-08-01

The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

EPA Science Inventory

Enantiomers, the mirror image isomers of chiral pollutants, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. Considerable research has shown, for example, that chiral pesticides are degraded selectively by micr...

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

PubMed

Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

2016-01-26

Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle

Chirality: a relational geometric-physical property.

PubMed

Gerlach, Hans

2013-11-01

The definition of the term chirality by Lord Kelvin in 1893 and 1904 is analyzed by taking crystallography at that time into account. This shows clearly that chirality is a relational geometric-physical property, i.e., two relations between isometric objects are possible: homochiral or heterochiral. In scientific articles the relational term chirality is often mistaken for the two valued measure for the individual (absolute) sense of chirality, an arbitrary attributive term. © 2013 Wiley Periodicals, Inc.

Chiral stationary phase optimized selectivity liquid chromatography: A strategy for the separation of chiral isomers.

PubMed

Hegade, Ravindra Suryakant; De Beer, Maarten; Lynen, Frederic

2017-09-15

Chiral Stationary-Phase Optimized Selectivity Liquid Chromatography (SOSLC) is proposed as a tool to optimally separate mixtures of enantiomers on a set of commercially available coupled chiral columns. This approach allows for the prediction of the separation profiles on any possible combination of the chiral stationary phases based on a limited number of preliminary analyses, followed by automated selection of the optimal column combination. Both the isocratic and gradient SOSLC approach were implemented for prediction of the retention times for a mixture of 4 chiral pairs on all possible combinations of the 5 commercial chiral columns. Predictions in isocratic and gradient mode were performed with a commercially available and with an in-house developed Microsoft visual basic algorithm, respectively. Optimal predictions in the isocratic mode required the coupling of 4 columns whereby relative deviations between the predicted and experimental retention times ranged between 2 and 7%. Gradient predictions led to the coupling of 3 chiral columns allowing baseline separation of all solutes, whereby differences between predictions and experiments ranged between 0 and 12%. The methodology is a novel tool allowing optimizing the separation of mixtures of optical isomers. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhancing and reducing chirality by opposite circularly-polarized light irradiation on crystalline chiral domains consisting of nonchiral photoresponsive W-shaped liquid crystal molecules.

PubMed

Choi, Suk-Won; Takezoe, Hideo

2016-09-28

We found possible chirality enhancement and reduction in chiral domains formed by photoresponsive W-shaped molecules by irradiation with circularly polarized light (CPL). The W-shaped molecules exhibit a unique smectic phase with spontaneously segregated chiral domains, although the molecules are nonchiral. The chirality control was generated in the crystalline phase, which shows chiral segregation as in the upper smectic phase, and the result appeared to be as follows: for a certain chiral domain, right-CPL stimuli enhanced the chirality, while left-CPL stimuli reduced the chirality, and vice versa for another chiral domain. Interestingly, no domain-size change could be observed after CPL irradiation, suggesting some changes in the causes of chirality. In this way, the present system can recognize the handedness of the applied chiral stimuli. In other words, the present material can be used as a sensitive chiral-stimuli-recognizing material and should find invaluable applications, including in chiroptical switches, sensors, and memories as well as in chiral recognition.

No chiral truncation of quantum log gravity?

NASA Astrophysics Data System (ADS)

Andrade, Tomás; Marolf, Donald

2010-03-01

At the classical level, chiral gravity may be constructed as a consistent truncation of a larger theory called log gravity by requiring that left-moving charges vanish. In turn, log gravity is the limit of topologically massive gravity (TMG) at a special value of the coupling (the chiral point). We study the situation at the level of linearized quantum fields, focussing on a unitary quantization. While the TMG Hilbert space is continuous at the chiral point, the left-moving Virasoro generators become ill-defined and cannot be used to define a chiral truncation. In a sense, the left-moving asymptotic symmetries are spontaneously broken at the chiral point. In contrast, in a non-unitary quantization of TMG, both the Hilbert space and charges are continuous at the chiral point and define a unitary theory of chiral gravity at the linearized level.

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.

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.

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis.

PubMed

Xia, Zhengqiang; Jing, Xu; He, Cheng; Wang, Xiaoge; Duan, Chunying

2017-11-13

The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal‒organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

Direct Detection of Hardly Detectable Hidden Chirality of Hydrocarbons and Deuterated Isotopomers by a Helical Polyacetylene through Chiral Amplification and Memory.

PubMed

Maeda, Katsuhiro; Hirose, Daisuke; Okoshi, Natsuki; Shimomura, Kouhei; Wada, Yuya; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Yashima, Eiji

2018-03-07

We report the first direct chirality sensing of a series of chiral hydrocarbons and isotopically chiral compounds (deuterated isotopomers), which are almost impossible to detect by conventional optical spectroscopic methods, by a stereoregular polyacetylene bearing 2,2'-biphenol-derived pendants. The polyacetylene showed a circular dichroism due to a preferred-handed helix formation in response to the hardly detectable hidden chirality of saturated tertiary or chiroptical quaternary hydrocarbons, and deuterated isotopomers. In sharp contrast to the previously reported sensory systems, the chirality detection by the polyacetylene relies on an excess one-handed helix formation induced by the chiral hydrocarbons and deuterated isotopomers via significant amplification of the chirality followed by its static memory, through which chiral information on the minute and hidden chirality can be stored as an excess of a single-handed helix memory for a long time.

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

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

Chiral anomaly, Berry phase, and chiral kinetic theory from worldlines in quantum field theory

NASA Astrophysics Data System (ADS)

Mueller, Niklas; Venugopalan, Raju

2018-03-01

In previous work, we outlined a worldline framework that can be used for systematic computations of the chiral magnetic effect (CME) in ultrarelativistic heavy-ion collisions. Towards this end, we first expressed the real part of the fermion determinant in the QCD effective action as a supersymmetric worldline action of spinning, colored, Grassmanian point particles in background gauge fields, with equations of motion that are covariant generalizations of the Bargmann-Michel-Telegdi and Wong equations. The chiral anomaly, in contrast, arises from the phase of the fermion determinant. Remarkably, the latter too can be expressed as a point particle worldline path integral, which can be employed to derive the anomalous axial vector current. We will show here how Berry's phase can be obtained in a consistent nonrelativistic adiabatic limit of the real part of the fermion determinant. Our work provides a general first principles demonstration that the topology of Berry's phase is distinct from that of the chiral anomaly confirming prior arguments by Fujikawa in specific contexts. This suggests that chiral kinetic treatments of the CME in heavy-ion collisions that include Berry's phase alone are incomplete. We outline the elements of a worldline covariant relativistic chiral kinetic theory that captures the physics of how the chiral current is modified by many-body scattering and topological fluctuations.

Chiral Superstructure Mesophases of Achiral Bent-Shaped Molecules - Hierarchical Chirality Amplification and Physical Properties.

PubMed

Le, Khoa V; Takezoe, Hideo; Araoka, Fumito

2017-07-01

Chiral mesophases in achiral bent-shaped molecules have attracted particular attention since their discovery in the middle 1990s, not only because of their homochirality and polarity, but also due to their unique physical/physicochemical properties. Here, the most intriguing results in the studies of such symmetry-broken states, mainly helical-nanofilament (HNF) and dark-conglomerate (DC) phases, are reviewed. Firstly, basic information on the typical appearance and optical activity in these phases is introduced. In the following section, the formation of mesoscopic chiral superstructures in the HNF and DC phases is discussed in terms of hierarchical chirality. Nanoscale phase segregation in mixture systems and gelation ability in the HNF phase are also described. In addition, some other related chiral phases of bent-shaped molecules are shown. Recent attempts to control such mesoscopic chiral structure and the alignment/confinement of HNFs are also discussed, along with several examples of their fascinating advanced physical properties, i.e. huge enhancement of circular dichroism, electro- and photo-tunable optical activities, chirality-induced nonlinear optics (second-harmonic-generation circular difference and electrogyration effect), enhanced hydrophobicity through the dual-scale surface morphological modulation, and photoconductivity in the HNF/fullerene binary system. Future prospects from basic science and application viewpoints are also indicated in the concluding section. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular chirality: language, history, and significance.

PubMed

Gal, Joseph

2013-01-01

In this chapter some background material concerning molecular chirality and enantiomerism is presented. First some basic chemical-molecular aspects of chirality are reviewed, after which certain relevant terminology whose use in the literature has been problematic is discussed. Then an overview is provided of some of the early discoveries that laid the foundations of the science of molecular chirality in chemistry and biology, including the discovery of the phenomenon of molecular chirality by L. Pasteur, the proposals for the asymmetric carbon atom by J.H. van 't Hoff and J.A. Lebel, Pasteur's discovery of biological enantioselectivity, the discovery of enantioselectivity at biological receptors by A. Piutti, the studies of enzymatic stereoselectivity by E. Fischer, and the work on enantioselectivity in pharmacology by A. Cushny. Finally, the role of molecular chirality in pharmacotherapy and new-drug development, arguably one of the main driving forces for the current intense interest in the phenomenon of molecular chirality, is discussed.

Stable Pentaquarks from Strange Chiral Multiplets

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

Silas Beane

2004-12-01

The assumption of strong diquark correlations in the QCD spectrum suggests flavor multiplets of hadrons that are degenerate in the chiral limit. Generally it would be unnatural for there to be degeneracy in the hadron spectrum that is not protected by a QCD symmetry. Here we show--for pentaquarks constructed from diquarks--that these degeneracies can be naturally protected by the full chiral symmetry of QCD. The resulting chiral multiplet structure recovers the ideally-mixed pentaquark mass spectrum of the diquark model, and interestingly, requires that the axial couplings of the pentaquarks to states outside the degenerate multiplets vanish in the chiral limit.more » This result suggests that if these hadrons exist, they are stable in the chiral limit and therefore have widths that scale as the fourth power of the kaon mass over the chiral symmetry breaking scale. Natural-size widths are of order a few MeV.« less

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

Chirality effect in disordered graphene ribbon junctions

NASA Astrophysics Data System (ADS)

Long, Wen

2012-05-01

We investigate the influence of edge chirality on the electronic transport in clean or disordered graphene ribbon junctions. By using the tight-binding model and the Landauer-Büttiker formalism, the junction conductance is obtained. In the clean sample, the zero-magnetic-field junction conductance is strongly chirality-dependent in both unipolar and bipolar ribbons, whereas the high-magnetic-field conductance is either chirality-independent in the unipolar or chirality-dependent in the bipolar ribbon. Furthermore, we study the disordered sample in the presence of magnetic field and find that the junction conductance is always chirality-insensitive for both unipolar and bipolar ribbons with adequate disorders. In addition, the disorder-induced conductance plateaus can exist in all chiral bipolar ribbons provided the disorder strength is moderate. These results suggest that we can neglect the effect of edge chirality in fabricating electronic devices based on the magnetotransport in a disordered graphene ribbon.

Chiral permselectivity in surface-modified nanoporous opal films.

PubMed

Cichelli, Julie; Zharov, Ilya

2006-06-28

Nanoporous 7 mum thin opal films comprising 35 layers of 200 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with chiral selector moieties on the silica surface. Diffusion of chiral redox species through the opals was studied by cyclic voltammetry. The chiral opal films demonstrate high selectivity for transport of one enantiomer over the other. This chiral permselectivity is attributed to the surface-facilitated transport utilizing noncovalent interactions between the chiral permeant molecules and surface-bound chiral selectors.

Chiral Symmetry Breaking and Complete Chiral Purity by Thermodynamic-Kinetic Feedback Near Equilibrium: Implications for the Origin of Biochirality

NASA Astrophysics Data System (ADS)

Viedma, Cristobal

2007-05-01

Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers-left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral crystals of left and right hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This ``thermodynamic-kinetic feedback near equilibrium'' is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.

Enantioselective environmental toxicology of chiral pesticides.

PubMed

Ye, Jing; Zhao, Meirong; Niu, Lili; Liu, Weiping

2015-03-16

The enantioselective environmental toxic effect of chiral pesticides is becoming more important. As the industry develops, increasing numbers of chiral insecticides and herbicides will be introduced into use, potentially posing toxic effects on nontarget living beings. Chiral pesticides, including herbicides such as acylanilides, phenoxypropanoic acids, and imidazolinones, and insecticides such as synthetic pyrethroids, organophosphates, and DDT often behave enantioselectively during agricultural use. These compounds also pose unpredictable enantioselective ecological threats to nontarget living beings and/or humans, affecting the food chain and entire ecosystems. Thus, to investigate the enantioselective toxic effects of chiral insecticides and herbicides is necessary during environmental protection. The environmental toxicology of chiral pesticides, especially the findings obtained from studies conducted in our laboratory during the past 10 years, is reviewed.

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.

Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

Chiral selection on inorganic crystalline surfaces

NASA Technical Reports Server (NTRS)

Hazen, Robert M.; Sholl, David S.

2003-01-01

From synthetic drugs to biodegradable plastics to the origin of life, the chiral selection of molecules presents both daunting challenges and significant opportunities in materials science. Among the most promising, yet little explored, avenues for chiral molecular discrimination is adsorption on chiral crystalline surfaces - periodic environments that can select, concentrate and possibly even organize molecules into polymers and other macromolecular structures. Here we review experimental and theoretical approaches to chiral selection on inorganic crystalline surfaces - research that is poised to open this new frontier in understanding and exploiting surface-molecule interactions.

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.

Some recent experimental results related to nuclear chirality

NASA Astrophysics Data System (ADS)

Timár, J.; Kuti, I.; Sohler, D.; Starosta, K.; Koike, T.; Paul, E. S.

2014-09-01

Detailed band structures of three chiral-candidate nuclei, 134Pr, 132La and 103Rh have been studied. The aim of the study was twofold. First, to try to explore the reasons behind the contradiction between the theoretically predicted chirality in these nuclei and the recently observed fingerprints that suggest non-chiral interpretation for the previous chiral candidate band doublets. Second, to search for multiple chiral bands of different types in these nuclei. In 134Pr a new πh11/2vh11/2 band has been observed besides the previously known chiral-candidate πh11/2vh11/2 doublet. This new band and the yrare πh11/2vh11/2 band show the expected features of a chiral doublet structure. This fact combined with the observed similarity between the band structures of 134Pr and 132La suggests that chirality might exist in these nuclei. The detailed study of the 103Rh band structure resulted in the observation of two new chiral-doublet looking structures besides the previously known one. This is indicative of possible existence of multiple chiral doublet structure in this nucleus.

Chiral topological insulator of magnons

NASA Astrophysics Data System (ADS)

Li, Bo; Kovalev, Alexey A.

2018-05-01

We propose a magnon realization of 3D topological insulator in the AIII (chiral symmetry) topological class. The topological magnon gap opens due to the presence of Dzyaloshinskii-Moriya interactions. The existence of the topological invariant is established by calculating the bulk winding number of the system. Within our model, the surface magnon Dirac cone is protected by the sublattice chiral symmetry. By analyzing the magnon surface modes, we confirm that the backscattering is prohibited. By weakly breaking the chiral symmetry, we observe the magnon Hall response on the surface due to opening of the gap. Finally, we show that by changing certain parameters, the system can be tuned between the chiral topological insulator, three-dimensional magnon anomalous Hall, and Weyl magnon phases.

Chiralities of spiral waves and their transitions.

PubMed

Pan, Jun-ting; Cai, Mei-chun; Li, Bing-wei; Zhang, Hong

2013-06-01

The chiralities of spiral waves usually refer to their rotation directions (the turning orientations of the spiral temporal movements as time elapses) and their curl directions (the winding orientations of the spiral spatial geometrical structures themselves). Traditionally, they are the same as each other. Namely, they are both clockwise or both counterclockwise. Moreover, the chiralities are determined by the topological charges of spiral waves, and thus they are conserved quantities. After the inwardly propagating spirals were experimentally observed, the relationship between the chiralities and the one between the chiralities and the topological charges are no longer preserved. The chiralities thus become more complex than ever before. As a result, there is now a desire to further study them. In this paper, the chiralities and their transition properties for all kinds of spiral waves are systemically studied in the framework of the complex Ginzburg-Landau equation, and the general relationships both between the chiralities and between the chiralities and the topological charges are obtained. The investigation of some other models, such as the FitzHugh-Nagumo model, the nonuniform Oregonator model, the modified standard model, etc., is also discussed for comparison.

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

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.

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.

Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

PubMed

Zhang, Ying; Ye, Jing; Liu, Min

2017-01-01

Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs

Effects of Fluctuations on Inhomogeneous Chiral Transitions

NASA Astrophysics Data System (ADS)

Lee, Tong-Gyu; Yoshiike, Ryo; Tatsumi, Toshitaka

We discuss the features of the order-parameter fluctuations in the normal phase near the phase boundary and their effects on the phase transition from the normal to the inhomogeneous phase with spatially modulated order parameter. Focusing on the chiral symmetry breaking, i.e., inhomogeneous chiral transition, we consider the fluctuation of the chiral pair consisting of quark-antiquark or quark-hole pair within the two-flavor Nambu-Jona-Lasinio model in the chiral limit. We clarify the roles of quantum and thermal fluctuations and also argue that anomalies for thermodynamic quantities in the inhomogeneous chiral transition should lead to phenomenological implications.

Chiral vortical effect generated by chiral anomaly in vortex-skyrmions

NASA Astrophysics Data System (ADS)

Volovik, G. E.

2017-03-01

We discuss the type of the general macroscopic parity-violating effects, when there is the current along the vortex, which is concentrated in the vortex core. We consider vortices in chiral superfluids with Weyl points. In the vortex core, the positions of the Weyl points form the skyrmion structure. We show that the mass current concentrated in such a core is provided by the spectral flow through the Weyl points according to the Adler-Bell-Jackiw equation for chiral anomaly.

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.

Chiral ionic liquids in chromatographic and electrophoretic separations.

PubMed

Kapnissi-Christodoulou, Constantina P; Stavrou, Ioannis J; Mavroudi, Maria C

2014-10-10

This report provides an overview of the application of chiral ionic liquids (CILs) in separation technology, and particularly in capillary electrophoresis and both gas and liquid chromatography. There is a large number of CILs that have been synthesized and designed as chiral agents. However, only a few have successfully been applied in separation technology. Even though this application of CILs is still in its early stages, the scientific interest is increasing dramatically. This article is focused on the use of CILs as chiral selectors, background electrolyte additives, chiral ligands and chiral stationary phases in electrophoretic and chromatographic techniques. Different examples of CILs, which contain either a chiral cation, a chiral anion or both, are presented in this review article, and their major advantages along with their potential applications in chiral electrophoretic and chromatographic recognition are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Chiral pesticides: identification, description, and environmental implications.

PubMed

Ulrich, Elin M; Morrison, Candice N; Goldsmith, Michael R; Foreman, William T

2012-01-01

Of the 1,693 pesticides considered in this review, 1,594 are organic chemicals, 47 are inorganic chemicals, 53 are of biological origin (largely non chemical; insect,fungus, bacteria, virus, etc.), and 2 have an undetermined structure. Considering that the EPA's Office of Pesticide Programs found 1,252 pesticide active ingredients(EPA Pesticides Customer Service 2011), we consider this dataset to be comprehensive; however, no direct comparison of the compound lists was undertaken. Of all pesticides reviewed, 482 (28%) are chiral; 30% are chiral when considering only the organic chemical pesticides. A graph of this distribution is shown in Fig. 7a. Each pesticide is classified with up to three pesticidal utilities (e.g., fungicide, plant growth regulator, rodenticide, etc.), taken first from the Pesticide Manual as a primary source, and the Compendium of Common Pesticide Names website as a secondary source. Of the chiral pesticides, 195 (34%) are insecticides (including attractants, pheromones, and repellents), 150 (27%) are herbicides (including plant growth regulators and herbicide safeners), 104 (18%) are fungicides, and 55 (10%)are acaricides. The distribution of chiral pesticides by utility is shown in Fig. 7b,including categories of pesticides that make up 3%t or less of the usage categories.Figure 7c shows a similar distribution of non chiral pesticide usage categories. Of the chiral pesticides, 270 (56%) have one chiral feature, 105 (22%) have two chiral features, 30 (6.2%) have three chiral features, and 29 (6.0%) have ten or more chiral features.Chiral chemicals pose many difficulties in stereospecific synthesis, characterization, and analysis. When these compounds are purposely put into the environment,even more interesting complications arise in tracking, monitoring, and predicting their fate and risks. More than 475 pesticides are chiral, as are other chiral contaminants such as pharmaceuticals, polychlorinated biphenyls, brominated flame retardants

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.

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

Chiral corrections to the Adler-Weisberger sum rule

NASA Astrophysics Data System (ADS)

Beane, Silas R.; Klco, Natalie

2016-12-01

The Adler-Weisberger sum rule for the nucleon axial-vector charge, gA , offers a unique signature of chiral symmetry and its breaking in QCD. Its derivation relies on both algebraic aspects of chiral symmetry, which guarantee the convergence of the sum rule, and dynamical aspects of chiral symmetry breaking—as exploited using chiral perturbation theory—which allow the rigorous inclusion of explicit chiral symmetry breaking effects due to light-quark masses. The original derivations obtained the sum rule in the chiral limit and, without the benefit of chiral perturbation theory, made various attempts at extrapolating to nonvanishing pion masses. In this paper, the leading, universal, chiral corrections to the chiral-limit sum rule are obtained. Using PDG data, a recent parametrization of the pion-nucleon total cross sections in the resonance region given by the SAID group, as well as recent Roy-Steiner equation determinations of subthreshold amplitudes, threshold parameters, and correlated low-energy constants, the Adler-Weisberger sum rule is confronted with experimental data. With uncertainty estimates associated with the cross-section parametrization, the Goldberger-Treimann discrepancy, and the truncation of the sum rule at O (Mπ4) in the chiral expansion, this work finds gA=1.248 ±0.010 ±0.007 ±0.013 .

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.

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

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.

Chiral discrimination in nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Lazzeretti, Paolo

2017-11-01

Chirality is a fundamental property of molecules whose spatial symmetry is characterized by the absence of improper rotations, making them not superimposable to their mirror image. Chiral molecules constitute the elementary building blocks of living species and one enantiomer is favoured in general (e.g. L-aminoacids and D-sugars pervade terrestrial homochiral biochemistry) because most chemical reactions producing natural substances are enantioselective. Since the effect of chiral chemicals and drugs on living beings can be markedly different between enantiomers, the quest for practical spectroscopical methods to scrutinize chirality is an issue of great importance and interest. Nuclear magnetic resonance (NMR) is a topmost analytical technique, but spectrometers currently used are ‘blind’ to chirality, i.e. unable to discriminate the two mirror-image forms of a chiral molecule, because, in the absence of a chiral solvent, the spectral parameters, chemical shifts and spin-spin coupling constants are identical for enantiomers. Therefore, the development of new procedures for routine chiral recognition would offer basic support to scientists. However, in the presence of magnetic fields, a distinction between true and false chirality is mandatory. The former epitomizes natural optical activity, which is rationalized by a time-even pseudoscalar, i.e. the trace of a second-rank tensor, the mixed electric dipole/magnetic dipole polarizability. The Faraday effect, magnetic circular dichroism and magnetic optical activity are instead related to a time-odd axial vector. The present review summarizes recent theoretical and experimental efforts to discriminate enantiomers via NMR spectroscopy, with the focus on the deep connection between chirality and symmetry properties under the combined set of fundamental discrete operations, namely charge conjugation, parity (space inversion) and time (motion) reversal.

Chiral magnetic effect in condensed matter systems

DOE PAGES

Li, Qiang; Kharzeev, Dmitri E.

2016-12-01

The chiral magnetic effect is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum anomaly in relativistic field theory of chiral fermions. In the quark-gluon plasma, the axial anomaly induces topological charge changing transition that results in the generation of electrical current along the magnetic field. In condensed matter systems, the chiral magnetic effect was first predicted in the gapless semiconductors with tow energy bands having pointlike degeneracies. In addition, thirty years later after this prediction, the chiral magnetic effect was finally observed in the 3Dmore » Dirac/Weyl semimetals.« less

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.

Illuminating the chirality of Weyl fermions

NASA Astrophysics Data System (ADS)

Ma, Qiong; Xu, Su-Yang; Chan, Ching-Kit; Zhang, Cheng-Long; Chang, Guoqing; Lin, Hsin; Jia, Shuang; Lee, Patrick; Gedik, Nuh; Jarillo-Herrero, Pablo

In particle physics, Weyl fermions (WF) are elementary particles that travel at the speed of light and have a definite chirality. In condensed matter, it has been recently realized that WFs can arise as magnetic monopoles in the momentum space of a novel topological metal, the Weyl semimetal (WSM). Their chirality, given by the sign of the monopole charge, is the defining property of a WSM, since it directly serves as the topological number and gives rise to exotic properties such as Fermi arcs and the chiral anomaly. Moreover, the two chiralities, analogous to the two valleys in 2D materials, lead to a new degree of freedom in a 3D crystal, suggesting novel pathways to store and carry information. By shining circularly polarized light on the WSM TaAs, we illuminate the chirality of the WFs and achieve an electrical current that is highly controllable based on the WFs' chirality. Our results open up a wide range of new possibilities for experimentally studying and controlling the WFs and their associated quantum anomalies by optical and electrical means, which suggest the exciting prospect of ``Weyltronics''.

Centre vortex removal restores chiral symmetry

NASA Astrophysics Data System (ADS)

Trewartha, Daniel; Kamleh, Waseem; Leinweber, Derek B.

2017-12-01

The influence of centre vortices on dynamical chiral symmetry breaking is investigated through the light hadron spectrum on the lattice. Recent studies of the quark propagator and other quantities have provided evidence that centre vortices are the fundamental objects underpinning dynamical chiral symmetry breaking in {SU}(3) gauge theory. For the first time, we use the chiral overlap fermion action to study the low-lying hadron spectrum on lattice ensembles consisting of Monte Carlo, vortex-removed, and vortex-projected gauge fields. We find that gauge field configurations consisting solely of smoothed centre vortices are capable of reproducing all the salient features of the hadron spectrum, including dynamical chiral symmetry breaking. The hadron spectrum on vortex-removed fields shows clear signals of chiral symmetry restoration at light values of the bare quark mass, while at heavy masses the spectrum is consistent with a theory of weakly interacting constituent quarks.

Controlling Chirality of Entropic Crystals

NASA Astrophysics Data System (ADS)

Damasceno, Pablo; Karas, Andrew; Schultz, Benjamin; Engel, Michael; Glotzer, Sharon

Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams. Work supported by the National Science Foundation, Division of Materials Research Award No. DMR 1120923, U.S. Army Research Office under Grant Award No. W911NF-10-1-0518, and also by the DOD/ASD (R&E) under Award No. N00244-09-1-0062.

Enantioselective recognition at mesoporous chiral metal surfaces.

PubMed

Wattanakit, Chularat; Côme, Yémima Bon Saint; Lapeyre, Veronique; Bopp, Philippe A; Heim, Matthias; Yadnum, Sudarat; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

2014-01-01

Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes.

Chiral fiber sensors

NASA Astrophysics Data System (ADS)

Kopp, Victor I.; Churikov, Victor M.; Singer, Jonathan; Neugroschl, Daniel; Genack, Azriel Z.

2010-04-01

We have fabricated a variety of chiral fiber sensors by twisting one or more standard or custom optical fibers with noncircular or nonconcentric core as they pass though a miniature oven. The resulting structures are as stable as the glass material and can be produced with helical pitch ranging from microns to hundreds of microns. The polarization selectivity of the chiral gratings is determined by the geometry of the fiber cross section. Single helix structures are polarization insensitive, while double helix gratings interact only with a single optical polarization component. Both single and double helix gratings may function as a fiber long period grating, coupling core and cladding modes or as a diffraction grating scattering light from the fiber core out of the fiber. The resulting dips in the transmission spectrum are sensitive to fiber elongation, twist and temperature, and (in the case of the long period gratings) to the refractive index of the surrounding medium. The suitability of chiral gratings for sensing temperature, elongation, twist and liquid levels will be discussed. Gratings made of radiation sensitive glass can be used to measure the cumulative radiation dose, while gratings made of radiation-hardened glass are suitable for stable sensing of the environment in nuclear power plants. Excellent temperature stability up to 900°C is found in pure silica chiral diffraction grating sensors.

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.

Cooperative expression of atomic chirality in inorganic nanostructures.

PubMed

Wang, Peng-Peng; Yu, Shang-Jie; Govorov, Alexander O; Ouyang, Min

2017-02-02

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks.

Cooperative expression of atomic chirality in inorganic nanostructures

PubMed Central

Wang, Peng-peng; Yu, Shang-Jie; Govorov, Alexander O; Ouyang, Min

2017-01-01

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks. PMID:28148957

Chiral Dynamics 2006

NASA Astrophysics Data System (ADS)

Ahmed, Mohammad W.; Gao, Haiyan; Weller, Henry R.; Holstein, Barry

2007-10-01

pt. A. Plenary session. Opening remarks: experimental tests of chiral symmetry breaking / A. M. Bernstein. [Double pie symbols] scattering / H. Leutwyler. Chiral effective field theory in a [Triangle]-resonance region / V. Pascalutsa. Some recent developments in chiral perturbation theory / Ulf-G. Mei ner. Chiral extrapolation and nucleon structure from the lattice / R.D. Young. Recent results from HAPPEX / R. Michaels. Chiral symmetries and low energy searches for new physics / M.J. Ramsey-Musolf. Kaon physics: recent experimental progress / M. Moulson. Status of the Cabibbo angle / V. Cirigliano. Lattice QCD and nucleon spin structure / J.W. Negele. Spin sum rules and polarizabilities: results from Jefferson lab / J-P Chen. Compton scattering and nucleon polarisabilities / Judith A. McGovern. Virtual compton scattering at MIT-bates / R. Miskimen. Physics results from the BLAST detector at the BATES accelerator / R.P. Redwine. The [Pie sympbol]NN system, recent progress / C. Hanhart. Application of chiral nuclear forces to light nuclei / A. Nogga. New results on few-body experiments at low energy / Y. Nagai. Few-body lattice calculations / M.J. Savage. Research opportunities at the upgraded HI?S facility / H.R. Weller -- pt. B. Goldstone boson dynamics. Working group summary: Goldstone Boson dynamics / G. Colangelo and S. Giovannella. Recent results on radiative Kaon decays from NA48 and NA48/2 / S.G. López. Cusps in K-->3 [Pie symbol] decays / B. Kubis. Recent KTeV results on radiative Kaon decays / M.C. Ronquest. The [Double pie symbols] scattering amplitude / J.R. Peláez. Determination of the Regge parameters in the [Double pie symbols] scattering amplitude / I. Caprini. e+e- Hadronic cross section measurement at DA[symbol]NE with the KLOE detector / P. Beltrame. Measurement of the form factors of e+e- -->2([Pie symbol]+[Pie symbol]-), pp and the resonant parameters of the heavy charmonia at BES / H. Hu. Measurement of e+e- multihadronic cross section below 4

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.

CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

EPA Science Inventory

Like amino acids, certain pesticides exist in "left-handed" and "right-handed" (chiral) forms. Commercially available chiral pesticides are produced as racemic mixtures in which the ratio of the two forms (or enantiomers) is 1:1. Enantiomers have the same ...

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.

Chemical synthesis of water-soluble, chiral conducting-polymer complexes

DOEpatents

Wang, Hsing-Lin; McCarthy, Patrick A.; Yang, Sze Cheng

2003-01-01

The template-guided synthesis of water-soluble, chiral conducting polymer complexes is described. Synthesis of water-soluble polyaniline complexes is achieved by carefully controlling the experimental parameters such as; acid concentration, ionic strength, monomer/template ratio, total reagent concentration, and order of reagent addition. Chiral (helical) polyaniline complexes can be synthesized by addition of a chiral inducing agent (chiral acid) prior to polymerization, and the polyaniline helix can be controlled by the addition of the (+) or (-) form of the chiral acid. Moreover the quantity of chiral acid and the salt content has a significant impact on the degree of chirality in the final polymer complexes. The polyaniline and the template have been found to be mixed at the molecular level which results in chiral complexes that are robust through repeated doping and dedoping cycles.

Chirality-Controlled Synthesis and Applications of Single-Wall Carbon Nanotubes.

PubMed

Liu, Bilu; Wu, Fanqi; Gui, Hui; Zheng, Ming; Zhou, Chongwu

2017-01-24

Preparation of chirality-defined single-wall carbon nanotubes (SWCNTs) is the top challenge in the nanotube field. In recent years, great progress has been made toward preparing single-chirality SWCNTs through both direct controlled synthesis and postsynthesis separation approaches. Accordingly, the uses of single-chirality-dominated SWCNTs for various applications have emerged as a new front in nanotube research. In this Review, we review recent progress made in the chirality-controlled synthesis of SWCNTs, including metal-catalyst-free SWCNT cloning by vapor-phase epitaxy elongation of purified single-chirality nanotube seeds, chirality-specific growth of SWCNTs on bimetallic solid alloy catalysts, chirality-controlled synthesis of SWCNTs using bottom-up synthetic strategy from carbonaceous molecular end-cap precursors, etc. Recent major progresses in postsynthesis separation of single-chirality SWCNT species, as well as methods for chirality characterization of SWCNTs, are also highlighted. Moreover, we discuss some examples where single-chirality SWCNTs have shown clear advantages over SWCNTs with broad chirality distributions. We hope this review could inspire more research on the chirality-controlled preparation of SWCNTs and equally important inspire the use of single-chirality SWCNT samples for more fundamental studies and practical applications.

Formation of Enhanced Uniform Chiral Fields in Symmetric Dimer Nanostructures

PubMed Central

Tian, Xiaorui; Fang, Yurui; Sun, Mengtao

2015-01-01

Chiral fields with large optical chirality are very important in chiral molecules analysis, sensing and other measurements. Plasmonic nanostructures have been proposed to realize such super chiral fields for enhancing weak chiral signals. However, most of them cannot provide uniform chiral near-fields close to the structures, which makes these nanostructures not so efficient for applications. Plasmonic helical nanostructures and blocked squares have been proved to provide uniform chiral near-fields, but structure fabrication is a challenge. In this paper, we show that very simple plasmonic dimer structures can provide uniform chiral fields in the gaps with large enhancement of both near electric fields and chiral fields under linearly polarized light illumination with polarization off the dimer axis at dipole resonance. An analytical dipole model is utilized to explain this behavior theoretically. 30 times of volume averaged chiral field enhancement is gotten in the whole gap. Chiral fields with opposite handedness can be obtained simply by changing the polarization to the other side of the dimer axis. It is especially useful in Raman optical activity measurement and chiral sensing of small quantity of chiral molecule. PMID:26621558

Chirality detection of enantiomers using twisted optical metamaterials

NASA Astrophysics Data System (ADS)

Zhao, Yang; Askarpour, Amir N.; Sun, Liuyang; Shi, Jinwei; Li, Xiaoqin; Alù, Andrea

2017-01-01

Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies.

Chirality detection of enantiomers using twisted optical metamaterials

PubMed Central

Zhao, Yang; Askarpour, Amir N.; Sun, Liuyang; Shi, Jinwei; Li, Xiaoqin; Alù, Andrea

2017-01-01

Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies. PMID:28120825

Chiral metamirrors for broadband spin-selective absorption

NASA Astrophysics Data System (ADS)

Jing, Liqiao; Wang, Zuojia; Yang, Yihao; Zheng, Bin; Liu, Yongmin; Chen, Hongsheng

2017-06-01

Chiral metamirrors are recently proposed metadevices that have the ability of selective reflection for the designated circularly polarized waves. However, previous chiral metamirrors only work in a narrow band, which would limit their potential applications in engineering. Here, we propose an approach towards broadband spin-selective absorption. By combining the chiral resonant modes of two asymmetric split-ring resonators, we design and construct a chiral metamirror that absorbs only the left-handed circularly waves over a broad frequency range. The measured results show a bandwidth of 5.1%, almost 96% larger than that of the narrowband metamirror. Furthermore, the proposed chiral metamirror exhibits prominent performance at oblique incidence, even when high-order diffraction appears. The total thickness of the metamirror is only one-ninth of the wavelength, highly suitable for on-chip integration. Our findings may provide an efficient approach to boost the working bandwidth of the chiral metamirror and could advance its applications in optical instruments.

Cosmic chirality both true and false.

PubMed

Barron, Laurence D

2012-12-01

The discrete symmetries of parity P, time reversal T, and charge conjugation C may be used to characterize the properties of chiral systems. It is well known that parity violation infiltrates into ordinary matter via an interaction between the nucleons and electrons, mediated by the Z(0) particle, that lifts the degeneracy of the mirror-image enantiomers of a chiral molecule. Being odd under P but even under T, this P-violating interaction exhibits true chirality and so may induce absolute enantioselection under all circumstances. It has been suggested that CP violation may also infiltrate into ordinary matter via a P-odd, T-odd interaction mediated by the (as yet undetected) axion. This CP-violating interaction exhibits false chirality and so may induce absolute enantioselection in processes far from equilibrium. Both true and false cosmic chirality should be considered together as possible sources of homochirality in the molecules of life. Copyright © 2012 Wiley Periodicals, Inc.

Centre vortex removal restores chiral symmetry

DOE PAGES

Trewartha, Daniel; Kamleh, Waseem; Leinweber, Derek B.

2017-11-15

The influence of centre vortices on dynamical chiral symmetry breaking is investigated through the light hadron spectrum on the lattice. Recent studies of the quark propagator and other quantities have provided evidence that centre vortices are the fundamental objects underpinning dynamical chiral symmetry breaking in SU(3) gauge theory. For the first time, we use the chiral overlap fermion action to study the low-lying hadron spectrum on lattice ensembles consisting of Monte Carlo, vortex-removed, and vortex-projected gauge fields. We find that gauge field configurations consisting solely of smoothed centre vortices are capable of reproducing all the salient features of the hadronmore » spectrum, including dynamical chiral symmetry breaking. In conclusion, the hadron spectrum on vortex-removed fields shows clear signals of chiral symmetry restoration at light values of the bare quark mass, while at heavy masses the spectrum is consistent with a theory of weakly-interacting constituent quarks.« less

Disordered two-dimensional electron systems with chiral symmetry

NASA Astrophysics Data System (ADS)

Markoš, P.; Schweitzer, L.

2012-10-01

We review the results of our recent numerical investigations on the electronic properties of disordered two dimensional systems with chiral unitary, chiral orthogonal, and chiral symplectic symmetry. Of particular interest is the behavior of the density of states and the logarithmic scaling of the smallest Lyapunov exponents in the vicinity of the chiral quantum critical point in the band center at E=0. The observed peaks or depressions in the density of states, the distribution of the critical conductances, and the possible non-universality of the critical exponents for certain chiral unitary models are discussed.

Chiral dynamics with (non)strange quarks

NASA Astrophysics Data System (ADS)

Kubis, Bastian; Meißner, Ulf-G.

2017-01-01

We review the results and achievements of the project B.3. Topics addressed include pion photoproduction off the proton and off deuterium, three-flavor chiral perturbation theory studies, chiral symmetry tests in Goldstone boson decays, the development of unitarized chiral perturbation theory to next-to-leading order, the two-pole structure of the Λ(1405), the dynamical generation of the lowest S11 resonances, the theory of hadronic atoms and its application to various systems, precision studies in light-meson decays based on dispersion theory, the Roy-Steiner analysis of pion-nucleon scattering, a high-precision extraction of the elusive pion-nucleon σ-term, and aspects of chiral dynamics in few-nucleon systems.

Chirality-induced negative refraction in magnetized plasma

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

Guo, B.

2013-09-15

Characteristic equations in magnetized plasma with chirality are derived in simple formulations and the dispersion relations for propagation parallel and perpendicular to the external magnetic field are studied in detail. With the help of the dispersion relations of each eigenwave, the author explores chirality-induced negative refraction in magnetized plasma and investigates the effects of parameters (i.e., chirality degree, external magnetic field, etc.) on the negative refraction. The results show that the chirality is the necessary and only one factor which leads to negative refraction without manipulating electrical permittivity and magnetic permeability. Both increasing the degree of chirality and reducing themore » external magnetic field can result in greater range negative refraction. Parameter dependence of the effects is calculated and discussed.« less

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

A web site for calculating the degree of chirality.

PubMed

Zayit, Amir; Pinsky, Mark; Elgavi, Hadassah; Dryzun, Chaim; Avnir, David

2011-01-01

The web site, http://www.csm.huji.ac.il/, uses the Continuous Chirality Measure to evaluate quantitatively the degree of chirality of a molecule, a structure, a fragment. The value of this measure ranges from zero, the molecule is achiral, to higher values (the upper limit is 100); the higher the chirality value, the more chiral the molecule is. The measure is based on the distance between the chiral molecule and the nearest structure that is achiral. Questions such as the following can be addressed: by how much is one molecule more chiral than the other? how does chirality change along conformational motions? is there a correlation between chirality and enantioselectivity in a series of molecules? Both elementary and advanced features are offered. Related calculation options are the symmetry measures and shape measures. Copyright © 2009 Wiley-Liss, Inc.

Staggered heavy baryon chiral perturbation theory

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

Bailey, Jon A.

2008-03-01

Although taste violations significantly affect the results of staggered calculations of pseudoscalar and heavy-light mesonic quantities, those entering staggered calculations of baryonic quantities have not been quantified. Here I develop staggered chiral perturbation theory in the light-quark baryon sector by mapping the Symanzik action into heavy baryon chiral perturbation theory. For 2+1 dynamical quark flavors, the masses of flavor-symmetric nucleons are calculated to third order in partially quenched and fully dynamical staggered chiral perturbation theory. To this order the expansion includes the leading chiral logarithms, which come from loops with virtual decuplet-like states, as well as terms of O(m{sub {pi}}{supmore » 3}), which come from loops with virtual octet-like states. Taste violations enter through the meson propagators in loops and tree-level terms of O(a{sup 2}). The pattern of taste symmetry breaking and the resulting degeneracies and mixings are discussed in detail. The resulting chiral forms are appropriate to lattice results obtained with operators already in use and could be used to study the restoration of taste symmetry in the continuum limit. I assume that the fourth root of the fermion determinant can be incorporated in staggered chiral perturbation theory using the replica method.« less

Chiral transcription in self-assembled tetrahedral Eu 4L 6 chiral cages displaying sizable circularly polarized luminescence

DOE PAGES

Yeung, Chi -Tung; Yim, King -Him; Wong, Ho -Yin; ...

2017-10-24

Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with different point chiralities, and observe their self-assembly into europium (Eu) tetrametallic tetrahedral cages. One ligand exhibits a highly diastereoselective assembly into homochiral (either ΔΔΔΔ or ΛΛΛΛ) Eu tetrahedral cages whereas the two other ligands, with two different approaches of loosened point chirality, lead to a significant breakdown of the diastereoselectivity to generate a mixture of (ΔΔΔΔ and ΛΛΛΛ) isomers. The cagesmore » are highly emissive (luminescence quantum yields of 16(1) to 18(1)%) and exhibit impressive circularly polarized luminescence properties (|g lum |: up to 0.16). With in-depth studies, we present an example that correlates the nonlinear enhancement of the chiroptical response to the nonlinearity dependence on point chirality.« less

Enantiomeric separations of chiral pharmaceuticals using chirally modified tetrahexahedral Au nanoparticles

NASA Astrophysics Data System (ADS)

Shukla, N.; Yang, D.; Gellman, A. J.

2016-06-01

Tetrahexahedral (THH, 24-sided) Au nanoparticles modified with D- or L-cysteine (Cys) have been used as enantioselective separators of the chiral pharmaceutical propranolol (PLL) in solution phase. Polarimetry has been used to measure the rotation of linearly polarized light by solutions containing mixtures of PLL and Cys/THH-Au NPs with varying enantiomeric excesses of each. Polarimetry yields clear evidence of enantiospecific adsorption of PLL onto the Cys/THH-Au NPs. This extends prior work using propylene oxide as a test chiral probe, by using the crystalline THH Au NPs with well-defined facets to separate a real pharmaceutical. This work suggests that chiral nanoparticles, coupled with a density separation method such as centrifugation, could be used for enantiomeric purification of real pharmaceuticals. A simple robust model developed earlier has also been used to extract the enantiospecific equilibrium constants for R- and S-PLL adsorption onto the D- and L-Cys/THH-Au NPs.

Chiral Crystallization of Ethylenediamine Sulfate

ERIC Educational Resources Information Center

Koby, Lawrence; Ningappa, Jyothi B.; Dakesssian, Maria; Cuccia, Louis A.

2005-01-01

The optimal conditions for the crystallization of achiral ethylenediamine sulfate into large chiral crystals that are ideal for polarimetry studies and observation using Polaroid sheets are presented. This experiment is an ideal undergraduate experiment, which clearly demonstrates the chiral crystallization of an achiral molecule.

Investigating the nature of chiral near-field interactions

NASA Astrophysics Data System (ADS)

Barr, Lauren E.; Horsley, Simon A. R.; Hooper, Ian R.; Eager, Jake K.; Gallagher, Cameron P.; Hornett, Samuel M.; Hibbins, Alastair P.; Hendry, Euan

2018-04-01

In recent years, there have been reports of enhanced chiroptical interactions in the near-fields of antennas, postulated to be mediated by high spatial gradients in the electromagnetic fields. Here, using gigahertz experimentation, we investigate the nature of the chiral near-field generated by an array of staggered-rod antennas through its interaction with an array of aligned, subwavelength metallic helices. This allows us to eliminate many potential origins of enhancements, such as those associated with plasmon-exciton interactions, and search solely for enhancements due to the high spatial gradients in the chirality of the fields around chiral antennas (so-called `superchiral fields'). By comparing the strength of the chiral interaction with our helices to that of a homogeneous chiral layer with effective material parameters, we find that the strength of this chiral interaction can be predicted using a completely local effective medium approximation. This suggests no obvious enhancement in the chiral interaction in the near-field and indicates that nonlocal interactions are negligible in this system.

Chiral magnetic effect in condensed matter systems

NASA Astrophysics Data System (ADS)

Li, Qiang; Kharzeev, Dmitri E.

2016-12-01

The chiral magnetic effect (CME) is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum chiral anomaly [S. L. Adler. Axial-vector vertex in spinor electrodynamics. Physical Review, 177, 2426 (1969), J. S. Bell and R. Jackiw. A PCAC puzzle: π 0 γγin the σ-model. Il Nuovo Cimento A, 60, 47-61 (1969)] in systems possessing charged chiral fermions. In quark-gluon plasma containing nearly massless quarks, the chirality imbalance is sourced by the topological transitions. In condensed matter systems, the chiral quasiparticles emerge in gapless semiconductors with two energy bands having pointlike degeneracies opening the path to the study of chiral anomaly [H. B. Nielsen and M. Ninomiya. The Adler-Bell-Jackiw anomaly and Weyl fermions in a crystal. Physics Letters B, 130, 389-396 (1983)]. Recently, these novel materials - so-called Dirac and Weyl semimetals have been discovered experimentally, are suitable for the investigation of the CME in condensed matter experiments. Here we report on the first experimental observation of the CME in a 3D Dirac semimetal ZrTe5 [Q. Li, D. E. Kharzeev, C. Zhang, Y. Huang, I. Pletikosić, A. V. Fedorov, R. D. Zhong, J. A. Schneeloch, G. D. Gu, and T. Valla. Chiral magnetic effect in ZrTe5. Nature Physics (2016) doi:10.1038/nphys3648].

Synergistic effects on enantioselectivity of zwitterionic chiral stationary phases for separations of chiral acids, bases, and amino acids by HPLC.

PubMed

Hoffmann, Christian V; Pell, Reinhard; Lämmerhofer, Michael; Lindner, Wolfgang

2008-11-15

In an attempt to overcome the limited applicability scope of earlier proposed Cinchona alkaloid-based chiral weak anion exchangers (WAX) and recently reported aminosulfonic acid-based chiral strong cation exchangers (SCX), which are conceptionally restricted to oppositely charged solutes, their individual chiral selector (SO) subunits have been fused in a combinatorial synthesis approach into single, now zwitterionic, chiral SO motifs. The corresponding zwitterionic ion-exchange-type chiral stationary phases (CSPs) in fact combined the applicability spectra of the parent chiral ion exchangers allowing for enantioseparations of chiral acids and amine-type solutes in liquid chromatography using polar organic mode with largely rivaling separation factors as compared to the parent WAX and SCX CSPs. Furthermore, the application spectrum could be remarkably expanded to various zwitterionic analytes such as alpha- and beta-amino acids and peptides. A set of structurally related yet different CSPs consisting of either a quinine or quinidine alkaloid moiety as anion-exchange subunit and various chiral or achiral amino acids as cation-exchange subunits enabled us to derive structure-enantioselectivity relationships, which clearly provided strong unequivocal evidence for synergistic effects of the two oppositely charged ion-exchange subunits being involved in molecular recognition of zwitterionic analytes by zwitterionic SOs driven by double ionic coordination.

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.

Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality

PubMed Central

Raymond, Michael J.; Ray, Poulomi; Kaur, Gurleen; Fredericks, Michael; Singh, Ajay V.; Wan, Leo Q.

2016-01-01

Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels. PMID:28360944

Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality.

PubMed

Raymond, Michael J; Ray, Poulomi; Kaur, Gurleen; Fredericks, Michael; Singh, Ajay V; Wan, Leo Q

2017-02-01

Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels.

Broken chiral symmetry on a null plane

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

Beane, Silas R., E-mail: silas@physics.unh.edu

2013-10-15

On a null-plane (light-front), all effects of spontaneous chiral symmetry breaking are contained in the three Hamiltonians (dynamical Poincaré generators), while the vacuum state is a chiral invariant. This property is used to give a general proof of Goldstone’s theorem on a null-plane. Focusing on null-plane QCD with N degenerate flavors of light quarks, the chiral-symmetry breaking Hamiltonians are obtained, and the role of vacuum condensates is clarified. In particular, the null-plane Gell-Mann–Oakes–Renner formula is derived, and a general prescription is given for mapping all chiral-symmetry breaking QCD condensates to chiral-symmetry conserving null-plane QCD condensates. The utility of the null-planemore » description lies in the operator algebra that mixes the null-plane Hamiltonians and the chiral symmetry charges. It is demonstrated that in a certain non-trivial limit, the null-plane operator algebra reduces to the symmetry group SU(2N) of the constituent quark model. -- Highlights: •A proof (the first) of Goldstone’s theorem on a null-plane is given. •The puzzle of chiral-symmetry breaking condensates on a null-plane is solved. •The emergence of spin-flavor symmetries in null-plane QCD is demonstrated.« less

Hierarchical chirality transfer in the growth of Towel Gourd tendrils

PubMed Central

Wang, Jian-Shan; Wang, Gang; Feng, Xi-Qiao; Kitamura, Takayuki; Kang, Yi-Lan; Yu, Shou-Wen; Qin, Qing-Hua

2013-01-01

Chirality plays a significant role in the physical properties and biological functions of many biological materials, e.g., climbing tendrils and twisted leaves, which exhibit chiral growth. However, the mechanisms underlying the chiral growth of biological materials remain unclear. In this paper, we investigate how the Towel Gourd tendrils achieve their chiral growth. Our experiments reveal that the tendrils have a hierarchy of chirality, which transfers from the lower levels to the higher. The change in the helical angle of cellulose fibrils at the subcellular level induces an intrinsic torsion of tendrils, leading to the formation of the helical morphology of tendril filaments. A chirality transfer model is presented to elucidate the chiral growth of tendrils. This present study may help understand various chiral phenomena observed in biological materials. It also suggests that chirality transfer can be utilized in the development of hierarchically chiral materials having unique properties. PMID:24173107

Chiral anomaly, Berry phase, and chiral kinetic theory from worldlines in quantum field theory

DOE PAGES

Mueller, Niklas; Venugopalan, Raju

2018-03-21

Here, we outline a novel chiral kinetic theory framework for systematic computations of the Chiral Magnetic Effect (CME) in ultrarelativistic heavy-ion collisions. The real part of the fermion determinant in the QCD effective action is expressed as a supersymmetric world-line action of spinning, colored, Grassmanian point particles in background gauge fields, with equations of motion that are covariant generalizations of the Bargmann-Michel-Telegdi and Wong equations. Berry’s phase is obtained in a consistent non-relativistic adiabatic limit. The chiral anomaly, in contrast, arises from the phase of the fermion determinant; its topological properties are therefore distinct from those of the Berry phase.more » We show that the imaginary contribution to the fermion determinant too can be expressed as a point particle world-line path integral and derive the corresponding anomalous axial vector current. Our results can be used to derive a covariant relativistic chiral kinetic theory including the effects of topological fluctuations that has overlap with classical-statistical simulations of the CME at early times and anomalous hydrodynamics at late times.« less

Chiral anomaly, Berry phase, and chiral kinetic theory from worldlines in quantum field theory

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

Mueller, Niklas; Venugopalan, Raju

Here, we outline a novel chiral kinetic theory framework for systematic computations of the Chiral Magnetic Effect (CME) in ultrarelativistic heavy-ion collisions. The real part of the fermion determinant in the QCD effective action is expressed as a supersymmetric world-line action of spinning, colored, Grassmanian point particles in background gauge fields, with equations of motion that are covariant generalizations of the Bargmann-Michel-Telegdi and Wong equations. Berry’s phase is obtained in a consistent non-relativistic adiabatic limit. The chiral anomaly, in contrast, arises from the phase of the fermion determinant; its topological properties are therefore distinct from those of the Berry phase.more » We show that the imaginary contribution to the fermion determinant too can be expressed as a point particle world-line path integral and derive the corresponding anomalous axial vector current. Our results can be used to derive a covariant relativistic chiral kinetic theory including the effects of topological fluctuations that has overlap with classical-statistical simulations of the CME at early times and anomalous hydrodynamics at late times.« less

Intelligent chiral sensing based on supramolecular and interfacial concepts.

PubMed

Ariga, Katsuhiko; Richards, Gary J; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P

2010-01-01

Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

Chirality measures of α-amino acids.

PubMed

Jamróz, Michał H; Rode, Joanna E; Ostrowski, Sławomir; Lipiński, Piotr F J; Dobrowolski, Jan Cz

2012-06-25

To measure molecular chirality, the molecule is treated as a finite set of points in the Euclidean R(3) space supplemented by k properties, p(1)((i)), p(2)((i)), ..., p(k)((i)) assigned to the ith atom, which constitute a point in the Property P(k) space. Chirality measures are described as the distance between a molecule and its mirror image minimized over all its arbitrary orientation-preserving isometries in the R(3) × P(k) Cartesian product space. Following this formalism, different chirality measures can be estimated by taking into consideration different sets of atomic properties. Here, for α-amino acid zwitterionic structures taken from the Cambridge Structural Database and for all 1684 neutral conformers of 19 biogenic α-amino acid molecules, except glycine and cystine, found at the B3LYP/6-31G** level, chirality measures have been calculated by a CHIMEA program written in this project. It is demonstrated that there is a significant correlation between the measures determined for the α-amino acid zwitterions in crystals and the neutral forms in the gas phase. Performance of the studied chirality measures with changes of the basis set and computation method was also checked. An exemplary quantitative structure–activity relationship (QSAR) application of the chirality measures was presented by an introductory model for the benchmark Cramer data set of steroidal ligands of the sex-hormone binding globulin.

Topological chiral phonons in center-stacked bilayer triangle lattices

NASA Astrophysics Data System (ADS)

Xu, Xifang; Zhang, Wei; Wang, Jiaojiao; Zhang, Lifa

2018-06-01

Since chiral phonons were found in an asymmetric two-dimensional hexagonal lattice, there has been growing interest in the study of phonon chirality, which were experimentally verified very recently in monolayer tungsten diselenide (2018 Science 359 579). In this work, we find chiral phonons with nontrivial topology in center-stacked bilayer triangle lattices. At the Brillouin-zone corners, (), circularly polarized phonons and nonzero phonon Berry curvature are observed. Moreover, we find that the phonon chirality remain robust with changing sublattice mass ratio and interlayer coupling. The chiral phonons at the valleys are demonstrated in doubler-layer sodium chloride along the [1 1 1] direction. We believe that the findings on topological chiral phonons in triangle lattices will give guidance in the study of chiral phonons in real materials and promote the phononic applications.

On stability, chirality measures, and theoretical VCD spectra of the chiral C58X2 fullerenes (X = N, B).

PubMed

Ostrowski, Sławomir; Jamróz, Michał H; Rode, Joanna E; Dobrowolski, Jan Cz

2012-01-12

The stability of all 23 C(58)N(2) and C(58)B(2) heterofullerenes in the singlet and triplet states was determined at the B3LYP/6-31G** level. In equilibrium mixture the achiral (1,4) C(58)N(2) isomer would be populated in ca. 95.8%, the chiral (1,16) one in ca. 3.3%, and the achiral (1,4) C(58)B(2) in 100%, whereas all triplet state isomers are less stable. Fourteen out of 23 C(58)X(2) are chiral. Four different chirality measures were calculated by our own CHIMEA program: pure geometrical, labeled, mass, and charge. Intercorrelations between the measures for all chiral compounds indicate that the pure geometrical chirality measure is unstable and should not be used in QSAR predictions of the other molecular properties, while the labeled and mass-weighted ones are promising QSAR descriptors. For each chiral C(58)N(2) molecule, some very strong VCD bands, of intensity comparable with that in the IR spectra, can serve in identification and characterization of the isomers.

Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

PubMed Central

Maity, Sibaprasad; Das, Priyadip; Reches, Meital

2015-01-01

Natural helical structures have inspired the formation of well-ordered peptide-based chiral nanostructures in vitro. These structures have drawn much attention owing to their diverse applications in the area of asymmetric catalysts, chiral photonic materials, and nanoplasmonics. The self-assembly of two enantiomeric fluorinated aromatic dipeptides into ordered chiral fibrillar nanostructures upon sonication is described. These fibrils form organogels. Our results clearly indicate that fluorine-fluorine interactions play an important role in self-assembly. Circular dichroism analysis revealed that both peptides (peptides 1 and 2), containing two fluorines, depicted opposite cotton effects in their monomeric form compared with their aggregated form. This shows that supramolecular chirality inversion took place during the stimuli-responsive self-aggregation process. Conversely, peptide 3, containing one fluorine, did not exhibit chirality inversion in sonication-induced organogelation. Therefore, our results clearly indicate that fluorination plays an important role in the organogelation process of these aromatic dipeptides. Our findings may have broad implications regarding the design of chiral nanostructures for possible applications such as chiroptical switches, asymmetric catalysis, and chiral recognitions. PMID:26553508

Minimally doubled fermions and spontaneous chiral symmetry breaking

NASA Astrophysics Data System (ADS)

Osmanaj (Zeqirllari), Rudina; Hyka (Xhako), Dafina

2018-03-01

Chiral symmetry breaking in massless QCD is a very important feature in the current understanding of low energy physics. Low - lying Dirac modes are suitable to help us understand the spontaneous chiral symmetry breaking, since the formation of a non zero chiral condensate is an effect of their accumulation near zero. The Banks - Casher relation links the spectral density of the Dirac operator to the condensate with an identity that can be read in both directions. In this work we propose a spectral method to achieve a reliable determination of the density of eigenvalues of Dirac operator near zero using the Gauss - Lanczos quadrature. In order to understand better the dynamical chiral symmetry breaking and use the method we propose, we have chosen to work with minimally doubled fermions. These kind of fermions have been proposed as a strictly local discretization of the QCD fermions action, which preserves chiral symmetry at finite cut-off. Being chiral fermions, is easier to work with them and their low - lying Dirac modes and to understand the dynamical spontaneous chiral symmetry breaking.

Spin-Wave Chirality and Its Manifestations in Antiferromagnets

NASA Astrophysics Data System (ADS)

Proskurin, Igor; Stamps, Robert L.; Ovchinnikov, Alexander S.; Kishine, Jun-ichiro

2017-10-01

As first demonstrated by Tang and Cohen in chiral optics, the asymmetry in the rate of electromagnetic energy absorption between left and right enantiomers is determined by an optical chirality density. Here, we demonstrate that this effect can exist in magnetic spin systems. By constructing a formal analogy with electrodynamics, we show that in antiferromagnets with broken chiral symmetry, the asymmetry in local spin-wave energy absorption is proportional to a spin-wave chirality density, which is a direct counterpart of optical zilch. We propose that injection of a pure spin current into an antiferromagnet may serve as a chiral symmetry breaking mechanism, since its effect in the spin-wave approximation can be expressed in terms of additional Lifshitz invariants. We use linear response theory to show that the spin current induces a nonequilibrium spin-wave chirality density.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

PubMed

Suzuki, Yumiko

2018-06-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines.

Chiral tunneling in a twisted graphene bilayer.

PubMed

He, Wen-Yu; Chu, Zhao-Dong; He, Lin

2013-08-09

The perfect transmission in a graphene monolayer and the perfect reflection in a Bernal graphene bilayer for electrons incident in the normal direction of a potential barrier are viewed as two incarnations of the Klein paradox. Here we show a new and unique incarnation of the Klein paradox. Owing to the different chiralities of the quasiparticles involved, the chiral fermions in a twisted graphene bilayer show an adjustable probability of chiral tunneling for normal incidence: they can be changed from perfect tunneling to partial or perfect reflection, or vice versa, by controlling either the height of the barrier or the incident energy. As well as addressing basic physics about how the chiral fermions with different chiralities tunnel through a barrier, our results provide a facile route to tune the electronic properties of the twisted graphene bilayer.

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)

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.

Selectively transporting small chiral particles with circularly polarized Airy beams.

PubMed

Lu, Wanli; Chen, Huajin; Guo, Sandong; Liu, Shiyang; Lin, Zhifang

2018-05-01

Based on the full wave simulation, we demonstrate that a circularly polarized vector Airy beam can selectively transport small chiral particles along a curved trajectory via the chirality-tailored optical forces. The transverse optical forces can draw the chiral particles with different particle chirality towards or away from the intensity maxima of the beam, leading to the selective trapping in the transverse plane. The transversely trapped chiral particles are then accelerated along a curved trajectory of the Airy beam by the chirality-tailored longitudinal scattering force, rendering an alternative way to sort and/or transport chiral particles with specified helicity. Finally, the underlying physics of the chirality induced transverse trap and de-trap phenomena are examined by the analytical theory within the dipole approximation.

Drag suppression in anomalous chiral media

DOE PAGES

Sadofyev, Andrey V.; Yin, Yi

2016-06-01

We study a heavy impurity moving longitudinal with the direction of an external magnetic field in an anomalous chiral medium. Such system would carry a non-dissipative current of chiral magnetic effect associated with the anomaly. We show, by generalizing Landau's criterion for super fluidity, that the "anomalous component" which gives rise to the anomalous transport will not contribute to the drag experienced by an impurity. We argue on a very general basis that those systems with a strong magnetic field would exhibit an interesting transport phenomenon$-$the motion of the heavy impurity is frictionless, in analogy to the case of amore » super fluid. Finally, we demonstrate and confirm our general results with two complementary examples: weakly coupled chiral fermion gases and strongly interacting chiral liquids.« less

Switching chiral solitons for algebraic operation of topological quaternary digits

NASA Astrophysics Data System (ADS)

Kim, Tae-Hwan; Cheon, Sangmo; Yeom, Han Woong

2017-02-01

Chiral objects can be found throughout nature; in condensed matter chiral objects are often excited states protected by a system's topology. The use of chiral topological excitations to carry information has been demonstrated, where the information is robust against external perturbations. For instance, reading, writing, and transfer of binary information have been demonstrated with chiral topological excitations in magnetic systems, skyrmions, for spintronic devices. The next step is logic or algebraic operations of such topological bits. Here, we show experimentally the switching between chiral topological excitations or chiral solitons of different chirality in a one-dimensional electronic system with Z4 topological symmetry. We found that a fast-moving achiral soliton merges with chiral solitons to switch their handedness. This can lead to the realization of algebraic operation of Z4 topological charges. Chiral solitons could be a platform for storage and operation of robust topological multi-digit information.

Doped Chiral Polymer Metamaterials

NASA Technical Reports Server (NTRS)

Kang, Jin Ho (Inventor); Gordon, Keith L. (Inventor); Sauti, Godfrey (Inventor); Bryant, Robert G. (Inventor); Park, Cheol (Inventor); Lowther, Sharon E. (Inventor)

2017-01-01

Some implementations provide a composite material that includes a first material and a second material. In some implementations, the composite material is a metamaterial. The first material includes a chiral polymer (e.g., crystalline chiral helical polymer, poly-.gamma.-benzyl-L-glutamate (PBLG), poly-L-lactic acid (PLA), polypeptide, and/or polyacetylene). The second material is within the chiral polymer. The first material and the second material are configured to provide an effective index of refraction value for the composite material of 1 or less. In some implementations, the effective index of refraction value for the composite material is negative. In some implementations, the effective index of refraction value for the composite material of 1 or less is at least in a wavelength of one of at least a visible spectrum, an infrared spectrum, a microwave spectrum, and/or an ultraviolet spectrum.

A chiral aluminum solvating agent (CASA) for 1H NMR chiral analysis of alcohols at low temperature.

PubMed

Seo, Min-Seob; Jang, Sumin; Kim, Hyunwoo

2018-03-16

A chiral aluminum solvating agent (CASA) was demonstrated to be a general and efficient reagent for 1H NMR chiral analysis of alcohols. The sodium salt of the CASA (CASA-Na) showed a complete baseline peak separation of the hydroxyl group for various chiral alcohols including primary, secondary, and tertiary alcohols with alkyl and aryl substituents in CD3CN. Due to the weak intermolecular interaction, 1H NMR measurement at low temperature (-40 to 10 °C) was required.

Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. I. Theory

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

Rogachevskii, Igor; Kleeorin, Nathan; Ruchayskiy, Oleg

2017-09-10

The magnetohydrodynamic (MHD) description of plasmas with relativistic particles necessarily includes an additional new field, the chiral chemical potential associated with the axial charge (i.e., the number difference between right- and left-handed relativistic fermions). This chiral chemical potential gives rise to a contribution to the electric current density of the plasma ( chiral magnetic effect ). We present a self-consistent treatment of the chiral MHD equations , which include the back-reaction of the magnetic field on a chiral chemical potential and its interaction with the plasma velocity field. A number of novel phenomena are exhibited. First, we show that themore » chiral magnetic effect decreases the frequency of the Alfvén wave for incompressible flows, increases the frequencies of the Alfvén wave and of the fast magnetosonic wave for compressible flows, and decreases the frequency of the slow magnetosonic wave. Second, we show that, in addition to the well-known laminar chiral dynamo effect, which is not related to fluid motions, there is a dynamo caused by the joint action of velocity shear and chiral magnetic effect. In the presence of turbulence with vanishing mean kinetic helicity, the derived mean-field chiral MHD equations describe turbulent large-scale dynamos caused by the chiral alpha effect, which is dominant for large fluid and magnetic Reynolds numbers. The chiral alpha effect is due to an interaction of the chiral magnetic effect and fluctuations of the small-scale current produced by tangling magnetic fluctuations (which are generated by tangling of the large-scale magnetic field by sheared velocity fluctuations). These dynamo effects may have interesting consequences in the dynamics of the early universe, neutron stars, and the quark–gluon plasma.« less

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.

Chirality and chiroptical properties of amyloid fibrils.

PubMed

Dzwolak, Wojciech

2014-09-01

Chirality of amyloid fibrils-linear beta-sheet-rich aggregates of misfolded protein chains-often manifests in morphological traits such as helical twist visible in atomic force microscopy and in chiroptical properties accessible to vibrational circular dichroism (VCD). According to recent studies the relationship between molecular chirality of polypeptide building blocks and superstructural chirality of amyloid fibrils may be more intricate and less deterministic than previously assumed. Several puzzling experimental findings have put into question earlier intuitive ideas on: 1) the bottom-up chirality transfer upon amyloidogenic self-assembly, and 2) the structural origins of chiroptical properties of protein aggregates. For example, removal of a single amino acid residue from an amyloidogenic all-L peptide was shown to reverse handedness of fibrils. On the other hand, certain types of amyloid aggregates revealed surprisingly strong VCD spectra with the sign and shape dependent on the conditions of fibrillation. Hence, microscopic and chiroptical studies have highlighted chirality as one more aspect of polymorphism of amyloid fibrils. This brief review is intended to outline the current state of research on amyloid-like fibrils from the perspective of their structural and superstructural chirality and chiroptical properties. © 2014 Wiley Periodicals, Inc.

Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

PubMed

Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming

2017-04-18

The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical

Inducing Axial Chirality in a Supramolecular Catalyst.

PubMed

Wenz, Katharina Marie; Leonhardt-Lutterbeck, Günter; Breit, Bernhard

2018-03-06

A new type of ligand, which is able to form axially chiral, supramolecular complexes was designed using DFT calculations. Two chiral monomers, each featuring a covalently bound chiral auxiliary, form a bidentate phosphine ligand with a twisted, hydrogen-bonded backbone upon coordination to a transition metal center which results in two diastereomeric, tropos complexes. The ratio of the diastereomers in solution is very temperature- and solvent-dependent. Rhodium and platinum complexes were analyzed through a combination of NMR studies, ESI-MS measurements, as well as UV-VIS and circular dichroism spectroscopy. The chiral self-organized ligands were evaluated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydrogenated amino acids and resulted in good conversion and high enantioselectivity. This research opens the way for new ligand designs based on stereocontrol of supramolecular assemblies through stereodirecting chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

PubMed Central

Suzuki, Yumiko

2018-01-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines. PMID:29861702

Chiroptical studies on supramolecular chirality of molecular aggregates.

PubMed

Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

2015-10-01

The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low-molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates. © 2015 Wiley Periodicals, Inc.

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.

Stereospecific ring expansion from orthocyclophanes with central chirality to metacyclophanes with planar chirality.

PubMed

Ishida, Naoki; Sawano, Shota; Murakami, Masahiro

2014-01-01

Carbon-carbon bonds constitute the major framework of organic molecules and carbon-hydrogen bonds are abundant in their peripheries. Such nonpolar σ-bonds are thermodynamically stable and kinetically inert in general. Nonetheless, selective activation of those ubiquitous bonds may offer a straightforward method to construct and/or functionalize organic skeletons. Herein we describe ring expansion from orthocyclophanes to metacyclophanes occurring upon sequential action of light and a metal catalyst. Formally, specific non-strained carbon-hydrogen and carbon-carbon bonds are cleaved and exchanged without elimination of any leaving groups. Notably, the product is energetically uphill from the starting material, but the endergonic photocyclization step makes it possible to drive the transformation forward. The ring expansion is extended to the stereospecific synthesis of metacyclophanes possessing planar chirality, during which central chirality on a tertiary carbon is transferred to planar chirality.

Intrinsic Chirality Origination in Carbon Nanotubes.

PubMed

Pierce, Neal; Chen, Gugang; P Rajukumar, Lakshmy; Chou, Nam Hawn; Koh, Ai Leen; Sinclair, Robert; Maruyama, Shigeo; Terrones, Mauricio; Harutyunyan, Avetik R

2017-10-24

Elucidating the origin of carbon nanotube chirality is key for realizing their untapped potential. Currently, prevalent theories suggest that catalyst structure originates chirality via an epitaxial relationship. Here we studied chirality abundances of carbon nanotubes grown on floating liquid Ga droplets, which excludes the influence of catalyst features, and compared them with abundances grown on solid Ru nanoparticles. Results of growth on liquid droplets bolsters the intrinsic preference of carbon nuclei toward certain chiralities. Specifically, the abundance of the (11,1)/χ = 4.31° tube can reach up to 95% relative to (9,4)/χ = 17.48°, although they have exactly the same diameter, (9.156 Å). However, the comparative abundances for the pair, (19,3)/χ = 7.2° and (17,6)/χ = 14.5°, with bigger diameter, (16.405 Å), fluctuate depending on synthesis temperature. The abundances of the same pairs of tubes grown on floating solid polyhedral Ru nanoparticles show completely different trends. Analysis of abundances in relation to nucleation probability, represented by a product of the Zeldovich factor and the deviation interval of a growing nuclei from equilibrium critical size, explain the findings. We suggest that the chirality in the nanotube in general is a result of interplay between intrinsic preference of carbon cluster and induction by catalyst structure. This finding can help to build the comprehensive theory of nanotube growth and offers a prospect for chirality-preferential synthesis of carbon nanotubes by the exploitation of liquid catalyst droplets.

Chiral filtration-induced spin/valley polarization in silicene line defects

NASA Astrophysics Data System (ADS)

Ren, Chongdan; Zhou, Benhu; Sun, Minglei; Wang, Sake; Li, Yunfang; Tian, Hongyu; Lu, Weitao

2018-06-01

The spin/valley polarization in silicene with extended line defects is investigated according to the chiral filtration mechanism. It is shown that the inner-built quantum Hall pseudo-edge states with identical chirality can serve as a chiral filter with a weak magnetic field and that the transmission process is restrained/strengthened for chiral states with reversed/identical chirality. With two parallel line defects, which act as natural chiral filtration, the filter effect is greatly enhanced, and 100% spin/valley polarization can be achieved.

Chiral Chlordane Components in Environmental Matrices

EPA Science Inventory

Chlordane, a persistent, bioaccumulative and toxic organochlorine pesticide, has been studied for many years. Since the advent of chiral analysis for environmental samples, over 2,400 measurements have been made of various chiral chlordane components. Chlordane enantiomer fractio...

Enantiospecific Detection of Chiral Nanosamples Using Photoinduced Force

NASA Astrophysics Data System (ADS)

Kamandi, Mohammad; Albooyeh, Mohammad; Guclu, Caner; Veysi, Mehdi; Zeng, Jinwei; Wickramasinghe, Kumar; Capolino, Filippo

2017-12-01

We propose a high-resolution microscopy technique for enantiospecific detection of chiral samples down to sub-100-nm size based on force measurement. We delve into the differential photoinduced optical force Δ F exerted on an achiral probe in the vicinity of a chiral sample when left and right circularly polarized beams separately excite the sample-probe interactive system. We analytically prove that Δ F is entangled with the enantiomer type of the sample enabling enantiospecific detection of chiral inclusions. Moreover, we demonstrate that Δ F is linearly dependent on both the chiral response of the sample and the electric response of the tip and is inversely related to the quartic power of probe-sample distance. We provide physical insight into the transfer of optical activity from the chiral sample to the achiral tip based on a rigorous analytical approach. We support our theoretical achievements by several numerical examples highlighting the potential application of the derived analytic properties. Lastly, we demonstrate the sensitivity of our method to enantiospecify nanoscale chiral samples with chirality parameter on the order of 0.01 and discuss how the sensitivity of our proposed technique can be further improved.

Cell chirality: emergence of asymmetry from cell culture.

PubMed

Wan, Leo Q; Chin, Amanda S; Worley, Kathryn E; Ray, Poulomi

2016-12-19

Increasing evidence suggests that intrinsic cell chirality significantly contributes to the left-right (LR) asymmetry in embryonic development, which is a well-conserved characteristic of living organisms. With animal embryos, several theories have been established, but there are still controversies regarding mechanisms associated with embryonic LR symmetry breaking and the formation of asymmetric internal organs. Recently, in vitro systems have been developed to determine cell chirality and to recapitulate multicellular chiral morphogenesis on a chip. These studies demonstrate that chirality is indeed a universal property of the cell that can be observed with well-controlled experiments such as micropatterning. In this paper, we discuss the possible benefits of these in vitro systems to research in LR asymmetry, categorize available platforms for single-cell chirality and multicellular chiral morphogenesis, and review mathematical models used for in vitro cell chirality and its applications in in vivo embryonic development. These recent developments enable the interrogation of the intracellular machinery in LR axis establishment and accelerate research in birth defects in laterality.This article is part of the themed issue 'Provocative questions in left-right asymmetry'. © 2016 The Author(s).

Cell chirality: emergence of asymmetry from cell culture

PubMed Central

Wan, Leo Q.; Chin, Amanda S.; Worley, Kathryn E.; Ray, Poulomi

2016-01-01

Increasing evidence suggests that intrinsic cell chirality significantly contributes to the left–right (LR) asymmetry in embryonic development, which is a well-conserved characteristic of living organisms. With animal embryos, several theories have been established, but there are still controversies regarding mechanisms associated with embryonic LR symmetry breaking and the formation of asymmetric internal organs. Recently, in vitro systems have been developed to determine cell chirality and to recapitulate multicellular chiral morphogenesis on a chip. These studies demonstrate that chirality is indeed a universal property of the cell that can be observed with well-controlled experiments such as micropatterning. In this paper, we discuss the possible benefits of these in vitro systems to research in LR asymmetry, categorize available platforms for single-cell chirality and multicellular chiral morphogenesis, and review mathematical models used for in vitro cell chirality and its applications in in vivo embryonic development. These recent developments enable the interrogation of the intracellular machinery in LR axis establishment and accelerate research in birth defects in laterality. This article is part of the themed issue ‘Provocative questions in left–right asymmetry’. PMID:27821525

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.

Spontaneous Planar Chiral Symmetry Breaking in Cells

NASA Astrophysics Data System (ADS)

Hadidjojo, Jeremy; Lubensky, David

Recent progress in animal development has highlighted the central role played by planar cell polarity (PCP) in epithelial tissue morphogenesis. Through PCP, cells have the ability to collectively polarize in the plane of the epithelium by localizing morphogenetic proteins along a certain axis. This allows direction-dependent modulation of tissue mechanical properties that can translate into the formation of complex, non-rotationally invariant shapes. Recent experimental observations[1] show that cells, in addition to being planar-polarized, can also spontaneously develop planar chirality, perhaps in the effort of making yet more complex shapes that are reflection non-invariant. In this talk we will present our work in characterizing general mechanisms that can lead to spontaneous chiral symmetry breaking in cells. We decompose interfacial concentration of polarity proteins in a hexagonal cell packing into irreducible representations. We find that in the case of polar concentration distributions, a chiral state can only be reached from a secondary instability after the cells are polarized. However in the case of nematic distributions, we show that a finite-amplitude (subcritical, or ``first-order'') nematic transition can send the system from disorder directly to a chiral state. In addition, we find that perturbing the system by stretching the hexagonal packing enables direct (supercritical, or ``second-order'') chiral transition in the nematic case. Finally, we do a Landau expansion to study competition between stretch-induced chirality and the tendency towards a non-chiral state in packings that have retained the full 6-fold symmetry.

Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

PubMed Central

Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

2016-01-01

The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

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).

Patterns and partners for chiral symmetry restoration

NASA Astrophysics Data System (ADS)

Gómez Nicola, A.; Ruiz de Elvira, J.

2018-04-01

We present and analyze a new set of Ward Identities which shed light on the distinction between different patterns of chiral symmetry restoration in QCD, namely O (4 ) vs O (4 )×U (1 )A. The degeneracy of chiral partners for all scalar and pseudoscalar meson nonet members is studied through their corresponding correlators. Around chiral symmetry degeneration of O (4 ) partners, our analysis predicts that U (1 )A partners are also degenerated. Our analysis also leads to I =1 /2 scalar-pseudoscalar partner degeneration at exact chiral restoration and supports ideal mixing between the η - η' and the f0(500 )- f0(980 ) mesons at O (4 )×U (1 )A restoration, with a possible range where the pseudoscalar mixing vanishes if the two transitions are well separated. We test our results with lattice data and provide further relevant observables regarding chiral and U (1 )A restoration for future lattice and model analyses.

FATE AND EFFECTS OF THE ENANTIOMERS OF CHIRAL ENVIRONMENTAL POLLUTANTS

EPA Science Inventory

Enantiomers, the mirror image isomers of chiral compounds, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. This holds true for pesticides, about 25% of which are chiral molecules, and other chiral environmental...

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.

Evidence of chiral bands in even-even nuclei

NASA Astrophysics Data System (ADS)

Petrache, C. M.; Lv, B. F.; Astier, A.; Dupont, E.; Wang, Y. K.; Zhang, S. Q.; Zhao, P. W.; Ren, Z. X.; Meng, J.; Greenlees, P. T.; Badran, H.; Cox, D. M.; Grahn, T.; Julin, R.; Juutinen, S.; Konki, J.; Pakarinen, J.; Papadakis, P.; Partanen, J.; Rahkila, P.; Sandzelius, M.; Saren, J.; Scholey, C.; Sorri, J.; Stolze, S.; Uusitalo, J.; Cederwall, B.; Aktas, Ö.; Ertoprak, A.; Liu, H.; Matta, S.; Subramaniam, P.; Guo, S.; Liu, M. L.; Zhou, X. H.; Wang, K. L.; Kuti, I.; Timár, J.; Tucholski, A.; Srebrny, J.; Andreoiu, C.

2018-04-01

Evidence for chiral doublet bands has been observed for the first time in the even-even nucleus 136Nd. One chiral band was firmly established. Four other candidates for chiral bands were also identified, which can contribute to the realization of the multiple pairs of chiral doublet bands (M χ D ) phenomenon. The observed bands are investigated by the constrained and tilted axis cranking covariant density functional theory (TAC-CDFT). Possible configurations have been explored. The experimental energy spectra, angular momenta, and B (M 1 )/B (E 2 ) values for the assigned configurations are globally reproduced by TAC-CDFT. Calculated results support the chiral interpretation of the observed bands, which correspond to shapes with maximum triaxiality induced by different multiquasiparticle configurations in 136Nd.

Chiral Plasmonic Nanostructures Fabricated by Circularly Polarized Light.

PubMed

Saito, Koichiro; Tatsuma, Tetsu

2018-05-09

The chirality of materials results in a wide variety of advanced technologies including image display, data storage, light management including negative refraction, and enantioselective catalysis and sensing. Here, we introduce chirality to plasmonic nanostructures by using circularly polarized light as the sole chiral source for the first time. Gold nanocuboids as precursors on a semiconductor were irradiated with circularly polarized light to localize electric fields at specific corners of the cuboids depending on the handedness of light and deposited dielectric moieties as electron oscillation boosters by the localized electric field. Thus, plasmonic nanostructures with high chirality were developed. The present bottom-up method would allow the large-scale and cost-effective fabrication of chiral materials and further applications to functional materials and devices.

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.

Emergence of Chiral Phases in Active Torque Dipole Systems

NASA Astrophysics Data System (ADS)

Fialho, Ana; Tjhung, Elsen; Cates, Michael; Marenduzzo, Davide

The common description of active particles as active force dipoles fails to take into account that active processes in biological systems often exhibit chiral asymmetries, generating active chiral processes and torque dipoles. Examples of such systems include cytoskeleton filaments which interact with motor proteins and beating cilia and flagella. In particular, the generation of active torques by the actomyosin cytoskeleton has been linked to the break of chiral symmetry at a cellular level. This phenomenon could constitute the primary determinant for the break of left-right symmetry in many living organisms, e.g. the position of the human heart within the human body. In order to account for the effects of chirality, we consider active torque dipoles which generate a chiral active stress. We characterize quasi-1D and 2D systems of torque dipoles, using a combination of linear stability analysis and numerical simulations (Lattice Boltzmann). Our results show that activity drives a spontaneous breaking of chiral symmetry, leading to the self-assembly of a chiral phase, in the absence of any thermodynamic interactions favoring cholesteric ordering. At high values of activity, we also observe labyrinthine patterns where the activity-induced chiral ordering is highly frustrated.

Chiral drag force

DOE PAGES

Rajagopal, Krishna; Sadofyev, Andrey V.

2015-10-05

Here, we provide a holographic evaluation of novel contributions to the drag force acting on a heavy quark moving through strongly interacting plasma. The new contributions are chiral in the sense that they act in opposite directions in plasmas containing an excess of left- or right-handed quarks. The new contributions are proportional to the coefficient of the axial anomaly, and in this sense also are chiral. These new contributions to the drag force act either parallel to or antiparallel to an external magnetic field or to the vorticity of the fluid plasma. In all these respects, these contributions to themore » drag force felt by a heavy quark are analogous to the chiral magnetic effect (CME) on light quarks. However, the new contribution to the drag force is independent of the electric charge of the heavy quark and is the same for heavy quarks and antiquarks, meaning that these novel effects do not in fact contribute to the CME current. We show that although the chiral drag force can be non-vanishing for heavy quarks that are at rest in the local fluid rest frame, it does vanish for heavy quarks that are at rest in a suitably chosen frame. In this frame, the heavy quark at rest sees counterpropagating momentum and charge currents, both proportional to the axial anomaly coefficient, but feels no drag force. This provides strong concrete evidence for the absence of dissipation in chiral transport, something that has been predicted previously via consideration of symmetries. Along the way to our principal results, we provide a general calculation of the corrections to the drag force due to the presence of gradients in the flowing fluid in the presence of a nonzero chemical potential. We close with a consequence of our result that is at least in principle observable in heavy ion collisions, namely an anticorrelation between the direction of the CME current for light quarks in a given event and the direction of the kick given to the momentum of all the heavy

Spin-Selective Transmission and Devisable Chirality in Two-Layer Metasurfaces.

PubMed

Li, Zhancheng; Liu, Wenwei; Cheng, Hua; Chen, Shuqi; Tian, Jianguo

2017-08-15

Chirality is a nearly ubiquitous natural phenomenon. Its minute presence in most naturally occurring materials makes it incredibly difficult to detect. Recent advances in metasurfaces indicate that they exhibit devisable chirality in novel forms; this finding offers an effective opening for studying chirality and its features in such nanostructures. These metasurfaces display vast possibilities for highly sensitive chirality discrimination in biological and chemical systems. Here, we show that two-layer metasurfaces based on twisted nanorods can generate giant spin-selective transmission and support engineered chirality in the near-infrared region. Two designed metasurfaces with opposite spin-selective transmission are proposed for treatment as enantiomers and can be used widely for spin selection and enhanced chiral sensing. Specifically, we demonstrate that the chirality in these proposed metasurfaces can be adjusted effectively by simply changing the orientation angle between the twisted nanorods. Our results offer simple and straightforward rules for chirality engineering in metasurfaces and suggest intriguing possibilities for the applications of such metasurfaces in spin optics and chiral sensing.

Chiral Magnetic Effect in Heavy Ion Collisions

DOE PAGES

Liao, Jinfeng

2016-12-01

The Chiral Magnetic Effect (CME) is a remarkable phenomenon that stems from highly nontrivial interplay of QCD chiral symmetry, axial anomaly, and gluonic topology. We show it is of fundamental importance to search for the CME in experiments. The heavy ion collisions provide a unique environment where a hot chiral-symmetric quark-gluon plasma is created, gluonic topological fluctuations generate chirality imbalance, and very strong magnetic fields |Β →|~m 2 π are present during the early stage of such collisions. Significant efforts have been made to look for CME signals in heavy ion collision experiments. Lastly, in this contribution we give amore » brief overview on the status of such efforts.« less

Chiral photonic crystal fibers with single mode and single polarization

NASA Astrophysics Data System (ADS)

Li, She; Li, Junqing

2015-12-01

Chiral photonic crystal fiber (PCF) with a solid core is numerically investigated by a modified chiral plane-wave expansion method. The effects of structural parameters and chirality strength are analyzed on single-polarization single-mode range and polarization states of guided modes. The simulation demonstrates that the chiral photonic crystal fiber compared to its achiral counterpart possesses another single-circular-polarization operation range, which is located in the short-wavelength region. The original single-polarization operation range in the long-wavelength region extends to the short wavelength caused by introducing chirality. Then this range becomes a broadened one with elliptical polarization from linear polarization. With increase of chirality, the two single-polarization single-mode ranges may fuse together. By optimizing the structure, an ultra-wide single-circular-polarization operation range from 0.5 μm to 1.67 μm for chiral PCF can be realized with moderate chirality strength.

Chirality Relay in 2,2'-Substituted 1,1'-Binaphthyl: Access to Propeller Chirality of the Tricoordinate Boron Center.

PubMed

Wang, Chen; Sun, Zuo-Bang; Xu, Qing-Wen; Zhao, Cui-Hua

2016-11-14

It is a challenging issue to achieve propeller chirality for triarylboranes owing to the low transition barrier between the P and M forms of the boron center. Herein, we report a new strategy to achieve propeller chirality of triarylboranes. It was found that the chirality relay from axially chiral 1,1'-binaphthyl to propeller chirality of the trivalent boron center can be realized when a Me 2 N and a Mes 2 B group (Mes=mesityl) are introduced at the 2,2'-positions of the 1,1'-binaphthyl skeleton (BN-BNaph) owing to the strong π-π interaction between the Me 2 N-bonded naphthyl ring and the phenyl ring of one adjacent Mes group, which not only exerts great steric hindrance on the rotation of the two Mes groups but also gives unequal stability to the two configurations of the boron center for a given configuration of the binaphthyl moiety. The stereostructures of the boron center were fully characterized through 1 H NMR spectroscopy, X-ray crystal analyses, and theoretical calculations. Detailed comparisons with the analog BN-Ph-BNaph, in which the Mes 2 B group is separated from 1,1'-binaphthyl by a para-phenylene spacer, confirmed the essential role of π-π interaction for the successful chirality relay in BN-BNaph. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heavy-light mesons in chiral AdS/QCD

NASA Astrophysics Data System (ADS)

Liu, Yizhuang; Zahed, Ismail

2017-06-01

We discuss a minimal holographic model for the description of heavy-light and light mesons with chiral symmetry, defined in a slab of AdS space. The model consists of a pair of chiral Yang-Mills and tachyon fields with specific boundary conditions that break spontaneously chiral symmetry in the infrared. The heavy-light spectrum and decay constants are evaluated explicitly. In the heavy mass limit the model exhibits both heavy-quark and chiral symmetry and allows for the explicit derivation of the one-pion axial couplings to the heavy-light mesons.

On consistency of hydrodynamic approximation for chiral media

NASA Astrophysics Data System (ADS)

Avdoshkin, A.; Kirilin, V. P.; Sadofyev, A. V.; Zakharov, V. I.

2016-04-01

We consider chiral liquids, that is liquids consisting of massless fermions and right-left asymmetric. In such media, one expects existence of electromagnetic current flowing along an external magnetic field, associated with the chiral anomaly. The current is predicted to be dissipation-free. We consider dynamics of chiral liquids, concentrating on the issues of possible instabilities and infrared sensitivity. Instabilities arise, generally speaking, already in the limit of vanishing electromagnetic constant, αel → 0. In particular, liquids with non-vanishing chiral chemical potential might decay into right-left asymmetric states containing vortices.

Cell chirality: its origin and roles in left–right asymmetric development

PubMed Central

Inaki, Mikiko; Liu, Jingyang

2016-01-01

An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by ‘cortical inheritance’. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left–right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla. This article is part of the themed issue ‘Provocative questions in left–right asymmetry’. PMID:27821533

Cell chirality: its origin and roles in left-right asymmetric development.

PubMed

Inaki, Mikiko; Liu, Jingyang; Matsuno, Kenji

2016-12-19

An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by 'cortical inheritance'. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left-right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla.This article is part of the themed issue 'Provocative questions in left-right asymmetry'. © 2016 The Authors.

Dispersion relations for electromagnetic wave propagation in chiral plasmas

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

Gao, M. X.; Guo, B., E-mail: binguo@whut.edu.cn; Peng, L.

2014-11-15

The dispersion relations for electromagnetic wave propagation in chiral plasmas are derived using a simplified method and investigated in detail. With the help of the dispersion relations for each eignwave, we explore how the chiral plasmas exhibit negative refraction and investigate the frequency region for negative refraction. The results show that chirality can induce negative refraction in plasmas. Moreover, both the degree of chirality and the external magnetic field have a significant effect on the critical frequency and the bandwidth of the frequency for negative refraction in chiral plasmas. The parameter dependence of the effects is calculated and discussed.

Diastereoselective synthesis of chiral 1,3-cyclohexadienals

PubMed Central

de la Granja, Ángela P.; Capitán, M. Carmen; Moro, R. F.; Marcos, Isidro S.; Garrido, Narciso M.; Sanz, Francisca; Calle, Emilio

2018-01-01

A novel approach to the production of chiral 1,3-cyclohexadienals has been developed. The organocatalysed asymmetric reaction of different β-disubstituted-α,β-unsaturated aldehydes with a chiral α,β-unsaturated aldehyde in the presence of a Jørgensen-Hayashi organocatalyst provides easy and stereocontrolled access to the cyclohexadienal backbone. This method allows for the synthesis of potential photoprotective chiral 1,3-cyclohexadienals and extra extended conjugation compounds in a simple manner. PMID:29438416

Diastereoselective synthesis of chiral 1,3-cyclohexadienals.

PubMed

Urosa, Aitor; Tobal, Ignacio E; de la Granja, Ángela P; Capitán, M Carmen; Moro, R F; Marcos, Isidro S; Garrido, Narciso M; Sanz, Francisca; Calle, Emilio; Díez, David

2018-01-01

A novel approach to the production of chiral 1,3-cyclohexadienals has been developed. The organocatalysed asymmetric reaction of different β-disubstituted-α,β-unsaturated aldehydes with a chiral α,β-unsaturated aldehyde in the presence of a Jørgensen-Hayashi organocatalyst provides easy and stereocontrolled access to the cyclohexadienal backbone. This method allows for the synthesis of potential photoprotective chiral 1,3-cyclohexadienals and extra extended conjugation compounds in a simple manner.

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.

Understanding Cooperative Chirality at the Nanoscale

NASA Astrophysics Data System (ADS)

Yu, Shangjie; Wang, Pengpeng; Govorov, Alexander; Ouyang, Min

Controlling chirality of organic and inorganic structures plays a key role in many physical, chemical and biochemical processes, and may offer new opportunity to create technology applications based on chiroptical effect. In this talk, we will present a theoretical model and simulation to demonstrate how to engineer nanoscale chirality in inorganic nanostructures via synergistic control of electromagnetic response of both lattice and geometry, leading to rich tunability of chirality at the nanoscale. Our model has also been applied to understand recent materials advancement of related control with excellent agreement, and can elucidate physical origins of circular dichroism features in the experiment.

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

Can the chirality of the ISM be measured

NASA Technical Reports Server (NTRS)

Pendleton, Y.; Sandford, S. A.; Werner, Michael W.; Lauer, J.; Chang, Sherwood

1990-01-01

Many moderately complex carbon-based molecules of the type associated with biological systems can exist in one of two mirror-image forms (left-handed and right-handed), which can be distinguished on the basis of their influence on the state of polarization of a light beam. Both forms are possible in nature; yet in living organisms it is invariably the rule that one of these two species predominates. This gives rise to a net chirality. One possible explanation for the net chirality is that the early earth was somehow seeded from the ISM with an excess of chiral organic compounds which led to the development of life forms which are based on left-handed amino acids and right-handed sugars. Molecular spectroscopy of the interstellar medium (ISM) has revealed a complex variety of molecular species similar to those thought to have been available in the oceans and atmospheres of the earth at the time life formed. The detection of such molecules demonstrates the generality of the chemical processes occurring in both environments. If this generality extends to the processes which produce chirality, it may be possible to detect a net chirality in the ISM. This is of particular interest because determining whether or not net chirality exists elsewhere in the universe is an essential aspect of understanding how life developed on earth and how widely distributed it might be. Researchers report preliminary results of a feasibility study to determine whether or not a net chirality in the ISM can be measured. If laboratory results identify candidate chiral molecules that might exist in the ISM, the next step in this feasibility study will be to estimate the detectability of the chiral signature in astrophysical environments.

Chiral discrimination of α-hydroxy acids and N-Ts-α-amino acids induced by tetraaza macrocyclic chiral solvating agents by using 1H NMR spectroscopy.

PubMed

Lv, Caixia; Feng, Lei; Zhao, Hongmei; Wang, Guo; Stavropoulos, Pericles; Ai, Lin

2017-02-21

In the field of chiral recognition, reported chiral discrimination by 1 H NMR spectroscopy has mainly focused on various chiral analytes with a single chiral center, regarded as standard chiral substrates to evaluate the chiral discriminating abilities of a chiral auxiliary. Among them, chiral α-hydroxy acids, α-amino acids and their derivatives are chiral organic molecules involved in a wide variety of biological processes, and also play an important role in the area of preparation of pharmaceuticals, as they are part of the synthetic process in the production of chiral drug intermediates and protein-based drugs. In this paper, several α-hydroxy acids and N-Ts-α-amino acids were used to evaluate the chiral discriminating abilities of tetraaza macrocyclic chiral solvating agents (TAMCSAs) 1a-1d by 1 H NMR spectroscopy. The results indicate that α-hydroxy acids and N-Ts-α-amino acids were successfully discriminated in the presence of TAMCSAs 1a-1d by 1 H NMR spectroscopy in most cases. The enantiomers of the α-hydroxy acids and N-Ts-α-amino acids were assigned based on the change of integration of the 1 H NMR signals of the corresponding protons. The enantiomeric excesses (ee) of N-Ts-α-amino acids 11 with different optical compositions were calculated based on the integration of the 1 H NMR signals of the CH 3 protons (Ts group) of the enantiomers of (R)- and (S)-11 in the presence of TAMCSA 1b. At the same time, the possible chiral discriminating behaviors have been discussed by means of the Job plots of (±)-2 with TAMCSAs 1b and proposed theoretical models of the enantiomers of 2 and 6 with TAMCSA 1a, respectively.

Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. II. Simulations

NASA Astrophysics Data System (ADS)

Schober, Jennifer; Rogachevskii, Igor; Brandenburg, Axel; Boyarsky, Alexey; Fröhlich, Jürg; Ruchayskiy, Oleg; Kleeorin, Nathan

2018-05-01

Using direct numerical simulations (DNS), we study laminar and turbulent dynamos in chiral magnetohydrodynamics with an extended set of equations that accounts for an additional contribution to the electric current due to the chiral magnetic effect (CME). This quantum phenomenon originates from an asymmetry between left- and right-handed relativistic fermions in the presence of a magnetic field and gives rise to a chiral dynamo. We show that the magnetic field evolution proceeds in three stages: (1) a small-scale chiral dynamo instability, (2) production of chiral magnetically driven turbulence and excitation of a large-scale dynamo instability due to a new chiral effect (α μ effect), and (3) saturation of magnetic helicity and magnetic field growth controlled by a conservation law for the total chirality. The α μ effect becomes dominant at large fluid and magnetic Reynolds numbers and is not related to kinetic helicity. The growth rate of the large-scale magnetic field and its characteristic scale measured in the numerical simulations agree well with theoretical predictions based on mean-field theory. The previously discussed two-stage chiral magnetic scenario did not include stage (2), during which the characteristic scale of magnetic field variations can increase by many orders of magnitude. Based on the findings from numerical simulations, the relevance of the CME and the chiral effects revealed in the relativistic plasma of the early universe and of proto-neutron stars are discussed.

From cosmic chirality to protein structure: Lord Kelvin's legacy.

PubMed

Barron, Laurence D

2012-11-01

A selection of my work on chirality is sketched in two distinct parts of this lecture. Symmetry and Chirality explains how the discrete symmetries of parity P, time reversal T, and charge conjugation C may be used to characterize the properties of chiral systems. The concepts of true chirality (time-invariant enantiomorphism) and false chirality (time-noninvariant enantiomorphism) that emerge provide an extension of Lord Kelvin's original definition of chirality to situations where motion is an essential ingredient thereby clarifying, inter alia, the nature of physical influences able to induce absolute enantioselection. Consideration of symmetry violations reveals that strict enantiomers (exactly degenerate) are interconverted by the combined CP operation. Raman optical activity surveys work, from first observation to current applications, on a new chiroptical spectroscopy that measures vibrational optical activity via Raman scattering of circularly polarized light. Raman optical activity provides incisive information ranging from absolute configuration and complete solution structure of smaller chiral molecules and oligomers to protein and nucleic acid structure of intact viruses. Copyright © 2012 Wiley Periodicals, Inc., A Wiley Company.

Chiral phases of fundamental and adjoint quarks

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

Natale, A. A.; Instituto de Física Teórica - UNESP Rua Dr. Bento T. Ferraz, 271, Bl.II - 01140-070, São Paulo, SP

2016-01-22

We consider a QCD chiral symmetry breaking model where the gap equation contains an effective confining propagator and a dressed gluon propagator with a dynamically generated mass. This model is able to explain the ratios between the chiral transition and deconfinement temperatures in the case of fundamental and adjoint quarks. It also predicts the recovery of the chiral symmetry for a large number of quarks (n{sub f} ≈ 11 – 13) in agreement with lattice data.

Chiral nematic porous germania and germanium/carbon films

NASA Astrophysics Data System (ADS)

Xu, Jing; Nguyen, Thanh-Dinh; Xie, Kai; Hamad, Wadood Y.; MacLachlan, Mark J.

2015-07-01

We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering.We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering. Electronic supplementary information (ESI) available: TGA, IR, Raman, TEM, SEM, BET. See DOI: 10.1039/c5nr02520f

In situ synthesis of di-n-butyl l-tartrate-boric acid complex chiral selector and its application in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shaoqiang; Chen, Yonglei; Zhu, Huadong; Zhu, Jinhua; Yan, Na; Chen, Xingguo

2009-11-06

A novel procedure for in situ assembling a complex chiral selector, di-n-butyl l-tartrate-boric acid complex, by the reaction of di-n-butyl l-tartrate with boric acid in a running buffer was reported and its application in the enantioseparation of beta-blockers and structural related compounds by chiral microemulsion electrokinetic chromatography (MEEKC) has been demonstrated. In order to achieve a good enantioseparation, the effect of dibutyl l-tartrate and sodium tetraborate concentration, surfactant identity and concentration, cosurfactant, buffer pH and composition, organic modifiers, as well as applied voltage and capillary length were investigated. Ten pairs of enantiomers that could not be separated with only dibutyl l-tartrate, obtained good chiral separation using the complex chiral selector; among them, seven pairs could be baseline resolved under optimized experimental conditions. The fixation of chiral centers by the formation of five-membered rings, and being oppositely charged with basic analytes were thought to be the key factors giving the complex chiral selector a superior chiral recognition capability. The effect of the molecular structure of analytes on enantioseparation was discussed in terms of molecular interaction.

Patterns of symmetry breaking in chiral QCD

NASA Astrophysics Data System (ADS)

Bolognesi, Stefano; Konishi, Kenichi; Shifman, Mikhail

2018-05-01

We consider S U (N ) Yang-Mills theory with massless chiral fermions in a complex representation of the gauge group. The main emphasis is on the so-called hybrid ψ χ η model. The possible patterns of realization of the continuous chiral flavor symmetry are discussed. We argue that the chiral symmetry is broken in conjunction with a dynamical Higgsing of the gauge group (complete or partial) by bifermion condensates. As a result a color-flavor locked symmetry is preserved. The 't Hooft anomaly matching proceeds via saturation of triangles by massless composite fermions or, in a mixed mode, i.e. also by the "weakly" coupled fermions associated with dynamical Abelianization, supplemented by a number of Nambu-Goldstone mesons. Gauge-singlet condensates are of the multifermion type and, though it cannot be excluded, the chiral symmetry realization via such gauge invariant condensates is more contrived (requires a number of four-fermion condensates simultaneously and, even so, problems remain) and less plausible. We conclude that in the model at hand, chiral flavor symmetry implies dynamical Higgsing by bifermion condensates.

Chromatographic Studies of Protein-Based Chiral Separations

PubMed Central

Bi, Cong; Zheng, Xiwei; Azaria, Shiden; Beeram, Sandya; Li, Zhao; Hage, David S.

2016-01-01

The development of separation methods for the analysis and resolution of chiral drugs and solutes has been an area of ongoing interest in pharmaceutical research. The use of proteins as chiral binding agents in high-performance liquid chromatography (HPLC) has been an approach that has received particular attention in such work. This report provides an overview of proteins that have been used as binding agents to create chiral stationary phases (CSPs) and in the use of chromatographic methods to study these materials and protein-based chiral separations. The supports and methods that have been employed to prepare protein-based CSPs will also be discussed and compared. Specific types of CSPs that are considered include those that employ serum transport proteins (e.g., human serum albumin, bovine serum albumin, and alpha1-acid glycoprotein), enzymes (e.g., penicillin G acylase, cellobiohydrolases, and α-chymotrypsin) or other types of proteins (e.g., ovomucoid, antibodies, and avidin or streptavidin). The properties and applications for each type of protein and CSP will also be discussed in terms of their use in chromatography and chiral separations. PMID:28344977

Multiple Chirality in Nuclear Rotation: A Microscopic View

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

Zhao, P. W.

Covariant density functional theory and three-dimensional tilted axis cranking are used to investigate multiple chirality in nuclear rotation for the first time in a fully self-consistent and microscopic way. Two distinct sets of chiral solutions with negative and positive parities, respectively, are found in the nucleus 106Rh. The negative-parity solutions reproduce well the corresponding experimental spectrum as well as the B(M1)/B(E2) ratios of the transition strengths. Finally, this indicates that a predicted positive-parity chiral band should also exist. Therefore, it provides a further strong hint that multiple chirality is realized in nuclei.

Multiple Chirality in Nuclear Rotation: A Microscopic View

DOE PAGES

Zhao, P. W.

2017-10-10

Covariant density functional theory and three-dimensional tilted axis cranking are used to investigate multiple chirality in nuclear rotation for the first time in a fully self-consistent and microscopic way. Two distinct sets of chiral solutions with negative and positive parities, respectively, are found in the nucleus 106Rh. The negative-parity solutions reproduce well the corresponding experimental spectrum as well as the B(M1)/B(E2) ratios of the transition strengths. Finally, this indicates that a predicted positive-parity chiral band should also exist. Therefore, it provides a further strong hint that multiple chirality is realized in nuclei.