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Sample records for bimolecular nucleophilic substitution

  1. Nucleophilic Substitution (SN2): Dependence on Nucleophile, Leaving Group, Central Atom, Substituents, and Solvent.

    Science.gov (United States)

    Hamlin, Trevor A; Swart, Marcel; Bickelhaupt, F Matthias

    2018-03-15

    The reaction potential energy surface (PES) and, thus, the mechanism of bimolecular nucleophilic substitution (SN2) depend profoundly on the nature of the nucleophile and leaving group, but also on the central, electrophilic atom, its substituents, as well as on the medium in which the reaction takes place. Here, we provide an overview of recent studies and demonstrate how changes in any one of the aforementioned factors affect the SN2 mechanism. One of the most striking effects is the transition from a double-well to a single-well PES when the central atom is changed from a second-period (e.g., carbon) to a higher-period element (e.g., silicon, germanium). Variations in nucleophilicity, leaving group ability and bulky substituents around a second-row element central atom can then be exploited to change the single-well PES back into a double-well. Reversely, these variations can also be used to produce a single-well PES for second-period elements, e.g., a stable pentavalent carbon species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Preparation and nucleophilic substitution of the 2,4,6 ...

    African Journals Online (AJOL)

    Three methods for preparation of D-amino acids by nucleophilic substitution on derivatives of their L-antipodes have been attempted. Nucleophilic substitution on optically active phenylalanine ethyl ester triphenylpyridinium salt yielded partial inverted azide products. The N,N-disulfonylimide intermediate of the same ester ...

  3. DFT analysis of the nucleophilicity of substituted pyridines and ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 4. DFT analysis of the nucleophilicity of substituted pyridines and prediction of new molecules having nucleophilic character stronger than 4-pyrrolidino pyridine. Kaustavmoni Deka Prodeep Phukan. Regular Articles Volume 128 Issue 4 April 2016 pp 633- ...

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

    Science.gov (United States)

    Sibbald, Paul A.

    2015-01-01

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

  5. Nucleophilic substitution as a mechanism of atrazine sequestration in soil

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Shao, Juan [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China)

    2015-03-02

    Highlights: • Atrazine tends to form nonextractable bound residue in soil. • Nucleophilic substitution is a pathway leading to atrazine sequestration in soil. • Sulfur containing amino acids are likely to play an important role as nucleophiles during this process. - Abstract: Formation of nonextractable residue was widely observed as a sink of atrazine (ATZ) in soil. However, the mechanisms by which ATZ binds to soil organic matter remain unclear. In this study, we demonstrated that neucleophilic substitution could serve an important pathway causing ATZ sequestration. The carbon bonded to the chlorine in ATZ molecule is partially positively charged due to the strong electronegativity of chlorine and is susceptible to the attack of nucleophiles such as aniline. Since aromatic amines are relatively rare in natural soils, amino acids/peptides were hypothesized to act as the main nucleophiles in real environment. However, substantially ATZ transformation was only observed in the presence of those species containing thiol functionality. Thus, we speculated that it was the thiol group in amino acids/peptides acting as the nucleophile. Nitrogen in amino acids was in fact not an active nucleophile toward ATZ. In addition to the sulfur-containing amino acids, other thiol compounds, and sulfide were also proved to be reactive to ATZ. Thus, the sequestration potential of ATZ probably correlates to the availability of thiol compounds in soil.

  6. preparation and nucleophilic substitution of the 2,4,6

    African Journals Online (AJOL)

    Mgina

    pyridinium salt 3 during preparation or could be the consequence of the nucleophilic substitution reaction. In case of the first presumption, racemization of 3 might have happened via acid mediated tautomerization of the vinylogous compound 5 , an intermediate formed during preparation of the triphenylpyridinium salt ...

  7. NUCLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN

    Directory of Open Access Journals (Sweden)

    Bambang Purwono

    2010-06-01

    Full Text Available The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded 93.28 %. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyanomethylbenzaldehyde in 54.39% yield. Reaction with methoxyde ion yielded 4-hydroxy- 3-methoxy-5-(methoxy -methylbenzaldehyde in 67.80% yield. The nucleophilic substitution reaction showed that trimethylamino substituent of quaternary Mannich base can act as a good leaving group on nucleophilic substitution reactions. Keywords: Mannich reaction, vanillin, nucleophilic substitution

  8. Transetherification on Polyols by Intra- and Intermolecular Nucleophilic Substitutions

    Science.gov (United States)

    Muraoka, Takahiro; Adachi, Kota; Chowdhury, Rainy; Kinbara, Kazushi

    2014-01-01

    Transetherification on polyols involving intra- and intermolecular nucleophilic substitutions is reported. Di- or trialkoxide formation of propane-1,3-diol or 2-(hydroxymethyl)propane-1,3-diol derivatives by NaH triggers the reaction via oxetanes formation, where the order to add NaH and a polyol significantly influences the yields of products. It was demonstrated that the protective group on the pentaerythritol skeleton is apparently transferred to the hydrophilic and hydrophobic chain molecules bearing a leaving group in one-step, and a protective group conversion from tosyl to benzyl was successful using a benzyl-appending triol to afford a desired product in 67% yield. PMID:24663293

  9. Experimental Determination of Activation Energy of Nucleophilic Aromatic Substitution on Porphyrins

    Science.gov (United States)

    Rizvi, Waqar; Khwaja, Emaad; Siddiqui, Saim; Bhupathiraju, N. V. S. Dinesh K.; Drain, Charles Michael

    2018-01-01

    A physical organic chemistry experiment is described for second-year college students. Students performed nucleophilic aromatic substitution (NAS) reactions on 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TPPF[subscript 20]) using three different nucleophiles. Substitution occurs preferentially at the 4-position ("para")…

  10. NUCLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN

    OpenAIRE

    Bambang Purwono; Estiana R. P. Daruningsih

    2010-01-01

    The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded 93.28 %. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyano)methylbenzaldehyde in 54.39% yiel...

  11. In situ nucleophilic substitutional growth of methylammonium lead iodide polycrystals.

    Energy Technology Data Exchange (ETDEWEB)

    Acik, Muge [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials and Nanoscience and Technology Division; Alam, Todd M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Organic Materials Science; Guo, Fangmin [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division; Ren, Yang [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division; Lee, Byeongdu [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division; Rosenberg, Richard A. [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS) and X-ray Science Division; Mitchell, JF [Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Kinaci, Alper [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials and Nanoscience and Technology Division; Chan, Maria [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials and Nanoscience and Technology Division; Darling, Seth B. [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials and Nanoscience and Technology Division; Univ. of Chicago, IL (United States). Inst. for Molecular Engineering

    2017-01-01

    Methylammonium lead iodide (MAPbIx) perovskites are organic-inorganic semiconductors that serve as the light-harvesting component of the photovoltaics, and are desirable with their long diffusion length yielding power conversion efficiencies of ≥22%. Conventional techniques grow perovskites by spin coating precursors on an oxide or a polymer substrate followed by annealing, however, use of high boiling point solvents and high temperatures hinder device stability and performance. Through a one-step, acid-catalyzed nucleophilic-substitutional crystal growth in polar protic solvents, we show evidence for the substrate- and annealing- free production of MAPbIx polycrystals that are metallic-lead-free with negligibly small amount of PbI2 precipitation (<10%). On the basis of this chemical composition, we have devised an in situ growth of highly air (upto ~1.5 months) and thermally-stable (≤300°C), tetragonal-phased, variable-sized polycrystals (~100 nm-10 μm) amendable for large-area deposition, and ultimately, large-scale manufacturing. This method is encouraging for stable optoelectronic devices, and leads to energy-efficient and low-cost processing.

  12. Enzymatic hydrolysis by transition-metal-dependent nucleophilic aromatic substitution.

    Science.gov (United States)

    Kalyoncu, Sibel; Heaner, David P; Kurt, Zohre; Bethel, Casey M; Ukachukwu, Chiamaka U; Chakravarthy, Srinivas; Spain, Jim C; Lieberman, Raquel L

    2016-12-01

    Nitroaromatic compounds are typically toxic and resistant to degradation. Bradyrhizobium species strain JS329 metabolizes 5-nitroanthranilic acid (5NAA), which is a molecule secreted by Streptomyces scabies, the plant pathogen responsible for potato scab. The first biodegradation enzyme is 5NAA-aminohydrolase (5NAA-A), a metalloprotease family member that converts 5NAA to 5-nitrosalicylic acid. We characterized 5NAA-A biochemically and obtained snapshots of its mechanism. 5NAA-A, an octamer that can use several divalent transition metals for catalysis in vitro, employs a nucleophilic aromatic substitution mechanism. Unexpectedly, the metal in 5NAA-A is labile but is readily loaded in the presence of substrate. 5NAA-A is specific for 5NAA and cannot hydrolyze other tested derivatives, which are likewise poor inhibitors. The 5NAA-A structure and mechanism expand our understanding of the chemical ecology of an agriculturally important plant and pathogen, and will inform bioremediation and biocatalytic approaches to mitigate the environmental and ecological impact of nitroanilines and other challenging substrates.

  13. REVISITING NUCLEOPHILIC SUBSTITUTION REACTIONS: MICROWAVE-ASSISTED SYNTHESIS OF AZIDES, THIOCYANATES AND SULFONES IN AQUEOUS MEDIUM

    Science.gov (United States)

    A practical, rapid and efficient microwave (MW) promoted synthesis of various azides, thiocyanates and sulfones, is described in aqueous medium. This general and expeditious MW-enhanced nucleophilic substitution approach uses easily accessible starting materials such as halides o...

  14. Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene

    Czech Academy of Sciences Publication Activity Database

    Ajenjo, Javier; Greenhall, M.; Zarantonello, C.; Beier, Petr

    2016-01-01

    Roč. 12, Feb 3 (2016), s. 192-197 ISSN 1860-5397 EU Projects: European Commission(XE) 607787 - FLUOR21 Institutional support: RVO:61388963 Keywords : direct fluorination * fluorine * nucleophilic aromatic substitution * pentafluorosulfanyl group * vicarious nucleophilic substitution Subject RIV: CC - Organic Chemistry Impact factor: 2.337, year: 2016 http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-12-21

  15. Nucleophilic Aromatic tele-Substitution of Hydrogen of 9-Nitroanthracene with 2-Naphthols and Phloroglucinol

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Su Yeon; Lim, Jin Woo; Nam, Kye Chun; Kim, Jae Nyoung [Chonnam National Univ., Gwangju (Korea, Republic of)

    2016-09-15

    Nucleophilic substitution reaction of hydrogen atom in electron-deficient arenes has been extensively studied. An addition of nucleophile to electron-deficient arenes such as nitroarene proceeds readily at the positions occupied by hydrogen atom to form σ{sup H}-adducts. A selective nucleophilic aromatic tele-substitution reaction has been observed in the reaction of 9-nitroanthracene with 2-naphthols, 1,3-cyclohexanediones, and phloroglucinol. The corresponding nitroanthracene derivatives, obtained by an ONSH process, were formed in variable yields as minor products depending on the substrates.

  16. Water promoted allylic nucleophilic substitution reactions of (E)-1,3 diphenylallyl acetate

    KAUST Repository

    Ghorpade, Seema Arun

    2017-11-30

    Transition metal free, water based, greener protocol for allylic alkylation, allylic amination, O-allylation of (E)-1,3-diphenylallyl acetate is described. The developed methodology is applicable for a wide range of nucleophiles furnishing excellent yields of corresponding products up to 87% under mild reaction conditions. A Distinct effect of water and base is explored for allylic nucleophilic substitution reactions of (E)-1,3-diphenylallyl acetate.

  17. The efficiency of the metal catalysts in the nucleophilic substitution of alcohols is dependent on the nucleophile and not on the electrophile.

    Science.gov (United States)

    Biswas, Srijit; Samec, Joseph S M

    2013-05-01

    In this study, we investigate the effect of the electrophiles and the nucleophiles for eight catalysts in the catalytic SN 1 type substitution of alcohols with different degree of activation by sulfur-, carbon-, oxygen-, and nitrogen-centered nucleophiles. The catalysts do not show any general variance in efficiency or selectivity with respect to the alcohols and follow the trend of alcohol reactivity. However, when it comes to the nucleophile, the eight catalysts show general and specific variances in the efficiency and selectivity to perform the desired substitution. Interestingly, the selectivity of the alcohols to produce the desired substitution products was found to be independent of the electrophilicity of the generated carbocations but highly dependent on the ease of formation of the cation. Catalysts based on iron(III), bismuth(III), and gold(III) show higher conversions for S-, C-, and N-centered nucleophiles, and Bi(III) was the most efficient catalyst in all combinations. Catalysts based on rhenium(I) or rhenium(VII), palladium(II), and lanthanum(III) were the most efficient in performing the nucleophilic substitution on the various alcohols with the O-centered nucleophiles. These catalysts generate the symmetrical ether as a by-product from the reactions of S-, C-, and N-centered nucleophiles as well, resulting in lower chemoselectivity. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Direct Amination of Nitro(pentafluorosulfanyl)benzenes through Vicarious Nucleophilic Substitution of Hydrogen

    Czech Academy of Sciences Publication Activity Database

    Pastýříková, Tereza; Iakobson, George; Vida, Norbert; Pohl, Radek; Beier, Petr

    -, č. 11 (2012), s. 2123-2126 ISSN 1434-193X R&D Projects: GA ČR GAP207/12/0072 Institutional research plan: CEZ:AV0Z40550506 Keywords : sulfur * amination * nucleophilic substitution * nitrogen heterocycles Subject RIV: CC - Organic Chemistry Impact factor: 3.344, year: 2012

  19. REVISITING CLASSICAL NUCLEOPHILIC SUBSTITUTIONS IN AQUEOUS MEDIUM: MICROWAVE-ASSISTED SYNTHESIS OF ALKYL AZIDES

    Science.gov (United States)

    An efficient and clean synthesis of alkyl azides using microwave (MW) radiation is described in aqueous medium by reacting alkyl halides or tosylates with alkali azides. This general and expeditious MW-enhanced approach to nucleophilic substitution reactions is applicable to the ...

  20. Oxidative nucleophilic substitution of hydrogen in nitro(pentafluorosulfanyl)benzenes with alkyl Grignard and lithium reagents

    Czech Academy of Sciences Publication Activity Database

    Vida, Norbert; Beier, Petr

    2012-01-01

    Roč. 143, SI (2012), s. 130-134 ISSN 0022-1139 R&D Projects: GA ČR GAP207/12/0072 Institutional support: RVO:61388963 Keywords : pentafluorosulfanyl group * nucleophilic aromatic substitutions * oxidations Subject RIV: CC - Organic Chemistry Impact factor: 1.939, year: 2012

  1. Synthesis of a Fluorescent Acridone Using a Grignard Addition, Oxidation, and Nucleophilic Aromatic Substitution Reaction Sequence

    Science.gov (United States)

    Goodrich, Samuel; Patel, Miloni; Woydziak, Zachary R.

    2015-01-01

    A three-pot synthesis oriented for an undergraduate organic chemistry laboratory was developed to construct a fluorescent acridone molecule. This laboratory experiment utilizes Grignard addition to an aldehyde, alcohol oxidation, and iterative nucleophilic aromatic substitution steps to produce the final product. Each of the intermediates and the…

  2. Mapping the Trajectory of Nucleophilic Substitution at Silicon Using a peri-Substituted Acenaphthyl Scaffold.

    Science.gov (United States)

    Hupf, Emanuel; Olaru, Marian; Raţ, Ciprian I; Fugel, Malte; Hübschle, Christian B; Lork, Enno; Grabowsky, Simon; Mebs, Stefan; Beckmann, Jens

    2017-08-04

    The second-order nucleophilic substitution (S N 2) reaction at a silicon atom is scrutinized by means of snapshots along a pseudoreaction coordinate. Phosphine and fluoride represent both attacking and leaving groups in the modeled S N 2 reaction. In the experimentally obtained 5-diphenylphosphinoacenaphth-6-yl-dimethylfluorosilane, 1, the phosphine and fluorosilane moieties are forced into immediate proximity through an acenaphthyl scaffold, that is, they exhibit peri interactions that serve as the model of the reactant ion-molecule complex and starting point for a theoretical potential-energy surface (PES) scan. Upon dissociation of fluoride, the experimentally obtained silylphosphonium cation 2 serves as a model of the product and end point of the PES scan. The pseudoreaction pathway is studied using geometric, energetic, spectroscopic, molecular-orbital, and topological real-space bonding indicators. It becomes evident that it is crucial to combine such methods to understand the pseudoreaction because they reveal different aspects based on different sensitivity to dispersive, electrostatic, and polar-covalent contributions to bonding, as shown by the reduced density gradient analysis. For example, atoms-in-molecules theory describes a late topological catastrophe, whereas the electron localizability indicator describes an early concerted reaction and natural resonance theory describes a more gradual change of properties. This case study encourages the use of a well-balanced toolbox equipped with complementary methods to emphasize different aspects of bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

    Directory of Open Access Journals (Sweden)

    Magnus Liljenberg

    2013-04-01

    Full Text Available A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the “σ-complex approach”, has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirements for predictive reactivity models for the pharmaceutical industry. We also present new results regarding the reaction rates and regioselectivities in nucleophilic substitution of fluorinated aromatics. They were rationalized by investigating linear correlations between experimental rate constants (k from the literature with a theoretical quantity, which we call the sigma stability (SS. The SS is the energy change associated with formation of the intermediate σ-complex by attachment of the nucleophile to the aromatic ring. The correlations, which include both neutral (NH3 and anionic (MeO− nucleophiles are quite satisfactory (r = 0.93 to r = 0.99, and SS is thus useful for quantifying both global (substrate and local (positional reactivity in SNAr reactions of fluorinated aromatic substrates. A mechanistic analysis shows that the geometric structure of the σ-complex resembles the rate-limiting transition state and that this provides a rationale for the observed correlations between the SS and the reaction rate.

  4. Unprecedented reactivity of an aluminium hydride complex with ArNH2BH3 : nucleophilic substitution versus deprotonation

    NARCIS (Netherlands)

    Harder, Sjoerd; Spielmann, Jan

    2011-01-01

    Reaction of DIPPnacnacAlH(2) with DIPPNH2BH3 did not give the anticipated deprotonation but nucleophilic substitution at B was observed instead. The product DIPPnacnacAl(BH4)(2) was isolated and structurally characterized. Nucleophilic displacement at B might play a role in mechanistic pathways

  5. Unprecedented reactivity of an aluminium hydride complex with ArNH2BH3: nucleophilic substitution versus deprotonation

    OpenAIRE

    Harder, Sjoerd; Spielmann, Jan

    2011-01-01

    Reaction of DIPPnacnacAlH(2) with DIPPNH2BH3 did not give the anticipated deprotonation but nucleophilic substitution at B was observed instead. The product DIPPnacnacAl(BH4)(2) was isolated and structurally characterized. Nucleophilic displacement at B might play a role in mechanistic pathways related to metal amidoborane complexes.

  6. Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates with Nitrogen and Oxygen Nucleophiles.

    Science.gov (United States)

    Najib, Atifah; Hirano, Koji; Miura, Masahiro

    2017-05-05

    A Pd/(R)-BINAP-catalyzed asymmetric benzylic substitution of secondary benzyl carbonates with amides and amines proceeds to form the corresponding optically active benzylamines in good yields with a high enantiomeric ratio. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner. Additionally, the asymmetric Pd catalysis can also be applicable to phenol nucleophiles, thus delivering chiral ethers with acceptable yields and enantioselectivity.

  7. Nucleophilic substitution and oxidative coupling in reaction of metallated lithium salt of acetic acid with 1,2-dibromoethane

    OpenAIRE

    Chanysheva, A.; Zorin, A.; Klimakov, V.; Spirikhin, L.; Zorin, V.

    2009-01-01

    When lithium salt of acetic acid metallated by lithium diisopropylamide in tetrahydrofuran interacts with 1,2-dibromoethane products of nucleophilic substitution of bromine atoms for oxycarbomethyl group and oxidative coupling of acetoxydianions are obtained.

  8. Unprecedented reactivity of an aluminium hydride complex with ArNH2BH3: nucleophilic substitution versus deprotonation.

    Science.gov (United States)

    Harder, Sjoerd; Spielmann, Jan

    2011-11-21

    Reaction of DIPPnacnacAlH(2) with DIPPNH(2)BH(3) did not give the anticipated deprotonation but nucleophilic substitution at B was observed instead. The product DIPPnacnacAl(BH(4))(2) was isolated and structurally characterized. Nucleophilic displacement at B might play a role in mechanistic pathways related to metal amidoborane complexes. This journal is © The Royal Society of Chemistry 2011

  9. Liquid ammonia as a dipolar aprotic solvent for aliphatic nucleophilic substitution reactions.

    Science.gov (United States)

    Ji, Pengju; Atherton, John; Page, Michael I

    2011-03-04

    The rate constants for the reactions of a variety of nucleophiles reacting with substituted benzyl chlorides in liquid ammonia (LNH(3)) have been determined. To fully interpret the associated linear free-energy relationships, the ionization constants of phenols ions in liquid ammonia were obtained using UV spectra. These equilibrium constants are the product of those for ion-pair formation and dissociation to the free ions, which can be separated by evaluating the effect of added ammonium ions. There is a linear relationship between the pK(a) of phenols in liquid ammonia and those in water of slope 1.68. Aminium ions exist in their unprotonated free base form in liquid ammonia and their ionization constants could not be determined by NMR. The rates of solvolysis of substituted benzyl chlorides in liquid ammonia at 25 °C show a Hammett ρ of zero, having little or no dependence upon ring substituents, which is in stark contrast with the hydrolysis rates of substituted benzyl halides in water, which vary 10(7) fold. The rate of substitution of benzyl chloride by substituted phenoxide ions is first order in the concentration of the nucleophile indicative of a S(N)2 process, and the dependence of the rate constants on the pK(a) of the phenol in liquid ammonia generates a Brønsted β(nuc) = 0.40. Contrary to the solvolysis reaction, the reaction of phenoxide ion with 4-substituted benzyl chlorides gives a Hammett ρ = 1.1, excluding the 4-methoxy derivative, which shows the normal positive deviation. The second order rate constants for the substitution of benzyl chlorides by neutral and anionic amines show a single Brønsted β(nuc) = 0.21 (based on the aqueous pK(a) of amine), but their dependence on the substituent in substituted benzyl chlorides varies with a Hammett ρ of 0 for neutral amines, similar to that seen for solvolysis, whereas that for amine anions is 0.93, similar to that seen for phenoxide ion.

  10. Enhanced Reactivity in Nucleophilic Acyl Substitution Ion/Ion Reactions Using Triazole-Ester Reagents

    Science.gov (United States)

    Bu, Jiexun; Peng, Zhou; Zhao, Feifei; McLuckey, Scott A.

    2017-07-01

    The acyl substitution reactions between 1-hydroxy-7-aza-benzotriazole (HOAt)/1-hydroxy-benzotriazole (HOBt) ester reagents and nucleophilic side chains on peptides have been demonstrated in the gas phase via ion/ion reactions. The HOAt/HOBt ester reagents were synthesized in solution and ionized via negative nano-electrospray ionization. The anionic reagents were then reacted with doubly protonated model peptides containing amines, guanidines, and imidazoles in the gas phase. The complexes formed in the reaction cell were further probed with ion trap collision induced dissociation (CID) yielding either a covalently modified analyte ion or a proton transfer product ion. The covalent reaction yield of HOAt/HOBt ester reagents was demonstrated to be higher than the yield with N-hydroxysuccinimide (NHS) ester reagents over a range of equivalent conditions. Density functional theory (DFT) calculations were performed with a primary amine model system for both triazole-ester and NHS-ester reactants, which indicated a lower transition state barrier for the former reagent, consistent with experiments. The work herein demonstrates that the triazole-ester reagents are more reactive, and therefore less selective, than the analogous NHS-ester reagent. As a consequence, the triazole-ester reagents are the first to show efficient reactivity with unprotonated histidine residues in the gas phase. For all nucleophilic sites and all reagents, covalent reactions are favored under long time, low amplitude activation conditions. This work presents a novel class of reagents capable of gas-phase conjugation to nucleophilic sites in analyte ions via ion/ion chemistry.

  11. Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide

    International Nuclear Information System (INIS)

    Adhikary, Keshab Kumar; Lee, Hai Whang

    2011-01-01

    Kinetic studies of the reactions of N-methyl-Y-α-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at 25.0 .deg. C. The Hammett plots for substituent X variations in the nucleophiles (log k N vs σ X ) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log k N vs pK a ) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log k N vs σ Y ) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant ρ XY values are all negative: ρ XY = -0.32 for X = Y = electron-donating: -0.22 for X = electron-withdrawing and Y = electron-donating: -1.80 for X = electron-donating and Y = electronwithdrawing: -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal (k H /k D > 1) for Y = electron-donating, while secondary inverse (k H /k D < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-α-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the α-carbon for Y = electronwithdrawing substituents

  12. Reduced Reactivity of Amines against Nucleophilic Substitution via Reversible Reaction with Carbon Dioxide.

    Science.gov (United States)

    Mohammed, Fiaz S; Kitchens, Christopher L

    2015-12-23

    The reversible reaction of carbon dioxide (CO₂) with primary amines to form alkyl-ammonium carbamates is demonstrated in this work to reduce amine reactivity against nucleophilic substitution reactions with benzophenone and phenyl isocyanate. The reversible formation of carbamates has been recently exploited for a number of unique applications including the formation of reversible ionic liquids and surfactants. For these applications, reduced reactivity of the carbamate is imperative, particularly for applications in reactions and separations. In this work, carbamate formation resulted in a 67% reduction in yield for urea synthesis and 55% reduction for imine synthesis. Furthermore, the amine reactivity can be recovered upon reversal of the carbamate reaction, demonstrating reversibility. The strong nucleophilic properties of amines often require protection/de-protection schemes during bi-functional coupling reactions. This typically requires three separate reaction steps to achieve a single transformation, which is the motivation behind Green Chemistry Principle #8: Reduce Derivatives. Based upon the reduced reactivity, there is potential to employ the reversible carbamate reaction as an alternative method for amine protection in the presence of competing reactions. For the context of this work, CO₂ is envisioned as a green protecting agent to suppress formation of n-phenyl benzophenoneimine and various n-phenyl-n-alky ureas.

  13. The definition of the applicability domain relevant to skin sensitization for the aromatic nucleophilic substitution mechanism.

    Science.gov (United States)

    Enoch, S J; Schultz, T W; Cronin, M T D

    2012-10-01

    This study outlines how a glutathione reactivity assay (so-called in chemico data) can be used to define the applicability domain for the nucleophilic aromatic substitution (S(N)Ar) reaction for benzenes. This reaction is one of the six mechanistic domains that have been shown to be important in toxicological endpoints in which the ability to bind covalently to a protein is a key molecular initiating event. This study has analysed the experimental data, allowing a clear and interpretable structure-activity relationship to be developed for the S(N)Ar domain. The applicability domain has resulted in a series of structural alerts. The definition of the applicability domain for the S(N)Ar reaction and the resulting structural alerts are likely to be beneficial in the development of computational tools for category formation and read-across. The study concludes with how this information can be used in the development of adverse outcome pathways.

  14. Sequential nucleophilic substitutions permit orthogonal click functionalization of multicomponent PEG brushes.

    Science.gov (United States)

    Sha, Jin; Lippmann, Ethan S; McNulty, Jason; Ma, Yulu; Ashton, Randolph S

    2013-09-09

    Multicomponent poly(ethylene glycol) (PEG) brushes (i.e., ≥ 2 adjacent PEG brushes) can be used to engineer culture substrates with microscale, nonfouling regions decorated with covalently immobilized ligands that mediate biospecific interactions. However, synthesizing such brushes with orthogonal immobilization chemistries to permit differential biofunctionalization is nontrivial and often requires synthesis of PEG-co-polymers. To simplify synthesis and enhance the versatility of such substrates, we developed a protocol for generating orthogonal click-functionalized multicomponent PEG brushes using sequential nucleophilic substitutions by sodium azide, ethanolamine, and propargylamine. The novel application of propargylamine-mediated substitution functionalizes PEG brushes with acetylene groups, and for the first time, ethanolamine-mediated substitution is shown to be sufficient for passivating the "living" polymer chain ends between brush synthesis steps. Thus, our multicomponent PEG brushes present dual orthogonal chemistries (i.e., azido and acetylene groups) for ligand immobilization via versatile copper-free click reactions, which are useful for in situ surface modifications during cell culture.

  15. Preparation of SF5 Aromatics by Vicarious Nucleophilic Substitution Reactions of Nitro(pentafluorosulfanyl)benzenes with Carbanions

    Czech Academy of Sciences Publication Activity Database

    Beier, Petr; Pastýříková, Tereza; Iakobson, George

    2011-01-01

    Roč. 76, č. 11 (2011), s. 4781-4786 ISSN 0022-3263 Institutional research plan: CEZ:AV0Z40550506 Keywords : sulfur pentafluorides * vicarious nucleophilic aromatic substitution * nitrobenzenes Subject RIV: CC - Organic Chemistry Impact factor: 4.450, year: 2011

  16. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

    Science.gov (United States)

    Mendes, Desiree E.; Schoffstall, Allen M.

    2011-01-01

    This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

  17. Influence of the milling parameters on the nucleophilic substitution reaction of activated β-cyclodextrins

    Directory of Open Access Journals (Sweden)

    László Jicsinszky

    2017-09-01

    Full Text Available The present work focuses on the mechanochemical preparation of industrially important β-cyclodextrin (CD derivatives. Activated CDs have been reacted with nitrogen and sulfur nucleophiles using a planetary mill equipped with stainless steel, zirconia and glass milling tools of different sizes. It is shown that the milling frequency and the number as well as the size of the milling balls have an effect on the nucleophilic reaction.

  18. Organolithium compounds in the nucleophilic substitution of hydrogen in arenes and hetarenes

    Science.gov (United States)

    Kovalev, I. S.; Kopchuk, D. S.; Zyryanov, G. V.; Rusinov, V. L.; Chupakhin, O. N.; Charushin, V. N.

    2015-12-01

    The review considers the most typical examples of the direct non-activated non-catalytic C-C bond formation in arenes and their metal complexes activated by electron-withdrawing substituents in the aromatic nucleus and in hetarenes (azines and their N-oxides, porphyrins, etc.) upon the reactions with aliphatic and (hetero)aromatic (hetero)organolithium nucleophiles. Particular attention is given to the direct introduction of nitroxide radicals and (hetero)organic moieties into mono-, di- and triazines and their N-oxides. The influence of the structures of the (hetero)aromatic substrate and the (hetero)organolithium nucleophile on the reaction pathway and rate and on the structure of the reaction product is analyzed. The bibliography includes 237 references. Dedicated to Academician N S Zefirov on the occasion of 80th birthday.

  19. Hydrogen bonding lowers intrinsic nucleophilicity of solvated nucleophiles.

    Science.gov (United States)

    Chen, Xin; Brauman, John I

    2008-11-12

    The relationship between nucleophilicity and the structure/environment of the nucleophile is of fundamental importance in organic chemistry. In this work, we have measured nucleophilicities of a series of substituted alkoxides in the gas phase. The functional group substitutions affect the nucleophiles through ion-dipole, ion-induced dipole interactions and through hydrogen bonding whenever structurally possible. This set of alkoxides serves as an ideal model system for studying nucleophiles under microsolvation settings. Marcus theory was applied to analyze the results. Using Marcus theory, we separate nucleophilicity into two independent components, an intrinsic nucleophilicity and a thermodynamic driving force determined solely by the overall reaction exothermicity. It is found that the apparent nucleophilicities of the substituted alkoxides are always much lower than those of the unsubstituted ones. However, ion-dipole, ion-induced dipole interactions, by themselves, do not significantly affect the intrinsic nucleophilicity; the decrease in the apparent nucleophilicity results from a weaker thermodynamic driving force. On the other hand, hydrogen bonding not only stabilizes the nucleophile but also increases the intrinsic barrier height by 3 to approximately 4 kcal mol (-1). In this regard, the hydrogen bond is not acting as a perturbation in the sense of an external dipole but more directly affects the electronic structure and reactivity of the nucleophilic alkoxide. This finding offers a deeper insight into the solvation effect on nucleophilicity, such as the remarkably lower reactivities in nucleophilic substitution reactions in protic solvents than in aprotic solvents.

  20. Direct no-carrier-added {sup 18}F-labelling of arenes via nucleophilic substitution on aryl(2-thienyl)iodonium salts

    Energy Technology Data Exchange (ETDEWEB)

    Ross, T.L.

    2006-01-15

    For in vivo imaging of molecular processes via positron emission tomography (PET) radiotracers of high specific activity are demanded. In case of the most commonly used positron emitter fluorine-18, this is only achievable with no-carrier-added [{sup 18}F]fluoride, which implies nucleophilic methods of {sup 18}F-substitution. Whereas electron deficient aromatic groups can be labelled in one step using no-carrier-added [{sup 18}F]fluoride, electron rich {sup 18}F-labelled aromatic molecules are only available by multi-step radiosyntheses or carrier-added electrophilic reactions. Here, diaryliodonium salts represent an alternative, since they have been proven as potent precursor for a direct nucleophilic {sup 18}F-introduction into aromatic molecules. Furthermore, as known from non-radioactive studies, the highly electron rich 2-thienyliodonium leaving group leads to a high regioselectivity in nucleophilic substitution reactions. Consequently, a direct nucleophilic no-carrier-added {sup 18}F-labelling of electron rich arenes via aryl(2-thienyl)iodonium precursors was developed in this work. The applicability of direct nucleophilic {sup 18}F-labelling was examined in a systematic study on eighteen aryl(2-thienyl)iodonium salts. As electron rich precursors the ortho-, meta- and para-methoxyphenyl(2-thienyl)iodonium bromides, iodides, tosylates and triflates were synthesised. In addition, para-substituted (R=BnO, CH{sub 3}, H, Cl, Br, I) aryl(2-thienyl)iodonium bromides were prepared as precursors with a systematically varying electron density. As first approach, the general reaction conditions of the nucleophilic {sup 18}F-substitution procedure were optimised. The best conditions for direct nucleophilic no-carrier-added {sup 18}F-labelling via aryl(2-thienyl)iodonium salts were found with dimethylformamide as solvent, a reaction temperature of 130{+-}3 C and 25 mmol/l as concentration of the precursor. (orig.)

  1. Direct no-carrier-added 18F-labelling of arenes via nucleophilic substitution on aryl(2-thienyl)iodonium salts

    International Nuclear Information System (INIS)

    Ross, T.L.

    2006-01-01

    For in vivo imaging of molecular processes via positron emission tomography (PET) radiotracers of high specific activity are demanded. In case of the most commonly used positron emitter fluorine-18, this is only achievable with no-carrier-added [ 18 F]fluoride, which implies nucleophilic methods of 18 F-substitution. Whereas electron deficient aromatic groups can be labelled in one step using no-carrier-added [ 18 F]fluoride, electron rich 18 F-labelled aromatic molecules are only available by multi-step radiosyntheses or carrier-added electrophilic reactions. Here, diaryliodonium salts represent an alternative, since they have been proven as potent precursor for a direct nucleophilic 18 F-introduction into aromatic molecules. Furthermore, as known from non-radioactive studies, the highly electron rich 2-thienyliodonium leaving group leads to a high regioselectivity in nucleophilic substitution reactions. Consequently, a direct nucleophilic no-carrier-added 18 F-labelling of electron rich arenes via aryl(2-thienyl)iodonium precursors was developed in this work. The applicability of direct nucleophilic 18 F-labelling was examined in a systematic study on eighteen aryl(2-thienyl)iodonium salts. As electron rich precursors the ortho-, meta- and para-methoxyphenyl(2-thienyl)iodonium bromides, iodides, tosylates and triflates were synthesised. In addition, para-substituted (R=BnO, CH 3 , H, Cl, Br, I) aryl(2-thienyl)iodonium bromides were prepared as precursors with a systematically varying electron density. As first approach, the general reaction conditions of the nucleophilic 18 F-substitution procedure were optimised. The best conditions for direct nucleophilic no-carrier-added 18 F-labelling via aryl(2-thienyl)iodonium salts were found with dimethylformamide as solvent, a reaction temperature of 130±3 C and 25 mmol/l as concentration of the precursor. (orig.)

  2. NCA nucleophilic radiofluorination on substituted benzaldehydes for the preparation of [18F]fluorinated aromatic amino acids

    International Nuclear Information System (INIS)

    Wadsak, Wolfgang; Wirl-Sagadin, Barbara; Mitterhauser, Markus; Mien, Leonhard-Key; Ettlinger, Dagmar E.; Keppler, Bernhard K.; Dudczak, Robert; Kletter, Kurt

    2006-01-01

    Nucleophilic aromatic substitution is a challenging task in radiochemistry. Therefore, a thorough evaluation and optimisation of this step is needed to provide a satisfactory tool for the routine preparation of [ 18 F]fluorinated aromatic amino acids. Two methods, already proposed elsewhere, were evaluated and improved. The yields for the radiofluorination were increased whereas activity loss during solid phase extraction was observed. Radiochemical yields for the two methods were 92.7±5.5% (method 1) and 92.1±12.3% (method 2) for conversion and 11.1±2.8% (method 1) and 34.8±0.6% (method 2) for purification, respectively. In total, we demonstrate an optimised method for the preparation of this important class of [ 18 F]fluorinated synthons for PET

  3. Solvent effects in the nucleophilic substitutions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate: trichloroethylene as solvent for stereoselective C- and O-glycosylations.

    Science.gov (United States)

    Kendale, Joanna C; Valentín, Elizabeth M; Woerpel, K A

    2014-07-18

    The selectivities of nucleophilic substitution reactions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate depend upon the reaction solvent. Polar solvents favor the formation of S(N)1 products, while nonpolar solvents favor S(N)2 products. Trichloroethylene was identified as the solvent most likely to give S(N)2 products in both C- and O-glycosylation reactions.

  4. Synthesis and reactivity of novel sulfur pentafluorides-Effect of the SF5 group on reactivity of nitrobenzenes in nucleophilic substitution

    Czech Academy of Sciences Publication Activity Database

    Beier, Petr

    2017-01-01

    Roč. 192, č. 2 (2017), s. 212-215 ISSN 1042-6507. [International Symposium on the Organic Chemistry of Sulfur (ISOCS) /27./. Jena, 26.07.2016-29.07.2016] Institutional support: RVO:61388963 Keywords : nucleophilic substitution * sulfur * fluorine * reaction rate Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 0.809, year: 2016

  5. Maleimide as an efficient nucleophilic partner in the aza-Morita-Baylis-Hillman reaction: synthesis of chiral 3-substituted-3-aminooxindoles.

    Science.gov (United States)

    Kumar, Akshay; Sharma, Vivek; Kaur, Jasneet; Kumar, Naveen; Chimni, Swapandeep Singh

    2015-05-28

    A highly enantioselective Morita-Baylis-Hillman reaction of maleimides with isatin derived ketimines has been developed to obtain enantiomerically enriched 3-substituted-3-aminooxindoles using β-isocupreidine as an organocatalyst. Maleimide acting as a nucleophile provides products with up to 99% ee.

  6. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions.

    Science.gov (United States)

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian; Bica, Katharina

    2016-05-21

    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions.

  7. Novel organophosphorus scaffolds of urease inhibitors obtained by substitution of Morita-Baylis-Hillman adducts with phosphorus nucleophiles.

    Science.gov (United States)

    Ntatsopoulos, Vassilis; Vassiliou, Stamatia; Macegoniuk, Katarzyna; Berlicki, Łukasz; Mucha, Artur

    2017-06-16

    The reactivity of Morita-Baylis-Hillman allyl acetates was employed to introduce phosphorus-containing functionalities to the side chain of the cinnamic acid conjugated system by nucleophilic displacement. The proximity of two acidic groups, the carboxylate and phosphonate/phosphinate groups, was necessary to form interactions in the active site of urease by recently described inhibitor frameworks. Several organophosphorus scaffolds were obtained and screened for inhibition of the bacterial urease, an enzyme that is essential for survival of urinary and gastrointestinal tract pathogens. α-Substituted phosphonomethyl- and 2-phosphonoethyl-cinnamate appeared to be the most potent and were further optimized. As a result, one of the most potent organophosphorus inhibitors of urease, α-phosphonomethyl-p-methylcinnamic acid, was identified, with K i  = 0.6 μM for Sporosarcina pasteurii urease. High complementarity to the enzyme active site was achieved with this structure, as any further modifications significantly decreased its affinity. Finally, this work describes the challenges faced in developing ligands for urease. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  8. One-pot regioselective synthesis of nitrophenyloxazolinyl styrene oxides by the Darzens reaction of vicarious nucleophilic substitution-formed carbanions of 2-dichloromethyl-4,4-dimethyloxazoline.

    Science.gov (United States)

    Florio, Saverio; Lorusso, Patrizia; Granito, Catia; Luisi, Renzo; Troisi, Luigino

    2004-07-23

    The vicarious nucleophilic substitution reaction of dichloromethyloxazoline 2 with nitrobenzene has been investigated. Treatment of 2 with t-BuOK followed by the addition of nitrobenzene leads to benzylic carbanions 4 or 9 depending upon the solvent used (DMSO, DMF, or THF). Subsequent treatment of 4 or 9 with aldehydes, in a Darzens-like reaction, furnishes very good yields of nitrophenyl oxazolinyloxiranes 8 and 11. 1,2-Dioxazolinyl-1,2-dinitrophenylethene 7 forms quantitatively when carbanion 4 is allowed to warm to room temperature in the absence of external electrophiles.

  9. New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+ as a Green Solid Catalyst

    Directory of Open Access Journals (Sweden)

    Lahouaria Medjdoub

    2016-08-01

    Full Text Available Nucleophilic substitution on hexachlorocyclotriphosphazene (HCCTP with allylamine in order to give hexa(allylaminocyclotriphosphazene (HACTP  is performed for the first time under mild conditions by using diethylether as solvent to replace benzene which is very toxic. The reaction time is reduced to half and also performed at room temperature but especially in the presence of an eco-catalyst called Maghnite-H+. This catalyst has a significant role in the industrial scale. In fact, the use of Maghnite is preferred for its many advantages: a very low purchase price compared to other catalysts, the easy removal of the reaction mixture. Then, Maghnite-H+ is became an excellent catalyst for many chemical reactions. The structure of HACTP synthesized in the presence of Maghnite-H+ to 5% by weight is confirmed by 1H-NMR, 13C-NMR, 31P-NMR (Nuclear magnetic resonance and FTIR (Fourier Transform Infrared spectroscopy. MALDI-TOF (Matrix-Assisted Laser Desorption/Ionisation-time-of-flight mass spectrometry is used to establish the molecular weight of HACTP which is 471 g/mol. DSC (Differential Scanning Calorimetery and TGA (Thermogravimetric Analysis show that HACTP is a crystalline product with a melting point of 88 °C. It is reactive after melting but is degraded from 230 °C. Copyright © 2016 BCREC GROUP. All rights reserved Received: 28th September 2015; Revised: 5th December 2015; Accepted: 4th January 2016 How to Cite: Medjdoub, L., Mohammed, B. (2016. New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+ as a Green Solid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 151-160 (doi:10.9767/bcrec.11.2.541.151-160 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.541.151-160

  10. Reaction of α-bromocyclopropyl phenyl ketones with lithium thiophenolate by a mechanism or latent nucleophilic substitution at the halogen atom

    International Nuclear Information System (INIS)

    Kulinkovich, O.G.; Tishchenko, I.G.; Sviridov, S.V.; Divak, V.A.

    1987-01-01

    The reaction of E-1-benzoyl-1-bromo-2-phenylcyclopropane with lithium thiophenolate in THF leads to the formation of E-1-benzoyl-2-phenyl-1-phenylthiocyclopropane. Phenyl α-phenylthiocyclopropyl ketones are also produced with good yields by the action of sodium thiophenolate on 7-endo-benzoyl-7-exo-bromobicyclo[4.1.0]-heptane, E-1-benzoyl-1-bromo-2-butylcyclopropane, and 1-benzoyl-1-bromocyclopropane, whereas Z-1-benzoyl-1-bromo-2-phenylcyclopropane undergoes reductive dehalogenation under analogous conditions. The stereochemical data and also the data on the composition of the products from the reaction in the presence of methanol indicate that the phenyl α-phenylthiocyclopropyl ketones are formed by a mechanism of latent nucleophilic substitution at the halogen atom in the initial α-bromocyclopropyl phenyl ketones. The PMR spectra of solutions of the substances in carbon tetrachloride or benzene were obtained on a Tesla BS-467A spectrometer at 60 MHz with HMDS as internal standard. The IR spectra of solutions of the substances in carbon tetrachloride were recorded on a Specord IR-75 spectrometer. The reactions were carried out in an atmosphere of dry argon

  11. Chiral phosphines in nucleophilic organocatalysis

    Directory of Open Access Journals (Sweden)

    Yumei Xiao

    2014-09-01

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

  12. Chemical dynamics simulations of X- + CH3Y → XCH3 + Y- gas-phase S(N)2 nucleophilic substitution reactions. Nonstatistical dynamics and nontraditional reaction mechanisms.

    Science.gov (United States)

    Manikandan, Paranjothy; Zhang, Jiaxu; Hase, William L

    2012-03-29

    Extensive classical chemical dynamics simulations of gas-phase X(-) + CH(3)Y → XCH(3) + Y(-) S(N)2 nucleophilic substitution reactions are reviewed and discussed and compared with experimental measurements and predictions of theoretical models. The primary emphasis is on reactions for which X and Y are halogen atoms. Both reactions with the traditional potential energy surface (PES), which include pre- and postreaction potential energy minima and a central barrier, and reactions with nontraditional PESs are considered. These S(N)2 reactions exhibit important nonstatistical atomic-level dynamics. The X(-) + CH(3)Y → X(-)---CH(3)Y association rate constant is less than the capture model as a result of inefficient energy transfer from X(-)+ CH(3)Y relative translation to CH(3)Y rotation and vibration. There is weak coupling between the low-frequency intermolecular modes of the X(-)---CH(3)Y complex and higher frequency CH(3)Y intramolecular modes, resulting in non-RRKM kinetics for X(-)---CH(3)Y unimolecular decomposition. Recrossings of the [X--CH(3)--Y](-) central barrier is important. As a result of the above dynamics, the relative translational energy and temperature dependencies of the S(N)2 rate constants are not accurately given by statistical theory. The nonstatistical dynamics results in nonstatistical partitioning of the available energy to XCH(3) +Y(-) reaction products. Besides the indirect, complex forming atomic-level mechanism for the S(N)2 reaction, direct mechanisms promoted by X(-) + CH(3)Y relative translational or CH(3)Y vibrational excitation are possible, e.g., the roundabout mechanism.

  13. Radiosynthesis of [131I]IAZGP via nucleophilic substitution and its biological evaluation as a hypoxia marker - is specific activity a factor influencing hypoxia-mapping ability of a hypoxia marker?

    International Nuclear Information System (INIS)

    Suehiro, Makiko; Burgman, Paul; Carlin, Sean; Burke, Sean; Yang Guangbin; Ouerfelli, Ouathek; Oehler-Janne, Christoph; O'Donoghue, Joseph; Ling, Clifton; Humm, John

    2009-01-01

    Introduction: The hypoxia marker IAZGP, 1-(6-deoxy-6-iodo-β-D-galactopyranosyl)-2-nitroimidazole, has been labeled with 123 I/ 124 I/ 125 I/ 131 I via iodine-radioiodine exchange, which gives the radiotracer in a specific activity of 10-90 MBq/μmol. We synthesized the same radiotracer possessing several hundred to thousand times higher specific activity (high-SA IAZGP) via nucleophilic substitution and compared its biological behavior with that of conventionally produced IAZGP (low-SA IAZGP) to determine if specific activity is a factor influencing cell uptake kinetics, biodistribution and intratumor microregional localization of the radiotracer. Methods: High-SA [ 131 I]IAZGP was prepared by substitution of the tosyl functionality with [ 131 I]iodide. In vitro uptake of high- and low-SA [ 131 I]IAZGP by HCT8 and HT29 cells was assessed in normoxic and hypoxic conditions. Biodistribution and intratumor localization of high- and low-SA [ 131 I]IAZGP were determined by injection into HT29 tumor-bearing mice. Results: The nucleophilic substitution reaction proceeded efficiently in acetonitrile at 150 o C, giving the final product in an average yield of 42% and an average specific activity of 30 GBq/μmol. In vitro, high-SA [ 131 I]IAZGP was incorporated into the tumor cells with similar kinetics and oxygen dependence to low-SA [ 131 I]IAZGP. In HT29 tumor-bearing mice, biodistributions of high- and low-SA [ 131 I]IAZGP were equivalent. Ex vivo autoradiography revealed heterogeneous intratumor localization of high-SA [ 131 I]IAZGP corresponding closely to distributions of other exogenous and endogenous hypoxia markers. Comparable microregional distribution patterns were observed with low-SA [ 131 I]IAZGP. Conclusions: Radiolabeled IAZGP produced via nucleophilic substitution is validated as an exogenous hypoxia marker. Specific activity does not appear to influence the in vivo hypoxia-mapping ability of the radiotracer.

  14. A critical study on borosilicate glassware and silica-based QMA's in nucleophilic substitution with [18F]fluoride: influence of aluminum, boron and silicon on the reactivity of [18F]fluoride.

    Science.gov (United States)

    Svadberg, A; Clarke, A; Dyrstad, K; Martinsen, I; Hjelstuen, O K

    2011-02-01

    Leachables of borosilicate glassware and silica-based anion exchange columns (QMAs) may influence nucleophilic substitution with [(18)F]fluoride ([(18)F]F(-)). Aluminum, boron and silicon, all constituents of borosilicate glass, were found as water soluble leachables in a typical PET synthesis setup. Relevant ranges of the leachable quantities were studied based on an experimental design, in which species of the three elements were added to the labeling of the precursor for anti-1-amino-3-[(18)F]fluorocyclobutyl-1-carboxylic acid ([(18)F]FACBC). Levels of 0.4-2 ppm aluminum as AlCl(3) had a strong negative influence on labeling yield while 4-20 ppm of boron as KBO(2) and 50-250 ppm of silicon as Na(2)SiO(3) did not have a significant impact. Interesting interaction effects between the elements were observed, where particularly KBO(2) reduced the negative effect of AlCl(3) on labeling yield. It can be concluded that leachables of borosilicate glassware easily can influence nucleophilic substitution with n.c.a. [(18)F]F(-) and give variable yields. Copyright © 2010. Published by Elsevier Ltd.

  15. A critical study on borosilicate glassware and silica-based QMA's in nucleophilic substitution with [{sup 18}F]fluoride: influence of aluminum, boron and silicon on the reactivity of [{sup 18}F]fluoride

    Energy Technology Data Exchange (ETDEWEB)

    Svadberg, A., E-mail: anders.svadberg@uit.n [University of Tromso, Institute of Pharmacy, Department of Pharmaceutics and Biopharmaceutics, N-9037 Tromso (Norway); Clarke, A.; Dyrstad, K.; Martinsen, I. [GE Healthcare MDx R and D, Nycoveien 2, NO-0401 Oslo (Norway); Hjelstuen, O.K. [University of Tromso, Institute of Pharmacy, Department of Pharmaceutics and Biopharmaceutics, N-9037 Tromso (Norway); GE Healthcare MDx R and D, Nycoveien 2, NO-0401 Oslo (Norway)

    2011-02-15

    Leachables of borosilicate glassware and silica-based anion exchange columns (QMAs) may influence nucleophilic substitution with [{sup 18}F]fluoride ([{sup 18}F]F{sup -}). Aluminum, boron and silicon, all constituents of borosilicate glass, were found as water soluble leachables in a typical PET synthesis setup. Relevant ranges of the leachable quantities were studied based on an experimental design, in which species of the three elements were added to the labeling of the precursor for anti-1-amino-3-[{sup 18}F]fluorocyclobutyl-1-carboxylic acid ([{sup 18}F]FACBC). Levels of 0.4-2 ppm aluminum as AlCl{sub 3} had a strong negative influence on labeling yield while 4-20 ppm of boron as KBO{sub 2} and 50-250 ppm of silicon as Na{sub 2}SiO{sub 3} did not have a significant impact. Interesting interaction effects between the elements were observed, where particularly KBO{sub 2} reduced the negative effect of AlCl{sub 3} on labeling yield. It can be concluded that leachables of borosilicate glassware easily can influence nucleophilic substitution with n.c.a. [{sup 18}F]F{sup -} and give variable yields.

  16. Use of fluorine-18 free of carrier for the synthesis of 2-[18 F]-fluoro-2-deoxy-d-glucose by nucleophilic substitution

    International Nuclear Information System (INIS)

    Garcia S, I.; Ramirez, F.M.

    1990-11-01

    Preliminary studies on the synthesis of 2 - [ 18 F]-fluoro-2-deoxy-d-glucose (2 - [ 18 F]-FDG) were carried out by means of the nucleophilic method proposed by K. Hamacher and the 18 F obtained in the Nuclear Reactor TRIGA Mark III of the Nuclear Center of Mexico. For the control of radiochemical quality it was used the chromatography technique in paper and silica gel with 4 solvent systems. The identification of the marked species with 18 F was carried out by means of comparison of its Rf with the Rf of the obtained not radioactive species, using the same synthesis method. (Author)

  17. Reaction of some ambident nucleophiles, thiourea, substituted thioureas, biuret and oxamide with uranyl nitrate and chloride and isolation of some novel adducts

    International Nuclear Information System (INIS)

    Bhattacharyya, R.G.; Doloi, N.C.

    1977-01-01

    The ambident nucleophiles, viz. thiourea (Tu), monobenzoylthiourea (MBTu), oxalythiourea (OxTu), biuret (BuH 2 ) and oxamide (OxamH 2 ) react with UO 2 (NO 3 ) 2 6H 2 O in acetonitrile medium via base hydrolysis affording hydroxo complexes of the types UO 2 (OH) 2 Tu, UO 2 (OH) 2 MBTu, UO 2 (OH) 2 OxTu, UO 2 (OH) 2 3BuH 2 and UO 2 (OH) 2 (OxamH 2 ) 2 . However UO 2 Cl 2 reacts with Tu and BuH 2 forming adducts UO 2 Cl 2 Tu and UO 2 Cl 2 BuH 2 respectively. The IR spectra reveal that thiourea is S-bonded to uranium and in the chloro complex biuret behaves as oxygen donor chelate while in the other case it is probably acting as a unidentate ligand. Oxamide behaves as an oxygen donor neutral chelating ligand. (author)

  18. Selection rules for bimolecular photoabsorption

    Science.gov (United States)

    Andrews, David L.; Bittner, Alexander M.

    1992-09-01

    Bimolecular photoabsorption is a term describing processes in which two molecules or other chemically distinct entities undergo simultaneous excitation to electronic excited states, the energy being provided by the absorption of one or more laser photons. These processes have previously been referred to as synergistic, cooperative, or mean-frequency absorption. This paper introduces a new terminology for the description of such phenomena and provides an overview of the features associated with bimolecular processes involving the absorption of one, two or three photons from a single laser beam. Emphasis is placed on a detailed symmetry analysis based on irreducible tensors, leading to a comprehensive treatment of the selection rules for all the major molecular point groups. Finally, attention is drawn to some systems in which these effects have been detected, and others in which they might be expected to occur.

  19. Kinetic study on SNAr reactions of 1-(Y-Substituted-phenoxy)-2,4-dinitrobenzenes with azide ion: Effect of changing nucleophile from hydroxide to zzide ion on reaction mechanism and reactivity

    International Nuclear Information System (INIS)

    Seo, Hyeon Ok; Kim, Min Young; Han, So Yeop; Um, Ik Hwan

    2015-01-01

    Second-order rate constants (k N3− ) for SNAr reactions of 1-(Y-substituted-phenoxy)-2,4-dinitrobenzenes (2a–2h) with math formula in 80 mol % H 2 O/20 mol % DMSO at 25.0 ± 0.1 °C have been measured spectrophotometrically. The Brønsted-type plot is linear with β lg = −0.38. The Hammett plots correlated with math formula and math formula constants exhibit highly scattered points. In contrast, the Yukawa–Tsuno plot results in an excellent linear correlation with ρ Y = 1.02 and r = 0.51, indicating that a negative charge develops partially on the O atom of the leaving Y-substituted-phenoxy moiety in the transition state. Accordingly, the reactions have been concluded to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs in the rate-determining step. Comparison of k N3− with the k OH− values reported previously for the corresponding reactions with OH − has revealed that math formula is only 6- to 26-fold less reactive than OH − toward substrates 2a–2h, although the former is over 11 pK a units less basic than the latter. Solvation and polarizability effects have been suggested to be responsible for the unusual reactivity shown by math formula and OH − . Effects of changing nucleophile from OH − to N 3 − on reaction mechanism and reactivity are discussed in detail

  20. A unique heterogeneous nucleophilic catalyst comprising methylated nitrogen-substituted porous silica provides high product selectivity for the Morita-Baylis-Hillman reaction.

    Science.gov (United States)

    Furukawa, Yutaro; Ogura, Masaru

    2014-01-08

    Methylated nitrogen-substituted microporous and mesoporous silica exhibited almost the same catalytic performance as that of a conventional homogeneous base catalyst. They also demonstrated unexpectedly high product selectivity for the Morita-Baylis-Hillman reaction of formaldehyde with methyl acrylate at high temperatures.

  1. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  2. Organocalcium-mediated nucleophilic alkylation of benzene.

    Science.gov (United States)

    Wilson, Andrew S S; Hill, Michael S; Mahon, Mary F; Dinoi, Chiara; Maron, Laurent

    2017-12-01

    The electrophilic aromatic substitution of a C-H bond of benzene is one of the archetypal transformations of organic chemistry. In contrast, the electron-rich π-system of benzene is highly resistant to reactions with electron-rich and negatively charged organic nucleophiles. Here, we report that this previously insurmountable electronic repulsion may be overcome through the use of sufficiently potent organocalcium nucleophiles. Calcium n -alkyl derivatives-synthesized by reaction of ethene, but-1-ene, and hex-1-ene with a dimeric calcium hydride-react with protio and deutero benzene at 60°C through nucleophilic substitution of an aromatic C-D/H bond. These reactions produce the n- alkyl benzenes with regeneration of the calcium hydride. Density functional theory calculations implicate an unstabilized Meisenheimer complex in the C-H activation transition state. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  3. XVIII Mendeleev congress on general and applied chemistry. Summaries of reports in five volumes. Volume 5. IV Russian-French symposium Supramolecular systems in chemistry and biology. II Russian-Indian symposium on organic chemistry. International symposium on present-day radiochemistry Radiochemistry: progress and prospects. International symposium Green chemistry, stable evolution and social responsibility of chemists. Symposium Nucleophilic hydrogen substitution in aromatic systems and related reactions

    International Nuclear Information System (INIS)

    2007-01-01

    The 5 volume of the XVIII Mendeleev congress on general and applied chemistry includes summaries of reports on the subjects of sypramolecular systems in chemistry and biology, organic chemistry, modern radiochemistry, green chemistry - development and social responsibility of chemists, nucleophilic hydrogen substitution in aromatic systems and related chemical reactions [ru

  4. Kinetic study on alkaline hydrolysis of Y-substituted phenyl X-substituted benzenesulfonates: Effects of changing nucleophile from azide to hydroxide ion on reactivity and transition-state structure

    International Nuclear Information System (INIS)

    Moon, Ji Hyun; Kim, Min Young; Han, So Yeop; Um, Ik Hwan

    2015-01-01

    Second-order rate constants (math formula) for alkaline hydrolysis of 2,4-dinitrophenyl X-substituted benzenesulfonates (1a–1f) and Y-substituted phenyl 4-nitrobezenesulfonates (2a–2g) have been measured spectrophotometrically. Comparison of math formula with the math formula values reported previously for the corresponding reactions with math formula has revealed that OH [BOND] is only 10 3 -fold more reactive than math formula, although the former is 11 pK a units more basic than the latter. The Yukawa–Tsuno plot for the reactions of 1a–1f results in an excellent linear correlation with ρ X  = 2.09 and r = 0.41. The Brønsted-type plot for the reactions of 2a–2g is linear with β lg  = −0.51, which is typical for reactions reported to proceed through a concerted mechanism. The Yukawa–Tsuno plot for the reactions of 2a–2g exhibits excellent linearity with ρ Y  = 1.85 and r = 0.25, indicating that a partial negative charge develops on the O atom of the leaving group in the transition state. Thus, the alkaline hydrolysis of 1a–1f and 2a–2g has been concluded to proceed through a concerted mechanism. Comparison of the ρ X and β lg values for the reactions with math formula ions suggests that the reactions with hydroxide ion proceed through a tighter transition-state structure than those with azide ion

  5. Conjugate Addition of Nucleophiles to the Vinyl Function of 2-Chloro-4-vinylpyrimidine Derivatives

    Directory of Open Access Journals (Sweden)

    Lucjan Strekowski

    2010-03-01

    Full Text Available Conjugate addition reaction of various nucleophiles across the vinyl group of 2-chloro-4-vinylpyrimidine, 2-chloro-4-(1-phenylvinylpyrimidine and 2-chloro-4-vinylquinazoline provides the corresponding 2-chloro-4-(2-substituted ethylpyrimidines and 2-chloro-4-(2-substituted ethylquinazolines. Treatment of these products, without isolation, with N-methylpiperazine results in nucleophilic displacement of chloride and yields the corresponding 2,4-disubstituted pyrimidines and quinazolines.

  6. Nucleophilic Addition of Reactive Dyes on Amidoximated Acrylic Fabrics

    Science.gov (United States)

    El-Shishtawy, Reda M.; El-Zawahry, Manal M.; Abdelghaffar, Fatma; Ahmed, Nahed S. E.

    2014-01-01

    Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% owf of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics. PMID:25258720

  7. Nucleophilic addition of reactive dyes on amidoximated acrylic fabrics.

    Science.gov (United States)

    El-Shishtawy, Reda M; El-Zawahry, Manal M; Abdelghaffar, Fatma; Ahmed, Nahed S E

    2014-01-01

    Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% of of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics.

  8. In vivo biodistribution of no-carrier-added 6-18F-fluoro-3,4-dihydroxy-L-phenylalanine (18F-DOPA), produced by a new nucleophilic substitution approach, compared with carrier-added 18F-DOPA, prepared by conventional electrophilic substitution.

    Science.gov (United States)

    Kuik, Willem-Jan; Kema, Ido P; Brouwers, Adrienne H; Zijlma, Rolf; Neumann, Kiel D; Dierckx, Rudi A J O; DiMagno, Stephen G; Elsinga, Philip H

    2015-01-01

    A novel synthetic approach to 6-(18)F-fluoro-3,4-dihydroxy-L-phenylalanine ((18)F-DOPA), involving the nucleophilic substitution of a diaryliodonium salt precursor with non-carrier-added (18)F-fluoride, yielded a product with a specific activity that was 3 orders of magnitude higher than the product of the conventional synthesis method, involving an electrophilic substitution of a trialkylstannane precursor with (18)F2. We performed a direct comparison of high- and low-specific-activity (18)F-DOPA in a neuroendocrine tumor model to determine whether this difference in specific activity has implications for the biologic behavior and imaging properties of (18)F-DOPA. (18)F-DOPA was produced via the novel synthesis method, yielding (18)F-DOPA-H with a high specific activity (35,050 ± 4,000 GBq/mmol). This product was compared in several experiments with conventional (18)F-DOPA-L with a low specific activity (11 ± 2 GBq/mmol). In vitro accumulation experiments with the human pancreatic neuroendocrine tumor cell line BON-1 were performed at both 0 °C and 37 °C and at 37 °C in the presence of pharmacologic inhibitors of proteins involved in the uptake mechanism of (18)F-DOPA. Small-animal PET experiments were performed in athymic nude mice bearing a BON-1 tumor xenograft. At 37 °C, the uptake of both (18)F-DOPA-H and (18)F-DOPA-L did not differ significantly during a 60-min accumulation experiment in BON-1 cells. At 0 °C, the uptake of (18)F-DOPA-L was significantly decreased, whereas the lower temperature did not alter the uptake of (18)F-DOPA-H. The pharmacologic inhibitors carbidopa and tetrabenazine also revealed differential effects between the 2 types of (18)F-DOPA in the 60-min accumulation experiment. The small-animal PET experiments did not show any significant differences in distribution and metabolism of (18)F-DOPA-H and (18)F-DOPA-L in carbidopa-pretreated mice. The advantages of the novel synthesis of (18)F-DOPA, which relies on nucleophilic

  9. Theoretical study on the nucleophilic fluoroalkylation of propylene oxide with fluorinated sulfones

    Directory of Open Access Journals (Sweden)

    Han Ling-Li

    2013-01-01

    Full Text Available The path of nucleophilic fluoroalkylation reaction of propylene oxide with PhSO2CYF- (Y=F,H, and PhSO2, respectively in gas phase and in Et2O solvent were studied theoretically. The nucleophilic fluoroalkylation of propylene oxide with fluorinated carbanions was probed by the reactivity comparison between (benzenesulfonylmonofluoromethyl anion (PhSO2CHF-, (benzenesulfonyl difluoromethyl anion (PhSO2CF2-, and bis(benzenesul-fonyl monofluoromethyl anion ((PhSO22CF-. The nucleophilicity reactivity order of PhSO2CYF- (Y = F, H, and PhSO2 is [(PhSO22CF-] > PhSO2CHF- > PhSO2CF2-, which indicates that introducing another electron-withdrawing benzenesulfonyl group is an effective way to significantly increase the nucleophilicity of the fluorinate carbanions. For comparison, we also studied the nucleophilic addition reactions of propylene oxide with chlorine substituted carbanion PhSO2CHCl-. The calculated results show that the nucleophilicity of PhSO2CYF- is better than that of PhSO2CHCl- for the ring opening reaction with propylene oxide. The calculated results are in good agreement with the available experiments.

  10. Convergent synthesis of 6-substituted phenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Lysén, M.; Kristensen, Jesper Langgaard; Vedsø, P.

    2002-01-01

    Chemical equation presented The addition of organometallic derivatives to the cyano group of 2-(2-fluorophenyl)benzonitrile followed by intramolecular nucleophilic substitution produces 6-substituted phenanthridines. Alkyllithiums, aryllithiums, and sterically nondemanding lithium amides reacted ...

  11. Aliphatic Nucleophilic Radio-fluorination

    International Nuclear Information System (INIS)

    Roeda, D.; Dolle, F.

    2010-01-01

    In this review we are looking at some aspects of nucleophilic aliphatic radio-fluorination, notably the labelled fluoride source, design aspects, the leaving group and the solvent. It should be clear that there is more to this branch of radiolabelling than one would suspect from the frequently used standard tosylate replacement with kryptofix/[ 18 F]fluoride in acetonitrile or DMSO. Competitive elimination can be a serious problem that can affect both yield and purification. De-protection of sensitive groups after radiolabelling and its possible side reactions can complicate purification. The right choice of leaving group and protecting groups may be crucial. Newer developments such as the use of tertiary alcohols or ionic liquids as solvents, long-chain poly-fluorinated sulphonate leaving groups facilitating fluorous solid phase extraction, or immobilisation of the precursor on a solid phase support may help to solve these problems, for example the longstanding problems with [ 18 F]FLT, whereas older concepts such as certain cyclic reactive entities for ring opening or even an abandoned reagent as [ 18 F]DAST should not be forgotten. (authors)

  12. Chemiluminescent detection systems of horseradish peroxidase employing nucleophilic acylation catalysts.

    Science.gov (United States)

    Marzocchi, Ettore; Grilli, Stefano; Della Ciana, Leopoldo; Prodi, Luca; Mirasoli, Mara; Roda, Aldo

    2008-06-15

    The light output of the peroxidase-catalyzed luminol chemiluminescent oxidation reaction can be greatly increased by incorporating different enhancers. Such an increase is attributed to the preferential oxidation of the enhancer by peroxidase intermediates and the rapid formation of enhancer radicals that, in turn, quickly oxidize luminol to its radical anion. These enhancers, which include substituted phenols, substituted boronic acids, indophenols, and N-alkyl phenothiazines, behave as electron transfer mediators. A further, very significant increase in light output was also observed by the addition of nucleophilic acylation catalyst to the enhancer/luminol/oxidant substrate. The effect of the new component is general and applicable to many of the known enhancers but is much more remarkable in association with phenothiazine enhancers (up to 10-fold light output). The addition of a nucleophilic acylation catalyst to these substrates lowered the limit of detection for horseradish peroxidase from 50 to 8 amol. Similar improvements were observed in "sandwich" enzyme-linked immunosorbent assays and Western blot assays.

  13. Analysis of Brownian Dynamics Simulations of Reversible Bimolecular Reactions

    KAUST Repository

    Lipková, Jana

    2011-01-01

    A class of Brownian dynamics algorithms for stochastic reaction-diffusion models which include reversible bimolecular reactions is presented and analyzed. The method is a generalization of the λ-bcȳ model for irreversible bimolecular reactions which was introduced in [R. Erban and S. J. Chapman, Phys. Biol., 6(2009), 046001]. The formulae relating the experimentally measurable quantities (reaction rate constants and diffusion constants) with the algorithm parameters are derived. The probability of geminate recombination is also investigated. © 2011 Society for Industrial and Applied Mathematics.

  14. Construction of a bimolecular fluorescence complementation (BiFC ...

    African Journals Online (AJOL)

    Protein–protein interactions are essential for signal transduction in cells. Bimolecular fluorescence complementation (BiFC) is a novel technology that utilises green fluorescent proteins to visualize protein–protein interactions and subcellular protein localisation. BiFC based on pSATN vectors are a good system for ...

  15. DFT analysis of the nucleophilicity of substituted pyridines and ...

    Indian Academy of Sciences (India)

    Dell

    ... Nσ, Nσ-calc, Nσ-pred indicate observed, calculated, predicted value for Hammett substituent constant and indicates mean of observed Hammett substituent constant. Partial least square (PLS) regression were performed to generate R2 and leave one out cross validated R2 (LOO-Q2) using statistical software MINITAB.3.

  16. Substituted quinolinones. Part 17: Some nucleophilic reactions with ...

    Indian Academy of Sciences (India)

    Author Affiliations. Mohamed Abass1 El-Hussain A Mohamed1 Aisha S Mayas2 Akram H Ibrahim3. Department of Chemistry, Faculty of Education, Ain Shams University, Roxy, Heliopolis 11757, Cairo, Egypt; Department of Chemistry, Faculty of Education, Sana'a University, Sana'a, Yemen; Curriculum Development Center ...

  17. DFT analysis of the nucleophilicity of substituted pyridines and ...

    Indian Academy of Sciences (India)

    Dorn F, Pfiffner A and Schlageter M 1991 ACS Sympo- sium Series 443 506. 6. Lee L F, Stikes G L, Normansell J E, Molyneaux J M,. Sing L Y L, Chupp J P, Parrish S K and Kaufmann J E. 1991 ACS Symposium Series 443 195. 7. Peine G, Hoffmann P, Seifert G and Schilling G 1985. Biochem. Physiol. Pflanzen 180 1. 8.

  18. DFT analysis of the nucleophilicity of substituted pyridines and ...

    Indian Academy of Sciences (India)

    Wu J, Kang S, Song B, Hu D, He M, Jin L and Yang S. 2012 Chem. Central J. 62 8. 4. Di X, Liu Y, Liu Y, Yu X, Xiao H, Tian X and Gao R. 2007 Pesticide Biochem. Physiol. 89 81. 5. Dorn F, Pfiffner A and Schlageter M 1991 ACS Sympo- sium Series 443 506. 6. Lee L F, Stikes G L, Normansell J E, Molyneaux J M,. Sing L Y L ...

  19. ESI-MS Investigation of an Equilibrium between a Bimolecular Quadruplex DNA and a Duplex DNA/RNA Hybrid.

    Science.gov (United States)

    Birrento, Monica L; Bryan, Tracy M; Samosorn, Siritron; Beck, Jennifer L

    2015-07-01

    Electrospray ionization mass spectrometry (ESI-MS) conditions were optimized for simultaneous observation of a bimolecular qDNA and a Watson-Crick base-paired duplex DNA/RNA hybrid. The DNA sequence used was telomeric DNA, and the RNA contained the template for telomerase-mediated telomeric DNA synthesis. Addition of RNA to the quadruplex DNA (qDNA) resulted in formation of the duplex DNA/RNA hybrid. Melting profiles obtained using circular dichroism spectroscopy confirmed that the DNA/RNA hybrid exhibited greater thermal stability than the bimolecular qDNA in solution. Binding of a 13-substituted berberine (1) derivative to the bimolecular qDNA stabilized its structure as evidenced by an increase in its stability in the mass spectrometer, and an increase in its circular dichroism (CD) melting temperature of 10°C. The DNA/RNA hybrid did not bind the ligand extensively and its thermal stability was unchanged in the presence of (1). The qDNA-ligand complex resisted unfolding in the presence of excess RNA, limiting the formation of the DNA/RNA hybrid. Previously, it has been proposed that DNA secondary structures, such as qDNA, may be involved in the telomerase mechanism. DNA/RNA hybrid structures occur at the active site of telomerase. The results presented in the current work show that if telomeric DNA was folded into a qDNA structure, it is possible for a DNA/RNA hybrid to form as is required during template alignment. The discrimination of ligand (1) for binding to the bimolecular qDNA over the DNA/RNA hybrid positions it as a useful compound for probing the role(s), if any, of antiparallel qDNA in the telomerase mechanism.

  20. NUCHLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN

    Directory of Open Access Journals (Sweden)

    Bambang Purwono

    2010-06-01

    Full Text Available The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded  93.28%. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyanomethylbenzaldehyde in 54.39% yield, with methoxyde ion obtained  4-hidroxy- 3-methoxy-5-(methoxy-methyl-benzaldehide in 67.80% yield. The nucleophilic substitution reaction showed that substituen of trimethylamino quaternary Mannich base can act as a good leaving on nucleophilic reaction substitutions.   Keywords: Mannich Reaction, Vanillin, nucleophilic substitution.

  1. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.

    2013-03-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  2. Nucleophilic difluoromethylation and difluoromethylenation of aldehydes

    Czech Academy of Sciences Publication Activity Database

    Beier, Petr; Alexandrova, Anastasia; Zibinsky, M.; Prakash, G. K. S.

    2008-01-01

    Roč. 64, č. 49 (2008), s. 10977-10985 ISSN 0040-4020 R&D Projects: GA ČR GP203/08/P310 Institutional research plan: CEZ:AV0Z40550506 Keywords : difluoromethylation * difluoromethylenation * phosphonate * nucleophilic addition Subject RIV: CC - Organic Chemistry Impact factor: 2.897, year: 2008

  3. One-pot functionalisation of N-substituted tetrahydroisoquinolines by photooxidation and tunable organometallic trapping of iminium intermediates.

    Science.gov (United States)

    Barham, Joshua P; John, Matthew P; Murphy, John A

    2014-01-01

    Nucleophilic trapping of iminium salts generated via oxidative functionalisation of tertiary amines is well established with stabilised carbon nucleophiles. The few reports of organometallic additions have limited scope of substrate and organometallic nucleophile. We report a novel, one-pot methodology that functionalises N-substituted tetrahydroisoquinolines by visible light-assisted photooxidation, followed by trapping of the resultant iminium ions with organometallic nucleophiles. This affords 1,2-disubstituted tetrahydroisoquinolines in moderate to excellent yields.

  4. Theory of Crowding Effects on Bimolecular Reaction Rates.

    Science.gov (United States)

    Berezhkovskii, Alexander M; Szabo, Attila

    2016-07-07

    An analytical expression for the rate constant of a diffusion-influenced bimolecular reaction in a crowded environment is derived in the framework of a microscopic model that accounts for: (1) the slowdown of diffusion due to crowding and the dependence of the diffusivity on the distance between the reactants, (2) a crowding-induced attractive short-range potential of mean force, and (3) nonspecific reversible binding to the crowders. This expression spans the range from reaction to diffusion control. Crowding can increase the reaction-controlled rate by inducing an effective attraction between reactants but decrease the diffusion-controlled rate by reducing their relative diffusivity.

  5. Experimental Determination of Gas Phase Thermodynamic Properties of Bimolecular Complexes

    Science.gov (United States)

    Hansen, Anne S.; Maroun, Zeina; Mackeprang, Kasper; Kjaergaard, Henrik G.

    2016-06-01

    Accurate determination of the atmospheric abundance of hydrogen bound bimolecular complexes is necessary, as hydrogen bonds are partly responsible for the formation and growth of aerosol particles. The abundance of a complex is related to the Gibbs free energy of complex formation (Δ G), which is often obtained from quantum chemical calculations that rely on calculated values of the enthalpy (Δ H) and entropy (Δ S) of complex formation. However, calculations of Δ H and in particular Δ S are associated with large uncertainties, and accurate experimental values are therefore crucial for theoretical benchmarking studies. Infrared measurements of gas phase hydrogen bound complexes were performed in the 300 to 373 K range, and lead to a purely experimental determination of Δ H using the van't Hoff equation. Equilibrium constants were determined by combining an experimental and calculated OH-stretching intensity, from which values of Δ G and hence Δ S could be determined. Thus we can determine Δ G, Δ H and Δ S for a bimolecular complex. We find that in the 300 to 373 K temperature range the determined Δ H and Δ S values are independent of temperature.

  6. Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions.

    Science.gov (United States)

    Morita, Yuya; Yamamoto, Tomohiro; Nagai, Hideoki; Shimizu, Yohei; Kanai, Motomu

    2015-06-10

    The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carboxylic acids with BH3·SMe2, after which the acids are able to act as carbon nucleophiles, i.e. enolates, in Mannich-type reactions. This reaction proceeds with a mild organic base (DBU) and exhibits high levels of functional group tolerance. The boron catalyst is highly chemoselective toward the COOH group, even in the presence of other carbonyl moieties, such as amides, esters, or ketones. Furthermore, this catalytic method can be extended to highly enantioselective Mannich-type reactions by using a (R)-3,3'-I2-BINOL-substituted boron catalyst.

  7. Use of fluorine-18 free of carrier for the synthesis of 2-[{sup 18} F]-fluoro-2-deoxy-d-glucose by nucleophilic substitution; Uso del fluor-18 libre de portador para la sintesis de la 2-[{sup 18} F]-fluoro-2-deoxi-d-glucosa por sustitucion nucleofilica

    Energy Technology Data Exchange (ETDEWEB)

    Garcia S, I.; Ramirez, F.M

    1990-11-15

    Preliminary studies on the synthesis of 2 - [{sup 18} F]-fluoro-2-deoxy-d-glucose (2 - [{sup 18} F]-FDG) were carried out by means of the nucleophilic method proposed by K. Hamacher and the {sup 18} F obtained in the Nuclear Reactor TRIGA Mark III of the Nuclear Center of Mexico. For the control of radiochemical quality it was used the chromatography technique in paper and silica gel with 4 solvent systems. The identification of the marked species with {sup 18} F was carried out by means of comparison of its Rf with the Rf of the obtained not radioactive species, using the same synthesis method. (Author)

  8. RPMDRATE: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    Science.gov (United States)

    Suleimanov, Yu. V.; Allen, J. W.; Green, W. H.

    2013-03-01

    We present RPMDRATE, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH4, OH+CH4 and H+C2H6 reactions. Catalogue identifier: AENW_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AENW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: MIT license No. of lines in distributed program, including test data, etc.: 94512 No. of bytes in distributed program, including test data, etc.: 1395674 Distribution format: tar.gz Programming language: Fortran 90/95, Python (version 2.6.x or later, including any version of Python 3, is recommended). Computer: Not computer specific. Operating system: Any for which Python, Fortran 90/95 compiler and the required external routines are available. Has the code been vectorized or parallelized?: The program can efficiently utilize 4096+ processors, depending on problem and available computer. At low temperatures, 110 processors are reasonable for a typical umbrella integration run with an analytic potential energy function and gradients on the latest x86-64 machines.

  9. NUCHLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN

    OpenAIRE

    Purwono, Bambang; Daruningsih, Estiana E.P

    2010-01-01

    The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded  93.28%. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyano)methylbenzaldehyde in 54.39% yield...

  10. Reactivity Studies of 2,6-Ditriazolylpurine Nucleosides with Nucleophiles

    OpenAIRE

    Kovaļovs, A; Novosjolova, I; Bizdēna, Ē; Turks, M

    2012-01-01

    Reaction of 2,6-ditriazolylpurine nucleosides with nucleophiles is mild and efficient route to C6 derivatization of purine base. To explore scope and limitations of the method, we studied reactivity of various N- and S-nucleophiles as well as kinetics for selected reactions.

  11. Activation of dinitrogen-derived hafnium nitrides for nucleophilic N-C bond formation with a terminal isocyanate.

    Science.gov (United States)

    Semproni, Scott P; Chirik, Paul J

    2013-12-02

    Better by Hf: Anion coordination to a bridging hafnocene nitride complex, prepared from CO-induced N2 cleavage, increases the nucleophilicity of the nitrogen atom, thus promoting additional NC bond formation with a typically inert terminal isocyanate ligand. This cascade sequence allows synthesis of otherwise challenging mono-substituted ureas using N2 , CO, and an appropriate electrophile. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    International Nuclear Information System (INIS)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound → bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN - , NCO - and NCS - . Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH 3 0H,F + C 2 H 5 OH,F + OH and F + H 2 . A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O( 3 P, 1 D) + HF and F + H 2 . The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H 2 system, comparisons with three-dimensional quantum calculations are made

  13. Very Low Rate Constants of Bimolecular CO Adsorption on Anionic Gold Clusters: Implications for Catalytic Activity

    Czech Academy of Sciences Publication Activity Database

    Balteanu, I.; Balaj, O. P.; Fox, B. S.; Beyer, M. K.; Bastl, Zdeněk; Bondybey, V. E.

    2003-01-01

    Roč. 5, - (2003), s. 1213-1218 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z4040901 Keywords : bimolecular * adsorption * catalytic activity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.959, year: 2003

  14. Olefination reactions of phosphorus-stabilized carbon nucleophiles.

    Science.gov (United States)

    Gu, Yonghong; Tian, Shi-Kai

    2012-01-01

    A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

  15. Perspective: Vibrational-induced steric effects in bimolecular reactions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Kopin, E-mail: kliu@po.iams.sinica.edu.tw [Institute of Atomic and Molecular Sciences (IAMS), Academia Sinica, P.O. Box 23-166, Taipei 10617, Taiwan (China)

    2015-02-28

    The concept of preferred collision geometry in a bimolecular reaction is at the heart of reaction dynamics. Exemplified by a series of crossed molecular beam studies on the reactions of a C–H stretch-excited CHD{sub 3}(v{sub 1} = 1) with F, Cl, and O({sup 3}P) atoms, two types of steric control of chemical reactivity will be highlighted. A passive control is governed in a reaction with strong anisotropic entry valley that can significantly steer the incoming trajectories. This disorientation effect is illustrated by the F and O({sup 3}P) + CHD{sub 3}(v{sub 1} = 1) reactions. In the former case, the long-range anisotropic interaction acts like an optical “negative” lens by deflecting the trajectories away from the favored transition-state geometry, and thus inhibiting the bond rupture of the stretch-excited CHD{sub 3}. On the contrary, the interaction between O({sup 3}P) and CHD{sub 3}(v{sub 1} = 1) behaves as a “positive” lens by funneling the large impact-parameter collisions into the cone of acceptance, and thereby enhances the reactivity. As for reactions with relatively weak anisotropic interactions in the entry valley, an active control can be performed by exploiting the polarization property of the infrared excitation laser to polarize the reactants in space, as demonstrated in the reaction of Cl with a pre-aligned CHD{sub 3}(v{sub 1} = 1) reactant. A simpler case, the end-on versus side-on collisions, will be elucidated for demonstrating a means to disentangle the impact-parameter averaging. A few general remarks about some closely related issues, such as mode-, bond-selectivity, and Polanyi’s rules, are made.

  16. Examination of Pyridazine as a Possible Scaffold for Nucleophilic Catalysis.

    Science.gov (United States)

    Tamaki, Airi; Kojima, Satoshi; Yamamoto, Yohsuke

    2016-10-07

    Pyridazines with amino groups positioned para to each aromatic ring nitrogen and fixed in six-membered rings were prepared. The representative symmetric amino N-Et derivative was found to slightly exceed DMAP in catalytic activity in the acetylation reaction of a tertiary alcohol in C 6 D 6 . Nucleophilicity eclipsing that of DMAP was established in competitive reactions using phenacyl bromide as the electrophile, and the unsymmetric N-Et derivative was revealed to have even higher nucleophilicity.

  17. Oxidative nucleophilic aromatic amination of nitrobenzenes

    Czech Academy of Sciences Publication Activity Database

    Khutorianskyi, Viktor V.; Sonawane, Manoj R.; Pošta, Martin; Klepetářová, Blanka; Beier, Petr

    2016-01-01

    Roč. 52, č. 45 (2016), s. 7237-7240 ISSN 1359-7345 R&D Projects: GA ČR GAP207/12/0072 Institutional support: RVO:61388963 Keywords : C-H amination * bond formation * substitution Subject RIV: CC - Organic Chemistry Impact factor: 6.319, year: 2016

  18. Photoinduced bimolecular electron transfer kinetics in small unilamellar vesicles

    International Nuclear Information System (INIS)

    Choudhury, Sharmistha Dutta; Kumbhakar, Manoj; Nath, Sukhendu; Pal, Haridas

    2007-01-01

    Photoinduced electron transfer (ET) from N,N-dimethylaniline to some coumarin derivatives has been studied in small unilamellar vesicles (SUVs) of the phospholipid, DL-α-dimyristoyl-phosphatidylcholine, using steady-state and time-resolved fluorescence quenching, both below and above the phase transition temperature of the vesicles. The primary interest was to examine whether Marcus inversion [H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4894 (1986)] could be observed for the present ET systems in these organized assemblies. The influence of the topology of SUVs on the photophysical properties of the reactants and consequently on their ET kinetics has also been investigated. Absorption and fluorescence spectral data of the coumarins in SUVs and the variation of their fluorescence decays with temperature indicate that the dyes are localized in the bilayer of the SUVs. Time-resolved area normalized emission spectra analysis, however, reveals that the dyes are distributed in two different microenvironments in the SUVs, which we attribute to the two leaflets of the bilayer, one toward bulk water and the other toward the inner water pool. The microenvironments in the two leaflets are, however, not indicated to be that significantly different. Time-resolved anisotropy decays were biexponential for all the dyes in SUVs, and this has been interpreted in terms of the compound motion model according to which the dye molecules can experience a fast wobbling-in-cone type of motion as well as a slow overall rotating motion of the cone containing the molecule. The expected bimolecular diffusion-controlled rates in SUVs, as estimated by comparing the microviscosities in SUVs (determined from rotational correlation times) and that in acetonitrile solution, are much slower than the observed fluorescence quenching rates, suggesting that reactant diffusion (translational) does not play any role in the quenching kinetics in the present systems. Accordingly, clear inversions are

  19. Nucleophilic targets in carcinogenesis, mutagenesis and chemotherapy of cancer.

    Science.gov (United States)

    Raikov, Z D; Christova-Georgieva, N I; Raikova, E T

    1987-01-01

    A hypothesis is suggested, which emphasizes the role in carcinogenesis of the attack on low molecular nucleophilic substances (LMN) by electrophilic agents - chemical carcinogens, phisical factors, and antitumor alkylating agents. The significance of the degree of nucleophilicity (electronic charge, order of bonds, index of valence) as a locus minoris resistentiae of the LMN in the electrophilic attack on the latter is emphasized as well as the probable role of the hydrogenated pteridines in influencing carcinogenesis by means of ascorbate, tocopherol, SH-containing compounds etc. In support of this hypothesis the preference of electrophilic agents (derivatives of nitrogen mustard and nitrosoureas) for the places with highest degree of nucleophilicity as targets, in experiments in vitro with nucleic bases and pteridines is emphasized.

  20. Amide synthesis by nucleophilic attack of vinyl azides.

    Science.gov (United States)

    Zhang, Feng-Lian; Wang, Yi-Feng; Lonca, Geoffroy Hervé; Zhu, Xu; Chiba, Shunsuke

    2014-04-22

    A method for the synthesis of amide-containing molecules was developed using vinyl azides as an enamine-type nucleophile towards carbon electrophiles, such as imines, aldehydes, and carbocations that were generated from alcohols in the presence of BF3 ⋅OEt2 . After nucleophilic attack of the vinyl azide, a substituent of the resulting iminodiazonium ion intermediate migrates to form a nitrilium ion, which is hydrolyzed to afford the corresponding amide. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Ring transformation of chromone-3-carboxamide under nucleophilic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, Magdy A., E-mail: magdy_ahmed1977@yahoo.com [Department of Chemistry, Faculty of Education, Ain Shams University, Cairo(Egypt)

    2013-11-15

    The chemical reactivity of chromone-3-carboxamide was studied towards a series of nitrogen and carbon nucleophiles. Treatment of carboxamide with some primary amines gave chromane-2,4-diones. Condensation of carboxamide with hydrazine hydrate, phenyl hydrazine and hydroxylamine hydrochloride afforded chromenopyrazoles and chromenoisoxazole, respectively. Reaction of carboxamide with guanidine hydrochloride, cyanoguanidine and thiourea resulted in ring transformation producing chromenopyridines. The chemical behavior of carboxamide was also studied towards ethylenediamine, o-phenylenediamine, 2-aminophenol and 2-aminothiophenol. A variety of products were isolated from the reaction of carboxamide with some carbon nucleophiles. (author)

  2. Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

    KAUST Repository

    Fetsch, Corinna

    2012-06-05

    Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions

    Czech Academy of Sciences Publication Activity Database

    Opekar, Stanislav; Pohl, Radek; Beran, Pavel; Rulíšek, Lubomír; Beier, Petr

    2014-01-01

    Roč. 20, č. 5 (2014), s. 1453-1458 ISSN 0947-6539 R&D Projects: GA ČR GP203/08/P310 Institutional support: RVO:61388963 Keywords : C1 building blocks * fluorine * nucleophilic addition * phosphanes * synthetic methods Subject RIV: CC - Organic Chemistry Impact factor: 5.731, year: 2014

  4. Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenylpropargyl alcohols

    Directory of Open Access Journals (Sweden)

    Gadi Ranjith Kumar

    2014-05-01

    Full Text Available The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenylpropargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions.

  5. Nucleophilic tetrafluoroethylation of carbonyl compounds with fluorinated sulfones

    Czech Academy of Sciences Publication Activity Database

    Václavík, Jiří; Chernykh, Yana; Jurásek, Bronislav; Beier, Petr

    2015-01-01

    Roč. 169, Jan (2015), s. 24-31 ISSN 0022-1139 R&D Projects: GA ČR GAP207/11/0421 Grant - others:GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : fluorine * tetrafluoroethylation * sulfones * nucleophilic addition * carbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 2.213, year: 2015

  6. Ab initio potential energy surfaces and quantum dynamics for polyatomic bimolecular reactions.

    Science.gov (United States)

    Fu, Bina; Zhang, Donghui

    2018-03-26

    There has been great progress in the development of potential energy surfaces (PESs) and quantum dynamics calculations in the gas phase. The establishment of fitting procedure for highly accurate PESs and new developments in quantum reactive scattering on reliable PESs allow accurate characterization of reaction dynamics beyond triatomic systems. This review will give the recent development in our group in constructing ab initio PESs based on the neural networks, and the time-dependent wave packet calculations for bimolecular reactions beyond three atoms. Bimolecular reactions of current interest to the community, namely, OH+H2, H+H2O, OH+CO, H+CH4 and Cl+CH4 are focused on. Quantum mechanical characterization of these reactions uncovers interesting dynamical phenomena with an unprecedented level of sophistication, and has greatly advanced our understanding of polyatomic reaction dynamics.

  7. General Allylic C–H Alkylation with Tertiary Nucleophiles

    Science.gov (United States)

    2015-01-01

    A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C–H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C–H reactivity are illustrated in an allylic C–H alkylation/Diels–Alder reaction cascade: a reactive diene is generated via intermolecular allylic C–H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids. PMID:24641574

  8. General allylic C-H alkylation with tertiary nucleophiles.

    Science.gov (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  9. Nucleophilic Substitution and Redox Reactions with alpha-Chloro beta-Oxo Sulfenyl Chlorides

    DEFF Research Database (Denmark)

    El-Essawy, Farag A.G.; Yassin, Salah M.; El-Sakka, Ibrahim A.

    1998-01-01

    prepared. Sulfenyl chlorides 1 and 4 have been derivatized with p-toluenesulfinate, methoxide, and cyanide ions as well as with primary and secondary amines, with thiophenol and with thiobenzoic acid. The molecular structure of thiocyanate 8a has been determined by X-ray crystallography....

  10. Mechanistic aspects of the nucleophilic substitution of pectin. On the formation of chloromethane

    DEFF Research Database (Denmark)

    Sailaukhanuly, Yerbolat; Sárossy, Zsuzsa; Carlsen, Lars

    2014-01-01

    Chloromethane, accounting for approximately 16% of the tropospheric chlorine, is mainly coming from natural sources. However anthropogenic activities, such as combustion of biomass may contribute significantly as well. The present study focuses on the thermal solid state reaction between pectin...... the chloride ion and the methyl ester moiety in pectin. It is suggested that the polymeric nature of pectin plays an active role by an enhanced transport of halides along the carbohydrate chain. Optimal reaction temperature is around 210 °C. At higher temperatures the yield of chloromethane decreases due...

  11. A General Catalytic Method for Nucleophilic Substitutions in High Cost- and Atom-Efficiency.

    Science.gov (United States)

    Huy, Peter; Filbrich, Isabel

    2018-03-05

    Herein, a general formamide catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol%) of inexpensive trichlorotriazine (TCT), is introduced. Importantly, the present work is the first example of a TCT mediated dehydroxychlorination of an OH-group containing substrate (e. g. alcohols and carboxylic acid), in which all three chlorine atoms of TCT are transferred onto the starting material. The consequently enhanced atom-economy facilitates a significantly improved waste balance (E-factors down to 4), cost-efficiency and scalability (>50 g). Furthermore, the current procedure is distinguished by high levels of functional group compatibility and stereoselectivity, as only weakly acidic cyanuric acid is released as exclusive by-product. Finally, a one-pot protocol for the preparation of amines, azides, ethers and sulfides enabled the synthesis of the drug Rivastigmine under twofold SN2-inversion, which demonstrates the high practical value of the presented method. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Concentrated Aqueous Sodium Tosylate as Green Medium for Alkene Oxidation and Nucleophilic Substitution Reactions.

    Science.gov (United States)

    Sela, Tal; Lin, Xiaoxi; Vigalok, Arkadi

    2017-11-03

    A hydrotropic solution of highly concentrated sodium tosylate (NaOTs) can be used as a recyclable medium for the environmentally benign oxidation of conjugated alkenes with H 2 O 2 . Both uncatalyzed and metal-catalyzed reactions provided the corresponding oxidation products in higher yields than in pure water or many common organic solvents.

  13. Homoaromatics as intermediates in the substitution reactions of 1,2,4,5-tetrazines with ammonia and hydrazine

    NARCIS (Netherlands)

    Counotte-Potman, A.

    1981-01-01

    This thesis describes some nucleophilic substitution reactions between the red 1,2,4,5-tetrazines and hydrazine-hydrate or ammonia. Special attention was paid to the occurrence of the S N (ANRORC) mechanism in these substitution reactions.

  14. Synthesis of substituted gamma-lactams through petasis-type addition of boronic acids to N-acyliminium lons

    DEFF Research Database (Denmark)

    Wu, Peng; Clausen, Mads Hartvig; Nielsen, Thomas Eiland

    2014-01-01

    Substituted g -lactams are important heterocyclic motifs found in various biologically active compounds and marketed drugs, such as glimepiride, doxapram, and levetiracetam. Among available m ethods for the synthesis of substituted g -lactams, the addition of nucleophiles to N -acyliminium ions...

  15. Turing instability and bifurcation analysis in a diffusive bimolecular system with delayed feedback

    Science.gov (United States)

    Wei, Xin; Wei, Junjie

    2017-09-01

    A diffusive autocatalytic bimolecular model with delayed feedback subject to Neumann boundary conditions is considered. We mainly study the stability of the unique positive equilibrium and the existence of periodic solutions. Our study shows that diffusion can give rise to Turing instability, and the time delay can affect the stability of the positive equilibrium and result in the occurrence of Hopf bifurcations. By applying the normal form theory and center manifold reduction for partial functional differential equations, we investigate the stability and direction of the bifurcations. Finally, we give some simulations to illustrate our theoretical results.

  16. Chiral bicycle imidazole nucleophilic catalysts: rational design, facile synthesis, and successful application in asymmetric Steglich rearrangement.

    Science.gov (United States)

    Zhang, Zhenfeng; Xie, Fang; Jia, Jia; Zhang, Wanbin

    2010-11-17

    A new type of chiral bicycle imidazole nucleophilic catalyst was rationally designed, facilely synthesized, and successfully applied in an asymmetric Steglich rearrangement with good to excellent yield and enantioselectivity at ambient temperature. Moreover, it can be easily recycled with almost no reduction of catalytic efficiency. This is the first example for the successful chiral imidazole nucleophilic catalyst without H-bonding assistance.

  17. Alpha-(trifluoromethyl)amine derivatives via nucleophilic trifluoromethylation of nitrones.

    Science.gov (United States)

    Nelson, D W; Owens, J; Hiraldo, D

    2001-04-20

    (Trifluoromethyl)trimethylsilane (TMSCF(3)) reacts with nitrones to afford alpha-(trifluoromethyl)hydroxylamines protected as O-trimethylsilyl ethers. Potassium t-butoxide initiates the nucleophilic trifluoromethylation. The reaction works best with alpha,N-diaryl nitrones, and the conditions are compatible with a range of substituents on the aryl groups. Acidic deprotection of the nitrone/TMSCF(3) adducts generates alpha-(trifluoromethyl)hydroxylamines. Catalytic hydrogenation of the adducts produces alpha-(trifluoromethyl)amines. Nitrone/TMSCF(3) adducts with strong electron-withdrawing groups on the alpha-aryl ring or heterocyclic alpha-aryl groups undergo an elimination/addition sequence to generate alpha,alpha-bis(trifluoromethyl)amines. Nitrones with alkyl groups bound directly to the 1,3-dipolar moiety fail to react with TMSCF(3), but trifluoromethylation of beta,gamma-unsaturated nitrones followed by reduction of the double bond can circumvent this limitation.

  18. Straightforward synthetic protocol for the introduction of stabilized C nucleophiles in the BODIPY core for advanced sensing and photonic applications.

    Science.gov (United States)

    Gutiérrez-Ramos, Brenda D; Bañuelos, Jorge; Arbeloa, Teresa; López Arbeloa, Iñigo; González-Navarro, Paulina E; Wrobel, Kazimierz; Cerdán, Luis; García-Moreno, Inmaculada; Costela, Angel; Peña-Cabrera, Eduardo

    2015-01-19

    A straightforward synthetic protocol to directly incorporate stabilized 1,3-dicarbonyl C nucleophiles to the meso position of BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) is reported. Soft nucleophiles generated by deprotonation of 1,3-dicarbonyl derivatives smoothly displace the 8-methylthio group from 8-(methylthio)BODIPY analogues in the presence of Cu(I) thiophenecarboxylate in stoichiometric amounts at room temperature. Seven highly fluorescent new derivatives are prepared with varying yields (20-92%) in short reaction times (5-30 min). The excellent photophysical properties of the new dyes allow focusing on applications never analyzed before for BODIPYs substituted with stabilized C nucleophiles such as pH sensors and lasers in liquid and solid state, highlighting the relevance of the synthetic protocol described in the present work. The attainment of these dyes, with strong UV absorption and highly efficient and stable laser emission in the green spectral region, concerns to one of the greatest challenges in the ongoing development of advanced photonic materials with relevant applications. In fact, organic dyes with emission in the green are the only ones that allow, by frequency-doubling processes, the generation of tunable ultraviolet (250-350 nm) radiation, with ultra-short pulses. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Multiple nucleophilic elbows leading to multiple active sites in a single module esterase from Sorangium cellulosum

    DEFF Research Database (Denmark)

    Udatha, D.B.R.K. Gupta; Madsen, Karina Marie; Panagiotou, Gianni

    2015-01-01

    The catalytic residues in carbohydrate esterase enzyme families constitute a highly conserved triad: serine, histidine and aspartic acid. This catalytic triad is generally located in a very sharp turn of the protein backbone structure, called the nucleophilic elbow and identified by the consensus...... sequence GXSXG. An esterase from Sorangium cellulosum Soce56 that contains five nucleophilic elbows was cloned and expressed in Escherichia coli and the function of each nucleophilic elbowed site was characterized. In order to elucidate the function of each nucleophilic elbow, site directed mutagenesis....... To our knowledge, this is the first report presenting the role of multiple nucleophilic elbows in the catalytic promiscuity of an esterase. Further structural analysis at protein unit level indicates the new evolutionary trajectories in emerging promiscuous esterases....

  20. Steric Effects of Solvent Molecules on SN2 Substitution Dynamics.

    Science.gov (United States)

    Liu, Xu; Xie, Jing; Zhang, Jiaxu; Yang, Li; Hase, William L

    2017-04-20

    Influences of solvent molecules on S N 2 reaction dynamics of microsolvated F - (H 2 O) n with CH 3 I, for n = 0-3, are uncovered by direct chemical dynamics simulations. The direct substitution mechanism, which is important without microsolvation, is quenched dramatically upon increasing hydration. The water molecules tend to force reactive encounters to proceed through the prereaction collision complex leading to indirect reaction. In contrast to F - (H 2 O), reaction with higher hydrated ions shows a strong propensity for ion desolvation in the entrance channel, diminishing steric hindrance for nucleophilic attack. Thus, nucleophilic substitution avoids the potential energy barrier with all of the solvent molecules intact and instead occurs through the less solvated barrier, which is energetically unexpected because the former barrier has a lower energy. The work presented here reveals a trade-off between reaction energetics and steric effects, with the latter found to be crucial in understanding how hydration influences microsolvated S N 2 dynamics.

  1. Simplified Representation of Partial and Total Rate Constants of Complex-Forming Bimolecular Reactions.

    Science.gov (United States)

    Troe, J

    2015-12-17

    The temperature and pressure dependence of partial and total rate constants of complex-forming bimolecular reactions are investigated with the goal to obtain simplified and compact rate constant expressions suitable for data compilations. The transition of the reactions from low pressure chemical activation to high pressure association character is analyzed. The two processes are modeled separately first by solving master equations, leading to "inverse" and "normal" falloff curves, respectively, and allowing for a compact representation of the separated rate constants. It is shown that broadening factors of the two falloff curves are different, and those of chemical activation often approaching unity. Coupling of the two separate processes then is modeled in a simplified manner. Finally, thermal redissociation of the adducts formed by association is accounted for.

  2. Kinetics and mechanism of bimolecular electron transfer reaction in quinone-amine systems in micellar solution

    International Nuclear Information System (INIS)

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2005-01-01

    Photoinduced electron transfer (ET) reactions between anthraquinone derivatives and aromatic amines have been investigated in sodium dodecyl sulphate (SDS) micellar solutions. Significant static quenching of the quinone fluorescence due to high amine concentration in the micellar phase has been observed in steady-state measurements. The bimolecular rate constants for the dynamic quenching in the present systems k q TR , as estimated from the time-resolved measurements, have been correlated with the free energy changes ΔG 0 for the ET reactions. Interestingly it is seen that the k q TR vs ΔG 0 plot displays an inversion behavior with maximum k q TR at around 0.7 eV, a trend similar to that predicted in Marcus ET theory. Like the present results, Marcus inversion in the k q TR values was also observed earlier in coumarin-amine systems in SDS and TX-100 micellar solutions, with maximum k q TR at around the same exergonicity. These results thus suggest that Marcus inversion in bimolecular ET reaction is a general phenomenon in micellar media. Present observations have been rationalized on the basis of the two-dimensional ET (2DET) theory, which seems to be more suitable for micellar ET reactions than the conventional ET theory. For the quinone-amine systems, it is interestingly seen that k q TR vs ΔG 0 plot is somewhat wider in comparison to that of the coumarin-amine systems, even though the maxima in the k q TR vs ΔG 0 plots appear at almost similar exergonicity for both the acceptor-donor systems. These observations have been rationalized on the basis of the differences in the reaction windows along the solvation axis, as envisaged within the framework of the 2DET theory, and arise due to the differences in the locations of the quinones and coumarin dyes in the micellar phase

  3. Substitutional analysis

    CERN Document Server

    Rutherford, Daniel Edwin

    2013-01-01

    Classic monograph, suitable for advanced undergraduates and graduate students. Topics include calculus of permutations and tableaux, semi-normal representation, orthogonal and natural representations, group characters, and substitutional equations. 1968 edition.

  4. Platinum Catalyzed Ring-Opening of 1,2-Cyclopropanated Sugars with O-Nucleophiles

    DEFF Research Database (Denmark)

    Beyer, Jürgen; Skaanderup, Philip Robert; Madsen, Robert

    1999-01-01

    In the presence of a catalytic amount of Zeise's dimer 1,2-cyclopropanated sugars undergo regioselective ring-opening at C-1 with O-nucleophiles including alcohols, phenols and water to produce 2-C-branched carbohydrates.......In the presence of a catalytic amount of Zeise's dimer 1,2-cyclopropanated sugars undergo regioselective ring-opening at C-1 with O-nucleophiles including alcohols, phenols and water to produce 2-C-branched carbohydrates....

  5. Hard and soft electrophilic and nucleophilic dissymmetry of α ...

    Indian Academy of Sciences (India)

    unsaturated ketones4 and β-haloketones5 to emerge as a most versatile method for the synthesis of 1,5-benzodiazepines. But the uti- lization of many of these processes in synthesis from unsymmetrically substituted o-phenylenediamines suf-.

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

    Science.gov (United States)

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

    2018-04-13

    The correlation between rapid initiation and rapid decomposition in olefin metathesis is probed for a series of fast-initiating Ru catalysts: the Hoveyda catalyst HII, RuCl2(L)(=CHC6H4-o-OiPr); the Grela catalyst nG (a derivative of HII with a nitro group para to OiPr); the Piers catalyst PII, [RuCl2(L)(=CHPCy3)]OTf; the third-generation Grubbs catalyst GIII, RuCl2(L)(py)2(=CHPh); and dianiline catalyst DA, RuCl2(L)(o-dianiline)(=CHPh) (L = H2IMes = N,N'-bis (mesityl)-imidazolin-2-ylidene). Prior studies of ethylene metathesis established that various Ru metathesis catalysts can decompose by -elimination of propene from metallacyclobutane RuCl2(H2IMes)(2-C3H6) Ru-2. The present work demonstrates that in metathesis of terminal olefins, -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 RuCl2(H2IMes)(=CH2) Ru-1. Direct evidence for methylidene coupling is presented, via the controlled decomposition of transiently-stabilized adducts of Ru-1, RuCl2(H2IMes)Ln(=CH2) (Ln = pyn'; n' = 1, 2, or o-dianiline). These adducts were synthesized by treating in situ-generated metallacyclobutane Ru-2 with pyridine or o-dianiline, and isolated at low temperature (-116 °C or -78 °C, respectively). On warming, both undergo methylidene coupling, liberating ethylene and forming RuCl2(H2IMes)Ln. 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.

  7. Theoretical exploration of the mechanism of riboflavin formation from 6,7-dimethyl-8-ribityllumazine: nucleophilic catalysis, hydride transfer, hydrogen atom transfer, or nucleophilic addition?

    Science.gov (United States)

    Breugst, Martin; Eschenmoser, Albert; Houk, K N

    2013-05-01

    The cofactor riboflavin is biochemically synthesized by a constitutionally intricate process in which two molecules of 6,7-dimethyl-8-ribityllumazine react with each other to form one molecule of the cofactor and one molecule of 5-amino-6-(ribitylamino)uracil. Remarkably, this complex molecular transformation also proceeds non-enzymatically in boiling aqueous solution at pH 7.3. Four different mechanistic pathways for this transformation (nucleophilic catalysis, hydride transfer, hydrogen atom transfer, and a nucleophilic addition mechanism) have now been analyzed by density functional theory [M06-2X/def2-TZVPP/CPCM//M06-2X/6-31+G(d,p)/IEFPCM]. On the basis of these computational results, a so far unpublished nucleophilic addition mechanism is the lowest energy pathway yielding riboflavin. The previously proposed mechanism involving nucleophilic catalysis is higher in energy but is still a viable alternative for an enzyme-catalyzed process assisted by suitably positioned catalytic groups. Pathways involving the transfer of a hydride ion or of a hydrogen atom are predicted to proceed through higher energy transition states and intermediates.

  8. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  9. The influence of the quencher concentration on the rate of simple bimolecular reaction: molecular dynamics study.

    Science.gov (United States)

    Litniewski, Marek

    2005-09-22

    The paper presents the results of large-scale molecular dynamics simulations of the irreversible bimolecular reaction A+B --> C+B for the simple liquid composed of mechanically identical soft spheres. The systems with the total number of molecules corresponding to 10(7)-10(9) are considered. The influence of the concentration of a quencher (B) on the surviving probability of A and the reaction rate is analyzed for a wide range of the concentrations and for two significantly different reduced densities. It is shown that the quencher concentration dependence effect (QCDE) is, in fact, a composition of two QCDE effects: the short-time QCDE that increases the reaction rate and the long-time QCDE that decreases it. The paper also analyzes the influence of the concentration on the steady-state rate constant, k(ss), obtained by integrating the surviving probability. The excess in k(ss) due to finite quencher concentration changes the sign from negative to positive while going from low to high concentrations. Generally, the excess is extremely weak. It attains a 1% level only if the concentration is very high.

  10. Real-time observation of intersystem crossing induced by charge recombination during bimolecular electron transfer reactions

    KAUST Repository

    Alsam, Amani Abdu

    2016-09-21

    Real-time probing of intersystem crossing (ISC) and triplet-state formation after photoinduced electron transfer (ET) is a particularly challenging task that can be achieved by time-resolved spectroscopy with broadband capability. Here, we examine the mechanism of charge separation (CS), charge recombination (CR) and ISC of bimolecular photoinduced electron transfer (PET) between poly[(9,9-di(3,3′-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and dicyanobenzene (DCB) using time-resolved spectroscopy. PET from PFN to DCB is confirmed by monitoring the transient absorption (TA) and infrared spectroscopic signatures for the radical ion pair (DCB─•-PFN+•). In addition, our time-resolved results clearly demonstrate that CS takes place within picoseconds followed by CR within nanoseconds. The ns-TA data exhibit the clear spectroscopic signature of PFN triplet-triplet absorption, induced by the CR of the radical ion pairs (DCB─•-PFN+•). As a result, the triplet state of PFN (3PFN*) forms and subsequently, the ground singlet state is replenished within microseconds. © 2016

  11. Interactions among the early Escherichia coli divisome proteins revealed by bimolecular fluorescence complementation.

    Science.gov (United States)

    Pazos, Manuel; Natale, Paolo; Margolin, William; Vicente, Miguel

    2013-12-01

    We used bimolecular fluorescence complementation (BiFC) assays to detect protein-protein interactions of all possible pairs of the essential Escherichia coli proto-ring components, FtsZ, FtsA and ZipA, as well as the non-essential FtsZ-associated proteins ZapA and ZapB. We found an unexpected interaction between ZipA and ZapB at potential cell division sites, and when co-overproduced, they induced long narrow constrictions at division sites that were dependent on FtsZ. These assays also uncovered an interaction between ZipA and ZapA that was mediated by FtsZ. BiFC with ZapA and ZapB showed that in addition to their expected interaction at midcell, they also interact at the cell poles. BiFC detected interaction between FtsZ and ZapB at midcell and close to the poles. Results from the remaining pairwise combinations confirmed known interactions between FtsZ and ZipA, and ZapB with itself. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

  12. Formulation and Evaluation of CTRW Governing Equations for Irreversible, Bimolecular Reactions During Transport

    Science.gov (United States)

    Hansen, S. K.; Berkowitz, B.

    2014-12-01

    The continuous time random walk (CTRW) formalism is a valuable tool for modeling both conservative and reversibly sorbing solute transport in heterogeneous porous media, underpinning both Eulerian (integrodifferential equation-based) and Lagrangian (particle tracking) approaches to transport modeling. More recently, there has been interest in modeling transport with irreversible reactions, and Lagrangian CTRW-based numerical models have been successfully applied to these problems. However, a corresponding Eulerian theory has been lacking. We recently developed Eulerian governing equations in the presence of irreversible bimolecular reactions, via the device of upscaling transport and treating reactions at a finer scale. The technique is generally valid, even in porous media that do not have an obvious division of length scales, subject to certain smoothness assumptions on the solution. We show that the governing equations we develop simplify, under appropriate circumstances, to both the generalized master equation for the unreactive CTRW and to the advection-dispersion-reaction equation. We also present a numerical corroboration of our development and its underlying smoothness assumptions obtained using a novel, indirect particle-tracking / partial differential equation hybrid technique. We discuss the implications of the new governing equations for practical reactive transport modeling and for conceptualization of subsurface processes, and highlight connections to other approaches. As applicable, we will also discuss aspects of numerical implementation.

  13. Solvent substitution

    International Nuclear Information System (INIS)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general ''Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated

  14. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  15. Sugar Substitutes

    Science.gov (United States)

    ... and drinks. You may have heard them called “artificial sweeteners” or “non-caloric sweeteners.” They can be used ... a food or drink contains. What sugar substitutes/artificial sweeteners are approved by the FDA? The following sugar ...

  16. Identification of ortho-Substituted Benzoic Acid/Ester Derivatives via the Gas-Phase Neighboring Group Participation Effect in (+)-ESI High Resolution Mass Spectrometry

    Science.gov (United States)

    Blincoe, William D.; Rodriguez-Granillo, Agustina; Saurí, Josep; Pierson, Nicholas A.; Joyce, Leo A.; Mangion, Ian; Sheng, Huaming

    2018-02-01

    Benzoic acid/ester/amide derivatives are common moieties in pharmaceutical compounds and present a challenge in positional isomer identification by traditional tandem mass spectrometric analysis. A method is presented for exploiting the gas-phase neighboring group participation (NGP) effect to differentiate ortho-substituted benzoic acid/ester derivatives with high resolution mass spectrometry (HRMS1). Significant water/alcohol loss (>30% abundance in MS1 spectra) was observed for ortho-substituted nucleophilic groups; these fragment peaks are not observable for the corresponding para and meta-substituted analogs. Experiments were also extended to the analysis of two intermediates in the synthesis of suvorexant (Belsomra) with additional analysis conducted with nuclear magnetic resonance (NMR), density functional theory (DFT), and ion mobility spectrometry-mass spectrometry (IMS-MS) studies. Significant water/alcohol loss was also observed for 1-substituted 1, 2, 3-triazoles but not for the isomeric 2-substituted 1, 2, 3-triazole analogs. IMS-MS, NMR, and DFT studies were conducted to show that the preferred orientation of the 2-substituted triazole rotamer was away from the electrophilic center of the reaction, whereas the 1-subtituted triazole was oriented in close proximity to the center. Abundance of NGP product was determined to be a product of three factors: (1) proton affinity of the nucleophilic group; (2) steric impact of the nucleophile; and (3) proximity of the nucleophile to carboxylic acid/ester functional groups. [Figure not available: see fulltext.

  17. Modeling Bimolecular Reactions and Transport in Porous Media Via Particle Tracking

    Energy Technology Data Exchange (ETDEWEB)

    Dong Ding; David Benson; Amir Paster; Diogo Bolster

    2012-01-01

    We use a particle-tracking method to simulate several one-dimensional bimolecular reactive transport experiments. In this numerical method, the reactants are represented by particles: advection and dispersion dominate the flow, and molecular diffusion dictates, in large part, the reactions. The particle/particle reactions are determined by a combination of two probabilities dictated by the physics of transport and energetics of reaction. The first is that reactant particles occupy the same volume over a short time interval. The second is the conditional probability that two collocated particles favorably transform into a reaction. The first probability is a direct physical representation of the degree of mixing in an advancing displacement front, and as such lacks empirical parameters except for the user-defined number of particles. This number can be determined analytically from concentration autocovariance, if this type of data is available. The simulations compare favorably to two physical experiments. In one, the concentration of product, 1,2-naphthoquinoe-4-aminobenzene (NQAB) from reaction between 1,2-naphthoquinone-4-sulfonic acid (NQS) and aniline (AN), was measured at the outflow of a column filled with glass beads at different times. In the other, the concentration distribution of reactants (CuSO_4 and EDTA^{4-}) and products (CuEDTA^{4-}) were quantified by snapshots of transmitted light through a column packed with cryloite sand. The thermodynamic rate coefficient in the latter experiment was 10^7 times greater than the former experiment, making it essentially instantaneous. When compared to the solution of the advection-dispersion-reaction equation (ADRE) with the well-mixed reaction coefficient, the experiments and the particle-tracking simulations showed on the order of 20% to 40% less overall product, which is attributed to poor mixing. The poor mixing also leads to higher product concentrations on the edges of the mixing zones, which the particle

  18. Hydrolyses of 2- and 4-fluoro N-heterocycles. 3. Nucleophilic catalysis by buffer bases in the general acid catalyzed hydrolysis of 4-fluoroquinaldine

    International Nuclear Information System (INIS)

    Muscio, O.J. Jr.; Theobald, P.G.; Rutherford, D.R.

    1989-01-01

    Pseudo-first-order rate constants and catalytic rate constants are reported for the buffer-catalyzed hydrolysis of 4-fluoroquinaldine (1) in carboxylic acid and phosphoric acid buffers. The buffer catalysis is consistent with specific acid, general base catalysis. Hydrolyses in 99% 18 O-labeled acetate, indicate that the predominant catalytic mode for the acetic acid/acetate buffer system is nucleophilic catalysis by the acetate anion coupled with specific acid catalysis. The other buffers presumably react in a similar manner. A Broensted-type plot of the catalytic rate constants for hydrolysis of protonated 1 has a slope of 0.57, with formate deviating positively from the line determined by acetate, chloroacetate, monohydrogen phosphate, and water. This Broensted slope is less than that found for hydrolysis of the 2-fluoro-1-methylpyridinium ion, 2, but is still within the range expected for aromatic nucleophilic substitution. Rate constants and 18 O-labeling results for hydrolysis in acetate buffer are also reported for 4-acetoxyquinaldine (3), the proposed intermediate in the acetate-catalyzed hydrolysis of 1. 15 references, 5 figures, 3 tables

  19. Peptidase family U34 belongs to the superfamily of N-terminal nucleophile hydrolases

    Science.gov (United States)

    Pei, Jimin; Grishin, Nick V.

    2003-01-01

    Peptidase family U34 consists of enzymes with unclear catalytic mechanism, for instance, dipeptidase A from Lactobacillus helveticus. Using extensive sequence similarity searches, we infer that U34 family members are homologous to penicillin V acylases (PVA) and thus potentially adopt the N-terminal nucleophile (Ntn) hydrolase fold. Comparative sequence and structural analysis reveals a cysteine as the catalytic nucleophile as well as other conserved residues important for catalysis. The PVA/U34 family is variable in sequence and exhibits great diversity in substrate specificity, to include enzymes such as choloyglycine hydrolases, acid ceramidases, isopenicillin N acyltransferases, and a subgroup of eukaryotic proteins with unclear function. PMID:12717035

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

    Science.gov (United States)

    Fan, Yi Chiao

    2014-01-01

    In nucleophilic phosphine catalysis, tertiary phosphines undergo conjugate additions to activated carbon–carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This Article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis. PMID:24196409

  1. One-pot facile synthesis of 4-amino-1,8-naphthalimide derived Tröger's bases via a nucleophilic displacement approach.

    Science.gov (United States)

    Shanmugaraju, Sankarasekaran; McAdams, Deirdre; Pancotti, Francesca; Hawes, Chris S; Veale, Emma B; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

    2017-09-13

    We report here a novel one-pot synthetic strategy for the synthesis of a family of N-alkyl-1,8-naphthalimide based Tröger's bases via a nucleophilic substitution reaction of a common 'precursor' (or a 'synthon') N-aryl-1,8-naphthalimide Tröger's base heated at 80 °C in neat aliphatic primary amine, in overall yield of 65-96%. This methodology provides an efficient and one-step facile route to design 1,8-naphthalimide derived Tröger's base structures in analytically pure form without the use of column chromatography purification, that can be used in medicinal chemistry and as supramolecular scaffolds. We also report the formation of the corresponding anhydride, and the crystallographic analysis of two of the resulting products, that of the N-phenyl-4-amino-1,8-naphthalimide and the anhydride derived Tröger's bases.

  2. The syn/anti-Dichotomy in the Palladium-Catalyzed Addition of Nucleophiles to Alkenes

    Czech Academy of Sciences Publication Activity Database

    Kočovský, Pavel; Bäckvall, J. E.

    2015-01-01

    Roč. 21, č. 1 (2015), s. 36-56 ISSN 0947-6539 Institutional support: RVO:61388963 Keywords : alkenes * catalysis * nucleophilic addition * palladium * stereochemistry Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015 http://onlinelibrary.wiley.com/doi/10.1002/chem.201404070/pdf

  3. Nucleophilic additions of [(diethoxyphosphoryl)difluoromethyl]lithium to a,b-unsaturated compounds

    Czech Academy of Sciences Publication Activity Database

    Cherkupally, Prabhakar; Beier, Petr

    2012-01-01

    Roč. 137, May (2012), s. 34-43 ISSN 0022-1139 R&D Projects: GA ČR GP203/08/P310 Institutional research plan: CEZ:AV0Z40550506 Keywords : 1,4-Addition * nucleophilic addition * difluoromethylphosphonate Subject RIV: CC - Organic Chemistry Impact factor: 1.939, year: 2012

  4. Nucleophilic difluoromethylenation of aldehydes and ketones using diethyl difluoro(trimethylsilyl)methylphosphonate

    Czech Academy of Sciences Publication Activity Database

    Alexandrova, Anastasia; Beier, Petr

    2009-01-01

    Roč. 130, č. 5 (2009), s. 493-500 ISSN 0022-1139 R&D Projects: GA ČR GP203/08/P310 Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphonates * phosphates * nucleophilic additions * difluoromethylene Subject RIV: CC - Organic Chemistry Impact factor: 1.730, year: 2009

  5. Organic Chemistry Students' Ideas about Nucleophiles and Electrophiles: The Role of Charges and Mechanisms

    Science.gov (United States)

    Anzovino, Mary E.; Bretz, Stacey Lowery

    2015-01-01

    Organic chemistry students struggle with reaction mechanisms and the electron-pushing formalism (EPF) used by practicing organic chemists. Faculty have identified an understanding of nucleophiles and electrophiles as one conceptual prerequisite to mastery of the EPF, but little is known about organic chemistry students' knowledge of nucleophiles…

  6. Ring opening of a resin-bound chiral aziridine with phenol nucleophiles

    DEFF Research Database (Denmark)

    Ottesen, Lars Korsgaard; Jaroszewski, Jerzy W; Franzyk, Henrik

    2010-01-01

    An efficient and versatile solid-phase route for the preparation of aryl-alkyl ethers is described. Regioselective ring opening of a resin-bound chiral aziridine with phenolic nucleophiles constitutes the key feature of the present protocol that allows incorporation of fluorescent moieties...

  7. Nucleophilic conjugate trifluoromethylation of chromones and activated alkenes under the action of Ruppert’s reagent

    Directory of Open Access Journals (Sweden)

    V. Ya. Sosnovskikh

    2017-05-01

    Full Text Available This review summarizes data on the reactions of chromones and activated alkenes with trimethyl(trifluoromethylsilane (Ruppert’s reagent, which occures as a nucleophilic 1,4-trifluoromethylation with high regioselectivity and good yields. The most important chemical properties of the formed products are also considered.

  8. Efficient Homodifunctional Bimolecular Ring-Closure Method for Cyclic Polymers by Combining RAFT and Self-Accelerating Click Reaction.

    Science.gov (United States)

    Qu, Lin; Sun, Peng; Wu, Ying; Zhang, Ke; Liu, Zhengping

    2017-08-01

    An efficient metal-free homodifunctional bimolecular ring-closure method is developed for the formation of cyclic polymers by combining reversible addition-fragmentation chain transfer (RAFT) polymerization and self-accelerating click reaction. In this approach, α,ω-homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, well-defined cyclic polymers are then prepared using the self-accelerating double strain-promoted azide-alkyne click (DSPAAC) reaction to ring-close the azide end-functionalized homodifunctional linear polymer precursors. Due to the self-accelerating property of DSPAAC ring-closing reaction, this novel method eliminates the requirement of equimolar amounts of telechelic polymers and small linkers in traditional bimolecular ring-closure methods. It facilitates this method to efficiently and conveniently produce varied pure cyclic polymers by employing an excess molar amount of DBA small linkers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Folding topology of a bimolecular DNA quadruplex containing a stable mini-hairpin motif within the diagonal loop.

    Science.gov (United States)

    Balkwill, Graham D; Garner, Thomas P; Williams, Huw E L; Searle, Mark S

    2009-02-06

    We describe the NMR structural characterisation of a bimolecular anti-parallel DNA quadruplex d(G(3)ACGTAGTG(3))(2) containing an autonomously stable mini-hairpin motif inserted within the diagonal loop. A folding topology is identified that is different from that observed for the analogous d(G(3)T(4)G(3))(2) dimer with the two structures differing in the relative orientation of the diagonal loops. This appears to reflect specific base stacking interactions at the quadruplex-duplex interface that are not present in the structure with the T(4)-loop sequence. A truncated version of the bimolecular quadruplex d(G(2)ACGTAGTG(2))(2), with only two core G-tetrads, is less stable and forms a heterogeneous mixture of three 2-fold symmetric quadruplexes with different loop arrangements. We demonstrate that the nature of the loop sequence, its ability to form autonomously stable structure, the relative stabilities of the hairpin loop and core quadruplex, and the ability to form favourable stacking interactions between these two motifs are important factors in controlling DNA G-quadruplex topology.

  10. Facile synthesis of 2-amino-4-alkoxypyrimidines via consecutive nucleophilic aromatic substitution (S{sub N}Ar) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Juhyeon; Cho, Yong Seo [Center for Neuro-Medicine, Brain Science Institute, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Min, Sun Joon [Dept. of Applied Chemistry, Hanyang University , Ansan (Korea, Republic of)

    2016-12-15

    A transition-metal-free and regioselective synthesis of a series of 2-amino-4-alkoxypyrimidines is described. The SNAr alkoxylation of 2,4-dichloropyrimidines regioselectively provided 2-chloro-4-alkoxypyrimidines, which were subsequently subject to the second SNAr amination with cyclic amines in the presence of triethylamine at high temperature to afford 2-amino-4-alkoxypyrimidines in good overall yield.

  11. [5C + 1N] Annulation of 2,4-pentadienenitriles with hydroxylamine: a synthetic route to multi-substituted 2-aminopyridines.

    Science.gov (United States)

    Xin, Xiaoqing; Huang, Peng; Xiang, Dexuan; Zhang, Rui; Zhao, Fengyu; Zhang, Ning; Dong, Dewen

    2013-02-14

    A facile and efficient synthetic route to multi-substituted 2-aminopyridines has been developed via a formal [5C + 1N] annulation of readily available 2,4-pentadienenitriles with hydroxylamine (NH(2)OH) under very mild conditions, which involves sequential intermolecular aza-nucleophilic addition of hydroxylamine, intramolecular aza-cyclization, and dehydration reactions.

  12. The Study of Substitution and Elimination Reactions Using Gas Chromatography: An Examination of the Effects of Alkane and Base Structure on Product Distributions

    Science.gov (United States)

    Wharry, Donald L.

    2011-01-01

    An experiment that compares product distribution obtained by either substitution or elimination utilizing alkyl bromides and methoxide, ethoxide, or t-butoxide as the base (or nucleophile) is described. The change in product distribution caused by steric effects of the base and substrate are readily apparent. Prior work on this experiment focused…

  13. Diastereoselective Three-Component Reactions of Chiral Nickel(II Glycinate for Convenient Synthesis of Novel α-Amino-β-Substituted-γ,γ-Disubstituted Butyric Acids

    Directory of Open Access Journals (Sweden)

    Rui Zhou

    2014-01-01

    Full Text Available The convenient, high yielding and diastereoselective synthesis of α-amino-β-substituted-γ,γ-disubstituted butyric acid derivatives was carried out by a three-component tandem reaction of a chiral equivalent of nucleophilic glycine. The reaction was performed smoothly under mild conditions and enabled the construction of two or three adjacent chiral centers in one step, thus affording a novel and convenient route to α-amino-β-substituted-γ,γ-disubstituted butyric acid derivatives.

  14. Nucleophilic reactions of hydrazido(2-) complexes of molybdenum and tungsten with succinyl dichloride and phenyl isocyanate

    International Nuclear Information System (INIS)

    Iwanami, Kiyotaka; Mizobe, Yasushi; Takahashi, Tamotsu; Kodama, Teruyuki; Uchida, Yasuzo

    1981-01-01

    Nucleophilic attack of the WNNH 2 group in the hydrazido(2-) complex [WF(NNH 2 )(dpe) 2 ][BF 4 ] (dpe = Ph 2 PCH 2 CH 2 PPh 2 ) on succinyl dichloride gives a novel ethanedioylhydrazido(2-) complex, [WF(NNCOCH 2 CH 2 CO)(dpe) 2 ][BF 4 ]. X-Ray structural analysis shows that the carbon, nitrogen, and oxygen atoms of the ethanedioylhydrazido(2-) ligand lie nearly in the same plane, indicating sp 2 character of the nitrogen atom bearing the two carbonyl groups. Phenyl isocyanate also undergoes nucleophilic attack by the hydrazido(2-) complex [MBr(NNH 2 )(dpe) 2 ]Br (M = Mo or W) to yield the phenylsemicarbazido(2-) type complex, [MBr(NNHCONHPh)(dpe) 2 ]Br. Treatment of the semicarbazido(2-) complex with triethylamine gives a new diazenido complex [MBr(NNCONHPh)(dpe) 2 ]. (author)

  15. A General Ligand Design for Gold Catalysis allowing Ligand-Directed Anti Nucleophilic Attack of Alkynes

    Science.gov (United States)

    Wang, Yanzhao; Wang, Zhixun; Li, Yuxue; Wu, Gongde; Cao, Zheng; Zhang, Liming

    2014-01-01

    Most homogenous gold catalyses demand ≥0.5 mol % catalyst loading. Due to the high cost of gold, these reactions are unlikely to be applicable in medium or large scale applications. Here we disclose a novel ligand design based on the privileged biphenyl-2-phosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3’ position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogeneous gold catalysis considering the spatial challenge of using ligand to reach antiapproaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalyzing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding. PMID:24704803

  16. Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

    Science.gov (United States)

    Pécharman, Anne-Frédérique; Colebatch, Annie L.; Hill, Michael S.; McMullin, Claire L.; Mahon, Mary F.; Weetman, Catherine

    2017-04-01

    Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B-B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N'-di-isopropyl carbodiimide and by density functional theory.

  17. Reactivity of 4'-substituted 2,4-dinitrodiphenyl sulfides and sulfones during alkaline hydrolysis in aqueous dioxane

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov, A.V.

    1986-01-10

    This paper studies the kinetics of alkaline hydrolysis of 4'-substituted 2,4-dinitrodiphenyl sulfides (I), 2,4-dinitrodiphenyl sulfones (II), and 1-substituted 2,4-dinitrobenzenes (III) in a 40% dioxane-water solution. Analysis of the results obtained are presented and it is shown that in its character, the influence of the substituents in carrying out the alkaline hydrolysis reaction in 40% dioxane for the reaction series (I) obeys the general patterns of activated nucleophilic substitution, with the exception of 2,4-dinitro-4'-methylthiodiphenyl sulfide.

  18. Nucleophilic stabilization of water-based reactive ink for titania-based thin film inkjet printing

    DEFF Research Database (Denmark)

    Gadea, Christophe; Marani, Debora; Esposito, Vincenzo

    2017-01-01

    -methyldiethanolamine (MDEA) used as nucleophilic ligand. The function of the ligand is to control the fast hydrolysis/condensation reactions in water for the metal alkoxide before deposition, leading to formation of the TiO2 only after the jet process. The evolution of the titanium-ligand interactions at increasing amount......Drop on demand deposition (DoD) of titanium oxide thin films (water-based solution by a combined use of titanium isopropoxide and n...

  19. Ring-Opening Reactions of the N-4-Nosyl Hough-Richardson Aziridine with Nitrogen Nucleophiles.

    Science.gov (United States)

    Ručil, Tomáš; Trávníček, Zdeněk; Cankař, Petr

    2017-01-06

    Dinosylated α-d-glucopyranoside was directly transformed into α-d-altropyranosides via in situ formed N-4-nosyl Hough-Richardson aziridine with nitrogen nucleophiles under mild conditions in fair to excellent yields. The scope of the aziridine ring-opening reaction was substantially broadened contrary to the conventional methods introducing solely the azide anion at high temperatures. If necessary, the N-4-nosyl Hough-Richardson aziridine can be isolated by filtration in a very good yield and high purity.

  20. Barbier Continuous Flow Preparation and Reactions of Carbamoyllithiums for Nucleophilic Amidation.

    Science.gov (United States)

    Ganiek, Maximilian A; Becker, Matthias R; Berionni, Guillaume; Zipse, Hendrik; Knochel, Paul

    2017-08-01

    An ambient temperature continuous flow method for nucleophilic amidation and thioamidation is described. Deprotonation of formamides by lithium diisopropylamine (LDA) affords carbamoyllithium intermediates that are quenched in situ with various electrophiles such as ketones, allyl bromides, Weinreb and morpholino amides. The nature of the reactive lithium intermediates and the thermodynamics of the metalation were further investigated by ab initio calculations and kinetic experiments. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Charge effect on the diffusion coefficient and the bimolecular reaction rate of diiodide anion radical in room temperature ionic liquids.

    Science.gov (United States)

    Nishiyama, Yoshio; Terazima, Masahide; Kimura, Yoshifumi

    2009-04-16

    The diffusion coefficients of diiodide anion radical, I(2)(-), in room temperature ionic liquids (RTILs) were determined by the transient grating (TG) method using the photochemical reaction of iodide. The diffusion coefficients we obtained were larger in RTILs than the theoretical predictions by the Stokes-Einstein relation, whereas both values are similar in conventional solvents. By comparison with the diffusion coefficients of neutral molecules, it was suggested that the Coulomb interaction between I(2)(-) and constituent ions of RTILs strongly affects the diffusion coefficients. The bimolecular reaction rates between I(2)(-) were calculated by the Debye-Smoluchowski equation using the experimentally determined diffusion coefficients. These calculated reaction rate were much smaller than the experimentally determined rates (Takahashi, K.; et al. J. Phys. Chem. B 2007, 111, 4807), indicating the charge screening effect of RTILs.

  2. Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

    Science.gov (United States)

    Nickolaisen, Scott L.; Friedl, Randall R.; Sander, Stanley P.

    1993-01-01

    The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

  3. Regioselective Nucleophilic Ring Opening of Epoxides and Aziridines derived from Homoallylic Alcohols

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Groth, Thomas

    1997-01-01

    The regioselectivity of nucleophilic ring opening of some 3,4-epoxy and 3,4-aziridino alcohols has been studied. The nucleophiles chosen were complex hydrides (LiAlH4, Red-Al and DIBAL) and Lipshutz- or Gilman-type organocuprate reagents. The C-4 substituent in the substrates was varied in order...... to study steric and electronic effects on the ring opening reactions. For alkyl substituents at C-4, most of the results can be explained on the basis of intramolecular delivery of the nucleophile to C-3 via a six-membered transition state, leading to 1,4-diols or 1,4-amino alcohol derivatives. In general......, the epoxy alcohols gave poorer regioselectivity than the N-tosyl aziridino alcohols, for which selectivities of >95:5 were routinely obtained. The activating effect of a phenyl group at C-4 led to a switch in regiochemistry, with the 1,3-diol or 1,3-amino alcohol derivative as the major product. (C) 1997...

  4. The optimization of 18F-nucleophilic fluorination reaction and its application in synthesis of VMAT2 imaging tracer: [18F]AV-133

    International Nuclear Information System (INIS)

    Liu Yajing; Zhu Lin; Karl, P.; Qu Wenchao

    2010-01-01

    Objective: The nucleophilic introduction of n.c.a. [ 18 F]F- into alkanes by nucleophilic reaction is the main method of preparing 18 F-labelled radiopharmaceuticals, and the efficient and rapid reaction is important in 18 F-labelled radiopharmaceuticals. Method: Using 2-(3-substitute propoxy)naphthalene as model compound, the optimal reaction condition was achieved by comparing the different [ 18 F]fluorination condition: 1)different leaving groups (-OTs, -I, -Br and -Cl), 2) different [ 18 F]fluorination catalysts (Kryptofix222/K 2 CO 3 and TBAHCO 3 ), 3) different reaction solvent (ACN, DMSO and DMF), 4) [ 18 F]fluorination temperature (40, 50 and 60 degree C) and 5) reaction time. The radiochemical yields were analyzed by TLC and HPLC. VMAT2 imaging tracer [ 18 F]AV-133 was synthesized under the optimal conditions. Results: From the experiment results, the reation activity was the highest when using -OTs as the leaving group, followed by -I and -Br, -Clunder the [ 18 F]fluorination condition of using K222/K 2 CO 3 as catalyst and ACN as solvent. And also, the radiochemical yield raised as the reaction time and temperature increased. The higher temperature, the shorter time to reach the equilibrium. When changing the solvent from ACN to DMSO, the radiochemical yields were increased. On the contrary, the radiochemical yields were decreasing by using DMF. Comparing the catalyst K222/K 2 CO 3 with TBAHCO 3 , the [ 18 F] fluorination of -OTs gave a higher radiochemical yield in the presence of K222/K 2 CO 3 . So the optimized [ 18 F]fluorination reaction condition was that choosing -OTs as the leaving group, the [ 18 F]fluorination reaction was efficient and gave higher radiochemical yield catalyzed by K222/K 2 CO 3 in DMSO at high temperature. [ 18 F]fluorination of AV-244 was found to provide the VMAT2 imaging tracer [ 18 F]AV-133 in 80 ± 2% radiochemical yield after reaction at 120 degree C for 3 min under optimized conditions. Conclusion: We have described an

  5. Reactions of benzene oxide, a reactive metabolite of benzene, with model nucleophiles and DNA.

    Science.gov (United States)

    Míčová, Kateřina; Linhart, Igor

    2012-10-01

    1. Reactivity of benzene oxide (BO), a reactive metabolite of benzene, was studied in model reactions with biologically relevant S- and N-nucleophiles by LC-ESI-MS. 2. Reaction with N-acetylcysteine (NAC) in aqueous buffer solutions gave N-acetyl-S-(6-hydroxycyclohexa-2,4-dien-1-yl)cysteine (pre-phenylmercapturic acid, PPhMA), which was easily dehydrated in acidic solutions to phenylmercapturic acid (PhMA). The yield of PPhMA + PhMA increased exponentially with pH up to 11% in the pH range from 5.5 to 11.4. 3. Primary 6-hydroxycyclohexa-2,4-dien-1-yl (HC) adducts were detected also in reactions of purine nucleosides and nucleotides under physiological conditions. After a vigorous acidic hydrolysis, all HC adducts were converted to corresponding phenyl purines, which were identified as 7-phenylguanine (7-PhG), 3-phenyladenine (3-PhA) and N(6)-phenyladenine (6-PhA). The yield of 7-PhG amounted to 14 ± 5 and 16 ± 7 ppm for 2'-deoxyguanosine and 2'-deoxyguanosine-5'-monophosphate, respectively, that of 6-PhA was 500 ± 70 and 455 ± 75 ppm with 2'-deoxyadenosine and 2'-deoxyadenosine-5'-phosphate, respectively, with only traces of 3-PhA. 4. Reactions with the DNA followed by acidic hydrolysis yielded 26 ± 11 ppm (mean ± SD; n = 9) of 7-PhG as the sole adduct detected. 5. In contrast to the reactions with S-nucleophiles, the reactivity of BO with nucleophilic sites in the DNA is very low and can therefore hardly account for a significant DNA damage caused by benzene.

  6. Cyclization of ortho-hydroxycinnamates to coumarins under mild conditions: A nucleophilic organocatalysis approach

    Directory of Open Access Journals (Sweden)

    Florian Boeck

    2012-09-01

    Full Text Available (E-Alkyl ortho-hydroxycinnamates cyclize to coumarins at elevated temperatures of 140–250 °C. We find that the use of tri-n-butylphosphane (20 mol % as a nucleophilic organocatalyst in MeOH solution allows cyclization to take place under much milder conditions (60–70 °C. Several coumarins were prepared, starting from ortho-hydroxyarylaldehydes, by Wittig reaction with Ph3P=CHCO2Me to (E-methyl ortho-hydroxycinnamates, followed by the phosphane catalyzed cyclization.

  7. Nucleophilic β-Carbon Activation of Propionic Acid as a 3-Carbon Synthon by Carbene Organocatalysis.

    Science.gov (United States)

    Jin, Zhichao; Jiang, Ke; Fu, Zhenqian; Torres, Jaume; Zheng, Pengcheng; Yang, Song; Song, Bao-An; Chi, Yonggui Robin

    2015-06-22

    Direct β-carbon activation of propionic acid (C2H5CO2H) by carbene organocatalysis has been developed. This activation affords the smallest azolium homoenolate intermediate (without any substituent) as a 3-carbon nucleophile for enantioselective reactions. Propionic acid is an excellent raw material because it is cheap, stable, and safe. This approach provides a much better solution to azolium homoenolate synthesis than the previously established use of acrolein (enal without any substituent), which is expensive, unstable, and toxic. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

    Directory of Open Access Journals (Sweden)

    Johannes Schörgenhumer

    2017-08-01

    Full Text Available Chiral phase-transfer catalysis is one of the major catalytic principles in asymmetric catalysis. A broad variety of different catalysts and their use for challenging applications have been reported over the last decades. Besides asymmetric C–C bond forming reactions the use of chiral phase-transfer catalysts for enantioselective α-heterofunctionalization reactions of prochiral nucleophiles became one of the most important field of application of this catalytic principle. Based on several highly spectacular recent reports, we thus wish to discuss some of the most important achievements in this field within the context of this review.

  9. Switching and sensing spin states of co-porphyrin in bimolecular reactions on Au111 using scanning tunneling microscopy.

    Science.gov (United States)

    Kim, Howon; Chang, Yun Hee; Lee, Soon-Hyeong; Kim, Yong-Hyun; Kahng, Se-Jong

    2013-10-22

    Controlling and sensing spin states of magnetic molecules at the single-molecule level is essential for spintronic molecular device applications. Here, we demonstrate that spin states of Co-porphyrin on Au(111) can be reversibly switched over by binding and unbinding of the NO molecule and can be sensed using scanning tunneling microscopy and spectroscopy (STM and STS). Before NO exposure, Co-porphryin showed a clear zero-bias peak, a signature of Kondo effect in STS, whereas after NO exposures, it formed a molecular complex, NO-Co-porphyrin, that did not show any zero-bias feature, implying that the Kondo effect was switched off by binding of NO. The Kondo effect could be switched back on by unbinding of NO through single-molecule manipulation or thermal desorption. Our density functional theory calculation results explain the observations with pairing of unpaired spins in dz(2) and ppπ* orbitals of Co-porphyrin and NO, respectively. Our study opens up ways to control molecular spin state and Kondo effect by means of enormous variety of bimolecular binding and unbinding reactions on metallic surfaces.

  10. Molecular beam studies of unimolecular and bimolecular chemical reaction dynamics using VUV synchrotron radiation as a product probe

    Energy Technology Data Exchange (ETDEWEB)

    Blank, David Andrew [Univ. of California, Berkeley, CA (United States)

    1997-08-01

    This dissertation describes the use of a new molecular beam apparatus designed to use tunable VUV synchrotron radiation for photoionization of the products from scattering experiments. The apparatus was built at the recently constructed Advanced Light Source at Lawrence Berkeley National Laboratory, a third generation 1-2 GeV synchrotron radiation source. The new apparatus is applied to investigations of the dynamics of unimolecular reactions, photodissociation experiments, and bimolecular reactions, crossed molecular beam experiments. The first chapter describes the new apparatus and the VUV radiation used for photoionization. This is followed by a number of examples of the many advantages provided by using VUV photoionization in comparison with the traditional technique of electron bombardment ionization. At the end of the chapter there is a discussion of the data analysis employed in these scattering experiments. The remaining four chapters are complete investigations of the dynamics of four chemical systems using the new apparatus and provide numerous additional examples of the advantages provided by VUV photoionizaiton of the products. Chapters 2-4 are photofragment translational spectroscopy studies of the photodissociation dynamics of dimethyl sulfoxide, acrylonitrile, and vinyl chloride following absorption at 193 mn. All of these systems have multiple dissociation channels and provide good examples of the ability of the new apparatus to unravel the complex UV photodissociation dynamics that can arise in small polyatomic molecules.

  11. Gateway Vectors for Simultaneous Detection of Multiple Protein-Protein Interactions in Plant Cells Using Bimolecular Fluorescence Complementation.

    Science.gov (United States)

    Kamigaki, Akane; Nito, Kazumasa; Hikino, Kazumi; Goto-Yamada, Shino; Nishimura, Mikio; Nakagawa, Tsuyoshi; Mano, Shoji

    2016-01-01

    Bimolecular fluorescence complementation (BiFC) is widely used to detect protein-protein interactions, because it is technically simple, convenient, and can be adapted for use with conventional fluorescence microscopy. We previously constructed enhanced yellow fluorescent protein (EYFP)-based Gateway cloning technology-compatible vectors. In the current study, we generated new Gateway cloning technology-compatible vectors to detect BiFC-based multiple protein-protein interactions using N- and C-terminal fragments of enhanced cyan fluorescent protein (ECFP), enhanced green fluorescent protein (EGFP), and monomeric red fluorescent protein (mRFP1). Using a combination of N- and C-terminal fragments from ECFP, EGFP and EYFP, we observed a shift in the emission wavelength, enabling the simultaneous detection of multiple protein-protein interactions. Moreover, we developed these vectors as binary vectors for use in Agrobacterium infiltration and for the generate transgenic plants. We verified that the binary vectors functioned well in tobacco cells. The results demonstrate that the BiFC vectors facilitate the design of various constructions and are convenient for the detection of multiple protein-protein interactions simultaneously in plant cells.

  12. Gateway Vectors for Simultaneous Detection of Multiple Protein−Protein Interactions in Plant Cells Using Bimolecular Fluorescence Complementation

    Science.gov (United States)

    Hikino, Kazumi; Goto-Yamada, Shino; Nishimura, Mikio; Nakagawa, Tsuyoshi; Mano, Shoji

    2016-01-01

    Bimolecular fluorescence complementation (BiFC) is widely used to detect protein—protein interactions, because it is technically simple, convenient, and can be adapted for use with conventional fluorescence microscopy. We previously constructed enhanced yellow fluorescent protein (EYFP)-based Gateway cloning technology-compatible vectors. In the current study, we generated new Gateway cloning technology-compatible vectors to detect BiFC-based multiple protein—protein interactions using N- and C-terminal fragments of enhanced cyan fluorescent protein (ECFP), enhanced green fluorescent protein (EGFP), and monomeric red fluorescent protein (mRFP1). Using a combination of N- and C-terminal fragments from ECFP, EGFP and EYFP, we observed a shift in the emission wavelength, enabling the simultaneous detection of multiple protein—protein interactions. Moreover, we developed these vectors as binary vectors for use in Agrobacterium infiltration and for the generate transgenic plants. We verified that the binary vectors functioned well in tobacco cells. The results demonstrate that the BiFC vectors facilitate the design of various constructions and are convenient for the detection of multiple protein—protein interactions simultaneously in plant cells. PMID:27490375

  13. The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2015-08-21

    Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  14. Bimolecular Complementation to Visualize Filovirus VP40-Host Complexes in Live Mammalian Cells: Toward the Identification of Budding Inhibitors

    Directory of Open Access Journals (Sweden)

    Yuliang Liu

    2011-01-01

    Full Text Available Virus-host interactions play key roles in promoting efficient egress of many RNA viruses, including Ebola virus (EBOV or “e” and Marburg virus (MARV or “m”. Late- (L- domains conserved in viral matrix proteins recruit specific host proteins, such as Tsg101 and Nedd4, to facilitate the budding process. These interactions serve as attractive targets for the development of broad-spectrum budding inhibitors. A major gap still exists in our understanding of the mechanism of filovirus budding due to the difficulty in detecting virus-host complexes and mapping their trafficking patterns in the natural environment of the cell. To address this gap, we used a bimolecular complementation (BiMC approach to detect, localize, and follow the trafficking patterns of eVP40-Tsg101 complexes in live mammalian cells. In addition, we used the BiMC approach along with a VLP budding assay to test small molecule inhibitors identified by in silico screening for their ability to block eVP40 PTAP-mediated interactions with Tsg101 and subsequent budding of eVP40 VLPs. We demonstrated the potential broad spectrum activity of a lead candidate inhibitor by demonstrating its ability to block PTAP-dependent binding of HIV-1 Gag to Tsg101 and subsequent egress of HIV-1 Gag VLPs.

  15. Configurationally stable, enantioenriched organometallic nucleophiles in stereospecific Pd-catalyzed cross-coupling reactions: an alternative approach to asymmetric synthesis

    Science.gov (United States)

    Wang, Chao-Yuan; Derosa, Joseph

    2015-01-01

    Several research groups have recently developed methods to employ configurationally stable, enantioenriched organometallic nucleophiles in stereospecific Pd-catalyzed cross-coupling reactions. By establishing the absolute configuration of a chiral alkyltin or alkylboron nucleophile prior to its use in cross-coupling reactions, new stereogenic centers may be rapidly and reliably generated with preservation of the known initial stereochemistry. While this area of research is still in its infancy, such stereospecific cross-coupling reactions may emerge as simple, general methods to access diverse, optically active products from common enantioenriched organometallic building blocks. This minireview highlights recent progress towards the development of general, stereospecific Pd-catalyzed cross-coupling reactions using configurationally stable organometallic nucleophiles. PMID:26388985

  16. Exploring the Catalytic Promiscuity of Phenolic Acid Decarboxylases: Asymmetric, 1,6-Conjugate Addition of Nucleophiles Across 4-Hydroxystyrene.

    Science.gov (United States)

    Payer, Stefan E; Sheng, Xiang; Pollak, Hannah; Wuensch, Christiane; Steinkellner, Georg; Himo, Fahmi; Glueck, Silvia M; Faber, Kurt

    2017-06-19

    The catalytic promiscuity of a ferulic acid decarboxylase from Enterobacter sp. (FDC_ E s) and phenolic acid decarboxylases (PADs) for the asymmetric conjugate addition of water across the C=C bond of hydroxystyrenes was extended to the N-, C- and S-nucleophiles methoxyamine, cyanide and propanethiol to furnish the corresponding addition products in up to 91% ee . The products obtained from the biotransformation employing the most suitable enzyme/nucleophile pairs were isolated and characterized after optimizing the reaction conditions. Finally, a mechanistic rationale supported by quantum mechanical calculations for the highly ( S )-selective addition of cyanide is proposed.

  17. In vitro visualization and characterization of wild type and mutant IDH homo- and heterodimers using Bimolecular Fluorescence Complementation.

    Science.gov (United States)

    Robinson, Gemma L; Philip, Beatrice; Guthrie, Matthew R; Cox, James E; Robinson, James P; VanBrocklin, Matthew W; Holmen, Sheri L

    2016-05-01

    Mutations in the metabolic enzyme isocitrate dehydrogenase (IDH) were recently found in ~80% of WHO grade II-III gliomas and secondary glioblastomas. These mutations reduce the enzyme's ability to convert isocitrate to α-ketoglutarate and, instead, confer a novel gain-of-function resulting in the conversion of α-ketoglutarate to 2-hydroxglutarate (2-HG). However, IDH mutations exist in a heterozygous state such that a functional wild type allele is retained. Recent data suggest that the ability of mutant IDH1, but not mutant IDH2, to produce 2-HG is dependent on the activity of the retained wild type allele. In this study, we aimed to further our understanding of the interaction and function of wild type and mutant IDH heterodimers utilizing Bimolecular Fluorescence Complementation (BiFC). Dimerization of wild type and mutant IDH monomers conjugated to the N- and C-terminus of Venus protein, respectively, is directly proportional to the amount of fluorescence emitted and can be used as an approach to visualize and assess IDH dimerization. Thus, we utilized this method to visualize IDH homo- and heterodimers and to examine their cellular physiology based on subcellular localization, NADPH production, and 2-HG levels. Our results demonstrate that wild type and mutant IDH1 or IDH2 heterodimers display similar physiological characteristics to that of mutant IDH1 or IDH2 homodimers with the exception of their ability to generate NADPH. IDH1 heterodimers consistently generate NADPH whereas IDH2 heterodimers do not. However, the presence of mutant IDH1 or IDH2 in homo- or heterodimer configurations consistently generates equivalent levels of 2-HG. Our data suggest that the wild type protein is not required for the generation of 2-HG.

  18. Direct nucleophilic difluoromethylation of aromatic isoxazoles activated by electron-withdrawing groups using (difluoromethyltrimethylsilane

    Directory of Open Access Journals (Sweden)

    Xin Wang

    2014-12-01

    Full Text Available The activation of aromatic diaryl isoxazoles with strong electron-withdrawing groups, such as the nitro, triflyl, and the phenylsulfonyl groups, at the 4-position has enabled the first regio- and diastereoselective difluoromethylation at the 5-position of isoxazoles by nucleophilic addition using (difluoromethyl trimethylsilane, Me3SiCF2H, to provide difluoromethylated isoxazolines in good yields. Conjugated styryl-4-nitroisoxazoles were also nicely converted into the corresponding CF2H adducts with high regio- and excellent diastereoselectivities. Since the trifluoromethylated analogs of the corresponding diaryl-isoxazolines are effective ectoparasiticides, represented by fluralaner, should a series of difluoromethylated isoxazolines be obtained, they would be of great importance as promising drug candidates in this field.

  19. Bis-tert-Alcohol-Functionalized Crown-6-Calix[4]arene: An Organic Promoter for Nucleophilic Fluorination.

    Science.gov (United States)

    Jadhav, Vinod H; Choi, Wonsil; Lee, Sung-Sik; Lee, Sungyul; Kim, Dong Wook

    2016-03-18

    A bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA) was designed and prepared as a multifunctional organic promoter for nucleophilic fluorinations with CsF. By formation of a CsF/BACCA complex, BACCA could release a significantly active and selective fluoride source for SN2 fluorination reactions. The origin of the promoting effects of BACCA was studied by quantum chemical methods. The role of BACCA was revealed to be separation of the metal fluoride to a large distance (>8 Å), thereby producing an essentially "free" F(-). The synergistic actions of the crown-6-calix[4]arene subunit (whose O atoms coordinate the counter-cation Cs(+)) and the terminal tert-alcohol OH groups (forming controlled hydrogen bonds with F(-)) of BACCA led to tremendous efficiency in SN2 fluorination of base-sensitive substrates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Taming of fluoroform: direct nucleophilic trifluoromethylation of Si, B, S, and C centers.

    Science.gov (United States)

    Prakash, G K Surya; Jog, Parag V; Batamack, Patrice T D; Olah, George A

    2012-12-07

    Fluoroform (CF(3)H), a large-volume by-product of the manufacture of Teflon, refrigerants, polyvinylidene fluoride (PVDF), fire-extinguishing agents, and foams, is a potent and stable greenhouse gas that has found little practical use despite the growing importance of trifluoromethyl (CF3) functionality in more structurally elaborate pharmaceuticals, agrochemicals, and materials. Direct nucleophilic trifluoromethylation using CF(3)H has been a challenge. Here, we report on a direct trifluoromethylation protocol using close to stoichiometric amounts of CF(3)H in common organic solvents such as tetrahydrofuran (THF), diethyl ether, and toluene. The methodology is widely applicable to a variety of silicon, boron, and sulfur-based electrophiles, as well as carbon-based electrophiles.

  1. Medicineringsfejl ved generisk substitution

    DEFF Research Database (Denmark)

    Rölfing, Jan

    2012-01-01

    Generic substitution is a major cause of medical mistakes in the general population. Danish legislation obligates pharmacies to substitute prescribed medicine with the cheapest equivalent formulation, despite variations in product name, packaging, shape and colour. Consequently, medical mistakes ...... occur. Scientific evidence on the consequences of generic substitution is sparse. Call upon fellow health workers to report medical mistakes to the national entities and scientific peers, in order to increase awareness and scientific evidence about the problem....

  2. Direct sp(3)C-H acroleination of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with nucleophilic catalysis.

    Science.gov (United States)

    Feng, Zhu-Jia; Xuan, Jun; Xia, Xu-Dong; Ding, Wei; Guo, Wei; Chen, Jia-Rong; Zou, You-Quan; Lu, Liang-Qiu; Xiao, Wen-Jing

    2014-04-07

    Sequence catalysis merging photoredox catalysis (PC) and nucleophilic catalysis (NC) has been realized for the direct sp(3) C-H acroleination of N-aryl-tetrahydroisoquinoline (THIQ). The reaction was performed under very mild conditions and afforded products in 50-91% yields. A catalytic asymmetric variant was proved to be successful with moderate enantioselectivities (up to 83 : 17 er).

  3. Organic Chemistry Students' Fragmented Ideas about the Structure and Function of Nucleophiles and Electrophiles: A Concept Map Analysis

    Science.gov (United States)

    Anzovino, Mary E.; Bretz, Stacey Lowery

    2016-01-01

    Organic chemistry students struggle with multiple aspects of reaction mechanisms and the curved arrow notation used by organic chemists. Many faculty believe that an understanding of nucleophiles and electrophiles, among other concepts, is required before students can develop fluency with the electronpushing formalism (EPF). An expert concept map…

  4. From α-nucleophiles to functionalized aggregates: exploring the reactivity of hydroxamate ion towards esterolytic reactions in micelles.

    Science.gov (United States)

    Singh, Namrata; Karpichev, Yevgen; Sharma, Rahul; Gupta, Bhanushree; Sahu, Arvind K; Satnami, Manmohan L; Ghosh, Kallol K

    2015-03-14

    Owing to the rising threats of neurotoxic organophosphosphorus compounds, facile and efficient decontamination systems are required. Since the last few decades, the search for promising α-nucleophiles for straightforward and eco-friendly decontamination reactions using α-nucleophiles has been considerably boosted up. Among these, hydroxamic acids have been widely studied due to their potential α-nucleophilicity towards carbon and phosphorus based esters. This account summarizes our research on α-nucleophilicity of hydroxamate ions in water and micelles towards esterolytic reactions. Efforts of our group in the last few years have been collectively judged and compared with the crucial findings of researchers in the relevant field. The present article sheds light on the rich chemistry of the hydroxamate ion as a perfect candidate to degrade organophosphorus esters (i.e. nerve agents, pesticides and their simulants) in water, in micelles of conventional surfactants, and in functionalized micelles. The current report also provides an insight into the possible nature and mechanisms of these reactions. A brief account of the biological activities of hydroxamic acids that have recently spurred research in medicine against some fatal diseases has been included.

  5. Chemistry of [(Perfluoroalkyl)Methyl] Oxiranes. Regioselectivity of Ring Opening with O-Nucleophiles and the Preparation of Amphiphilic Monomers

    Czech Academy of Sciences Publication Activity Database

    Církva, Vladimír; Améduri, B.; Boutevin, B.; Paleta, O.

    1997-01-01

    Roč. 84, č. 1 (1997), s. 53-61 ISSN 0022-1139 Institutional research plan: CEZ:AV0Z4072921 Keywords : fluoroalkyl thiiranes * nucleophilic oxirane ring opening Subject RIV: CC - Organic Chemistry Impact factor: 0.714, year: 1997

  6. Vectors for multi-color bimolecular fluorescence complementation to investigate protein-protein interactions in living plant cells

    Directory of Open Access Journals (Sweden)

    Kuang Lin-Yun

    2008-10-01

    Full Text Available Abstract Background The investigation of protein-protein interactions is important for characterizing protein function. Bimolecular fluorescence complementation (BiFC has recently gained interest as a relatively easy and inexpensive method to visualize protein-protein interactions in living cells. BiFC uses "split YFP" tags on proteins to detect interactions: If the tagged proteins interact, they may bring the two split fluorophore components together such that they can fold and reconstitute fluorescence. The sites of interaction can be monitored using epifluorescence or confocal microscopy. However, "conventional" BiFC can investigate interactions only between two proteins at a time. There are instances when one may wish to offer a particular "bait" protein to several "prey" proteins simultaneously. Preferential interaction of the bait protein with one of the prey proteins, or different sites of interaction between the bait protein and multiple prey proteins, may thus be observed. Results We have constructed a series of gene expression vectors, based upon the pSAT series of vectors, to facilitate the practice of multi-color BiFC. The bait protein is tagged with the C-terminal portion of CFP (cCFP, and prey proteins are tagged with the N-terminal portions of either Venus (nVenus or Cerulean (nCerulean. Interaction of cCFP-tagged proteins with nVenus-tagged proteins generates yellow fluorescence, whereas interaction of cCFP-tagged proteins with nCerulean-tagged proteins generates blue fluorescence. Additional expression of mCherry indicates transfected cells and sub-cellular structures. Using this system, we have determined in both tobacco BY-2 protoplasts and in onion epidermal cells that Agrobacterium VirE2 protein interacts with the Arabidopsis nuclear transport adapter protein importin α-1 in the cytoplasm, whereas interaction of VirE2 with a different importin α isoform, importin α-4, occurs predominantly in the nucleus. Conclusion Multi

  7. Use of X-ray diffraction, molecular simulations, and spectroscopy to determine the molecular packing in a polymer-fullerene bimolecular crystal

    KAUST Repository

    Miller, Nichole Cates

    2012-09-05

    The molecular packing in a polymer: fullerene bimolecular crystal is determined using X-ray diffraction (XRD), molecular mechanics (MM) and molecular dynamics (MD) simulations, 2D solid-state NMR spectroscopy, and IR absorption spectroscopy. The conformation of the electron-donating polymer is significantly disrupted by the incorporation of the electron-accepting fullerene molecules, which introduce twists and bends along the polymer backbone and 1D electron-conducting fullerene channels. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Science.gov (United States)

    2010-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject to...

  9. Electricity/oil substitution

    International Nuclear Information System (INIS)

    Melvin, J.G.

    1980-09-01

    The extent to which electricity could substitute for imported oil in Canada is assessed and it is concluded that the bulk of projected oil imports could be displaced. This substitution of electricity for oil could be largely completed within two decades, with existing technology, using Canadian resources. The substitution of electricity for imported oil would result in relatively low energy costs and would stimulate economic growth. Energy self-sufficiency through the substitution of electricity for oil is uniquely a Canadian option; it is not open to other industrial countries. The option exists because of Canada's resources of oil sands for essential liquid fuels, hydraulic and nuclear electrical potential, and natural gas as an interim source of energy. While other countries face an energy crisis due to declining supplies of oil, Canada faces opportunities. The policies of Federal and Provincial governments, as perceived by individual decision makers, will have a major influence on Canada's ability to realize opportunities. (auth)

  10. Reactivity of 5a,6-anhydrotetracycline platinum(II) complex with biological nucleophiles: a theoretical study

    International Nuclear Information System (INIS)

    Marcial, Bruna L.; Santos, Helio F. dos; Costa, Luiz Antonio S.; Almeida, Wagner B. de

    2008-01-01

    This paper describes a theoretical analysis of the interaction between 5a,6-anhydrotetracycline platinum(II) complex (AHTC-Pt) and some biological nucleophiles; adenine (A), guanine (G), cysteine (Cys) and methionine (Met). The aquated species [Pt(AHTC)Cl(H 2 O)] + was taken as reagent for the processes studied here. For DNA bases (A and G), the calculated values for ΔG a,aq at the B3LYP/6-311+G(2d,p) level were 21.7 and 20.7 kcal mol -1 for interaction with A and G, respectively, which are in accordance with the expected behavior of faster process involving G. These values are higher than the experimental activation energy for the parent compound cisplatin (18.5 kcal mol -1 for interaction with G). For the process involving the amino-acids, the barriers were 17.6 (Cys) and 18.5 kcal mol -1 (Met), which are lower than the observed values for cisplatin (20.5 and 20.2 kcal mol -1 , respectively). These outcomes show that AHTC-Pt hybrid complex may be considered a promising lead compound in the development of novel anticancer drugs based on platinum complex. (author)

  11. Reactivity of 5a,6-anhydrotetracycline platinum(II) complex with biological nucleophiles: a theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Marcial, Bruna L.; Santos, Helio F. dos [Universidade Federal de Juiz de Fora (UFJF), MG (Brazil). Dept. de Quimica. Nucleo de Estudos em Quimica Computacional; Costa, Luiz Antonio S. [Escola Preparatoria de Cadetes do Ar, Barbacena, MG (Brazil). Comando da Aeronautica. Dept. de Ensino da Aeronautica; Almeida, Wagner B. de [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica. Lab. de Quimica Computacional e Modelagem Molecular]. E-mail: helio.santos@ufjf.edu.br

    2008-07-01

    This paper describes a theoretical analysis of the interaction between 5a,6-anhydrotetracycline platinum(II) complex (AHTC-Pt) and some biological nucleophiles; adenine (A), guanine (G), cysteine (Cys) and methionine (Met). The aquated species [Pt(AHTC)Cl(H{sub 2}O)]{sup +} was taken as reagent for the processes studied here. For DNA bases (A and G), the calculated values for {delta}G{sub a,aq} at the B3LYP/6-311+G(2d,p) level were 21.7 and 20.7 kcal mol{sup -1} for interaction with A and G, respectively, which are in accordance with the expected behavior of faster process involving G. These values are higher than the experimental activation energy for the parent compound cisplatin (18.5 kcal mol{sup -1} for interaction with G). For the process involving the amino-acids, the barriers were 17.6 (Cys) and 18.5 kcal mol{sup -1} (Met), which are lower than the observed values for cisplatin (20.5 and 20.2 kcal mol{sup -1}, respectively). These outcomes show that AHTC-Pt hybrid complex may be considered a promising lead compound in the development of novel anticancer drugs based on platinum complex. (author)

  12. Steric Effect on the Nucleophilic Reactivity of Nickel(III) Peroxo Complexes.

    Science.gov (United States)

    Kim, Jalee; Shin, Bongki; Kim, Hyunjeong; Lee, Junhyung; Kang, Joongoo; Yanagisawa, Sachiko; Ogura, Takashi; Masuda, Hideki; Ozawa, Tomohiro; Cho, Jaeheung

    2015-07-06

    A set of nickel(III) peroxo complexes bearing tetraazamacrocyclic ligands, [Ni(III)(TBDAP)(O2)](+) (TBDAP = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane) and [Ni(III)(CHDAP)(O2)](+) (CHDAP = N,N'-dicyclohexyl-2,11-diaza[3.3](2,6)pyridinophane), were prepared by reacting [Ni(II)(TBDAP)(NO3)(H2O)](+) and [Ni(II)(CHDAP)(NO3)](+), respectively, with H2O2 in the presence of triethylamine. The mononuclear nickel(III) peroxo complexes were fully characterized by various physicochemical methods, such as UV-vis, electrospray ionization mass spectrometry, resonance Raman, electron paramagnetic resonance, and X-ray analysis. The spectroscopic and structural characterization clearly shows that the NiO2 cores are almost identical where the peroxo ligand is bound in a side-on fashion. However, the different steric properties of the supporting ligands were confirmed by X-ray crystallography, where the CHDAP ligand gives enough space around the Ni core compared to the TBDAP ligand. The nickel(III) peroxo complexes showed reactivity in the oxidation of aldehydes. In the aldehyde deformylation reaction, the nucleophilic reactivity of the nickel(III) peroxo complexes was highly dependent on the steric properties of the macrocyclic ligands, with a reactivity order of [Ni(III)(TBDAP)(O2)](+) < [Ni(III)(CHDAP)(O2)](+). This result provides fundamental insight into the mechanism of the structure (steric)-reactivity relationship of metal peroxo intermediates.

  13. The substitutability of reinforcers

    OpenAIRE

    Green, Leonard; Freed, Debra E.

    1993-01-01

    Substitutability is a construct borrowed from microeconomics that describes a continuum of possible interactions among the reinforcers in a given situation. Highly substitutable reinforcers, which occupy one end of the continuum, are readily traded for each other due to their functional similarity. Complementary reinforcers, at the other end of the continuum, tend to be consumed jointly in fairly rigid proportion, and therefore cannot be traded for one another except to achieve that proportio...

  14. Synthesis of substituted pyrazines

    Science.gov (United States)

    Pagoria, Philip F.; Zhang, Mao Xi

    2016-10-04

    A method for synthesizing a pyrazine-containing material according to one embodiment includes contacting an iminodiacetonitrile derivative with a base and a reagent selected from a group consisting of hydroxylamine, a hydroxylamine salt, an aliphatic primary amine, a secondary amine, an aryl-substituted alkylamine a heteroaryl-substituted alkyl amine, an alcohol, an alkanolamine and an aryl alcoholamine. Additional methods and several reaction products are presented. ##STR00001##

  15. Gas phase studies of the Pesci decarboxylation reaction: synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions.

    Science.gov (United States)

    O'Hair, Richard A J; Rijs, Nicole J

    2015-02-17

    promoting the formation of the organometallic ion. Where isomeric organometallic ions are generated and normal MS approaches cannot distinguish them, we describe approaches to elucidate the decarboxylation mechanism via determination of their structure. These "unmasked" organometallic ions, [RM(L)n](x), can also be structurally interrogated spectroscopically or via CID. We have thus compared the gas-phase structures and decomposition of several highly reactive and synthetically important organometallic ions for the first time. Perhaps the most significant aspect of this work is the study of bimolecular reactions, which provides experimental information on mechanistically obscure bond-formation and cross-coupling steps and the intrinsic reactivity of ions. We have sought to understand transformations of substrates including acid-base and hydrolysis reactions, along with reactions resulting in C-C bond formation. Our studies also allow a direct comparison of the performance of different metal catalysts in the individual elementary steps associated with protodecarboxylation and decarboxylative alkylation cycles. Electronic structure (DFT and ab initio) and dynamics (RRKM) calculations provide further mechanistic insights into these reactions. The broad implications of this research are that new reactions can be discovered and that the performance of metal catalysts can be evaluated in terms of each of their elementary steps. This has been particularly useful for the study of metal-mediated decarboxylation reactions.

  16. Nucleophile-directed selectivity towards linear carbonates in the niobium pentaethoxide-catalysed cycloaddition of CO2 and propylene oxide

    KAUST Repository

    Dutta, Barnali

    2014-01-01

    Homoleptic Nb-complexes combined with selected organic nucleophiles generate very active catalytic systems for the cycloaddition of propylene oxide and CO2 under ambient conditions. An unprecedented reaction pathway towards an acyclic organic carbonate is observed when extending the study to [Nb(OEt)5] in combination with 4-dimethylamino-pyridine (DMAP) or tetra-n-butylammonium bromide (TBAB). Mechanistic insights of the reaction are provided based on experimental and spectroscopic evidences. This journal is © the Partner Organisations 2014.

  17. Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Munoz, Jose Luis [GENZ - Grupo de Investigacion Enzimologia, Departamento de Bioquimica y Biologia Molecular-A, Facultad de Biologia, Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia, E-30100 Espinardo, Murcia (Spain); Berna, Jose [Grupo de Quimica Organica Sintetica, Departamento de Quimica Organica, Facultad de Quimica Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia (Spain); Garcia-Molina, Maria del Mar; Garcia-Molina, Francisco [GENZ - Grupo de Investigacion Enzimologia, Departamento de Bioquimica y Biologia Molecular-A, Facultad de Biologia, Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia, E-30100 Espinardo, Murcia (Spain); Garcia-Ruiz, Pedro Antonio [QCPAI - Grupo de Quimica de Carbohidratos, Polimeros y Aditivos Industriales, Departamento de Quimica Organica, Facultad de Quimica Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia (Spain); Varon, Ramon [Departamento de Quimica-Fisica, Escuela de Ingenieros Industriales de Albacete, Universidad de Castilla la Mancha, Avda. Espana s/n. Campus Universitario, E-02071 Albacete (Spain); and others

    2012-07-27

    Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemical shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that

  18. Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

    International Nuclear Information System (INIS)

    Muñoz-Muñoz, Jose Luis; Berna, Jose; García-Molina, María del Mar; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon

    2012-01-01

    Highlights: ► The action the copper complexes and tyrosinase on phenols is equivalent. ► Isotope effect showed that nucleophilic attack to copper atom may be the slower step. ► The value of ρ (Hammett constant) supports an electrophilic aromatic substitution. ► Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k cat m and the Michaelis constant, K M m . Analysis of these data taking into account chemical shifts of the carbon atom supporting the hydroxyl group (δ) and σ p + , enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E ox (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant ρ of −1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k cat f n /k cat f 0 against n (atom fractions of deuterium), where k cat f n is the catalytic constant for a molar fraction of deuterium (n) and k cat f 0 is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that only one of the proton transfer processes from the hydroxyl groups involved the catalytic cycle is responsible for the isotope effects. We suggest that this step is the proton transfer from the hydroxyl group

  19. Bone substitute biomaterials

    CERN Document Server

    Mallick, K

    2014-01-01

    Bone substitute biomaterials are fundamental to the biomedical sector, and have recently benefitted from extensive research and technological advances aimed at minimizing failure rates and reducing the need for further surgery. This book reviews these developments, with a particular focus on the desirable properties for bone substitute materials and their potential to encourage bone repair and regeneration. Part I covers the principles of bone substitute biomaterials for medical applications. One chapter reviews the quantification of bone mechanics at the whole-bone, micro-scale, and non-scale levels, while others discuss biomineralization, osteoductivization, materials to fill bone defects, and bioresorbable materials. Part II focuses on biomaterials as scaffolds and implants, including multi-functional scaffolds, bioceramics, and titanium-based foams. Finally, Part III reviews further materials with the potential to encourage bone repair and regeneration, including cartilage grafts, chitosan, inorganic poly...

  20. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  1. The influence of the "cage" effect on the mechanism of reversible bimolecular multistage chemical reactions proceeding from different sites in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2016-08-28

    Manifestations of the "cage" effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the "cage complex," just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of the "cage" effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.

  2. [Artificial bone substitutes].

    Science.gov (United States)

    Koníček, Petr

    Bone tissue substitutes are divided into basic classification with its pros and cons described. Arteficial bone grafts are especially pointed out in article, publishing our own experience with two specific synthetic preps. Finally there is a blink in the near future of bone tissue augmentation.

  3. 2-Chlorophenyl Zinc Bromide: A Convenient Nucleophile for the Mannich-Related Multicomponent Synthesis of Clopidogrel and Ticlopidine

    Directory of Open Access Journals (Sweden)

    Isabelle Aillaud

    2010-11-01

    Full Text Available A methodological study devoted to the Mannich-like multicomponent synthesis of the antiplatelet agent (±‑clopidogrel (7 and the ethyl ester analogue 6 is described. The process involves the formation of 2-chlorophenyl zinc bromide (2 and its subsequent reaction with an alkyl glyoxylate and 4,5,6,7-tetrahydrothieno[3,2-c]pyridine (3. We demonstrate that the organozinc reagent 2 also constitutes a very convenient nucleophile for the multicomponent synthesis of the benzylamine core of ticlopidine (9.

  4. [Currently available skin substitutes].

    Science.gov (United States)

    Oravcová, Darina; Koller, Ján

    2014-01-01

    The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. Autologous split or full-thickness skin graft are the best definitive burn wound coverage, but it is constrained by the limited available sources, especially in major burns. Donor site morbidities in term of additional wounds and scarring are also of concern of the autograft application. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. This paper reviews currently available skin substitutes, produced in not for-profit skin banks as well as commercially available. They are divided according to type of material included, as biological, biosynthetic and synthetic and named respectively.

  5. How Do Nutritional Antioxidants Really Work: Nucleophilic Tone and Para-Hormesis Versus Free Radical Scavenging in vivo

    Science.gov (United States)

    Forman, Henry Jay; Davies, Kelvin J. A.; Ursini, Fulvio

    2013-01-01

    We present arguments for an evolution in our understanding of how antioxidants in fruits and vegetables exert their health-protective effects. There is much epidemiological evidence for disease prevention by dietary antioxidants and chemical evidence that such compounds react in one-electron reactions with free radicals in vitro. Nonetheless, kinetic constraints indicate that in vivo scavenging of radicals is ineffective in antioxidant defense. Instead, enzymatic removal of non-radical electrophiles, such as hydroperoxides, in two-electron redox reactions is the major antioxidant mechanism. Furthermore, we propose that a major mechanism of action for nutritional antioxidants is the paradoxical oxidative activation of the Nrf2 (NF-E2-related factor 2) signaling pathway, which maintains protective oxidoreductases and their nucleophilic substrates. This maintenance of ‘Nucleophilic Tone,’ by a mechanism that can be called ‘Para-Hormesis,’ provides a means for regulating physiological non-toxic concentrations of the non-radical oxidant electrophiles that boost antioxidant enzymes, and damage removal and repair systems (for proteins, lipids, and DNA), at the optimal levels consistent with good health. PMID:23747930

  6. Acid dissociation constant and apparent nucleophilicity of lysine-501 of the alpha-polypeptide of sodium and potassium ion activated adenosinetriphosphatase

    International Nuclear Information System (INIS)

    Xu, K.Y.

    1989-01-01

    A combination of competitive labeling with [ 3 H]acetic anhydride and immunoaffinity chromatography is described that permits the assignment of the acid dissociation constant and the absolute nucleophilicity of individual lysines in a native enzyme. The acid dissociation constant of lysine-501 of the alpha-polypeptide in native (Na+ + K+)-ATPase was determined. This lysine had a normal pKa of 10.4. The rate constant for the reaction of the free base of lysine-501 with acetic anhydride at 10 degrees C is 400 M-1 s-1. This value is only 30% that for a fully accessible lysine in a protein. The lower than normal apparent nucleophilicity suggests that lysine-501 is hindered from reacting with its intrinsic nucleophilicity by the tertiary structure of the enzyme and is consistent with its location within a pocket that forms the active site upon the surface of the native protein

  7. Resources, recycle, and substitution

    International Nuclear Information System (INIS)

    Wymer, R.G.

    A two-fold strategy appears necessary to ensure that the resource needs of the developed and developing nations are met. First, recycle and substitution must be encouraged in those instances where they do find application. Although these measures have limited applicability, they may be of vital importance in those instances where they do apply; in any event, they buy time. Second, practical and economical technologies must be developed to exploit the lower-grade and marginal ores and the oftentimes abundant but highly refractory ores, as well as to greatly increase the recovery of secondary elements present in the ores - elements whose form and amounts in the ores make them economically unrecoverable by themselves, but which are economically recoverable as by-products. It is often the case that if these elements are not recovered during the initial mining and milling operations, they are rendered unrecoverable, in a practical sense, forever. Furthermore, they may even become environmental pollutants. Specific examples of recovery from refractory ores, by-product recovery, and recycle are given. Also, some suggestions of substitutes for important resources are tabulated

  8. Glycosyl Cross-Coupling of Anomeric Nucleophiles: Scope, Mechanism, and Applications in the Synthesis of Aryl C-Glycosides.

    Science.gov (United States)

    Zhu, Feng; Rodriguez, Jacob; Yang, Tianyi; Kevlishvili, Ilia; Miller, Eric; Yi, Duk; O'Neill, Sloane; Rourke, Michael J; Liu, Peng; Walczak, Maciej A

    2017-12-13

    Stereoselective manipulations at the C1 anomeric position of saccharides are one of the central goals of preparative carbohydrate chemistry. Historically, the majority of reactions forming a bond with anomeric carbon has focused on reactions of nucleophiles with saccharide donors equipped with a leaving group. Here, we describe a novel approach to stereoselective synthesis of C-aryl glycosides capitalizing on the highly stereospecific reaction of anomeric nucleophiles. First, methods for the preparation of anomeric stannanes have been developed and optimized to afford both anomers of common saccharides in high anomeric selectivities. We established that oligosaccharide stannanes could be prepared from monosaccharide stannanes via O-glycosylation with Schmidt-type donors, glycal epoxides, or under dehydrative conditions with C1 alcohols. Second, we identified a general set of catalytic conditions with Pd 2 (dba) 3 (2.5 mol%) and a bulky ligand (JackiePhos, 10 mol%) controlling the β-elimination pathway. We demonstrated that the glycosyl cross-coupling resulted in consistently high anomeric selectivities for both anomers with mono- and oligosaccharides, deoxysugars, saccharides with free hydroxyl groups, pyranose, and furanose substrates. The versatility of the glycosyl cross-coupling reaction was probed in the total synthesis of salmochelins (siderophores) and commercial anti-diabetic drugs (gliflozins). Combined experimental and computational studies revealed that the β-elimination pathway is suppressed for biphenyl-type ligands due to the shielding of Pd(II) by sterically demanding JackiePhos, whereas smaller ligands, which allow for the formation of a Pd-F complex, predominantly result in a glycal product. Similar steric effects account for the diminished rates of cross-couplings of 1,2-cis C1-stannanes with aryl halides. DFT calculations also revealed that the transmetalation occurs via a cyclic transition state with retention of configuration at the anomeric

  9. Live cell imaging of interactions between replicase and capsid protein of Brome mosaic virus using Bimolecular Fluorescence Complementation: implications for replication and genome packaging.

    Science.gov (United States)

    Chaturvedi, Sonali; Rao, A L N

    2014-09-01

    In Brome mosaic virus, it was hypothesized that a physical interaction between viral replicase and capsid protein (CP) is obligatory to confer genome packaging specificity. Here we tested this hypothesis by employing Bimolecular Fluorescent Complementation (BiFC) as a tool for evaluating protein-protein interactions in living cells. The efficacy of BiFC was validated by a known interaction between replicase protein 1a (p1a) and protein 2a (p2a) at the endoplasmic reticulum (ER) site of viral replication. Additionally, co-expression in planta of a bona fide pair of interacting protein partners of p1a and p2a had resulted in the assembly of a functional replicase. Subsequent BiFC assays in conjunction with mCherry labeled ER as a fluorescent cellular marker revealed that CP physically interacts with p2a, but not p1a, and this CP:p2a interaction occurs at the cytoplasmic phase of the ER. The significance of the CP:p2a interaction in BMV replication and genome packaging is discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Development of bimolecular fluorescence complementation using rsEGFP2 for detection and super-resolution imaging of protein-protein interactions in live cells.

    Science.gov (United States)

    Wang, Sheng; Ding, Miao; Chen, Xuanze; Chang, Lei; Sun, Yujie

    2017-06-01

    Direct visualization of protein-protein interactions (PPIs) at high spatial and temporal resolution in live cells is crucial for understanding the intricate and dynamic behaviors of signaling protein complexes. Recently, bimolecular fluorescence complementation (BiFC) assays have been combined with super-resolution imaging techniques including PALM and SOFI to visualize PPIs at the nanometer spatial resolution. RESOLFT nanoscopy has been proven as a powerful live-cell super-resolution imaging technique. With regard to the detection and visualization of PPIs in live cells with high temporal and spatial resolution, here we developed a BiFC assay using split rsEGFP2, a highly photostable and reversibly photoswitchable fluorescent protein previously developed for RESOLFT nanoscopy. Combined with parallelized RESOLFT microscopy, we demonstrated the high spatiotemporal resolving capability of a rsEGFP2-based BiFC assay by detecting and visualizing specifically the heterodimerization interactions between Bcl-x L and Bak as well as the dynamics of the complex on mitochondria membrane in live cells.

  11. Vacancy-induced initial decomposition of condensed phase NTO via bimolecular hydrogen transfer mechanisms at high pressure: a DFT-D study.

    Science.gov (United States)

    Liu, Zhichao; Wu, Qiong; Zhu, Weihua; Xiao, Heming

    2015-04-28

    Density functional theory with dispersion-correction (DFT-D) was employed to study the effects of vacancy and pressure on the structure and initial decomposition of crystalline 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (β-NTO), a high-energy insensitive explosive. A comparative analysis of the chemical behaviors of NTO in the ideal bulk crystal and vacancy-containing crystals under applied hydrostatic compression was considered. Our calculated formation energy, vacancy interaction energy, electron density difference, and frontier orbitals reveal that the stability of NTO can be effectively manipulated by changing the molecular environment. Bimolecular hydrogen transfer is suggested to be a potential initial chemical reaction in the vacancy-containing NTO solid at 50 GPa, which is prior to the C-NO2 bond dissociation as its initiation decomposition in the gas phase. The vacancy defects introduced into the ideal bulk NTO crystal can produce a localized site, where the initiation decomposition is preferentially accelerated and then promotes further decompositions. Our results may shed some light on the influence of the molecular environments on the initial pathways in molecular explosives.

  12. Live cell imaging of interactions between replicase and capsid protein of Brome mosaic virus using Bimolecular Fluorescence Complementation: Implications for replication and genome packaging

    Energy Technology Data Exchange (ETDEWEB)

    Chaturvedi, Sonali; Rao, A.L.N., E-mail: arao@ucr.edu

    2014-09-15

    In Brome mosaic virus, it was hypothesized that a physical interaction between viral replicase and capsid protein (CP) is obligatory to confer genome packaging specificity. Here we tested this hypothesis by employing Bimolecular Fluorescent Complementation (BiFC) as a tool for evaluating protein–protein interactions in living cells. The efficacy of BiFC was validated by a known interaction between replicase protein 1a (p1a) and protein 2a (p2a) at the endoplasmic reticulum (ER) site of viral replication. Additionally, co-expression in planta of a bona fide pair of interacting protein partners of p1a and p2a had resulted in the assembly of a functional replicase. Subsequent BiFC assays in conjunction with mCherry labeled ER as a fluorescent cellular marker revealed that CP physically interacts with p2a, but not p1a, and this CP:p2a interaction occurs at the cytoplasmic phase of the ER. The significance of the CP:p2a interaction in BMV replication and genome packaging is discussed. - Highlights: • YFP fusion proteins of BMV p1a and p2a are biologically active. • Self-interaction was observed for p1a, p2a and CP. • CP interacts with p2a but not p1a. • Majority of reconstituted YFP resulting from bona fide fusion protein partners localized on ER.

  13. Live cell imaging of interactions between replicase and capsid protein of Brome mosaic virus using Bimolecular Fluorescence Complementation: Implications for replication and genome packaging

    International Nuclear Information System (INIS)

    Chaturvedi, Sonali; Rao, A.L.N.

    2014-01-01

    In Brome mosaic virus, it was hypothesized that a physical interaction between viral replicase and capsid protein (CP) is obligatory to confer genome packaging specificity. Here we tested this hypothesis by employing Bimolecular Fluorescent Complementation (BiFC) as a tool for evaluating protein–protein interactions in living cells. The efficacy of BiFC was validated by a known interaction between replicase protein 1a (p1a) and protein 2a (p2a) at the endoplasmic reticulum (ER) site of viral replication. Additionally, co-expression in planta of a bona fide pair of interacting protein partners of p1a and p2a had resulted in the assembly of a functional replicase. Subsequent BiFC assays in conjunction with mCherry labeled ER as a fluorescent cellular marker revealed that CP physically interacts with p2a, but not p1a, and this CP:p2a interaction occurs at the cytoplasmic phase of the ER. The significance of the CP:p2a interaction in BMV replication and genome packaging is discussed. - Highlights: • YFP fusion proteins of BMV p1a and p2a are biologically active. • Self-interaction was observed for p1a, p2a and CP. • CP interacts with p2a but not p1a. • Majority of reconstituted YFP resulting from bona fide fusion protein partners localized on ER

  14. Bimolecular interaction of argpyrimidine (a Maillard reaction product) in in vitro non-enzymatic protein glycation model and its potential role as an antiglycating agent.

    Science.gov (United States)

    Bhattacherjee, Abhishek; Dhara, Kaliprasanna; Chakraborti, Abhay Sankar

    2017-09-01

    Non- enzymatic glycation, also known as Maillard reaction, is one of the most important and investigated reactions in biochemistry. Maillard reaction products (MRPs) like protein-derived advanced glycation end products (AGEs) are often referred to cause pathophysiological complications in human systems. On contrary, several MRPs are exogenously used as antioxidant, antimicrobial and flavouring agents. In the preset study, we have shown that argpyrimidine, a well-established AGE, interacts with bovine serum albumin (BSA) and glucose individually in standard BSA-glucose model system and successfully inhibits glycation of the protein. Bimolecular interaction of argpyrimidine with glucose or BSA has been studied independently. Chromatographic purification, different spectroscopic studies and molecular modeling have been used to evaluate the nature and pattern of interactions. Binding of argpyrimidine with BSA prevents incorporation of glucose inside the native protein. Argpyrimidine can also directly entrap glucose. Both these interactions may be associated with the antiglycation potential of argpyrimidine, indicating a beneficial function of an AGE. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Living Polymerization of N -Substituted β-Alanine N -Carboxyanhydrides: Kinetic Investigations and Preparation of an Amphiphilic Block Copoly-β-Peptoid

    KAUST Repository

    Grossmann, Arlett

    2012-07-03

    Poly(α-peptoid)s (N-substituted polyglycines) are interesting peptidomimetic biomaterials that have been discussed for many applications. Poly(β-peptoid)s (N-substituted poly-β-alanines), although equally intriguing, have received much less attention. Here we present results that suggest that while N-substituted β-alanine N-carboxyanhydrides can undergo a living nucleophilic ring-opening polymerization, the solubility of poly(β-peptoid)s can be very poor, which contributes to the limited accessibility using other synthetic approaches. The living character of the polymerization was utilized for the preparation of the first polymerized amphiphilic block copoly-β-peptoid. Our results may open a new route towards highly defined functional poly(β-peptoid)s which could represent biomaterials. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide*♦

    Science.gov (United States)

    Cuevasanta, Ernesto; Lange, Mike; Bonanata, Jenner; Coitiño, E. Laura; Ferrer-Sueta, Gerardo; Filipovic, Milos R.; Alvarez, Beatriz

    2015-01-01

    Hydrogen sulfide (H2S) is increasingly recognized to modulate physiological processes in mammals through mechanisms that are currently under scrutiny. H2S is not able to react with reduced thiols (RSH). However, H2S, more precisely HS−, is able to react with oxidized thiol derivatives. We performed a systematic study of the reactivity of HS− toward symmetric low molecular weight disulfides (RSSR) and mixed albumin (HSA) disulfides. Correlations with thiol acidity and computational modeling showed that the reaction occurs through a concerted mechanism. Comparison with analogous reactions of thiolates indicated that the intrinsic reactivity of HS− is 1 order of magnitude lower than that of thiolates. In addition, H2S is able to react with sulfenic acids (RSOH). The rate constant of the reaction of H2S with the sulfenic acid formed in HSA was determined. Both reactions of H2S with disulfides and sulfenic acids yield persulfides (RSSH), recently identified post-translational modifications. The formation of this derivative in HSA was determined, and the rate constants of its reactions with a reporter disulfide and with peroxynitrite revealed that persulfides are better nucleophiles than thiols, which is consistent with the α effect. Experiments with cells in culture showed that treatment with hydrogen peroxide enhanced the formation of persulfides. Biological implications are discussed. Our results give light on the mechanisms of persulfide formation and provide quantitative evidence for the high nucleophilicity of these novel derivatives, setting the stage for understanding the contribution of the reactions of H2S with oxidized thiol derivatives to H2S effector processes. PMID:26269587

  17. Reactions of substituted vinyl cations in acetonitrile solution as studied by flash photolysis

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Shinjiro (Kyushu Univ., Fukuoka (Japan). Dept. of Applied Chemistry); Zhu Qinqin; Schnabel, W. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.))

    1988-07-01

    Vinyl cations I{sub a}{sup +}, I{sub b}{sup +}, I{sub c}{sup +} of the structure R{sub 2}'C=C{sup +}R'' (I{sub a}{sup +}: R'=R''=anisyl; I{sub b}{sup +}: R2 = phenyl, R'' = anisyl, I{sub c}{sup +}:R' = methyl, R'' = anisyl) were generated by flash photolysis of corresponding bromides. Lifetime measurements yielded the following: substitution of aromatic groups in 2-position by methyl groups largely improved the electrophilicity of the vinyl cations. The nucleophilicity of typical compounds (ketone, ester, alcohol, olefin) was measured. (orig.).

  18. Stereocontrolled generation of nucleophilic (Z)- or (E)-α-fluoroalkenylchromium reagents via carbon-fluorine bond activation: highly stereoselective synthesis of (E)- or (Z)-β-fluoroallylic alcohols.

    Science.gov (United States)

    Nihei, Takashi; Yokotani, Saya; Ishihara, Takashi; Konno, Tsutomu

    2014-02-14

    Highly nucleophilic (Z)- or (E)-α-fluoroalkenylchromium species could be generated in a stereoselective manner via C-F bond activation of CBrF2-containing molecules, and they reacted smoothly with various aldehydes to give (E)- or (Z)-β-fluoroallylic alcohol derivatives in high yields, respectively.

  19. Origin of Enhanced Reactivity of a Microsolvated Nucleophile in Ion Pair SN2 Reactions: The Cases of Sodium p-Nitrophenoxide with Halomethanes in Acetone.

    Science.gov (United States)

    Li, Qiang-Gen; Xu, Ke; Ren, Yi

    2015-04-30

    In a kinetic experiment on the SN2 reaction of sodium p-nitrophenoxide with iodomethane in acetone-water mixed solvent, Humeres et al. (J. Org. Chem. 2001, 66, 1163) found that the reaction depends strongly on the medium, and the fastest rate constant was observed in pure acetone. The present work tries to explore why acetone can enhance the reactivity of the title reactions. Accordingly, we make a mechanistic study on the reactions of sodium p-nitrophenoxide with halomethanes (CH3X, X = Cl, Br, I) in acetone by using a supramolecular/continuum model at the PCM-MP2/6-311+G(d,p)//B3LYP/6-311+G(d,p) level, in which the ion pair nucleophile is microsolvated by one to three acetone molecules. We compared the reactivity of the microsolvated ion pair nucleophiles with solvent-free ion pair and anionic ones. Our results clearly reveal that the microsolvated ion pair nucleophile is favorable for the SN2 reactions; meanwhile, the origin of the enhanced reactivity induced by microsolvation of the nucleophile is discussed in terms of the geometries of transition state (TS) structures and activation strain model, suggesting that lower deformation energies and stronger interaction energies between the deformed reactants in the TS lead to the lower overall reaction barriers for the SN2 reaction of microsolvated sodium p-nitrophenoxide toward halomethanes in acetone.

  20. Nucleophilic 18F-Labeling of Spirocyclic Iodonium Ylide or Boronic Pinacol Ester Precursors - Advantages and Disadvantages

    DEFF Research Database (Denmark)

    Petersen, Ida Nymann; Kristensen, Jesper Langgaard; Herth, Matthias Manfred

    2017-01-01

    The field of labeling electron-rich aryl compounds with nucleophilic [18F]fluoride has recently expanded with radiofluorination strategies that apply boronic esters or spirocyclic iodonium ylides as precursors. Herein, we present a direct comparison of these strategies by using nine chemically di...

  1. Radical addition reactions of fluorinated species Part 6. Regioselectivity of the Addition of Nucleophilic Radicals to Halogenopropenes and Evidence for a Steric Effect of the Chlorine Substituent

    Czech Academy of Sciences Publication Activity Database

    Paleta, O.; Církva, Vladimír; Budková, Z.; Böhm, S.

    1997-01-01

    Roč. 86, č. 2 (1997), s. 155-171 ISSN 0022-1139 Institutional research plan: CEZ:AV0Z4072921 Keywords : halogenopropenes * nucleophilic radical addition * regioselectivity Subject RIV: CC - Organic Chemistry Impact factor: 0.714, year: 1997

  2. 4,5-Bis(dialkylamino)-substituted imidazolium systems: facile access to N-heterocyclic carbenes with self-umpolung option.

    Science.gov (United States)

    Huber, Stefan M; Heinemann, Frank W; Audebert, Pierre; Weiss, Robert

    2011-11-11

    The first synthesis of 4,5-bis-(dimethylamino)-substituted imidazolium compounds was developed, which is based on the reaction of a 1,2-diamino-1,2-bis(phosphonio)ethene with lithiated formamidines. This represents the first application of this class of ethene derivatives for the preparation of heterocycles. These N-heterocyclic carbene (NHC) precursors show a remarkably reduced basicity and nucleophilicity of their NMe2 groups, which is due to the strong anomeric interactions of the latter with the imidazolium core. According to DFT calculations, these NHCs are capable of self-umpolung if sufficiently strong acceptor substituents are introduced at the carbene center. To test the self-umpolung capabilities of the NHCs, various substituents were attached to the carbene center and the obtained compounds were characterized by single-crystal X-ray analysis as well as quantum chemical computations. Strong acceptor substituents are required to induce self-umpolung, such as in the phosphonio-substituted derivative, for which partial self-umpolung was found. The N,N′-bis(4-dimethylaminophenyl)-substituted imidazolium compound represents a special case, as it incorporates as much as three two-step redox systems within the NHC framework. This will probably result in a high electronic flexibility of the corresponding nucleophilic carbenes, especially when they serve as ligands in transition metal complexes.

  3. Substitution in recreation choice behavior

    Science.gov (United States)

    George L. Peterson; Daniel J. Stynes; Donald H. Rosenthal; John F. Dwyer

    1985-01-01

    This review discusses concepts and theories of substitution in recreation choice. It brings together the literature of recreation research, psychology, geography, economics, and transportation. Parallel and complementary developments need integration into an improved theory of substitution. Recreation decision behavior is characterized as a nested or sequential choice...

  4. Biological background of dermal substitutes

    NARCIS (Netherlands)

    van der Veen, V. C.; van der Wal, M.B.; van Leeuwen, M.C.; Ulrich, M.; Middelkoop, E.

    2010-01-01

    Dermal substitutes are of major importance in treating full thickness skin defects, both in acute and chronic wounds. In this review we will outline specific requirements of three classes of dermal substitutes:-natural biological materials, with a more or less intact extracellular matrix

  5. A fluorescent bimolecular complementation screen reveals MAF1, RNF7 and SETD3 as PCNA-associated proteins in human cells

    Science.gov (United States)

    Cooper, Simon E; Hodimont, Elsie; Green, Catherine M

    2015-01-01

    The proliferating cell nuclear antigen (PCNA) is a conserved component of DNA replication factories, and interactions with PCNA mediate the recruitment of many essential DNA replication enzymes to these sites of DNA synthesis. A complete description of the structure and composition of these factories remains elusive, and a better knowledge of them will improve our understanding of how the maintenance of genome and epigenetic stability is achieved. To fully characterize the set of proteins that interact with PCNA we developed a bimolecular fluorescence complementation (BiFC) screen for PCNA-interactors in human cells. This 2-hybrid type screen for interactors from a human cDNA library is rapid and efficient. The fluorescent read-out for protein interaction enables facile selection of interacting clones, and we combined this with next generation sequencing to identify the cDNAs encoding the interacting proteins. This method was able to reproducibly identify previously characterized PCNA-interactors but importantly also identified RNF7, Maf1 and SetD3 as PCNA-interacting proteins. We validated these interactions by co-immunoprecipitation from human cell extracts and by interaction analyses using recombinant proteins. These results show that the BiFC screen is a valuable method for the identification of protein-protein interactions in living mammalian cells. This approach has potentially wide application as it is high throughput and readily automated. We suggest that, given this interaction with PCNA, Maf1, RNF7, and SetD3 are potentially involved in DNA replication, DNA repair, or associated processes. PMID:26030842

  6. Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

    International Nuclear Information System (INIS)

    Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Turks, Maris; Cooper, William J.

    2013-01-01

    Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×10 9 , (1.07±0.07)×10 10 , (7.48±0.17)×10 9 , (7.31±0.29)×10 9 , (5.47±0.25)×10 9 , (6.94±0.10)×10 9 (M −1 s −1 ), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×10 9 , (8.98±0.27)×10 9 , (5.39±0.21)×10 9 , (4.33±0.17)×10 9 , (4.72±0.15)×10 9 , (1.42±0.02)×10 9 (M −1 s −1 ), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated. - Highlights: • Free radical chemistry of salicylic and 4 methyl salicylic acids is investigated. • The transient absorptions spectra for model compounds are measured. • Absolute bimolecular reaction rate constants for hydroxyl radical are determined. • Solvated electron reaction rate constants are calculated. • The use of salicylic acids as models for pharmaceuticals is explored

  7. Simple, heart-smart substitutions

    Science.gov (United States)

    ... food choices does not mean you have to sacrifice flavor. The key is to substitute less healthy ... trout, and mackerel. Shrimp has less cholesterol than chicken, pork, or beef. Choose lean meats. They have ...

  8. bis(n'-substituted a

    African Journals Online (AJOL)

    Preferred Customer

    substituted acetohydrazide) ... biological activity associated with their corresponding hydrazones attributed to the presence of the active ... Hence, in this paper, we are reporting eco-friendly synthesis of some new Schiff bases by condensing 2 ...

  9. N-substituted iminodiacetic acids

    International Nuclear Information System (INIS)

    Nunn, A.; Loberg, M.

    1982-01-01

    The chemical preparation of several new N-substituted iminodiacetic acid derivatives are described. These compounds when complexed with sup(99m)Tc provide useful radiopharmaceuticals for the external imaging of the hepatobiliary system. (U.K.)

  10. Title: Elucidation of Environmental Fate of Artificial Sweeteners (Aspartame, Acesulfame K and Saccharin) by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Possible Reaction By-Products

    Science.gov (United States)

    Teraji, T.; Arakaki, T.; Suzuka, T.

    2012-12-01

    Use of artificial sweeteners in beverages and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame, acefulfame K and saccharin and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far for aspartame was (2.6±1.2)×109 M-1 s-1 at pH = 3.0 and (4.9±2.3)×109 M-1 s-1 at pH = 5.5. Little effect was seen by changing the temperatures between 15 and 40 oC. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, +8.5 kJ mol-1 at pH = 5.5, which could be regarded as zero. We will report bimolecular rate constants at different pHs and temperatures for acesulfame K and saccharin, as well. Possible reaction by-products for aspartame will be also reported. We will further discuss the fate of aspartame in the coastal environment.

  11. Nitric oxide is reduced to HNO by proton-coupled nucleophilic attack by ascorbate, tyrosine, and other alcohols. A new route to HNO in biological media?

    Science.gov (United States)

    Suarez, Sebastián A; Neuman, Nicolás I; Muñoz, Martina; Álvarez, Lucía; Bikiel, Damián E; Brondino, Carlos D; Ivanović-Burmazović, Ivana; Miljkovic, Jan Lj; Filipovic, Milos R; Martí, Marcelo A; Doctorovich, Fabio

    2015-04-15

    The role of NO in biology is well established. However, an increasing body of evidence suggests that azanone (HNO), could also be involved in biological processes, some of which are attributed to NO. In this context, one of the most important and yet unanswered questions is whether and how HNO is produced in vivo. A possible route concerns the chemical or enzymatic reduction of NO. In the present work, we have taken advantage of a selective HNO sensing method, to show that NO is reduced to HNO by biologically relevant alcohols with moderate reducing capacity, such as ascorbate or tyrosine. The proposed mechanism involves a nucleophilic attack to NO by the alcohol, coupled to a proton transfer (PCNA: proton-coupled nucleophilic attack) and a subsequent decomposition of the so-produced radical to yield HNO and an alkoxyl radical.

  12. Bimolecular reaction of CH3 + CO in solid p-H2: infrared absorption of acetyl radical (CH3CO) and CH3-CO complex.

    Science.gov (United States)

    Das, Prasanta; Lee, Yuan-Pern

    2014-06-28

    We have recorded infrared spectra of acetyl radical (CH3CO) and CH3-CO complex in solid para-hydrogen (p-H2). Upon irradiation at 248 nm of CH3C(O)Cl/p-H2 matrices, CH3CO was identified as the major product; characteristic intense IR absorption features at 2990.3 (ν9), 2989.1 (ν1), 2915.6 (ν2), 1880.5 (ν3), 1419.9 (ν10), 1323.2 (ν5), 836.6 (ν7), and 468.1 (ν8) cm(-1) were observed. When CD3C(O)Cl was used, lines of CD3CO at 2246.2 (ν9), 2244.0 (ν1), 1866.1 (ν3), 1046.7 (ν5), 1029.7 (ν4), 1027.5 (ν10), 889.1 (ν6), and 723.8 (ν7) cm(-1) appeared. Previous studies characterized only three vibrational modes of CH3CO and one mode of CD3CO in solid Ar. In contrast, upon photolysis of a CH3I/CO/p-H2 matrix with light at 248 nm and subsequent annealing at 5.1 K before re-cooling to 3.2 K, the CH3-CO complex was observed with characteristic IR features at 3165.7, 3164.5, 2150.1, 1397.6, 1396.4, and 613.0 cm(-1). The assignments are based on photolytic behavior, observed deuterium isotopic shifts, and a comparison of observed vibrational wavenumbers and relative IR intensities with those predicted with quantum-chemical calculations. This work clearly indicates that CH3CO can be readily produced from photolysis of CH3C(O)Cl because of the diminished cage effect in solid p-H2 but not from the reaction of CH3 + CO because of the reaction barrier. Even though CH3 has nascent kinetic energy greater than 87 kJ mol(-1) and internal energy ∼42 kJ mol(-1) upon photodissociation of CH3I at 248 nm, its energy was rapidly quenched so that it was unable to overcome the barrier height of ∼27 kJ mol(-1) for the formation of CH3CO from the CH3 + CO reaction; a barrierless channel for formation of a CH3-CO complex was observed instead. This rapid quenching poses a limitation in production of free radicals via bimolecular reactions in p-H2.

  13. Detection of Heteromers Formed by Cannabinoid CB1, Dopamine D2, and Adenosine A2A G-Protein-Coupled Receptors by Combining Bimolecular Fluorescence Complementation and Bioluminescence Energy Transfer

    Directory of Open Access Journals (Sweden)

    Gemma Navarro

    2008-01-01

    Full Text Available Functional interactions in signaling occur between dopamine D2 (D2R and cannabinoid CB1 (CB1R receptors, between CB1R and adenosine A2A (A2AR receptors, and between D2R and A2AR. Furthermore, direct molecular interactions have been reported for the pairs CB1R-D2R, A2AR-D2R, and CB1R-A2AR. Here a combination of bimolecular fluorescence complementation and bioluminescence energy transfer techniques was used to identify the occurrence of D2R-CB1R-A2AR hetero-oligomers in living cells.

  14. Glassy carbon electrode modified with horse radish peroxidase/organic nucleophilic-functionalized carbon nanotube composite for enhanced electrocatalytic oxidation and efficient voltammetric sensing of levodopa

    Energy Technology Data Exchange (ETDEWEB)

    Shoja, Yalda; Rafati, Amir Abbas, E-mail: aa_rafati@basu.ac.ir; Ghodsi, Javad

    2016-01-01

    A novel and selective enzymatic biosensor was designed and constructed for voltammetric determination of levodopa (L-Dopa) in aqueous media (phosphate buffer solution, pH = 7). Biosensor development was on the basis of to physically immobilizing of horse radish peroxidase (HRP) as electrochemical catalyst by sol–gel on glassy carbon electrode modified with organic nucleophilic carbon nanotube composite which in this composite p-phenylenediamine (pPDA) as organic nucleophile chemically bonded with functionalized MWCNT (MWCNT-COOH). The results of this study suggest that prepared bioorganic nucleophilic carbon nanotube composite (HRP/MWCNT-pPDA) shows fast electron transfer rate for electro oxidation of L-Dopa because of its high electrochemical catalytic activity toward the oxidation of L-Dopa, more −NH{sub 2} reactive sites and large effective surface area. Also in this work we measured L-Dopa in the presence of folic acid and uric acid as interferences. The proposed biosensor was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), FT-IR spectroscopy and cyclic voltammetry (CV). The differential pulse voltammetry (DPV) was used for determination of L-Dopa from 0.1 μM to 1.9 μM with a low detection limit of 40 nM (for S/N = 3) and sensitivity was about 35.5 μA/μM. Also this biosensor has several advantages such as rapid response, high stability and reproducibility. - Highlights: • Glassy carbon electrode modified by a novel composite in which pPDA as nucleophile is chemically attached to MWCNTs. • The developed biosensor exhibited excellent electrocatalytic activity in electrochemically determination of L-Dopa. • The biosensor showed acceptable sensitivity, reproducibility, detection limit, selectivity and stability. • MWCNT-pPDA provides a good electrical conductivity and large effective surface area for enzyme immobilization.

  15. Asymmetric Mannich reactions of imidazo[2,1-b]thiazole-derived nucleophiles with (S(S))-N-tert-butanesulfinyl (3,3,3)-trifluoroacetaldimine.

    Science.gov (United States)

    Mei, Haibo; Xie, Chen; Wu, Lingmin; Soloshonok, Vadim A; Han, Jianlin; Pan, Yi

    2013-12-14

    Asymmetric Mannich reactions of imidazo[2,1-b]thiazole-derived nucleophiles with (SS)-N-tert-butanesulfinyl (3,3,3)-trifluoroacetaldimine were found to proceed with reasonably good yields (55%-79%) and exceptionally high stereoselectivity (>99 : 1 dr). This method presents a general approach for the preparation of a new type of biologically relevant compounds containing pharmacophoric imidazo[2,1-b]thiazole and (trifluoro)ethylamine groups.

  16. Magnesium-mediated benzothiazole activation: a room-temperature cascade of C-H deprotonation, C-C coupling, ring-opening, and nucleophilic addition reactions.

    Science.gov (United States)

    Blair, Victoria L; Clegg, William; Kennedy, Alan R; Livingstone, Zoe; Russo, Luca; Hevia, Eva

    2011-10-10

    Ligand domin(o)ated: In contrast to the straightforward deprotonation of benzothiazole using Grignard reagents, treatment of benzothiazole with 1 leads to a novel type of activation. The initial magnesiation initiates an unstoppable domino reaction of C-C coupling, ring opening, nucleophilic addition, and deprotonation to give 2. THF=tetrahydrofuran. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. SYNTHESIS 7-O-CARBOXYMETHYL-3’,4’-DIMETHOXYISOFLAVONE

    Directory of Open Access Journals (Sweden)

    Andi Hairil Alimuddin

    2012-12-01

    Full Text Available Synthesis of 7-O-carboxymethyl-3',4'-dimethoxyisoflavone from 7-hydroxy-3',4'-dimethoxyisoflavone derived from eugenol had been done. 7-hydroxy-3',4'-dimethoxyisoflavone was first converted into 7-O-ethoxycarbonylmethyl-3',4'-dimethoxyisoflavone via substitution of hydroxyl group at 7-O position by ethyl-2 chloro acetate through bimolecular nucleophilic substitution reaction (SN2. Hydrolysis of ester group of 7-O-ethoxycarbonylmethyl-3',4'-dimethoxyisoflavone using KOH produce 7-O-carboxymethyl-3',4'-dimethoxyisoflavone in 93.4% yield as a white solid with melting point of 155-159 °C.

  18. 2-Substituted 7-trifluoromethyl-thiadiazolopyrimidones as alkaline phosphatase inhibitors. Synthesis, structure activity relationship and molecular docking study.

    Science.gov (United States)

    Jafari, Behzad; Ospanov, Meirambek; Ejaz, Syeda Abida; Yelibayeva, Nazym; Khan, Shafi Ullah; Amjad, Sayyeda Tayyeba; Safarov, Sayfidin; Abilov, Zharylkasyn A; Turmukhanova, Mirgul Zh; Kalugin, Sergey N; Ehlers, Peter; Lecka, Joanna; Sévigny, Jean; Iqbal, Jamshed; Langer, Peter

    2018-01-20

    Alkaline Phosphatases (APs) play a key role in maintaining a ratio of phosphate to inorganic pyrophosphate (P i /PP i ) and thus regulate extracellular matrix calcification during bone formation and growth. Among different isozymes of AP, aberrant increase in the level of tissue non-specific alkaline phosphatase (TNAP) is strongly associated with vascular calcification and end-stage renal diseases. In this context, we synthesized a novel series of fluorinated pyrimidone derivatives, i.e., 2-bromo-7-trifluoromethyl-5-oxo-5H-1,3,4-thiadiazolepyrimidones. The bromine functionality was further used for derivatisation by nucleophilic aromatic substitution using amines as nucleophiles as well as by Palladium catalysed Suzuki-Miyaura reactions. The synthesized derivatives were found potent but non-selective inhibitors of both isozymes of AP. Arylated thiadiazolopyrimidones exhibited stronger inhibitory activities than 2-amino-thiadiazolopyrimidones. The binding modes and possible interactions of the most active inhibitor within the active site of the enzyme were observed by molecular docking studies. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  19. Electrochemical and Spin-Trapping Properties of para-substituted α-Phenyl-N-tert-butyl Nitrones

    International Nuclear Information System (INIS)

    Rosselin, Marie; Tuccio, Béatrice; Pério, Pierre; Villamena, Frederick A.; Fabre, Paul-Louis; Durand, Grégory

    2016-01-01

    Nitrones are known both as therapeutic antioxidants and efficient spin-traps. In this work, the redox behavior of various para-substituted α-phenyl-N-tert-butyl nitrones (PBN) was studied by cyclic voltammetry. The polar effect of the substituents was found to correlate with the electrochemical properties of the nitronyl function. Compounds bearing an electron-withdrawing group were more easily reduced than those having an electron-donating group and an opposite trend was observed for the oxidation. Ease of oxidation was also computationally rationalized using DFT approach showing increased ease of oxidation with electron donating functionalities. Since electrochemical properties of nitrones are known to correlate with biological properties, this work provides insights in the design of potent nitrone antioxidants. Using cyclic voltammetry the relative rate of superoxide trapping by nitrones was investigated and compared to the classical antioxidant BHT. The determination of the relative rate of phenyl radical trapping was also carried out but showed no clear correlation with the nature of the substituents. This indicates the absence of a polar effect in agreement with previous data and further supports the intermediate nature, that is, non- or weakly nucleophile, of phenyl radical. On the contrary kinetics of hydroxymethyl radical trapping was found to correlate with the nature of the substituents, demonstrating the nucleophilic nature of its addition onto nitrones.

  20. Synthesis of carbasugars from aldonolactones, part III - A study on the allylic substitution of (1R,5R,8R)- and (1R,5R,8S)-8-hydroxy-2-oxabicyclo[3.3.0]oct-6-en-3-one derivatives - Preparation of (1S,2R,3R)-9-[2-hydroxy-3-(2-hydroxyethyl)cyclopent-4-en-1-yl]-9H-adenine

    DEFF Research Database (Denmark)

    Johansen, Steen Karsk; Lundt, Inge

    2001-01-01

    with these nucleophiles. Additionally, Mitsunobu substitution of (1R,5R,8R)-8-hydroxy-2-oxabicyclo[3.3.0]oct-B-en-3-one (3) with 6-chloropurine, followed by reduction of the lactone moiety and treatment with Liquid ammonia, gave the carbocyclic nucleoside (1S,2R,3R)-9-[2-hydroxy-3-(2-hydroxyethyl)cyclopent-4-en-1-yl]-9H...

  1. Modulation of cyanoalanine synthase and O-acetylserine (thiol) lyases A and B activity by beta-substituted alanyl and anion inhibitors.

    Science.gov (United States)

    Warrilow, Andrew G S; Hawkesford, Malcolm J

    2002-03-01

    The reaction mechanisms of three enzymes belonging to a single gene family are compared: a cyanoalanine synthase and two isoforms of O-acetylserine (thiol) lyase (O-ASTL) isolated from spinach (Spinacea oleracea L. cv. Medina). O-ASTL represents a major regulatory point in the S-assimilatory pathway, and the related cyanoalanine synthase, which is specific to the mitochondrial compartment, has evolved an independent function of cyanide detoxification. All three enzymes catalysed both the cysteine synthesis and cyanoalanine synthesis reactions although with different efficiencies, and which may be explained by a single amino acid substitution in the substrate-binding pocket of the enzyme. Substituted alanine and nucleophillic inhibitors caused predominantly non-competitive inhibition, indicating binding to both E- and F-forms of the enzyme in a bi-bi ping-pong kinetic model. Michaelis-Menten kinetics were observed when the alanyl substrate was varied in the presence and absence of inhibitors. The use of alanyl inhibitors has shown that the alanyl half-cycle of both the cysteine synthesis and cyanoalanine synthesis reactions of cyanoalanine synthase and O-acetylserine (thiol) lyases are similar. This is in contrast to the results observed with nucleophillic inhibitors, which have shown that the mechanisms of anion binding and processing differ between cyanoalanine synthase and O-ASTLs.

  2. LOW TEMPERATURE FORMATION OF NITROGEN-SUBSTITUTED POLYCYCLIC AROMATIC HYDROCARBONS (PANHs)—BARRIERLESS ROUTES TO DIHYDRO(iso)QUINOLINES

    Energy Technology Data Exchange (ETDEWEB)

    Parker, Dorian S. N.; Yang, Tao; Dangi, Beni B.; Kaiser, Ralf I. [Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States); Bera, Partha P.; Lee, Timothy J., E-mail: ralfk@hawaii.edu, E-mail: Timothy.J.Lee@nasa.gov [Space Science and Astrobiology Division, NASA Ames Research Center, Moffett Field, Mountain View, CA 94035 (United States)

    2015-12-20

    Meteorites contain bio-relevant molecules such as vitamins and nucleobases, which consist of aromatic structures with embedded nitrogen atoms. Questions remain over the chemical mechanisms responsible for the formation of nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) in extraterrestrial environments. By exploiting single collision conditions, we show that a radical mediated bimolecular collision between pyridyl radicals and 1,3-butadiene in the gas phase forms nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) 1,4-dihydroquinoline and to a minor amount 1,4-dihydroisoquinoline. The reaction proceeds through the formation of a van der Waals complex, which circumnavigates the entrance barrier implying it can operate at very low kinetic energy and therefore at low temperatures of 10 K as present in cold molecular clouds such as TMC-1. The discovery of facile de facto barrierless exoergic reaction mechanisms leading to PANH formation could play an important role in providing a population of aromatic structures upon which further photo-processing of ice condensates could occur to form nucleobases.

  3. C-Terminally modified peptides via cleavage of the HMBA linker by O-, N- or S-nucleophiles

    DEFF Research Database (Denmark)

    Hansen, Jonas; Diness, Frederik; Meldal, Morten Peter

    2016-01-01

    A large variety of C-terminally modified peptides was obtained by nucleophilic cleavage of the ester bond in solid phase linked peptide esters of 4-hydroxymethyl benzamide (HMBA). The developed methods provided peptides, C-terminally functionalized as esters, amides and thioesters, with high purity...... directly from the resin in a single reaction step. A comprehensive screening of the reaction conditions and scope for nucleophilic cleavage of peptides from the HMBA linker was performed....

  4. Approaches in Substitution of Organic Solvents

    DEFF Research Database (Denmark)

    Jacobsen, Thomas

    2000-01-01

    In substitution of harmful chemicals or products with less harmful or harmless ones, there are different approaches according to the different situations, the technical requirements to the substitutes, and the goals for the substitution. Three different cases are presented. The substitution process...

  5. Synthesis and Optical Properties of Near-Infrared meso-Phenyl-Substituted Symmetric Heptamethine Cyanine Dyes

    Directory of Open Access Journals (Sweden)

    Andrew Levitz

    2018-01-01

    Full Text Available Heptamethine cyanine dyes are a class of near infrared fluorescence (NIRF probes of great interest in bioanalytical and imaging applications due to their modifiability, allowing them to be tailored for particular applications. Generally, modifications at the meso-position of these dyes are achieved through Suzuki-Miyaura C-C coupling and SRN1 nucleophilic substitution of the chlorine atom at the meso-position of the dye. Herein, a series of 15 meso phenyl-substituted heptamethine cyanines was synthesized utilizing a modified dianil linker. Their optical properties, including molar absorptivity, fluorescence, Stokes shift, and quantum yield were measured. The HSA binding affinities of two representative compounds were measured and compared to that of a series of trimethine cyanines previously synthesized by our lab. The results indicate that the binding of these compounds to HSA is not only dependent on hydrophobicity, but may also be dependent on steric interferences in the binding site and structural dynamics of the NIRF compounds.

  6. Commercial formalin substitutes for histopathology

    DEFF Research Database (Denmark)

    Prentø, P; Lyon, H

    1997-01-01

    We compared the performance of six commercial fixatives proposed to be formalin substitutes with the performance of buffered formalin, Clarke's ethanol-acetic acid, and ethanol, using rat liver, small intestine, and kidney. We investigated the rate of penetration, mode of fixation, extent...... performed equally well on all tissues tested. While several of the commercial fixatives appeared to preserve liver tissue at 200x, the preservation of kidney, intestinal villi, and smooth muscle was unacceptable. Histological distortion, cell shrinkage and vacuolization were prominent when the substitutes...... was obtained by combining formalin fixation with antigen retrieval. We conclude that none of the proposed commercial substitutes for buffered formalin are adequate for critical histology or histopathology....

  7. Polymer Main-Chain Substitution Effects on the Efficiency of Nonfullerene BHJ Solar Cells

    KAUST Repository

    Firdaus, Yuliar

    2017-07-21

    “Nonfullerene” acceptors are proving effective in bulk heterojunction (BHJ) solar cells when paired with selected polymer donors. However, the principles that guide the selection of adequate polymer donors for high-efficiency BHJ solar cells with nonfullerene acceptors remain a matter of some debate and, while polymer main-chain substitutions may have a direct influence on the donor–acceptor interplay, those effects should be examined and correlated with BHJ device performance patterns. This report examines a set of wide-bandgap polymer donor analogues composed of benzo[1,2-b:4,5-b′]dithiophene (BDT), and thienyl ([2H]T) or 3,4-difluorothiophene ([2F]T) motifs, and their BHJ device performance pattern with the nonfullerene acceptor “ITIC”. Studies show that the fluorine- and ring-substituted derivative PBDT(T)[2F]T largely outperforms its other two polymer donor counterparts, reaching power conversion efficiencies as high as 9.8%. Combining several characterization techniques, the gradual device performance improvements observed on swapping PBDT[2H]T for PBDT[2F]T, and then for PBDT(T)[2F]T, are found to result from (i) notably improved charge generation and collection efficiencies (estimated as ≈60%, 80%, and 90%, respectively), and (ii) reduced geminate recombination (being suppressed from ≈30%, 25% to 10%) and bimolecular recombination (inferred from recombination rate constant comparisons). These examinations will have broader implications for further studies on the optimization of BHJ solar cell efficiencies with polymer donors and a wider range of nonfullerene acceptors.

  8. Efficient synthesis of substituted dihydrotetraazapentacenes.

    Science.gov (United States)

    Seillan, Claire; Brisset, Hugues; Siri, Olivier

    2008-09-18

    We describe a versatile and very efficient synthesis of previously unknown substituted 5,14-dihydro-5,7,12,14-tetraazapentacenes (DHTAPs). A structural study by NMR spectroscopy showed that the conjugated pi-system of the pentacyclic skeleton rearranges depending on the electronic effect of the substituent(s).

  9. Tax rates as strategic substitutes

    NARCIS (Netherlands)

    H. Vrijburg (Hendrik); R.A. de Mooij (Ruud)

    2016-01-01

    textabstractThis paper analytically derives conditions under which the slope of the tax-reaction function is negative in a classical tax competition model. If countries maximize welfare, a negative slope (reflecting strategic substitutability) occurs under relatively mild conditions. The strategic

  10. Story of skeletally substituted benzenes

    Indian Academy of Sciences (India)

    Unknown

    corresponds to the out-of-plane distortion of the hydrogen atom connected to the heteroatoms, which is then ..... etc. exhibits significant localization.24 The skeletally substituted benzenes considered in the study with a wide ... involving cationic and anionic systems are expected to show considerable localization. In. Table 3.

  11. Uranium nucleophilic carbene complexes

    International Nuclear Information System (INIS)

    Tourneux, Jean-Christophe

    2012-01-01

    The only stable f-metal carbene complexes (excluding NHC) metals f present R 2 C 2- groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the di-anion C{Ph 2 P(=S)} 2 2- (SCS 2- ) to extend the organometallic chemistry of this element in its various oxidation states (+3-+6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U. We first isolated the reactants M(SCHS) (M = Li and K) and demonstrated the role of the cation M + on the evolution of the di-anion M 2 SCS (M = Li, K, Tl) which is transformed into LiSCHS in THF or into product of intramolecular cyclization K 2 [C(PhPS) 2 (C 6 H 4 )]. We have developed the necessary conditions mono-, bis- and tris-carbene directly from the di-anion SCS 2- and UCl 4 , as the precursor used in uranium chemistry. The protonolysis reactions of amides compounds (U-NEt 2 ) by the neutral ligand SCH 2 S were also studied. The compounds [Li(THF)] 2 [U(SCS)Cl 3 ] and [U(SCS)Cl 2 (THF) 2 ] were then used to prepare a variety of cyclopentadienyl and mono-cyclo-octa-tetra-enyliques uranium(IV) carbene compounds of the DFT analysis of compounds [M(SCS)Cl 2 (py) 2 ] and [M(Cp) 2 (SCS)] (M = U, Zr) reveals the strong polarization of the M=C double bond, provides information on the nature of the σ and π interactions in this binding, and shows the important role of f orbitals. The influence of ancillary ligands on the M=C bond is revealed by examining the effects of replacing Cl - ligands and pyridine by C 5 H 5 - groups. Mulliken and NBO analyzes show that U=C bond, unlike the Zr=C bond, is not affected by the change in environment of the metal center. While the oxidation tests of carbene complexes of U(IV) were disappointing, the first carbene complex of uranium (VI), [UO 2 (SCS)(THF) 2 ], was isolated with the uranyl ion UO 2 2+ . The reactions of compounds UO 2 X 2 (X = I, OTf) with anions SCS 2- and SCHS - provide the first notable developments in the organometallic chemistry of the uranyl ion. DFT studies show the essentially ionic binding U(VI)-R and U(VI)=C and the small contribution of 5f orbitals covalently. (author) [fr

  12. Dynamics of the NbCl5-catalyzed cycloaddition of propylene oxide and CO2: Assessing the dual role of the nucleophilic co-catalysts

    KAUST Repository

    D'Elia, Valerio

    2014-07-23

    A mechanistic study on the synthesis of propylene carbonate (PC) from CO2 and propylene oxide (PO) catalyzed by NbCl5 and organic nucleophiles such as 4-dimethylaminopyridine (DMAP) or tetra-n-butylammonium bromide (NBu4Br) is reported. A combination of in situ spectroscopic techniques and kinetic studies has been used to provide detailed insight into the reaction mechanism, the formation of intermediates, and interactions between the reaction partners. The results of DFT calculations support the experimental observations and allow us to propose a mechanism for this reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Formation of Mono- and Bis-Michael Adducts by the Reaction of Nucleophilic Amino Acids with Hydroxymethylvinyl Ketone, a Reactive Metabolite of 1,3-Butadiene

    Science.gov (United States)

    Barshteyn, Nella; Elfarra, Adnan A.

    2009-01-01

    Previously, our laboratory has shown that hydroxymethylvinyl ketone (HMVK), a Michael acceptor oxidation product of the 1,3-butadiene metabolite, 3-butene-1,2-diol, readily reacts with hemoglobin at physiological conditions and that mass spectrometry of trypsin digested peptides suggested adduct formation with various nucleophilic amino acids. In the present study, we characterized reactions of HMVK (3 mM) with three model nucleophilic amino acids (6 and/or 15 mM): N-acetyl-L-cysteine (NAC), L-valinamide, and N-acetyl-L-lysine (NAL). NAC was the most reactive toward HMVK followed by L-valinamide and NAL. HMVK incubations with each amino acid at pH 7.4, 37°C resulted in formation of a mono-Michael adduct. In addition, HMVK incubated with NAL gave rise to two additional bis-Michael adducts characterized by LC/MS, LC/MS/MS, 1H NMR, and 1H-detected heteronuclear single quantum correlation (HSQC). The relative ratios of areas of NAL monoadduct (adduct 1) and diadducts (adducts 2 and 3) at 6 h were 49, 21, and 30% of total product area, respectively. Formation of adduct 2 was dependent upon the presence of both adduct 1 and HMVK whereas formation of adduct 3 was dependent upon presence of adduct 2 only. Monoadducts were formed by a Michael addition reaction of one HMVK moiety with nucleophilic amino acid whereas NAL diadducts were products of two Michael addition reactions of 2 HMVK moieties followed by enolization and formation of an octameric cyclic product. NAL diadduct (adduct 3) was formed by loss of a water molecule from adduct 2 followed by autooxidation of one of the hydroxy groups yielding a diketone conjugated system. Collectively, our results provide strong evidence that HMVK can react with various nucleophilic residues and form different types of adducts suggesting that a variety of proteins may be subjected to these modifications which could result in loss of protein function. PMID:19317513

  14. A method to quantify quinone reaction rates with wine relevant nucleophiles: a key to the understanding of oxidative loss of varietal thiols.

    Science.gov (United States)

    Nikolantonaki, Maria; Waterhouse, Andrew L

    2012-08-29

    Quinones are key reactive electrophilic oxidation intermediates in wine. To address this question, the model 4-methyl-1,2-benzoquinone was prepared to study how it reacts with wine nucleophiles. Those investigated included the varietal volatile thiols 4-methyl-4-sulfanylpentan-2-one (4MSP), 3-sulfanylhexan-1-ol (3SH), and 2-furanmethanethiol (2FMT); hydrogen sulfide (H2S); glutathione (GSH); sulfur dioxide; ascorbic acid (AA); and the amino acids methionine (Met) and phenylalanine (Phe) in the first kinetic study of these reactions. Products were observed in fair to quantitative yields, but yields were negligible for the amino acids. The reaction rates of 4-methyl-1,2-benzoquinone toward the nucleophiles were quantified by UV-vis spectrometry monitoring the loss of the quinone chromophore. The observed reaction rates spanned three orders of magnitude, from the unreactive amino acids (Met and Phe) (KNu = 0.0002 s(-1)) to the most reactive nucleophile, hydrogen sulfide (KH2S = 0.4188 s(-1)). Analysis of the kinetic data showed three categories. The first group consisted of the amino acids (Met and Phe) having rates of essentially zero. Next, phloroglucinol has a low rate (KPhl = 0.0064 s(-1)). The next group of compounds includes the volatile thiols having increasing reactions rates K as steric inhibition declined (K4MSP = 0.0060 s(-1), K3SH = 0.0578 s(-1), and K2FMT = 0.0837 s(-1)). These volatile thiols (4MSP, 3SH, 2FMT), important for varietal aromas, showed lower K values than those of the third group, the wine antioxidant compounds (SO2, GSH, AA) and H2S (KNu = 0.3343-0.4188 s(-1)). The characterization of the reaction products between the nucleophiles and 4-methyl-1,2-benzoquinone was performed by using HPLC with high-resolution MS analysis. This study presents the first evidence that the antioxidant compounds, H2S, and wine flavanols could react preferentially with oxidation-induced quinones under specific conditions, providing insight into a mechanism for

  15. Smart Phones and their Substitutes

    DEFF Research Database (Denmark)

    Bødker, Mads; Gimpel, Gregory; Hedman, Jonas

    2009-01-01

    Drawing on data from a longitudinal field study, this paper investigates the influence of existing, better and stand-alone technology substitutes on the use of smart phones. By applying prospect theory, media richness theory, and business model literature, the purpose of this paper is to improve...... our understanding of the role of substitutes, device content fit issues, and implications for business models by asking the question: What is an effective business model to address the relationship between user preference and the fit of the smart phone and everyday task? The field study data suggest...... the need for business models to recognize that adoption decisions are reference-dependent and strongly influenced by the fit between task and smart phone....

  16. Substituting oil by electric power

    International Nuclear Information System (INIS)

    Lichtenberg, H.

    1981-01-01

    Parting from the development of primary energy use the author refers to the latest investigations and results presented on the 1980 World Energy Conference and with special regard to oil points out the threatening exhaustion of fossil energy resources. Maintaining the economic structure of the Federal Republic of Germany implies an orientation away from oil. Due to its flexible application technology and quasi-inexhaustible energy resources electric power may substantially contribute to oil substitution which as a matter of fact is of particular interest in connection with the heat market. Coal alone cannot substitute both oil and nuclear energy. Thus, the above postulates the use of the latter. Leaving nuclear energy inactive today will effect an increase in the demand for oil the negative consequences of which would weight heavily upon the anyhow unbalanced import/export ratio of the Federal Republic of Germany. (orig.) [de

  17. 40 CFR 721.9100 - Substituted quinoline.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted quinoline. 721.9100... Substances § 721.9100 Substituted quinoline. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted quinoline (PMN P-93-1183) is...

  18. Substituted Indoleacetic Acids Tested in Tissue Cultures

    DEFF Research Database (Denmark)

    Engvild, Kjeld Christensen

    1978-01-01

    Monochloro substituted IAA inhibited shoot induction in tobacco tissue cultures about as much as IAA. Dichloro substituted IAA inhibited shoot formation less. Other substituted IAA except 5-fluoro- and 5-bromoindole-3-acetic acid were less active than IAA. Callus growth was quite variable...

  19. Substituted Indoleacetic Acids Tested in Tissue Cultures

    DEFF Research Database (Denmark)

    Engvild, Kjeld Christensen

    1978-01-01

    Monochloro substituted IAA inhibited shoot induction in tobacco tissue cultures about as much as IAA. Dichloro substituted IAA inhibited shoot formation less. Other substituted IAA except 5-fluoro- and 5-bromoindole-3-acetic acid were less active than IAA. Callus growth was quite variable and not...... and not correlated with auxin strength measured in the Avena coleoptile test....

  20. 40 CFR 721.9488 - Substituted resorcinols.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted resorcinols. 721.9488... Substances § 721.9488 Substituted resorcinols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as substituted resorcinols (PMNs P-95-1103, P...

  1. Resonance Energy Transfer Studies from Derivatives of Thiophene Substituted 1,3,4-Oxadiazoles to Coumarin-334 Dye in Liquid and Dye-Doped Polymer Media

    Science.gov (United States)

    Naik, Lohit; Deshapande, Narahari; Khazi, Imtiyaz Ahamed M.; Malimath, G. H.

    2018-02-01

    In the present work, we have carried out energy transfer studies using newly synthesised derivatives of thiophene substituted 1,3,4-oxadiazoles namely, 2-(-4-(thiophene-3-yl)phenyl)-5-(5-(thiophene-3-yl)thiophene-2-yl)-1,3,4-oxadiazole [TTO], 2-(-4-(benzo[b]thiophene-2-yl)phenyl)-5-(5-(benzo[b]thiophene-2-yl)-1,3,4-oxadiozole [TBO] and 2-(4-(4-(trifluoromethyl)phenyl)phenyl)-5-(5-(4-(trifluoromethyl)phenyl)thiophen-2-yl)-1,3,4-oxadiazole [TMO] as donors and laser dye coumarin-334 as acceptor in ethanol and dye-doped polymer (poly(methyl methacrylate) (PMMA)) media following steady-state and time-resolved fluorescence methods. Bimolecular quenching constant ( k q), translation diffusion rate parameter ( k d), diffusion length ( D l), critical transfer distance ( R 0), donor- acceptor distance ( r) and energy transfer efficiency ( E T) are calculated. It is observed that, critical transfer distance is more than the diffusion length for all the pairs. Further, bimolecular quenching constant is also more than the translation diffusion rate parameter. Hence, our experimental findings suggest that overall energy transfer is due to Förster resonance energy transfer (FRET) between donor and acceptor in both the media and for all the pairs. In addition, considerable increase in fluorescence intensity and energy transfer efficiency is observed in dye-doped polymer matrix systems as compared to liquid media. This suggests that, these donor-acceptor pairs doped in PMMA matrix may be used for applications such as energy transfer dye lasers (ETDL) to improve the efficiency and photostability, to enhance tunability and for plastic scintillation detectors.

  2. Onium ions. XVI. Hydrogen--deuterium exchange accompanying the cleavage of ammonium (tetradeuterioammonium) trifluoroacetate by lithium deuteride (hydride) indicating Sn2 like nucleophilic displacement at quaternary nitrogen through pentacoordinated NH5

    International Nuclear Information System (INIS)

    Olah, G.A.; Donovan, D.J.; Shen, J.; Klopman, G.

    1975-01-01

    The reactions of ammonium trifluoroacetate and lithium hydride, of ammonium trifluoroacetate and lithium deuteride, and of tetradeuteroammonium trifluoroacetate and lithium hydride were studied in an attempt to prove experimentally nucleophilic displacement through the formation of pentacoordinated NH 5 . Significant isotopic scramblings were observed in the reaction products. An analysis of possible side reactions indicated that the most reasonable explanation for the reaction products obtained is the attack of D - on the quarternary hydrogen of NH 4 + in an SN2-like fashion causing exchange to occur via pentacoordinated NH 4 D. The possibility of a real pentacoordinated intermediate was also considered. CNDO/2 calculations show that a nucleophilic attack on hydrogen is favored, but the alternative attack on nitrogen can not be dismissed because of the experimental data. The reaction of NF 4 + SbF 6 - and LiF could indicate the possibility of nucleophilic attack on nitrogen. (U.S.)

  3. What happened to blood substitutes?

    Science.gov (United States)

    Stowell, C P

    2005-11-01

    Concerns about the safety and adequacy of the blood supply have fostered twenty years of research into the so-called "blood substitutes" among them the oxygen carriers based on modified hemoglobin. Although none of these materials has yet been licensed for use in North America or Europe, the results of research and clinical trials have increased our understanding of oxygen delivery and its regulation. In particular, the examination of the basis for the vasoactivity observed with some of the hemoglobin based oxygen carriers has led to the insight that several colligative properties of hemoglobin solutions, such as their diffusion coefficient for oxygen, viscosity and colloid oncotic pressure, are important determinants of efficacy.

  4. Biologic and synthetic skin substitutes: An overview.

    Science.gov (United States)

    Halim, Ahmad Sukari; Khoo, Teng Lye; Mohd Yussof, Shah Jumaat

    2010-09-01

    The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substitutes can be divided into two main classes, namely, biological and synthetic substitutes. The biological skin substitutes have a more intact extracellular matrix structure, while the synthetic skin substitutes can be synthesised on demand and can be modulated for specific purposes. Each class has its advantages and disadvantages. The biological skin substitutes may allow the construction of a more natural new dermis and allow excellent re-epithelialisation characteristics due to the presence of a basement membrane. Synthetic skin substitutes demonstrate the advantages of increase control over scaffold composition. The ultimate goal is to achieve an ideal skin substitute that provides an effective and scar-free wound healing.

  5. Biologic and synthetic skin substitutes: An overview

    Directory of Open Access Journals (Sweden)

    Halim Ahmad

    2010-10-01

    Full Text Available The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substitutes can be divided into two main classes, namely, biological and synthetic substitutes. The biological skin substitutes have a more intact extracellular matrix structure, while the synthetic skin substitutes can be synthesised on demand and can be modulated for specific purposes. Each class has its advantages and disadvantages. The biological skin substitutes may allow the construction of a more natural new dermis and allow excellent re-epithelialisation characteristics due to the presence of a basement membrane. Synthetic skin substitutes demonstrate the advantages of increase control over scaffold composition. The ultimate goal is to achieve an ideal skin substitute that provides an effective and scar-free wound healing.

  6. Hydroxy-substituted polyenaminonitrile as a soluble precursor for rigid-rod polybenzoxazole

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ji Heung; Lee, Jae Kwan [Sungkyunkwan Univ., Suwon (Korea, Republic of)

    2001-09-01

    (1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FR-IR and thermal analysis (DSC and TGA)

  7. Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

    Science.gov (United States)

    Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

    2018-05-01

    The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

  8. Statistical Physics of Complex Substitutive Systems

    Science.gov (United States)

    Jin, Qing

    Diffusion processes are central to human interactions. Despite extensive studies that span multiple disciplines, our knowledge is limited to spreading processes in non-substitutive systems. Yet, a considerable number of ideas, products, and behaviors spread by substitution; to adopt a new one, agents must give up an existing one. This captures the spread of scientific constructs--forcing scientists to choose, for example, a deterministic or probabilistic worldview, as well as the adoption of durable items, such as mobile phones, cars, or homes. In this dissertation, I develop a statistical physics framework to describe, quantify, and understand substitutive systems. By empirically exploring three collected high-resolution datasets pertaining to such systems, I build a mechanistic model describing substitutions, which not only analytically predicts the universal macroscopic phenomenon discovered in the collected datasets, but also accurately captures the trajectories of individual items in a complex substitutive system, demonstrating a high degree of regularity and universality in substitutive systems. I also discuss the origins and insights of the parameters in the substitution model and possible generalization form of the mathematical framework. The systematical study of substitutive systems presented in this dissertation could potentially guide the understanding and prediction of all spreading phenomena driven by substitutions, from electric cars to scientific paradigms, and from renewable energy to new healthy habits.

  9. Studies on the chemical behavior of 3-(nitroacetyl)-1-ethyl-4-hydroxyquinoline-2(1H)-one towards some electrophilic and nucleophilic reagents

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, Magdy A.; Hassanin, Hany M.; Gabr, Yassin A.; Alnamer, Youssef A., E-mail: magdy_ahmed1977@yahoo.com [Department of Chemistry, Faculty of Education, Ain Shams University, Cairo (Egypt)

    2012-05-15

    A variety of heterocyclic systems linked to 1-ethylquinolin-2(1H)-one was prepared from reaction of 3-(nitroacetyl)-1-ethyl-4-hydroxyquinoline-2(1H)-one with some electrophilic and nucleophilic reagents. Besides its cyclization to 5-ethyl-2-(hydroxyimino)-2,3,4,5- tetrahydrofuro[3,2-c]quinoline-3,4-dione, the 3-(nitroacetyl)-1-ethyl-4-hydroxyquinoline-2(1H)- one has been brominated, chlorinated, formylated, acetylated, and condensed with chromone-3- carbonitrile and 2-amino-3-formylchromone. Some new pyrazolo[4,3-c]quinoline, pyrimido[5,4-c] quinoline and quinolino[4,3-b][1,5]benzodiazepine derivatives were also synthesized. (author)

  10. Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

    Science.gov (United States)

    Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

    2017-03-17

    A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O 2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O 2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. O-O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O-O radical coupling.

    Science.gov (United States)

    Shaffer, David W; Xie, Yan; Concepcion, Javier J

    2017-10-16

    In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O-O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O-O bond formation step as the key step in water oxidation catalysis. The two main pathways to accomplish this step, single-site water nucleophilic attack and O-O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.

  12. Synthesis of symmetrical 2,2',4,4'-tetrasubstituted [4,4'-bithiazole]-5,5'(4H,4'H)-diones and their reactions with some nucleophiles

    DEFF Research Database (Denmark)

    Andersen, Kenneth K.; Bray, Diana D.; Kjær, Anders

    1997-01-01

    Symmetrical 2,2',4,4'-tetrasubstituted [4,4'-bithiazole]-5,5'(4H,4'H)-diones were obtained in high yields by oxidation of 5-(4H)-thiazolones by KMnO4 in acetic acid. In some cases, the isomeric 2,4'- and 2,2'-bithiazolones were also formed. Results from two crossover reactions were consistent......,4'-dibenzyl-[4,4'-bithiazole]-5,5'(4H,4'H)-dione were treated with nocleophiles. The former gave imide derivatives of alfa,alfa-dehydrodimeric amino acids when the nucleophile was L-alanine ethyl ester or 1-butylamine. The structure of one of the reaction products, (4R*,5R*)-2,5-diphenyl-2-thiazoline-4......(N-carboxythioanhydride)s of leucine treated with glycine ethyl ester gave a bicyclic derivative of the alfa,alfa-dehydrodimeric amino acid....

  13. Substitution dynamical systems spectral analysis

    CERN Document Server

    Queffélec, Martine

    2010-01-01

    This volume mainly deals with the dynamics of finitely valued sequences, and more specifically, of sequences generated by substitutions and automata. Those sequences demonstrate fairly simple combinatorical and arithmetical properties and naturally appear in various domains. As the title suggests, the aim of the initial version of this book was the spectral study of the associated dynamical systems: the first chapters consisted in a detailed introduction to the mathematical notions involved, and the description of the spectral invariants followed in the closing chapters. This approach, combined with new material added to the new edition, results in a nearly self-contained book on the subject. New tools - which have also proven helpful in other contexts - had to be developed for this study. Moreover, its findings can be concretely applied, the method providing an algorithm to exhibit the spectral measures and the spectral multiplicity, as is demonstrated in several examples. Beyond this advanced analysis, many...

  14. Controversial issues of maternity substitution

    Directory of Open Access Journals (Sweden)

    Andy Pușcă

    2009-06-01

    Full Text Available Substitute maternity consists in a woman carrying a pregnancy (the implant of an embryo, at therequest of a sterile couple, most of the times in exchange of a sum of money, with her commitment tounconditionally give away the newborn after birth to the couple she concluded the agreement with. Manycontroversies emerged in what concerns the contract between the sterile couple and the carrying mother,especially when this contract is by onerous title, which happens in most of the cases. In that a civil contract? Is ita sales contract for the child? Is it a contract to provide services? Is it body marketing? Between total prohibitionand excessive liberalism, the middle way, which is the regulation according to ethical religious, cultural andsocial norms of each community, represents a realistic solution.

  15. Type Substitution for Object-Oriented Programming

    DEFF Research Database (Denmark)

    Schwartzbach, Michael Ignatieff; Palsberg, Jens

    1990-01-01

    Genericity allows the substitution of types in a class. This is usually obtained through parameterized classes, although they are inflexible since any class can be inherited but is not in itself parameterized. We suggest a new genericity mechanism, type substitution, which is a subclassing concep...

  16. Educators Take Another Look at Substitutes

    Science.gov (United States)

    Zubrzycki, Jaclyn

    2012-01-01

    The mythology surrounding the substitute teacher is not a pretty one: Paper airplanes, lost learning, bullying. But as schools collect more information about teacher absenteeism and its consequences, districts and schools are exploring ways to professionalize substitute teaching--or experiment with alternative ways of coping with teacher absences.…

  17. Strategic Resource Extraction And Substitute Development

    NARCIS (Netherlands)

    Michielsen, T.O.

    2013-01-01

    Abstract We analyze a dynamic game between a buyer and a seller of an exhaustible resource. The seller chooses resource supply; the buyer can pay a fixed cost to invent a perfect substitute for the resource at any time. In closed-loop equilibrium, the buyer adopts the substitute when the resource is

  18. Multisensory integration, sensory substitution and visual rehabilitation

    DEFF Research Database (Denmark)

    Proulx, Michael J; Ptito, Maurice; Amedi, Amir

    2014-01-01

    Sensory substitution has advanced remarkably over the past 35 years since first introduced to the scientific literature by Paul Bach-y-Rita. In this issue dedicated to his memory, we describe a collection of reviews that assess the current state of neuroscience research on sensory substitution, v......, visual rehabilitation, and multisensory processes....

  19. Current bone substitutes for implant dentistry.

    Science.gov (United States)

    Yamada, Masahiro; Egusa, Hiroshi

    2017-09-15

    Alveolar ridge augmentation is essential for success in implant therapy and depends on the biological performance of bone graft materials. This literature review aims to comprehensively explain the clinically relevant capabilities and limitations of currently available bone substitutes for bone augmentation in light of biomaterial science. The biological performance of calcium phosphate-based bone substitutes was categorized according to space-making capability, biocompatibility, bioabsorption, and volume maintenance over time. Each category was reviewed based on clinical studies, preclinical animal studies, and in vitro studies. Currently available bone substitutes provide only osteoconduction as a scaffold but not osteoinduction. Particle size, sensitivity to enzymatic or chemical dissolution, and mechanical properties affect the space-making capability of bone substitutes. The nature of collagen fibers, particulate size, and release of calcium ions influence the biocompatibility of bone substitutes. Bioabsorption of bone substitutes is determined by water solubility (chemical composition) and acid resistance (integrity of apatite structure). Bioabsorption of remnant bone substitute material and volume maintenance of the augmented bone are inversely related. It is necessary to improve the biocompatibility of currently available bone substitutes and to strike an appropriate balance between bioabsorption and volume maintenance to achieve ideal bone remodeling. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  20. Substitute Teachers: Making Lost Days Count

    Science.gov (United States)

    True, Charlene; Butler, Kyle; Sefton, Rachel

    2011-01-01

    As K-12 teachers and administrators grow increasingly concerned with issues of accountability, research-based methods, and intervention strategies, little discussion exists on the impact of substitute teachers in the classroom. In the rush to analyze test scores, are the days covered by substitute teachers even considered? Though districts are…

  1. Substitution between cars within the household

    DEFF Research Database (Denmark)

    De Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    2016-01-01

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars of different fuel efficiency in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate – for each car owned by the household...... – own and cross-price effects of increases in fuel costs per kilometre. The empirical results show that failure to capture substitution between cars within the household can result in substantial misspecification biases. Ignoring substitution, the basic model yielded fuel price elasticities of 0.......98 and 1.41 for the primary and secondary cars, respectively. Accounting for substitution effects, these figures reduce to, respectively, 0.32 and 0.45. Consistent with substitution behaviour, we find that the fuel price elasticity of fuel demand exceeds the elasticity of kilometre demands with respect...

  2. Aluminum substitution in goethite in lake ore

    Directory of Open Access Journals (Sweden)

    Carlson, L.

    1995-06-01

    Full Text Available The extent of substitution of Fe by Al in goethite in 32 lake ore samples collected from 11 lakes in Finland varied between 0 and 23 mol-%. The data indicated a negative relationship between Al-substitution and the particle size of lake ore. Differences in the Al-substitution were apparent between sampling sites, suggesting that kinetic and environmental variation in lake ore formation influences the substitution. Non-substituted goethite is formed in coarse-grained sediments with locally high concentrations of Fe due to iron-rich springs. Unit cell edge lengths and volumes of goethite varied as function of Al-subsitution but deviated from the Vegard relationship towards higher values.

  3. Phosphorylation of 5-substituted NH-tetrazoles with dimethyl chloroacetylenephosphonate

    Czech Academy of Sciences Publication Activity Database

    Iakobson, George; Erkhitueva, E. B.; Svintsitskaya, N. I.

    2015-01-01

    Roč. 85, č. 9 (2015), s. 2219-2221 ISSN 1070-3632 Institutional support: RVO:61388963 Keywords : NH-tetrazoles * chloroacetylenephosphonate * tetrazole-containing vinylphosphonates * nucleophilic addition Subject RIV: CC - Organic Chemistry Impact factor: 0.481, year: 2015

  4. Kinetics and mechanism of the ligand substitution reaction of di- ...

    Indian Academy of Sciences (India)

    The kinetics of the interaction between diethyldithiocarbamate (Et2DTC) and the title complex has been studied spectrophotometrically in aqueous medium as a function of nucleophile concentration, temperature and pH at constant ionic strength. The reaction is a two-step process in which the first step is liganddependent, ...

  5. Synthesized 2-Substituted-3-Phenylthiazolidine-4-ones as Potent ...

    African Journals Online (AJOL)

    HP

    pyrazole-4-carboxaldehyde and the nucleophillic nitrogen atom of the amine. Preparation of ... analyzed by ESI method using Thermo Fennigan mass spectrophotometer. Elemental analyses were recorded using Thermo Finnigan FLASH. EA 1112 CHN analyzer. TLC was ...... catalyst which counters balance between.

  6. cyclo-addition reaction of triplet carbonyl compounds to substituted ...

    Indian Academy of Sciences (India)

    Unknown

    the observed regioselectivity is explained using a series of DFT-based reactivity indices. In the first step, we use the local .... the system undergoes a nucleophilic, electrophilic or radical attack. ..... Vertical ionization energies I, electron affinities A, global softnesses S, condensed spin density Ns, Fukui functions f and local ...

  7. Uproar over Milk Substitutes Act.

    Science.gov (United States)

    1993-11-15

    Health policy activists lobbied 7 years for the Infant Milk Substitutes, Feeding Bottles and Infant Food Bill. Proponents of the bill say that it basically curtails unethical marketing practices, not the sales of baby foods, and argue that it was conceived to reduce the trend of mothers over-diluting commercial milk in order to reduce household expenses as well as stem the potential erosion of knowledge on locally available weaning foods. Even though the bill will become an Act only after its rules and regulations have been finalized, the government has already banned baby food advertisements on television and in other electronic media under its control. Women's groups now argue that the bill tends to focus almost exclusively upon the welfare of children and compromises the position of women who can not lactate adequately. Moreover, they hold that the bill may be used to compel wives to stay out of the formal workforce so that they may feed their babies. The intention of the bill may be meaningless without complementary legislation addressing the problems of working mothers. Specifically, amendments to the Maternity Benefits Act of 1961 would extend maternity leave to 4 months after delivery and lengthen the duration of nursing breaks. It is, however, feared that these changes may reduce employment prospects for women.

  8. Substituted Hydroxyapatites with Antibacterial Properties

    Directory of Open Access Journals (Sweden)

    Joanna Kolmas

    2014-01-01

    Full Text Available Reconstructive surgery is presently struggling with the problem of infections located within implantation biomaterials. Of course, the best antibacterial protection is antibiotic therapy. However, oral antibiotic therapy is sometimes ineffective, while administering an antibiotic at the location of infection is often associated with an unfavourable ratio of dosage efficiency and toxic effect. Thus, the present study aims to find a new factor which may improve antibacterial activity while also presenting low toxicity to the human cells. Such factors are usually implemented along with the implant itself and may be an integral part of it. Many recent studies have focused on inorganic factors, such as metal nanoparticles, salts, and metal oxides. The advantages of inorganic factors include the ease with which they can be combined with ceramic and polymeric biomaterials. The following review focuses on hydroxyapatites substituted with ions with antibacterial properties. It considers materials that have already been applied in regenerative medicine (e.g., hydroxyapatites with silver ions and those that are only at the preliminary stage of research and which could potentially be used in implantology or dentistry. We present methods for the synthesis of modified apatites and the antibacterial mechanisms of various ions as well as their antibacterial efficiency.

  9. Substituted Hydroxyapatites with Antibacterial Properties

    Science.gov (United States)

    Kolmas, Joanna; Groszyk, Ewa; Kwiatkowska-Różycka, Dagmara

    2014-01-01

    Reconstructive surgery is presently struggling with the problem of infections located within implantation biomaterials. Of course, the best antibacterial protection is antibiotic therapy. However, oral antibiotic therapy is sometimes ineffective, while administering an antibiotic at the location of infection is often associated with an unfavourable ratio of dosage efficiency and toxic effect. Thus, the present study aims to find a new factor which may improve antibacterial activity while also presenting low toxicity to the human cells. Such factors are usually implemented along with the implant itself and may be an integral part of it. Many recent studies have focused on inorganic factors, such as metal nanoparticles, salts, and metal oxides. The advantages of inorganic factors include the ease with which they can be combined with ceramic and polymeric biomaterials. The following review focuses on hydroxyapatites substituted with ions with antibacterial properties. It considers materials that have already been applied in regenerative medicine (e.g., hydroxyapatites with silver ions) and those that are only at the preliminary stage of research and which could potentially be used in implantology or dentistry. We present methods for the synthesis of modified apatites and the antibacterial mechanisms of various ions as well as their antibacterial efficiency. PMID:24949423

  10. Substituted androstanes as aromatase inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Levina, Inna S [N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)

    1998-11-30

    The synthesis and structure-activity relationships of inhibitors of steroid aromatase which catalyses the last stage of a multistep biotransformation of cholesterol into estrogens, viz., aromatisation of C{sub 19}-steroids into C{sub 18}-phenolic steroids, are discussed. Compounds of the androstane series which are structurally related to the natural substrate, viz., androst-4-ene-3,17-dione, are the subjects of consideration. The review encompasses problems of synthesis of various substituted androstanes and their aromatase-inhibiting activities and structural requirements for selective specific aromatase inhibitors based on in vitro and in vivo structure-activity studies of compounds synthesised, their biological properties and the results of clinical trials. Special attention is paid to practical applications of aromatase inhibitors in the treatment of hormone-dependent mammary and ovarian tumours as well as benign prostatic tumours. In writing this report, the author has used all the information currently available in the chemical, biochemical, endocrinological and medicinal literature as well as in patents. The bibliography includes 173 references.

  11. Substituted androstanes as aromatase inhibitors

    Science.gov (United States)

    Levina, Inna S.

    1998-11-01

    The synthesis and structure-activity relationships of inhibitors of steroid aromatase which catalyses the last stage of a multistep biotransformation of cholesterol into estrogens, viz., aromatisation of C19-steroids into C18-phenolic steroids, are discussed. Compounds of the androstane series which are structurally related to the natural substrate, viz., androst-4-ene-3,17-dione, are the subjects of consideration. The review encompasses problems of synthesis of various substituted androstanes and their aromatase-inhibiting activities and structural requirements for selective specific aromatase inhibitors based on in vitro and in vivo structure-activity studies of compounds synthesised, their biological properties and the results of clinical trials. Special attention is paid to practical applications of aromatase inhibitors in the treatment of hormone-dependent mammary and ovarian tumours as well as benign prostatic tumours. In writing this report, the author has used all the information currently available in the chemical, biochemical, endocrinological and medicinal literature as well as in patents. The bibliography includes 173 references.

  12. The radiochemistry of [18 F]-FDG: the first experience in Mexico

    International Nuclear Information System (INIS)

    Lopez D, F.A.

    2004-01-01

    The present work describes the more used method for the synthesis of 2 - [ 18 F] - fluorine-2-deoxy-D-glucose that is the more used radiopharmaceutical in the nuclear medicine in the cancer diagnostic. The process consists on two chemical reactions: i) [ 18 F - ] - nucleophilic radio fluorination and i i) a hydrolysis catalyzed by acid. The first reaction incorporates to the [ 18 F]- fluorine labelled inside the organic precursor 1,3,4,6-tetra- O -acetil-2- O-trifluoromethanesulfonyl- β-D-mannopyranose (triflate of mannose). The mechanism of this reaction is a bimolecular nucleophilic substitution (SN 2 ) with the ion [ 18 F - ] - fluoride; in the second reaction, the hydrolysis of those protective acetyl groups generate the hydroxyl groups free of the [ 18 F]-FDG. The process includes an azeotropic distillation and several purification steps. (Author)

  13. The radiochemistry of [{sup 18} F]-FDG: the first experience in Mexico; La radioquimica del [{sup 18} F]-FDG: la primera experiencia en Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Lopez D, F.A. [Unidad PET-Ciclotron, Facultad de Medicina, UNAM, Av. Universidad 3000, Ciudad Universitaria, Coyoacan, 04500 Mexico, D. F. (Mexico)]. e-mail: fred-alonso@correo.unam.mx

    2004-07-01

    The present work describes the more used method for the synthesis of 2 - [{sup 18} F] - fluorine-2-deoxy-D-glucose that is the more used radiopharmaceutical in the nuclear medicine in the cancer diagnostic. The process consists on two chemical reactions: i) [{sup 18} F{sup -}] - nucleophilic radio fluorination and i i) a hydrolysis catalyzed by acid. The first reaction incorporates to the [{sup 18} F]- fluorine labelled inside the organic precursor 1,3,4,6-tetra- O -acetil-2- O-trifluoromethanesulfonyl- {beta}-D-mannopyranose (triflate of mannose). The mechanism of this reaction is a bimolecular nucleophilic substitution (SN{sub 2}) with the ion [{sup 18} F{sup -}] - fluoride; in the second reaction, the hydrolysis of those protective acetyl groups generate the hydroxyl groups free of the [{sup 18} F]-FDG. The process includes an azeotropic distillation and several purification steps. (Author)

  14. Modeling competitive substitution in a polyelectrolyte complex

    International Nuclear Information System (INIS)

    Peng, B.; Muthukumar, M.

    2015-01-01

    We have simulated the invasion of a polyelectrolyte complex made of a polycation chain and a polyanion chain, by another longer polyanion chain, using the coarse-grained united atom model for the chains and the Langevin dynamics methodology. Our simulations reveal many intricate details of the substitution reaction in terms of conformational changes of the chains and competition between the invading chain and the chain being displaced for the common complementary chain. We show that the invading chain is required to be sufficiently longer than the chain being displaced for effecting the substitution. Yet, having the invading chain to be longer than a certain threshold value does not reduce the substitution time much further. While most of the simulations were carried out in salt-free conditions, we show that presence of salt facilitates the substitution reaction and reduces the substitution time. Analysis of our data shows that the dominant driving force for the substitution process involving polyelectrolytes lies in the release of counterions during the substitution

  15. Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

    Science.gov (United States)

    Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

    2015-07-23

    The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

  16. Elasticity of Substitution and Antidumping Measures

    DEFF Research Database (Denmark)

    Drud Hansen, Jørgen; Meinen, Philipp; Nielsen, Jørgen Ulff-Møller

    therefore also vary inversely with the elasticity of substitution at least for countries which have a strong focus on prices in the determination of their anti-dumping measures. We test this for ten countries from 1990 to 2009 using data on anti-dumping from Chad Bown (2010) and US-data at 8-digit level......Abstract This paper analyzes the role of the elasticity of substitution for anti-dumping decisions across countries. In monopolistic competition models with cost heterogeneous firms across countries, price differences vary inversely with the elasticity of substitution. Anti-dumping duties should...

  17. Biologic and synthetic skin substitutes: An overview

    OpenAIRE

    Halim, Ahmad Sukari; Khoo, Teng Lye; Mohd. Yussof, Shah Jumaat

    2010-01-01

    The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substit...

  18. Vitreous substitutes:challenges and directions

    Directory of Open Access Journals (Sweden)

    Qian-Ying Gao

    2015-06-01

    Full Text Available Thenatural vitreous body has a fine structure and complex functions. The imitation of the natural vitreous body by vitreous substitutes is a challenging work for both researchers and ophthalmologists. Gases, silicone oil, heavy silicone oil and hydrogels, particularly the former two vitreous substitutes are clinically widely used with certain complications. Those, however, are not real artificial vitreous due to lack of structure and function like the natural vitreous body. This article reviews the situations, challenges, and future directions in the development of vitreous substitutes, particularly the experimental and clinical use of a new artificial foldable capsular vitreous body .

  19. Questioning nuclear waste substitution: a case study.

    Science.gov (United States)

    Marshall, Alan

    2007-03-01

    This article looks at the ethical quandaries, and their social and political context, which emerge as a result of international nuclear waste substitution. In particular it addresses the dilemmas inherent within the proposed return of nuclear waste owned by Japanese nuclear companies and currently stored in the United Kingdom. The UK company responsible for this waste, British Nuclear Fuels Limited (BNFL), wish to substitute this high volume intermediate-level Japanese-owned radioactive waste for a much lower volume of much more highly radioactive waste. Special focus is given to ethical problems that they, and the UK government, have not wished to address as they move forward with waste substitution. The conclusion is that waste substitution can only be considered an ethical practice if a set of moderating conditions are observed by all parties. These conditions are listed and, as of yet, they are not being observed.

  20. Towards hemerythrin-based blood substitutes: Comparative ...

    Indian Academy of Sciences (India)

    related reactivity is lower than that of hemoglobin, which may warrant investigation of hemerythrin as raw material for artificial oxygen carriers ('blood substitutes'). We report here the first biological tests for hemerythrin and its chemical derivatives, ...

  1. Symbolic Substitution Methods For Optical Computing

    Science.gov (United States)

    Murdocca, M. J.; Huang, A.

    1989-02-01

    Symbolic substitution is a method of computing based on parallel binary pattern replacement, that can be implemented with simple optical components and regular free-space interconnection schemes. A two-dimensional pattern is searched for in parallel in an array and is replaced with another pattern. Pattern transformation rules can be applied sequentially or in parallel to realize complex functions. When the substitution space is modified to be loge SIT connected for N binary spots, and masks are allowed to customize the system, then optical digital circuits using symbolic substitution for network interconnects can be made nearly as efficient in terms of gate count and circuit depth as conventional arbitrary interconnection schemes allow. We describe an optical setup that requires no more than a fanin and fanout of two using optically nonlinear logic devices and a free space interconnection scheme based on symbolic substitution.

  2. Synthesis and biological activities of substituted N ...

    African Journals Online (AJOL)

    use

    2011-12-07

    Dec 7, 2011 ... The present study describes the synthesis, antioxidant and antibacterial activities of substituted N'- benzoylhydrazone derivatives, to ... addition, the dramatically rising prevalence of multidrug- resistant microbial infections has ...... extract of Chinese green tea (Camellia sinensis) on Listeria monocytogenes.

  3. SYNTHESIS OF SUBSTITUTED FLAVONE DERIVATIVES AS ...

    African Journals Online (AJOL)

    Preferred Customer

    results showed that this skeletal framework exhibited marked potency as antimicrobial agents. KEY WORDS. KEY WORDS: Chalcone ... It showed significant role in pharmaceutical effects [1] including leishmanicidal activity, oviposter ... new substituted flavone derivative as potent antimicrobial agent. EXPERIMENTAL.

  4. Transnationalism and integration : complements or Substitutes?

    NARCIS (Netherlands)

    Dekker, B.; Siegel, M.

    2013-01-01

    This paper investigates the relationship between transnational practices and integration by testing whether they are substitutes or complements. For this purpose, we use a multidimensional transnationalism index. The index includes three dimensions of transnational practices, including migrants'

  5. Development of a diesel substitute fuel

    Energy Technology Data Exchange (ETDEWEB)

    Reiter, Anton; Mair-Zelenka, Philipp [Graz Univ. of Technology (Austria). Inst. of Chemical Engineering and Environmental Technology; Zeymer, Marc [OMV Refining and Marketing GmbH, Vienna (Austria). MRDI-D Product Development and Innovation

    2013-06-01

    Substitute fuels composed of few real chemical compounds are an alternative characterisation approach for conventional fuels as opposed to the traditional pseudo-component method. With the algorithm proposed in this paper the generation of such substitutes will be facilitated and well-established thermodynamic methods can be applied for physical property-data prediction. Based on some quality criteria like true boiling-point curve, liquid density, C/H ratio, or cloud point of a target fuel a surrogate which meets these properties is determined by fitting its composition. The application and capabilities of the algorithm developed are demonstrated by means of an exemplary diesel substitute fuel. The substitute mixture obtained can be generated and used for evaluation of property-prediction methods. Furthermore this approach can help to understand the effects of mixing fossil fuels with biogenic compounds. (orig.)

  6. 47 CFR 76.110 - Substitutions.

    Science.gov (United States)

    2010-10-01

    ... blackout rules at § 76.111, substitute a program from any other television broadcast station. Programs... CABLE TELEVISION SERVICE Network Non-duplication Protection, Syndicated Exclusivity and Sports Blackout...

  7. Substituted hydroxyapatites for biomedical applications: A review

    Czech Academy of Sciences Publication Activity Database

    Šupová, Monika

    2015-01-01

    Roč. 41, č. 8 (2015), s. 9203-9231 ISSN 0272-8842 Institutional support: RVO:67985891 Keywords : bioapatite * calcium phosphate * hydroxyapatite * substitution Subject RIV: JJ - Other Materials Impact factor: 2.758, year: 2015

  8. Synthesis of substituted 2-cyanoarylboronic esters

    DEFF Research Database (Denmark)

    Lysén, Morten; Hansen, Henriette M; Begtrup, Mikael

    2006-01-01

    The synthesis of substituted 2-cyanoarylboronic esters is described via lithiation/in situ trapping of the corresponding methoxy-, trifluoromethyl-, fluoro-, chloro-, and bromobenzonitriles. The crude arylboronic esters were obtained in high yields and purities and with good regioselectivities....

  9. Substitution within the Danish printing industry

    DEFF Research Database (Denmark)

    Larsen, Henrik Fred; Bøg, Carsten

    2009-01-01

    The implementation of the EU REACH regulation will most probably promote substitution within sectors handling a lot of different chemicals like the printing industry. With the aim of being at the cutting edge of this development the Danish EPA together with the Danish printing industry and IPU...... are running a substitution project. A major part of the work has been mapping the presence of chemicals which are potential candidates for substitution (e.g. PBT, CMR, vPvB, EDS) within the Danish printing industry and this work was recently finished. The mapping comprises a combination of a literature study...... total 15 substances) were found in the Danish printing industry. This paper presents the results of the mapping of chemical candidates and the first results on preparing for actual substitutions....

  10. Towards hemerythrin-based blood substitutes

    Indian Academy of Sciences (India)

    related reactivity is lower than that of hemoglobin, which may warrant investigation of hemerythrin as raw material for artificial oxygen carriers ('blood substitutes'). We report here the first biological tests for hemerythrin and its chemical derivatives, ...

  11. Product portfolio optimization based on substitution

    DEFF Research Database (Denmark)

    Myrodia, Anna; Moseley, A.; Hvam, Lars

    2017-01-01

    The development of production capabilities has led to proliferation of the product variety offered to the customer. Yet this fact does not directly imply increase of manufacturers' profitability, nor customers' satisfaction. Consequently, recent research focuses on portfolio optimization through...... substitution and standardization techniques. However when re-defining the strategic market decisions are characterized by uncertainty due to several parameters. In this study, by using a GAMS optimization model we present a method for supporting strategic decisions on substitution, by quantifying the impact...

  12. Substitutability between Equity REITs and Mortgage REITs

    OpenAIRE

    Ming-Long Lee; Kevin C.H. Chiang

    2004-01-01

    This study extends Seck’s (1996) approach to investigate the degree of substitutability between equity real estate investment trusts (EREITs) and mortgage real estate investment trusts (MREITs). The variance ratio test and the variance decomposition of forecast errors yield results indicating the existence of informational commonality between EREITs and MREITs. The findings indicate that the two types of REITs are substitutable. A direct implication is that investors who believe they have s...

  13. Competition Among Near-Substitutable Systems

    Science.gov (United States)

    2012-09-01

    the context of the dominant “Weapon System Franchise ” model of competition for major defense acquisition programs (MDAPs). Competition between near...leading to the award of a franchise . AoAs or other cost-effectiveness analyses can be pivotal in bringing attention to near-substitute systems. However...Symposium, 18-19 Sep 2012, Fort Belvoir, VA. U.S. Government or Federal Rights License 14. ABSTRACT We define near-substitutable systems as systems that

  14. Trace maps of general substitutional sequences

    International Nuclear Information System (INIS)

    Kolar, M.; Nori, F.

    1990-01-01

    It is shown that for arbitrary n, there exists a trace map for any n-letter substitutional sequence. Trace maps are explicitly obtained for the well-known circle and Rudin-Shapiro sequences which can be defined by means of substitution rules on three and four letters, respectively. The properties of the two trace maps and their consequences for various spectral properties are briefly discussed

  15. Diphosphorus-substituted derivatives of ketones

    International Nuclear Information System (INIS)

    Novikova, Z.S.; Kurkin, A.N.; Lutsenko, I.F.

    1986-01-01

    The structure of C,0-diphosphorus-substituted derivatives of ketones formed in the phosphorylation of sodium enolates of C-phosphorus-substituted ketones depends on the structure of the phosphorus-containing group in the molecule of the original ketone; increase in the electron-acceptor power of the substituents on the phosphorus atom and rise in its valence favor the formation of β-phosphorus-containing vinyl esters of phosphorus acids

  16. Substituting missing data in compositional analysis

    Energy Technology Data Exchange (ETDEWEB)

    Real, Carlos, E-mail: carlos.real@usc.es [Area de Ecologia, Departamento de Biologia Celular y Ecologia, Escuela Politecnica Superior, Universidad de Santiago de Compostela, 27002 Lugo (Spain); Angel Fernandez, J.; Aboal, Jesus R.; Carballeira, Alejo [Area de Ecologia, Departamento de Biologia Celular y Ecologia, Facultad de Biologia, Universidad de Santiago de Compostela, 15782 Santiago de Compostela (Spain)

    2011-10-15

    Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study. - Highlights: > Missing values in multivariate data sets must be substituted prior to analysis. > The substituted values can modify the structure of the data set. > We developed a method to estimate the magnitude of the alterations. > The method is simple and based on the Mantel test. > The method allowed the identification of problematic variables in a sample data set. - A method is presented for the assessment of the possible distortions in multivariate analysis caused by the substitution of missing values.

  17. Genome-Wide Bimolecular Fluorescence Complementation-Based Proteomic Analysis of Toxoplasma gondii ROP18’s Human Interactome Shows Its Key Role in Regulation of Cell Immunity and Apoptosis

    Directory of Open Access Journals (Sweden)

    Jing Xia

    2018-02-01

    Full Text Available Toxoplasma gondii rhoptry protein ROP18 (TgROP18 is a key virulence factor secreted into the host cell during invasion, where it modulates the host cell response by interacting with its host targets. However, only a few TgROP18 targets have been identified. In this study, we applied a high-throughput protein–protein interaction (PPI screening in human cells using bimolecular fluorescence complementation (BiFC to identify the targets of Type I strain ROP18 (ROP18I and Type II strain ROP18 (ROP18II. From a pool of more than 18,000 human proteins, 492 and 141 proteins were identified as the targets of ROP18I and ROP18II, respectively. Gene ontology, search tool for the retrieval of interacting genes/proteins PPI network, and Ingenuity pathway analyses revealed that the majority of these proteins were associated with immune response and apoptosis. This indicates a key role of TgROP18 in manipulating host’s immunity and cell apoptosis, which might contribute to the immune escape and successful parasitism of the parasite. Among the proteins identified, the immunity-related proteins N-myc and STAT interactor, IL20RB, IL21, ubiquitin C, and vimentin and the apoptosis-related protein P2RX1 were further verified as ROP18I targets by sensitized emission-fluorescence resonance energy transfer (SE-FRET and co-immunoprecipitation. Our study substantially contributes to the current limited knowledge on human targets of TgROP18 and provides a novel tool to investigate the function of parasite effectors in human cells.

  18. Synthesis of symmetrical 2,2',4,4'-tetrasubstituted [4,4'-bithiazole]-5,5'(4H,4'H)-diones and their reactions with some nucleophiles

    DEFF Research Database (Denmark)

    Andersen, Kenneth K.; Bray, Diana D.; Kjær, Anders

    1997-01-01

    Symmetrical 2,2',4,4'-tetrasubstituted [4,4'-bithiazole]-5,5'(4H,4'H)-diones were obtained in high yields by oxidation of 5-(4H)-thiazolones by KMnO4 in acetic acid. In some cases, the isomeric 2,4'- and 2,2'-bithiazolones were also formed. Results from two crossover reactions were consistent...... with a free radical mechanism. Four series of thiazolones were prepared, each based on a different substituent at the 2-position; i.e., phenyl, ethoxy, ethyl and ethylthio. The effect of substituents on the isomer distributions of the dehydrodimers indicated that electronic factors were less important than......,4'-dibenzyl-[4,4'-bithiazole]-5,5'(4H,4'H)-dione were treated with nocleophiles. The former gave imide derivatives of alfa,alfa-dehydrodimeric amino acids when the nucleophile was L-alanine ethyl ester or 1-butylamine. The structure of one of the reaction products, (4R*,5R*)-2,5-diphenyl-2-thiazoline-4...

  19. A Novel Strategy for Biomass Upgrade: Cascade Approach to the Synthesis of Useful Compounds via C-C Bond Formation Using Biomass-Derived Sugars as Carbon Nucleophiles.

    Science.gov (United States)

    Yamaguchi, Sho; Baba, Toshihide

    2016-07-20

    Due to the depletion of fossil fuels, biomass-derived sugars have attracted increasing attention in recent years as an alternative carbon source. Although significant advances have been reported in the development of catalysts for the conversion of carbohydrates into key chemicals (e.g., degradation approaches based on the dehydration of hydroxyl groups or cleavage of C-C bonds via retro-aldol reactions), only a limited range of products can be obtained through such processes. Thus, the development of a novel and efficient strategy targeted towards the preparation of a range of compounds from biomass-derived sugars is required. We herein describe the highly-selective cascade syntheses of a range of useful compounds using biomass-derived sugars as carbon nucleophiles. We focus on the upgrade of C2 and C3 oxygenates generated from glucose to yield useful compounds via C-C bond formation. The establishment of this novel synthetic methodology to generate valuable chemical products from monosaccharides and their decomposed oxygenated materials renders carbohydrates a potential alternative carbon resource to fossil fuels.

  20. Synthesis of six epoxyketooctadecenoic acid (EKODE) isomers, their generation from nonenzymatic oxidation of linoleic acid, and their reactivity with imidazole nucleophiles.

    Science.gov (United States)

    Lin, De; Zhang, Jianye; Sayre, Lawrence M

    2007-12-07

    As a class of linoleic acid oxidation products, epoxyketooctadecenoic acids (EKODEs), are formed in vivo and in vitro by a free radical mechanism initiated by either enzymatic or nonenzymatic pathways. They have so far been made available in small-scale quantities, often as isomeric mixtures, from reductive decomposition of linoleic acid-derived hydroperoxides. There is major interest in these compounds owing to their highly potent biological activities and their ability to covalently modify proteins. The synthesis of six EKODE regio- and stereoisomers, two trans alpha',beta'-epoxy-alpha,beta-enones, and two trans and the two cis gamma,delta,-epoxy-alpha,beta-enones was accomplished, with the key steps being Wittig-type reactions and aldol condensations. All six EKODE isomers were confirmed by HPLC to be generated in the autoxidation of linoleic acid promoted by Fe(II)/ascorbic acid through spiking in of authentic samples. On the basis of evidence for EKODE modification of protein His residues, the reactions of Nalpha-benzoyl-L-histidine with autoxidizing linoleic acid and with the individual EKODE isomers were compared, as were the kinetics of the various EKODE reactions with imidazole nucleophiles. The structures of His-EKODE-(E)-I adducts were confirmed to reflect conjugate addition (epoxide ring remains intact) through an NMR study of the reaction of imidazole with a generic EKODE-(E)-I analog. The synthesis of the EKODE isomers makes these important molecules available for further chemical and biological evaluation.

  1. Tether-directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

    Directory of Open Access Journals (Sweden)

    Cox Liam R

    2007-02-01

    Full Text Available Abstract Background Using a silyl tether to unite an aldehyde electrophile and allylsilane nucleophile into a single molecule allows a subsequent Lewis-acid-mediated allylation to proceed in an intramolecular sense and therefore receive all the benefits associated with such processes. However, with the ability to cleave the tether post allylation, a product that is the result of a net intermolecular reaction can be obtained. In the present study, four diastereoisomeric β-silyloxy-α-methyl aldehydes, which contain an allylsilane tethered through the β-carbinol centre, have been prepared, in order to probe how the relative configuration of the two stereogenic centres affects the efficiency and selectivity of the intramolecular allylation. Results Syn-aldehydes, syn-4a and syn-4b, both react poorly, affording all four possible diastereoisomeric oxasilacycle products. In contrast, the anti aldehydes anti-4a and anti-4b react analogously to substrates that lack substitution at the α-site, affording only two of the four possible allylation products. Conclusion The outcome of the reaction with anti-aldehydes is in accord with reaction proceeding through a chair-like transition state (T.S.. In these systems, the sense of 1,3-stereoinduction can be rationalised by the aldehyde electrophile adopting a pseudoaxial orientation, which will minimise dipole-dipole interactions in the T.S. The 1,4-stereoinduction in these substrates is modest and seems to be modulated by the R substituent in the starting material. In the case of the syn-substrates, cyclisation through a chair T.S. is unlikely as this would require the methyl substituent α to the reacting carbonyl group to adopt an unfavourable pseudoaxial position. It is therefore proposed that these substrates react through poorly-defined T.S.s and consequently exhibit essentially no stereoselectivity.

  2. 40 CFR Appendix B to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

    Science.gov (United States)

    2010-07-01

    ... Conditions Application Substitute Decision Conditions Comments CFC-12 Automobile Motor Vehicle Air... refrigerant. CFC-12 Automobile Motor Vehicle Air Conditioning (New equipment only) R-152a as a substitute for... excluding the space enclosed by the ducting in the HVAC module. Refrigerants—Acceptable Subject to Narrowed...

  3. The definition of the toxicologically relevant applicability domain for the SNAr reaction for substituted pyridines and pyrimidines.

    Science.gov (United States)

    Enoch, S J; Cronin, M T D; Schultz, T W

    2013-01-01

    This study outlines how results from a glutathione reactivity assay (so-called in chemico data) can be used to define the applicability domain for the nucleophilic aromatic substitution (SNAr) reaction for nitrogen-containing aromatic compounds. SNAr is one of the six mechanistic domains that have been shown to be important in toxicological endpoints in which the ability to bind covalently to a protein is a key molecular initiating event. This study has analysed experimental data (2 h RC50 values), allowing a clear and interpretable structure-activity relationship to be developed for pyridines and pyrimidines which reside within the SNAr domain. The in-ring nitrogen(s) act as activating groups in the SNAr reaction. The position(s) of the in-ring nitrogen(s) as well as other activating groups, especially in relationship to the leaving group, affect reactive potency. The experimentally defined applicability domain has resulted in a series of structural alerts. These results build on early work on the benzene derivatives residing in the SNAr domain. The definition of the applicability domain for the SNAr reaction and the resulting structural alerts are likely to be beneficial in the development of computational tools for category formation and read-across in hazard identification, and the development of adverse outcome pathways.

  4. Quantitative Structure–Property Relationship (QSPR Models for a Local Quantum Descriptor: Investigation of the 4- and 3-Substituted-Cinnamic Acid Esterification

    Directory of Open Access Journals (Sweden)

    Cláudio E. Rodrigues-Santos

    2015-09-01

    Full Text Available In this work, the theoretical description of the 4- and 3-substituted-cinnamic acid esterification with different electron donating and electron withdrawing groups was performed at the B3LYP and M06-2X levels, as a two-step process: the O-protonation and the nucleophile attack by ethanol. In parallel, an experimental work devoted to the synthesis and characterization of the substituted-cinnamate esters has also been performed. In order to quantify the substituents effects, quantitative structure–property relationship (QSPR models based on the atomic charges, Fukui functions and the Frontier Effective-for-Reaction Molecular Orbitals (FERMO energies were investigated. In fact, the Fukui functions, ƒ+C and ƒ−O, indicated poor correlations for each individual step, and in contrast with the general literature, the O-protonation step is affected both by the FERMO energies and the O-charges of the carbonyl group. Since the process was shown to not be totally described by either charge- or frontier-orbitals, it is proposed to be frontier-charge-miscere controlled. Moreover, the observed trend for the experimental reaction yields suggests that the electron withdrawing groups favor the reaction and the same was observed for Step 2, which can thus be pointed out as the determining step.

  5. Substitution between Cars within the Household

    DEFF Research Database (Denmark)

    de Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate—for each car owned by the household—own and cross-price effects...... of increases in fuel costs per kilometre. The empirical results show that failure to capture substitution between cars within the household can result in substantial misspecification biases. Ignoring substitution, we estimate fuel price elasticities of –0.81 and -0.65 for the primary and secondary cars...... efficient car, finding partial support for the underlying hypothesis. More importantly, the results of this extended model emphasize the importance of behavioural differences related to the position of the most fuel efficient car in the household, suggesting that households’ fuel efficiency choices...

  6. Substitute energy resource policy in Japan

    International Nuclear Information System (INIS)

    Umehara, Katsuhiko

    1980-01-01

    Japan depends 88% of energy resources and 99.8% of petroleum on imports. The solution of energy problems is now made internationally. As the means for Japan, there are the substitution of other resources for petroleum and its promotion. However, this involves the considerable funds for the development and utilization, which must be borne by the people in the form of tax. For governmental financing, a special account must be set up for the particular purpose. In the research and development of new energy resources, new institution is required. The following matters are described: petroleum shortage coming even in 1980s, the international need of substitute energy development, the need for establishing measures for substitute energy resources, acquisition of the funds, special-account governmental financing, and an institute of new energy development. (author)

  7. [Contingency management in opioid substitution treatment].

    Science.gov (United States)

    Specka, M; Böning, A; Scherbaum, N

    2011-07-01

    The majority of opiate-dependent patients in substitution treatment show additional substance-related disorders. Concomitant use of heroin, alcohol, benzodiazepines or cocaine compromises treatment success. Concomitant drug use may be treated by using contingency management (CM) which is based on learning theory. In CM, abstinence from drugs, as verified by drug screenings, is reinforced directly and contingently. Reinforcers used in CM studies with substituted patients were, amongst others, vouchers and take-home privileges. Studies in the USA show a medium average effect of CM on drug consumption rates and abstinence. The effects decrease markedly after the end of the intervention. We discuss whether CM is applicable within the German substitution treatment system and how it can be combined with other interventions such as selective detoxification treatments or cognitive-behavioural programmes. © Georg Thieme Verlag KG Stuttgart · New York.

  8. Biomaterials in search of a meniscus substitute.

    Science.gov (United States)

    Rongen, Jan J; van Tienen, Tony G; van Bochove, Bas; Grijpma, Dirk W; Buma, Pieter

    2014-04-01

    The menisci fulfill key biomechanical functions in the tibiofemoral (knee) joint. Unfortunately meniscal injuries are quite common and most often treated by (partial) meniscectomy. However, some patients experience enduring symptoms, and, more importantly, it leads to an increased risk for symptomatic osteoarthritis. Over the past decades, researchers have put effort in developing a meniscal substitute able to prevent osteoarthritis and treat enduring clinical symptoms. Grossly, two categories of substitutes are observed: First, a resorbable scaffold mimicking biomechanical function which slowly degrades while tissue regeneration and organization is promoted. Second, a non resorbable, permanent implant which mimics the biomechanical function of the native meniscus. Numerous biomaterials with different (material) properties have been used in order to provide such a substitute. Nevertheless, a clinically applicable cartilage protecting material is not yet emerged. In the current review we provide an overview, and discuss, these different materials and extract recommendations regarding material properties for future developmental research. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Nucleophilic behavior of lysine-501 of the alpha-polypeptide of sodium and potassium ion activated adenosinetriphosphatase consistent with a role in binding adenosine triphosphate

    International Nuclear Information System (INIS)

    Xu, K.Y.; Kyte, J.

    1989-01-01

    An immunoadsorbent specific for the carboxy-terminal sequence -GAPER, which comprises residues 502-506 of the alpha-polypeptide of ovine sodium and potassium ion activated adenosinetriphosphatase [(Na+ + K+)-ATPase], was used to isolate the products of the reaction between the lysine immediately preceding this sequence in the intact protein and either [3H]acetic anhydride or fluorescein 5'-isothiocyanate. Changes in the apparent nucleophilicity of this lysine, Lys501, were observed with both reagents when ATP was bound by the intact, native enzyme poised in the E1 conformation or when the structure of the enzyme was changed from the E1 conformation into the E2-P conformation. With both reagents, a decrease of more than 4-fold in the yield of incorporation occurred during the former change, but a decrease of only 2-fold occurred during the latter. Because a much larger decrease occurred when ATP was bound in the absence of a conformational change than occurred when a major conformational change took place in the absence of the occupation of the active site, these changes in the incorporation of [3H]acetyl suggest that Lys501 from the alpha polypeptide is directly involved in binding ATP within the active site of (Na+ + K+)-ATPase. The immunochemical reactions between the specific polyclonal antibodies raised against the sequence-GAPER and denatured or enzymically active (Na+ + K+)-ATPase were also investigated. Western blots and the inhibition of enzymic activity caused by the antibody have shown that it can bind to both the denatured and the native form of the alpha-polypeptide, respectively

  10. Nucleophilic radiosynthesis of 2-[{sup 18}F]fluoro-2-deoxy-D-galactose from Talose triflate and biodistribution in a porcine model

    Energy Technology Data Exchange (ETDEWEB)

    Frisch, Kim, E-mail: frisch@pet.auh.d [PET Centre, Aarhus University Hospital, DK-8000 Aarhus (Denmark); Bender, Dirk; Hansen, Soren B. [PET Centre, Aarhus University Hospital, DK-8000 Aarhus (Denmark); Keiding, Susanne [PET Centre, Aarhus University Hospital, DK-8000 Aarhus (Denmark); Department of Medicine V (Hepatology and Gastroenterology), Aarhus University Hospital, DK-8000 Aarhus (Denmark); Sorensen, Michael [PET Centre, Aarhus University Hospital, DK-8000 Aarhus (Denmark)

    2011-05-15

    Introduction: The galactose analogue 2-[{sup 18}F]fluoro-2-deoxy-D-galactose (FDGal) is a promising positron emission tomography (PET) tracer for studies of regional differences in liver metabolic function and for clinical evaluation of patients with liver cirrhosis and patients undergoing treatment of liver diseases. However, there is an unmet need for routine production of FDGal from readily available starting material. In this study, we present the preparation of FDGal with high radiochemical purity and in amounts sufficient for clinical investigations from commercially available Talose triflate (1,3,4,6-tetra-O-acetyl-2-O-trifluoromethanesulfonyl-{beta}-D-talopyranose). In addition, the biodistribution of FDGal in the pig is presented. Methods: FDGal was prepared by nucleophilic fluorination of Talose triflate followed by basic hydrolysis. The entire synthesis was performed using the GE TRACERlab MX 2-[{sup 18}F]fluoro-2-deoxy-D-glucose (FDG) synthesizer and existing methods for quality control of FDG were applied. Biodistribution of FDGal was studied by successive whole-body PET recordings of two anaesthetized 37-kg pigs. Results: Up to 3.7 GBq sterile, pyrogen-free and no-carrier-added FDGal was produced with a radiochemical yield of 3.8{+-}1.2% and a radiochemical purity of 98{+-}1% (42 productions; yield is decay corrected). The adopted quality control methods for FDG were directly applicable for FDGal. Biodistribution studies in the pig revealed the liver and the urinary bladder as critical organs in terms of radiation dose. Conclusion: Commercially available Talose triflate is a suitable starting material for routine productions of FDGal. The presented radiosynthesis and quality control methods allow for the production of pure, no-carrier-added FDGal in sufficient amounts for clinical PET-investigations of the liver.

  11. Substitution between cars within the household

    DEFF Research Database (Denmark)

    De Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    The purpose of this paper is to study to what extent two-car households substitute the use of their less fuel efficient car by the use of their more fuel efficient car after an increase in fuel prices. Based on a simple theoretical framework we use a large sample of detailed Danish data on two-car...... households to estimate, for each car owned by the household, own and cross-price effects of increases in fuel costs per kilometer. The empirical results point at important substitution effects, so that models that estimate responses to fuel prices on the implicit or explicit assumption of one car per...

  12. Analysis of chemical equilibrium of silicon-substituted fluorescein and its application to develop a scaffold for red fluorescent probes.

    Science.gov (United States)

    Hirabayashi, Kazuhisa; Hanaoka, Kenjiro; Takayanagi, Toshio; Toki, Yuko; Egawa, Takahiro; Kamiya, Mako; Komatsu, Toru; Ueno, Tasuku; Terai, Takuya; Yoshida, Kengo; Uchiyama, Masanobu; Nagano, Tetsuo; Urano, Yasuteru

    2015-09-01

    Fluorescein is a representative green fluorophore that has been widely used as a scaffold of practically useful green fluorescent probes. Here, we report synthesis and characterization of a silicon-substituted fluorescein, i.e., 2-COOH TokyoMagenta (2-COOH TM), which is a fluorescein analogue in which the O atom at the 10' position of the xanthene moiety of fluorescein is replaced with a Si atom. This fluorescein analogue forms a spirolactone ring via intramolecular nucleophilic attack of the carboxylic group in a pH-dependent manner. Consequently, 2-COOH TM exhibits characteristic large pH-dependent absorption and fluorescence spectral changes: (1) 2-COOH TM is colorless at acidic pH, whereas fluorescein retains observable absorption and fluorescence even at acidic pH, and the absorption maximum is also shifted; (2) the absorption spectral change occurs above pH 7.0 for 2-COOH TM and below pH 7.0 for fluorescein; (3) 2-COOH TM shows a much sharper pH response than fluorescein because of its pKa inversion, i.e., pKa1 > pKa2. These features are also different from those of a compound without the carboxylic group, 2-Me TokyoMagenta (2-Me TM). Analysis of the chemical equilibrium between pH 3.0 and 11.0 disclosed that 2-COOH TM favors the colorless and nonfluorescent lactone form, compared with fluorescein. Substitution of Cl atoms at the 4' and 5' positions of the xanthene moiety of 2-COOH TM to obtain 2-COOH DCTM shifted the equilibrium so that the new derivative exists predominantly in the strongly fluorescent open form at physiological pH (pH 7.4). To demonstrate the practical utility of 2-COOH DCTM as a novel scaffold for red fluorescent probes, we employed it to develop a probe for β-galactosidase.

  13. Understanding bimolecular machines: Theoretical and experimental approaches

    Science.gov (United States)

    Goler, Adam Scott

    This dissertation concerns the study of two classes of molecular machines from a physical perspective: enzymes and membrane proteins. Though the functions of these classes of proteins are different, they each represent important test-beds from which new understanding can be developed by the application of different techniques. HIV1 Reverse Transcriptase is an enzyme that performs multiple functions, including reverse transcription of RNA into an RNA/DNA duplex, RNA degradation by the RNaseH domain, and synthesis of dsDNA. These functions allow for the incorporation of the retroviral genes into the host genome. Its catalytic cycle requires repeated large-scale conformational changes fundamental to its mechanism. Motivated by experimental work, these motions were studied theoretically by the application of normal mode analysis. It was observed that the lowest order modes correlate with largest amplitude (low-frequency) motion, which are most likely to be catalytically relevant. Comparisons between normal modes obtained via an elastic network model to those calculated from the essential dynamics of a series of all-atom molecular dynamics simulations show the self-consistency between these calculations. That similar conformational motions are seen between independent theoretical methods reinforces the importance of large-scale subdomain motion for the biochemical action of DNA polymerases in general. Moreover, it was observed that the major subunits of HIV1 Reverse Transcriptase interact quasi-harmonically. The 5HT3A Serotonin receptor and P2X1 receptor, by contrast, are trans-membrane proteins that function as ligand gated ion channels. Such proteins feature a central pore, which allows for the transit of ions necessary for cellular function across a membrane. The pore is opened by the ligation of binding sites on the extracellular portion of different protein subunits. In an attempt to resolve the individual subunits of these membrane proteins beyond the diffraction limit, a super-localization microscope capable of reconstructing super-resolution images was constructed. This novel setup allows for the study of discrete state kinetic mechanisms with spatial resolution good enough to distinguish individual binding sites of these membrane proteins. Further use of this technique may allow for the study of allostery and subunit specific stoichiometry in the presence of agonist or antagonist ligands relevant to pharmacology.

  14. Substituting freshwater: Can ocean desalination and water recycling capacities substitute for groundwater depletion in California?

    Science.gov (United States)

    Badiuzzaman, Pierre; McLaughlin, Eoin; McCauley, Darren

    2017-12-01

    While the sustainability of resource depletion is a longstanding environmental concern, wider attention has recently been given to growing water scarcity and groundwater depletion. This study seeks to test the substitutability assumption embedded in weak sustainability indicators using a case study of Californian water supply. The volume of groundwater depletion is used as a proxy for unsustainable water consumption, and defined by synthesising existing research estimates into low, medium and high depletion baselines. These are compared against projected water supply increases from ocean desalination and water recycling by 2035, to determine whether new, drought-proof water sources can substitute for currently unsustainable groundwater consumption. Results show that the maximum projected supply of new water, 2.47 million acre-feet per year (MAF/yr), is sufficient to meet low depletion estimates of 2.02 MAF/yr, but fails to come near the high depletion estimate of 3.44 MAF/yr. This does not necessarily indicate physical limitations of substitutability, but more so socio-economic limitations influenced by high comparative costs. By including capacities in demand-substitutability via urban water conservation, maximum predicted capacities reach 5.57 MAF/yr, indicating wide room for substitution. Based on these results, investment in social and institutional capital is an important factor to enhance demand-side substitutability of water and other natural resources, which has been somewhat neglected by the literature on the substitutability of natural resources. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Effect of electron-withdrawing power of the substituted group on• OH ...

    Indian Academy of Sciences (India)

    In neutral aqueous solution of (phenylthio)acetic acid, hydroxyl radical is observed to react with a bimolecular rate constant of 7.2 × 109 dm3 mol-1 s-1 and the transient absorption bands are assigned to ∙ OH radical addition to benzene and sulphur with a rough estimated values of 50 and 40% respectively. The reaction of ...

  16. substitution line for resistance to stripe rust

    Indian Academy of Sciences (India)

    2011-08-19

    Aug 19, 2011 ... c Indian Academy of Sciences. RESEARCH ARTICLE. Molecular cytogenetic characterization of a new wheat Secale africanum. 2R a. (2D) substitution line for resistance to stripe rust. MENGPING LEI, GUANGRONG LI, SUFEN ZHANG, CHENG LIU and ZUJUN YANG. ∗. School of Life Science and ...

  17. Biological activities of substituted trichostatic acid derivatives

    Indian Academy of Sciences (India)

    New substituted trichostatic acid derivatives have been synthesized and evaluated for their biological activities towards the H661 non-small lung cancer cell line. These syntheses were achieved by alkylation of propiophenones to introduce the side chain with a terminal precursor of hydroxamic acid and aminobenzamide ...

  18. 3-Substituted 2-phenyl-indoles

    DEFF Research Database (Denmark)

    Johansson, Karl Henrik; Jørgensen, T.B.; Gloriam, D.E.

    2013-01-01

    -indoles with a variety of substituents at the indole 3-position. Herein we describe the development of optimised and efficient synthetic routes to a series of new 2-phenyl-indole building blocks 3 to 9 and show that these can be used to generate a broad variety of 3-substituted 2-phenyl-indoles of interest to medicinal...

  19. chromic transitions in phenyl-substituted polythiophenes

    African Journals Online (AJOL)

    The solvatochromic and thermochromic behaviours of phenyl-substituted polythiophenes were studied. The pristine polymers, upon dissolution in chloroform, exhibited blue-shifted absorption. The solid films of the polymers showed significant blue-shifted as well as red-shifted absorptions when heated. While the addition of ...

  20. CHROMIC TRANSITIONS IN PHENYL-SUBSTITUTED ...

    African Journals Online (AJOL)

    a

    in order to explain the relationship between optical properties and chemical structure [1-6]. These studies have also opened new possibilities for applications in chemical and biochemical sensors [7-10]. The chromic behaviours of substituted polythiophenes depend on conformational transitions of the polythiophene ...

  1. Fossil Fuels, Backstop Technologies, and Imperfect Substitution

    NARCIS (Netherlands)

    van der Meijden, G.C.; Pittel, Karen; van der Ploeg, Frederick; Withagen, Cees

    2014-01-01

    This chapter studies the transition from fossil fuels to backstop technologies in a general equilibrium model in which growth is driven by research and development. The analysis generalizes the existing literature by allowing for imperfect substitution between fossil fuels and the new energy

  2. Symptomatic hemorrhagic complications associated with dural substitutes

    Directory of Open Access Journals (Sweden)

    Po-Yuan Chen

    2018-01-01

    Conclusion: The increased risk of hemorrhagic complications associated with craniotomy is modified by choice of dural replacement. Our results could assist clinicians in their decision-making with respect to the optimal timing for synthetic dural substitutes in patients with tumor infiltration of the patient's dura, severe brain swelling in traumatic brain injury, or a result of shrinkage from exposure and electrocautery.

  3. Additive and Substitutive Borrowing against Semantic Broadening ...

    African Journals Online (AJOL)

    additive borrowing from substitutive ones. Architecture, Iron-Smelting and Pottery within the Realm of. African Past. The architectural power of African societies is .... paa roof. ---. Kihehe. G62 likang'a roof lwangiko 'roof'. Runyambo JE21 omusakaaro roof ibaati 'roof'. Luzinza. JE23 oluswi roof. ---. Kijita. JE25 oluswi roof. ---.

  4. Additive and Substitutive Borrowing against Semantic Broadening ...

    African Journals Online (AJOL)

    The thrust of this paper lies on semantic changes associated with additive and substitutive borrowing in Bantu-speaking communities in Tanzania. Due to contact of languages, semantic differences of the terms related to architectural structures emanate. Apart from data from a few elderly native speakers, research was ...

  5. A DENSITY FUNCTIONAL THEORY STUDY OF SUBSTITUTED ...

    African Journals Online (AJOL)

    In this work the electronic and thermodynamic properties of both neutral and radical cationic oligothiophene chains with up to eight thiophene units, substituted and bridged oligothiophenes are investigated by performing hybrid DFT (BH and HLYP) and Hartree-Fock calculations using 6-31G* and 6-311G** basis sets.

  6. Electrochemical oxidation of substituted benzylamines in aquo ...

    Indian Academy of Sciences (India)

    Electrochemical oxidation of nine para- and meta-substituted benzylamines in varying mole fractions of acetic acid in water has been investigated in the presence of 0.1 M sulphuric acid as supporting electrolyte. The oxidation potentials correlate well with Hammett's substituent constants affording negative reaction ...

  7. Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent

    2016-01-01

    The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asymmetric hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee

  8. Endogenous cueing attenuates object substitution masking.

    Science.gov (United States)

    Germeys, Filip; Pomianowska, I; De Graef, P; Zaenen, P; Verfaillie, K

    2010-07-01

    Object substitution masking (OSM) is a form of visual masking in which a briefly presented target surrounded by four small dots is masked by the continuing presence of the four dots after target offset. A major parameter in the prediction of OSM is the time required for attention to be directed to the target following its onset. Object substitution theory (Di Lollo et al. in J Exp Psychol Gen 129:481-507, 2000) predicts that the sooner attention can be focused at the target's location, the less masking will ensue. However, recently Luiga and Bachmann (Psychol Res 71:634-640, 2007) presented evidence that precueing of attention to the target location prior to target-plus-mask onset by means of a central (endogenous) arrow cue does not reduce OSM. When attention was cued exogenously, OSM was attenuated. Based on these results, Luiga and Bachmann argued that object substitution theory should be adapted by differentiating the ways of directing attention to the target location. The goal of the present study was to further examine the dissociation between the effects of endogenous and exogenous precueing on OSM. Contrary to Luiga and Bachmann, our results show that prior shifts of attention to the target location initiated by both exogenous and endogenous cues reduce OSM as predicted by object substitution theory and its computational model CMOS.

  9. P. Electricity demand, substitution and resources

    International Nuclear Information System (INIS)

    1976-01-01

    This report discusses the demand for electricity in New Zealand, the accuracy of demand predictions, and whether some other form of energy could be substituted for electricity. It then discusses past and possible future electricity generation in New Zealand by geothermal steam and hydro power and the resources of gas and coal that could be made available for electricity generation

  10. Synthesis of enantiopure 3-substituted morpholines

    DEFF Research Database (Denmark)

    Bornholdt, Jan; Felding, Jakob; Kristensen, Jesper Langgaard

    2010-01-01

    Enantiopure 3-substituted morpholines were assembled through ring-opening of a N-2-benzothiazolesulfonyl (Bts) activated aziridine with organocuprates followed by a ring annulation reaction with a vinylsulfonium salt under microwave conditions. Deprotection of the N-Bts group proceeds under very ...

  11. Coal as a Substitute for Carbon Black

    Science.gov (United States)

    Kushida, R. O.

    1982-01-01

    New proposal shows sprayed coal powder formed by extrusion of coal heated to plastic state may be inexpensive substitute for carbon black. Carbon black is used extensively in rubber industry as reinforcing agent in such articles as tires and hoses. It is made from natural gas and petroleum, both of which are in short supply.

  12. Trace maps for arbitrary substitution sequences

    International Nuclear Information System (INIS)

    Avishai, Y.

    1993-01-01

    The discovery of quasi-crystals and their 1-dimensional modeling have led to a deep mathematical study of Schroedinger operators with an arbitrary deterministic potential sequence. In this work we address this problem and find trace maps for an arbitrary substitution sequence. our trace maps have lower dimensionality than those of Kolar and Nori, which make them quite attractive for actual applications. (authors)

  13. Synthesis and electrochemical studies of phenylazo substituted ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 112; Issue 6. Synthesis and electrochemical studies of phenylazo substituted tetraaza macrocyclic complexes of Ni(II). Randhir Singh Suresh Kumar Amarendra Bhattacharya. Inorganic and Analytical Volume 112 Issue 6 December 2000 pp 601-605 ...

  14. Substitution between cars within the household

    NARCIS (Netherlands)

    de Borger, B.; Mulalic, I.; Rouwendal, J.

    2016-01-01

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars of different fuel efficiency in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate - for each car owned by the household

  15. Substitute fluid examinations for liquid manure

    Directory of Open Access Journals (Sweden)

    Schrader Kevin

    2017-01-01

    Full Text Available For the farming industry it is essential to use liquid manure as natural fertilizer. Through new agricultural regulation 2015 in Germany the industry must develop new liquid manure spreader systems because the ammonia and methane emission are limited. In a research project the University of Applied Sciences Zwickau and some other industry partners will develop such a new innovative liquid manure spreader. The new liquid manure spreader should use pulsating air to distribute the liquid manure exactly. The pulsating air, which flows through the pipelines, should be analysed at a test station. For examinations at this test station it is important to find another substitute fluid because liquid manure smells strong, is not transparent and is also not homogeneous enough for scientific investigations. Furthermore it is important to ensure that the substitute fluid is, like liquid manure, a non-Newtonian fluid. The substitute fluid must be a shear-thinning substance - this means the viscosity decrease at higher shear rate. Many different samples like soap-water-farragoes, jelly-water-farragoes, agar-water-farragoes, soap-ethanol-farragoes and more are, for the project, examined in regard of their physical properties to find the best substitute fluid. The samples are examined at the rotational viscometer for viscosity at various shear rates and then compared with the viscosity values of liquid manure.

  16. Law of substitution for mixed arrays

    International Nuclear Information System (INIS)

    Koudelka, A.J.

    1987-01-01

    The nuclear safety justification of a mixed array of dissimilar fissile units of metal units and dilute solution units, according to Clayton, has been a persistent and nagging problem. Dissimilar uranium metal or dissimilar uranium solution units in a mixed array can also create a modeling nightmare for the nuclear criticality safety engineer. Now, a calculational method known as the Law of Substitution has been developed to ensure that the k/sub eff/ of an array of uranium metal and uranium solution units will satisfy any k/sub eff/ limit set by the nuclear safety engineer. The nuclear criticality safety engineer can utilize the Law of Substitution to safely mix or substitute different uranium metal units, different uranium solution units, and more importantly, uranium metal and dilute UO 2 solution units in an array. The Law of Substitution is as follows: (1) calculate the k/sub eff/ of each unit type in its own infinite planar array. (2) Determine the edge-to-edge spacing of the infinite planar array of each type of unit to satisfy a desired k/sub eff/. (3) Select the largest edge-to-edge spacing from among the similar units in their infinite planar arrays and use that spacing for the finite or infinite planar array of mixed units

  17. doped cadmium potassium phosphate hexahydrate: A substitutional ...

    Indian Academy of Sciences (India)

    Single crystal EPR studies of VO(II)-doped cadmium potassium phosphate hexahydrate (CPPH) have been carried out at room temperature. The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice only substitutionally in place of Cd(II). Spin Hamiltonian ...

  18. Synthesis and electrochemical studies of phenylazo substituted ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. Synthesis and characterization of some phenyl azo substituted tetraaza macrocyclic complexes of Ni(II) are reported. Electrochemical behaviour of these macrocyclic complexes has been examined using polarographic, voltammetric and spectroscopic techniques. These studies show that both the ligand and the ...

  19. Density functional study of S(N) 2 substitution reactions for CH(3) Cl + CX(1) X(2•-) (X(1) X(2) = HH, HF, HCl, HBr, HI, FF, ClCl, BrBr, and II).

    Science.gov (United States)

    Liang, Jun-Xi; Geng, Zhi-Yuan; Wang, Yong-Cheng

    2012-03-05

    A systematic investigation on the S(N) 2 displacement reactions of nine carbene radical anions toward the substrate CH(3) Cl has been theoretically carried out using the popular density functional theory functional BHandHLYP level with different basis sets 6-31+G (d, p)/relativistic effective core potential (RECP), 6-311++G (d, p)/RECP, and aug-cc-pVTZ/RECP. The studied models are CX(1) X(2•-) + CH(3) Cl → X(2) X(1) CH(3) C(•) + Cl(-) , with CX(1) X(2•-) = CH(2) (•-) , CHF(•-) , CHCl(•-) , CHBr(•-) , CHI(•-) , CF(2) (•-) , CCl(2) (•-) , CBr(2) (•-) , and CI(2) (•-) . The main results are proposed as follows: (a) Based on natural bond orbital (NBO), proton affinity (PA), and ionization energy (IE) analysis, reactant CH(2) (•-) should be a strongest base among the anion-containing species (CX(1) X(2•-) ) and so more favorable nucleophile. (b) Regardless of frontside attacking pathway or backside one, the S(N) 2 reaction starts at an identical precomplex whose formation with no barrier. (c) The back-S(N) 2 pathway is much more preferred than the front-S(N) 2 one in terms of the energy gaps [ΔE cent≠(front)-ΔE cent≠(back)], steric demand, NBO population analysis. Thus, the back-S(N) 2 reaction was discussed in detail. On the one hand, based on the energy barriers (ΔE cent≠ and ΔE ovr≠) analysis, we have strongly affirmed that the stabilization of back attacking transition states (b-TSs) presents increase in the order: b-TS-CI(2) < b-TS-CBr(2) < b-TS-CCl(2) < b-TS-CHI < b-TS-CHBr < b-TS-CHCl < b-TS-CF(2) < b-TS-CHF < b-TS-CH(2) . On the other hand, depended on discussions of the correlations of ΔE ovr≠ with influence factors (PA, IE, bond order, and ΔE def≠), we have explored how and to what extent they affect the reactions. Moreover, we have predicted that the less size of substitution (α-atom) required for the gas-phase reaction with α-nucleophile is related to the α-effect and estimated that the reaction

  20. Substitution treatment for opioid addicts in Germany

    Directory of Open Access Journals (Sweden)

    Gerlach Ralf

    2007-02-01

    Full Text Available Abstract Background After a long and controversial debate methadone maintenance treatment (MMT was first introduced in Germany in 1987. The number of patients in MMT – first low because of strict admission criteria – increased considerably since the 1990s up to some 65,000 at the end of 2006. In Germany each general practitioner (GP, who has completed an additional training in addiction medicine, is allowed to prescribe substitution drugs to opioid dependent patients. Currently 2,700 GPs prescribe substitution drugs. Psychosocial care should be made available to all MMT patients. Results The results of research studies and practical experiences clearly indicate that patients benefit substantially from MMT with improvements in physical and psychological health. MMT proves successful in attaining high retention rates (65 % to 85 % in the first years, up to 50 % after more than seven years and plays a major role in accessing and maintaining ongoing medical treatment for HIV and hepatitis. MMT is also seen as a vital factor in the process of social re-integration and it contributes to the reduction of drug related harms such as mortality and morbidity and to the prevention of infectious diseases. Some 10 % of MMT patients become drug-free in the long run. Methadone is the most commonly prescribed substitution medication in Germany, although buprenorphine is attaining rising importance. Access to MMT in rural areas is very patchy and still constitutes a problem. There are only few employment opportunities for patients participating in MMT, although regular employment is considered unanimously as a positive factor of treatment success. Substitution treatment in German prisons is heterogeneous in access and treatment modalities. Access is very patchy and the number of inmates in treatment is limited. Nevertheless, substitution treatment plays a substantial part in the health care system provided to drug users in Germany. Conclusion In Germany, a

  1. Signalization and stimulus-substitution in Pavlov's theory of conditioning.

    Science.gov (United States)

    García-Hoz, Víctor

    2003-11-01

    The concept of conditioning as signalization proposed by Ivan P. Pavlov (1927, 1928) is studied in relation to the theory of stimulus-substitution, which is also attributed to him. In the so-called theory of stimulus-substitution a distinction must be made between an empirical principle of substitution and an actual theory of substitution, which can adopt different forms. The Pavlovian theory of substitution--which conceives substitution as a substitution of the unconditioned stimulus (US) by the conditioned stimulus (CS) in the activation of the representation of the former--can be understood as an explanation or model of signalization. Signalization and substitution are answers to different questions, and the level of analysis to which signalization corresponds, is that which concerns the nature of conditioning as an operation of the animal in the environment.

  2. Stereoselective synthesis of 2,3-disubstituted indoline, pyrrolidine and cyclic ether-fused 1,2-dihydroquinoline derivatives using alkyne iminium ion cyclization of vinylogous carbamates: switch of regioselectivity using an internal hydroxy group as a nucleophile.

    Science.gov (United States)

    Gharpure, Santosh J; Prasath, V; Kumar, Vinod

    2015-09-14

    An intramolecular, alkyne iminium ion cyclization of vinylogous carbamates derived from o-alkynyl anilines and N-protected homopropargyl amines is developed for the stereoselective construction of trans-2,3-disubstituted indolines and pyrrolidine derivatives, respectively. The regioselectivity of the alkyne iminium ion cyclization could be switched using a hydroxy group as an internal nucleophile resulting in cyclic ether-fused 1,2-dihydroquinolines. The entire process of nitrogen heterocycle formation can also be carried out in a 'one-pot' manner starting from o-iodo aniline derivatives.

  3. Characterization of hydroxyapatite substituted with silicon

    International Nuclear Information System (INIS)

    Silva, H.M. da; Soares, G.A.; Mateescu, M.; Anselme, K.; Palard, M.; Champion, E.

    2009-01-01

    Incorporation of silicon (Si) ions into hydroxyapatite structure (HA) influences on physical, chemical and physiological properties. Some studies reported the improved bioactivity Si substitution, and it also accelerates the biomineralization process. The main objective of this work is to characterize stoichiometric hydroxyapatite and hydroxyapatite substituted with 1.13% in weight of Si (SiHA) using a wet precipitation method followed by a heat treatment. SEM/EDS, AFM, DRX and FTIR analyses were used to characterize the samples. EDS and FTIR results confirmed the presence of Si. Silicon induces small changes on crystal structure of HA, not detected on X-ray diffraction patterns of sintered tablets of SiHA and HA. No secondary phases were observed, that indicates the Si had entered the HA lattice. (author)

  4. Meat analogues: Health promising sustainable meat substitutes.

    Science.gov (United States)

    Kumar, Pavan; Chatli, M K; Mehta, Nitin; Singh, Parminder; Malav, O P; Verma, Akhilesh K

    2017-03-24

    There is a scarcity of protein of high biological value due to rapid increase in the world population and limited natural resources. Meat is a good source of protein of high biological value but converting the vegetable protein into animal protein is not economical. There is a trend of production of healthy and delicious meat free food for satisfaction of vegetarian and personal well beings. This resulted in increasing use of low cost vegetable protein such as textured soy protein, mushroom, wheat gluten, pulses etc as a substitute for animal-protein. These simulated meat-like products, with similar texture, flavor, color, and nutritive value can be substituted directly for meat to all sections of the society.

  5. What governs nitrogen configuration in substituted aminophosphines?

    OpenAIRE

    Wodrich, Matthew D.; Vargas, Alfredo; Morgantini, Pierre-Yves; Merino, Gabriel; Corminboeuf, Anne-Clémence

    2009-01-01

    The trigonal planar geometry of the nitrogen atom in commonly used phosphoramidite ligands is not in line with the traditional valence shell electron pair repulsion (VSEPR) model. In this work, the effects governing nitrogen configuration in several substituted aminophosphines, A2PNB2 (A or B¼H, F, Cl, Br, Me, OMe, BINOP), are examined using modern computational analytic tools. The electron delocalization descriptions provided by both electron localization function (ELF) and block localized w...

  6. Substitution biases in price indices during transition

    Czech Academy of Sciences Publication Activity Database

    Hanousek, Jan; Filer, Randall K.

    2004-01-01

    Roč. 21, č. 2 (2004), s. 167-177 ISSN 0167-8000 R&D Projects: GA MŠk ME 595 Institutional research plan: CEZ:AV0Z7085904 Keywords : price liberalization * substitution bias * transition economies Subject RIV: AH - Economics http://search. ebscohost .com/login.aspx?direct=true&db=a9h&AN=17109091&site=ehost-live

  7. Neutron scattering from a substitutional mass defect

    International Nuclear Information System (INIS)

    Williams, R.D.; Lovesey, S.W.

    1985-06-01

    The dynamic structure factor is calculated for a low concentration of light mass scatterers substituted in a cubic crystal matrix. A new numerical method for the exact calculation is demonstrated. A local density of states for the low momentum transfer limit, and the shifts and widths of the oscillator peaks in the high momentum transfer limit are derived. The limitations of an approximation which decouples the defect from the lattice is discussed. (author)

  8. Not-so-healthy sugar substitutes?

    OpenAIRE

    Swithers, Susan E.

    2016-01-01

    Replacing sugar-sweetened beverages with diet soft drinks containing sugar substitutes that provide few or no calories has been suggested as one strategy for promoting improved public health outcomes. However, current scientific evidence indicates that routine consumption of beverages with non-nutritive sweeteners not only fails to prevent disease, but is associated with increases in risks for the same health outcomes associated with sugar-sweetened beverages, including type 2 diabetes, cardi...

  9. Gd-substituted Bi-2223 superconductor

    Indian Academy of Sciences (India)

    resistivity with a view to study metal-to-insulator transition, (2) the XRD patterns of the specimens with a view to study the .... values [4] of the transition temperatures for Gd-substituted (BiPb)-2212 specimens. The specimens of Batches I and II with x > 0.4 .... (retd) P N Dheer and Dr R G Sharma. 540. Pramana – J. Phys., Vol.

  10. 40 CFR 721.640 - Amine substituted metal salts.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amine substituted metal salts. 721.640... Substances § 721.640 Amine substituted metal salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as amine substituted metal salts...

  11. 40 CFR 721.2527 - Substituted diphenylazo dye (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted diphenylazo dye (generic... Specific Chemical Substances § 721.2527 Substituted diphenylazo dye (generic name). (a) Chemical substance... substituted diphenylazo dye (PMN P-95-514) is subject to reporting under this section for the significant new...

  12. 21 CFR 184.1259 - Cocoa butter substitute.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cocoa butter substitute. 184.1259 Section 184.1259... Listing of Specific Substances Affirmed as GRAS § 184.1259 Cocoa butter substitute. (a) The common or usual name for the triglyceride 1-palmitoyl-2-oleoyl-3-stearin is “cocoa butter substitute primarily...

  13. Freeze substitution in 3 hours or less.

    Science.gov (United States)

    McDonald, K L; Webb, R I

    2011-09-01

    Freeze substitution is a process for low temperature dehydration and fixation of rapidly frozen cells that usually takes days to complete. New methods for freeze substitution have been developed that require only basic laboratory tools: a platform shaker, liquid nitrogen, a metal block with holes for cryotubes and an insulated container such as an ice bucket. With this equipment, excellent freeze substitution results can be obtained in as little as 90 min for cells of small volume such as bacteria and tissue culture cells. For cells of greater volume or that have significant diffusion barriers such as cuticles or thick cell walls, one can extend the time to 3 h or more with dry ice. The 3-h method works well for all manner of specimens, including plants and Caenorhabditis elegans as well as smaller samples. Here, we present the basics of the techniques and some results from Nicotiana leaves, C. elegans adult worms, Escherichia coli and baby hamster kidney tissue culture cells. © 2011 The Authors Journal of Microscopy © 2011 Royal Microscopical Society.

  14. Substitution and addition reactions of •OH with p-substituted-phenols

    Science.gov (United States)

    Albarrán, Guadalupe; Galicia-Jiménez, Eduardo; Mendoza, Edith; Schuler, Robert H.

    2017-04-01

    The directing effect of a hydroxyl group on the substitution and addition reactions of •OH to the substituted and free positions in aromatic rings of p-substituted-phenols were studied in aqueous solutions containing either K3Fe(CN)6 as an oxidant of the substituted hydroxycyclohexadienyl radical initially formed or using ascorbic acid. The results showed that the attack of the •OH to the substituted position (ipso position) was followed by elimination of the substituent producing hydroquinone. The addition reaction of the •OH to the free position on the ring produced 4-substituent-catechol and 4-substituent-resorcinol derivatives. Identification and quantification of the radiolytic products were carried out using high performance liquid chromatography. The results of the yields are given for the p-halogen-phenols (p-X-Ph) p-F-Ph, p-Cl-Ph, p-Br-Ph and p-I-Ph. Other compounds, p-nitro-Ph, p-OH-benzoic acid, p-OH-benzonitrile, p-OH-benzaldehyde, p-OH-anisole and p-OH-benzyl alcohol (represented as p-Z-Ph), were only studied using K3Fe(CN)6 as the oxidant. The results show that the p-X-Ph are attacked by the •OH at the ipso position to the halogen in the proportion 1:0.53:0.46:0.11 for F>Cl>Br>I. The •OH attacked at the ipso position to the p-Z-Phs through a substitution reaction, which depended on the substituent group. Thus, the strongly deactivating groups produced less hydroquinone, indicating less substitution reaction than the strongly activating groups.

  15. Constant-Length Random Substitutions and Gibbs Measures

    Science.gov (United States)

    Maldonado, C.; Trejo-Valencia, L.; Ugalde, E.

    2018-04-01

    This work is devoted to the study of processes generated by random substitutions over a finite alphabet. We prove, under mild conditions on the substitution's rule, the existence of a unique process which remains invariant under the substitution, and which exhibits a polynomial decay of correlations. For constant-length substitutions, we go further by proving that the invariant state is precisely a Gibbs measure which can be obtained as the projective limit of its natural Markovian approximations. We end up the paper by studying a class of substitutions whose invariant state is the unique Gibbs measure for a hierarchical two-body interaction.

  16. Mechanistic studies on β-ketoacyl thiolase from Zoogloea ramigera: Identification of the active-site nucleophile as Cys89, its mutation to Ser89, and kinetic and thermodynamic characterization of wild-type and mutant enzymes

    International Nuclear Information System (INIS)

    Thompson, S.; Mayerl, F.; Walsh, C.T.; Peoples, O.P.; Masamune, S.; Sinskey, A.J.

    1989-01-01

    Thiolase proceeds via covalent catalysis involving an acetyl-S-enzyme. The active-site thiol nucleophile is identified as Cys 89 by acetylation with [ 14 C]acetyl-CoA, rapid denaturation, tryptic digestion, and sequencing of the labeled peptide. The native acetyl enzyme is labile to hydrolytic decomposition with t 1/2 of 2 min at pH 7, 25 degree C. Cys 89 has been converted to the alternate nucleophile Ser 89 by mutagenesis and the C89S enzyme overproduced, purified, and assessed for activity. The Ser 89 enzyme retains 1% of the V max of the Cys 89 enzyme in the direction of acetoacetyl-CoA thiolytic cleavage and 0.05% of the V max in the condensation of two acetyl-CoA molecules. A covalent acetyl-O-enzyme intermediate is detected on incubation with [ 14 C]acetyl-CoA and isolation of the labeled Ser 89 -containing tryptic peptide. Comparisons of the Cys 89 and Ser 89 enzymes have been made for kinetic and thermodynamic stability of the acetyl enzyme intermediates both by isolation and by analysis of [ 32 P]CoASH/acetyl-CoA partial reactions and for rate-limiting steps in catalysis with trideuterioacetyl-CoA

  17. New ruthenium nitrosyl complexes with tris(1-pyrazolyl)methane (tpm) and 2,2'-bipyridine (bpy) coligands. Structure, spectroscopy, and electrophilic and nucleophilic reactivities of bound nitrosyl.

    Science.gov (United States)

    Videla, Mariela; Jacinto, Julian S; Baggio, Ricardo; Garland, María T; Singh, Priti; Kaim, Wolfgang; Slep, Leonardo D; Olabe, José A

    2006-10-16

    The new compound [Ru(bpy)(tpm)NO](ClO4)3 [tpm = tris(1-pyrazolyl)methane; bpy = 2,2'-bipyridine] has been prepared in a stepwise procedure that involves the conversion of [Ru(bpy)(tpm)Cl]+ into the aqua and nitro intermediates, followed by acidification. The diamagnetic complex crystallizes to exhibit distorted octahedral geometry around the metal, with the Ru-N(O) bond length 1.774(12) A and the RuNO angle 179.1(12) degrees , typical for a {RuNO}6 description. The [Ru(bpy)(tpm)NO]3+ ion (I) has been characterized by 1H NMR and IR spectroscopies (nu(NO) = 1959 cm(-1)) and through density functional theory calculations. Intense electronic transitions in the 300-350-nm region are assigned through time-dependent (TD)DFT as intraligand pi --> pi for bpy and tpm. The dpi --> pi(bpy) metal-to-ligand charge-transfer transitions appear at higher energies. Aqueous cyclic voltammetric studies show a reversible wave at 0.31 V (vs Ag/AgCl, 3 M Cl-), which shifts to 0.60 V in MeCN, along with the onset of a wave of an irreversible process at -0.2 V. The waves are assigned to the one- and two-electron reductions centered at the NO ligand, leading to species with {RuNO}(7) and {RuNO}(8) configurations, respectively. Controlled potential reduction of I in MeCN led to the [Ru(bpy)(tpm)NO]2+ ion (II), revealing a significant downward shift of nu(NO) to 1660 cm(-1) as well as changes in the electronic absorption bands. II was also characterized by electron paramagnetic resonance, showing an anisotropic signal at 110 K that arises from an S = 1/2 electronic ground state; the g-matrix components and hyperfine coupling tensor resemble the behavior of related {RuNO}7 complexes. Both I and II were characterized through their main reactivity modes, electrophilic and nucleophilic, respectively. The addition of OH- into I generated the nitro complex, with k(OH) = 3.05 x 10(6) M(-1) s(-1) (25 degrees C). This value is among the highest obtained for related nitrosyl complexes and correlates

  18. Alkylation of N-substituted 2-phenylacetamides

    Directory of Open Access Journals (Sweden)

    SLOBODAN D. PETROVIC

    2004-10-01

    Full Text Available Various N-substituted phenylacetamides were alkylated using different alkylating agents under neutral and basic conditions. Reactions were performed at different reaction temperatures and in various solvents. Also, a number of various catalysts were used including phase-transfer catalysts. Reactions were followed using GC or GC-MS technique and the presence as well as the yields of the alkylation products were established. Generally, the best yield and high selectivity in the studied reactions were achieved under basic conditions where in the certain cases some products, mostly N-product, were obtained solely in quantitative yields.

  19. Chemical substitution in the undergraduate chemistry curriculum

    Science.gov (United States)

    Brook, Bryan David

    A recommended method for source reduction of pollutants is chemical substitution, in which hazardous materials are substituted for less hazardous materials. Here lab experiments and demonstrations were designed using household chemicals. The advantages include easy accessibility to low cost materials and minimal waste in comparison to traditional experiments. Students also showed more interest in performing experiments using familiar products. A Handbook of Household Chemicals was created. Using chemicals in the Handbook, qualitative and quantitative experiments are described that only require simple equipment. In addition, chemicals are identified in a quantitative analysis experiment with applications for upper level classes. Experiments requiring the use of water condensers were modified using an ice cooled condenser. The condenser, developed in our laboratory, is useful for distillation and reflux experiments where running water is not practical. Finally, demonstrations were designed for an overhead projector to be used in large classrooms. The experiments and demos can be used in any secondary school, college or university. The laboratory exercises can also accompany long distance learning and Internet chemistry courses. Several experiments using consumer products have been incorporated into the Pennsylvania Department of Education Science In Motion project. The program provides a van equipped with instruments and chemicals to be taken to local schools. Overall, the experiments discussed here provide a safe and low-cost alternative to traditional experiments.

  20. Fluorescence of Hydroxyphenyl-Substituted "Click" Triazoles.

    Science.gov (United States)

    Meisner, Quinton J; Accardo, Joseph V; Hu, Guoxiang; Clark, Ronald J; Jiang, De-En; Zhu, Lei

    2018-03-22

    The structural and optical properties of hydroxyphenyl-substituted-1,2,3-triazole molecules ("click" triazoles) are described. "Click" triazoles are prepared from the copper(I)-catalyzed azide-alkyne cycloaddition reactions. The alkyne-derived C4 substituent of a "click" triazole engages in electronic conjugation more effectively with the triazolyl core than the azide-derived N1 substituent. Furthermore, triazolyl group exerts a stronger electron-withdrawing effect on the N1 than the C4 substituent. Therefore, the placement of an electron-donating group at either C4 or N1 position and the presence or the absence of an intramolecular hydrogen bond (HB) have profound influences on the optical properties of these compounds. The reported "click" triazoles have fluorescence quantum yields in the range of 0.1-0.3 and large apparent Stokes shifts (8000-13 000 cm -1 ) in all tested solvents. Deprotonation of "click" triazoles with a C4 hydroxyphenyl group increases their Stokes shifts; while the opposite (or quenching) occurs to the triazoles with an N1 hydroxyphenyl substituent. For the triazoles that contain intramolecular HBs, neither experimental nor computational results support a model of excited state intramolecular proton transfer (ESIPT). Rather, the excited state internal (or intramolecular) charge transfer (ICT) mechanism is more suitable to explain the fluorescence properties of the hydroxyphenyl-substituted "click" triazoles; specifically, the large Stokes shifts of these compounds.

  1. Advances in Osteobiologic Materials for Bone Substitutes.

    Science.gov (United States)

    Hasan, Anwarul; Byambaa, Batzaya; Morshed, Mahboob; Cheikh, Mohammad Ibrahim; Shakoor, Rana Abdul; Mustafy, Tanvir; Marei, Hany

    2018-04-27

    A significant challenge in the current orthopedics is the development of suitable osteobiologic materials that can replace the conventional allografts, autografts and xenografts, and thereby serve as implant materials as bone substitutes for bone repair or remodeling. The complex biology behind the nano-microstructure of bones and their repair mechanisms, which involve various types of chemical and biomechanical signaling amongst different cells, has set strong requirements for biomaterials to be used in bone tissue engineering. This review presents an overview of various types of osteobiologic materials to facilitate the formation of the functional bone tissue and healing of the bone, covering metallic, ceramic, polymeric and cell-based graft substitutes, as well as some biomolecular strategies including stem cells, extracellular matrices, growth factors and gene therapies. Advantages and disadvantages of each type, particularly from the perspective of osteoinductive and osteoconductive capabilities, are discussed. Although the numerous challenges of bone regeneration in tissue engineering and regenerative medicine are yet to be entirely addressed, further advancements in osteobiologic materials will pave the way towards engineering fully functional bone replacement grafts. This article is protected by copyright. All rights reserved.

  2. Muon-Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution.

    Science.gov (United States)

    Goli, Mohammad; Shahbazian, Shant

    2016-02-12

    Isotope substitutions are usually conceived to play a marginal role on the structure and bonding pattern of molecules. However, a recent study [Angew. Chem. Int. Ed. 2014, 53, 13706-13709; Angew. Chem. 2014, 126, 13925-13929] further demonstrates that upon replacing a proton with a positively charged muon, as the lightest radioisotope of hydrogen, radical changes in the nature of the structure and bonding of certain species may take place. The present report is a primary attempt to introduce another example of structural transformation on the basis of the malonaldehyde system. Accordingly, upon replacing the proton between the two oxygen atoms of malonaldehyde with the positively charged muon a serious structural transformation is observed. By using the ab initio nuclear-electronic orbital non-Born-Oppenheimer procedure, the nuclear configuration of the muon-substituted species is derived. The resulting nuclear configuration is much more similar to the transition state of the proton transfer in malonaldehyde rather than to the stable configuration of malonaldehyde. The comparison of the "atoms in molecules" (AIM) structure of the muon-substituted malonaldehyde and the AIM structure of the stable and the transition-state configurations of malonaldehyde also unequivocally demonstrates substantial similarities of the muon-substituted malonaldehyde to the transition state. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Competition Derived from Innovation as a Substitution Threat

    DEFF Research Database (Denmark)

    Howells, John

    2003-01-01

    This paper is a review of the role of innovation as substitution threat. The interesting strategy for those facing what in retrospect proves to be full substitution is the strategy of 'switch' to the substituting technology. the context-dependent uncedrtainty involved in the switch decision is ex...... transistor. The case material is used to introduce the problem competition policy has when faced with competition derived from innovation.......This paper is a review of the role of innovation as substitution threat. The interesting strategy for those facing what in retrospect proves to be full substitution is the strategy of 'switch' to the substituting technology. the context-dependent uncedrtainty involved in the switch decision...

  4. Tissue reaction and material characteristics of four bone substitutes

    DEFF Research Database (Denmark)

    Jensen, S S; Aaboe, M; Pinholt, E M

    1996-01-01

    The aim of the present study was to qualitatively and quantitatively compare the tissue reactions around four different bone substitutes used in orthopedic and craniofacial surgery. Cylinders of two bovine bone substitutes (Endobon and Bio-Oss) and two coral-derived bone substitutes (Pro Osteon 500......-Oss was osseointegrated to a higher degree than the other biomaterials. Material characteristics obtained by diffuse reflectance infrared Fourier transform spectrometry analysis and energy-dispersive spectrometry did not explain the differences in biologic behavior....

  5. Spectroscopic Evidence for Covalent Binding of Sulfadiazine to Natural Soils via 1,4-nucleophilic addition (Michael Type Addition) studied by Spin Labeling ESR

    Science.gov (United States)

    Aleksandrova, Olga

    2015-04-01

    with different polarity. As shown by the spin labeling ESR experiment, molecules modeling SDZ were promptly bound to non-hydrolysable network of soil organic matter only via the aromatic amines that was accompanied by a prompt enlargement of humic particles binding aromatic amines, whereas binding of decomposition products of SDZ to humic acids of soil via the aliphatic amines was not observable. The ESR spectra obviously showed a single-phase process of covalent binding of the aromatic amines. Repeated washouts of labeled soil samples using distil water and ultrafiltration through the membrane of 5000 MWCO PES confirmed irreversible binding of the aromatic amines, and showed that via the aliphatic amines, binding of SDZ or decomposition products of SDZ to soil might also occur but reversibly and only to small soil molecules, which don't enter into the composition of non-hydrolysable part of soil organic matter. SL ESR experiments of different soils at the presence of Laccase highlighted that covalent binding of the aromatic amines to humic particles occurred in the specific hydrophobic areas of soil found as depleted in oxygen. All measured data evidenced that first, SDZ might be decomposed that allowed for measuring the same change of a paramagnetic signal of soil organic matter influenced by both aromatic and aliphatic amines as in the experiment of the interaction of soil with SDZ. Second, a decomposition product of SDZ with the aromatic amine might be bound to non-hydrolysable parts of soil organic matter under specific anaerobic conditions only via 1,4 - nucleophilic addition, Michael-type addition. Gulkowska, A., Thalmann, B., D., Hollender, J., & Krauss, M. (2014). Chemosphere, 107, 366 - 372. Müller, T., Rosendahl, I., Focks, A., Siemens, J., Klasmeier, J., & Matthies. (2013). Environmental Pollution, 172,180 - 185. Nowak, K.M., Miltner, A., Gehre, M., Schaeffer, A., & Kaestner, M. (2011). Environmental Science & Technology 45, 999 - 1006. Weber, E.J., Spidle

  6. Technological substitution options for controlling greenhouse gas emissions

    International Nuclear Information System (INIS)

    Barbier, E.B.; Burgess, J.C.; Pearce, D.W.

    1991-01-01

    This chapter is concerned with technological options for greenhouse gas substitution. The authors interpret the term substitution to exclude energy conservation/efficiency measures, investments in afforestation (sinks), and greenhouse gas removal or abatement technologies. Their working definition of greenhouse gas substitution includes (1) replacement technologies, for example, substituting a greenhouse gas technology with a nongreenhouse gas technology; and (2) reduction technologies, for example, substituting a greenhouse gas technology with an alternative technology that reduces greenhouse gas emissions. Essentially, replacement technologies involve 100 percent reduction in CO 2 ; reduction technologies involve a partial reduction in CO 2 . Of the man-made sources of greenhouse gases, energy is the most important and is expected to contribute to at least half of the global warming effect in the near future. The majority of this impact is from fossil fuel combustion as a source of carbon dioxide (CO 2 ), although fossil fuels also contribute significantly to methane (CH 4 ), to nitrous oxide (N 2 O), and to low-level ozone (O 3 ) through production of various nitrogen gases (NO x ) and carbon monoxide (CO). This study analyzes the available greenhouse gas substitutions and their costs. The authors concentrate particularly on substitutions for fossil-fuel combustion and CFC production and consumption. They conclude by summarizing the potential for greenhouse gas substitution, the cost-effectiveness of the various options and the design of incentives for substitution

  7. Import Substitution in Regional Industrial Production: Theoretical and Practical Aspects

    Directory of Open Access Journals (Sweden)

    Yevgeniy Georgievich Animitsa

    2015-09-01

    Full Text Available The article proves the important role of import substitution in the economic security protection of state and its regions, especially in times of crisis, geopolitical and economical instability. The authors argue that the problem of import substitution is not modern, trendy scientific stream. The issue of displacement of import goods by domestic ones was brought up in famous classic theories of mercantilists. The particular emphasis is placed on the analysis and systematization of different scientific approaches, which are utilized by native and foreign scientists to bring out the matter of “import substitution,” to determine its essential characteristics. The authors suggest their own interpretation of the import substitution notion. In the article, the most significant pro and contra arguments in import substitution policy are defined. The regional aspects in the import substitution are approved: case study — organization of industrial import substitution in the Sverdlovsk region. In the article, the authors analyze the subject matter of the Program “Development of Intraregional Industrial Cooperation and Implementation of an Import Substitution in Branches of Industry in the Sverdlovsk Region.” It is resumed, that active policy of import substitution in the industry may become the driver of regional economic development.

  8. Modulating the pH-activity profile of cellulase by substitution: replacing the general base catalyst aspartate with cysteinesulfinate in cellulase A from Cellulomonas fimi.

    Science.gov (United States)

    Cockburn, Darrell W; Vandenende, Chris; Clarke, Anthony J

    2010-03-09

    Cellulase A (CenA) from Cellulomonas fimi is an inverting glycoside hydrolase and a member of family 6 of the CAZy database classification system. We replaced its putative catalytic base aspartyl residues, Aps392 and Asp216, with cysteinesulfinate using a combination of site-directed mutagenesis and chemical modification to investigate the applicability of this approach for the modulation of enzymatic properties. The substituted cysteinyl residues were oxidized to cysteinesulfinic acid with hydrogen peroxide, and the resulting protein products were demonstrated to retain their native structure. Oxidation of the Asp392Cys mutant enzyme restored 52% of wild-type activity when assessed at pH 7.5, whereas Asp216Cys CenA remained inactive. This suggests that Asp216 is not the catalytic base and provides further support for Asp392 performing this role. Similar substitution of the catalytic acid residue Asp252 or the catalytic nucleophile of the retaining enzyme Cel5A from Thermobifida fusca failed to produce active enzymes. This indicates a potential utility of this approach for uniquely identifying catalytic base residues. The replacement of Asp392 with cysteinesulfinate induced an acidic shift in the pH profile of the enzyme such that this enzyme derivative was more active than wild-type CenA below pH 5.5. These data demonstrate the potential of combining site-directed mutagenesis with chemical modification as a viable approach for the modulation of cellulases, and potentially other glycoside hydrolases, at low pH.

  9. Time and Money - Are they Substitutes?

    DEFF Research Database (Denmark)

    Bonke, Jens; Deding, Mette; Lausten, Mette

    In this paper, we analyse the distribution of time and money for Danish wage earner couples, where time is defined as leisure time and money as extended income, i.e. the sum of disposable income and the value of housework. The hypothesis is that individuals being rich in one dimension are more...... likely to be poor in the other dimension, such that individuals can be classified as either money-poor/time-rich or money-rich/time-poor. We analyse two different distributions of income, where the first assumes no sharing and the second complete sharing of income between spouses. The data are from...... the Danish Time-Use Survey 2001, merged with register data. Results show that the substitution of money for time is more prominent for women than for men, because they have a larger income share of time-intensive value of housework, while men have the larger share of disposable income. Furthermore, when...

  10. Hazardous Solvent Substitution Data System tutorial

    Energy Technology Data Exchange (ETDEWEB)

    Twitchell, K.E.; Skinner, N.L.

    1993-07-01

    This manual is the tutorial for the Hazardous Solvent Substitution Data System (HSSDS), an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS data base contains product information, material safety data sheets, toxicity reports, usage reports, biodegradable data, product chemical element lists, and background information on solvents. HSSDS use TOPIC{reg_sign} to search for information based on a query defined by the user. TOPIC provides a full text retrieval of unstructured source documents. In this tutorial, a series of lessons is provided that guides the user through basic steps common to most queries performed with HSSDS. Instructions are provided for both window-based and character-based applications.

  11. Semiconducting behavior of substitutionally doped bilayer graphene

    Science.gov (United States)

    Mousavi, Hamze; Khodadadi, Jabbar; Grabowski, Marek

    2018-02-01

    In the framework of the Green's functions approach, random tight-binding model and using the coherent potential approximation, electronic characteristics of the bilayer graphene are investigated by exploring various forms of substitutional doping of a single or both layers of the system by either boron and (or) nitrogen atoms. The results for displacement of the Fermi level resemble the behavior of acceptor or donor doping in a conventional semiconductor, dependent on the impurity type and concentration. The particular pattern of doping of just one layer with one impurity type is most efficient for opening a gap within the energy bands which could be tuned directly by impurity concentration. Doping both layers at the same time, each with one impurity type, leads to an anomaly whereby the gap decreases with increasing impurity concentration.

  12. Development of a piezoelectric bone substitute material

    CERN Document Server

    Al-Bader, Y A

    2000-01-01

    The thesis deals with the preparation and testing of ceramic compositions to be used as bone substitute. The proposed composition consisted of calcium enriched calcium phosphate, kaolin and barium titanate in different ratios. The homogeneous powder mixture was dry pressed at different pressures and fired at temperatures up to 1350 degC for different soaking times. The physical properties of the fired compacts that were tested are bulk density and porosity. These were determined as function of pressing pressure, firing temperature and soaking time for different compositions. The mechanical properties investigated were the ultimate compressive strength and Young's modulus, which were determined for different compositions and forming pressures. The electrical properties investigated were D.C. characteristics (resistivity) and A.C. characteristics (A.C. resistivity, dielectric constant, dielectric loss and loss tangent). The piezoelectric behaviour of the fired compacts was investigated and the piezoelectric coe...

  13. Gas substitution method and device for glovebox

    Energy Technology Data Exchange (ETDEWEB)

    Eto, Jun-ya

    1996-09-10

    The device of the present invention comprises (1) a gas substituting channel which allows only discharge of gases in a main body box, (2) a balloon disposed in the main body box, (3) a gas supply channel for supplying atmospheric gases to the balloon, and (4) a direction control means for connecting/switching the space in the balloon to the supply channel and the space out of the balloon in the main body box. The balloon is inflated to discharge the gases out of the balloon in the main body box from the main body box. The atmospheric gases in the balloon at which the total amount of oxygen is reduced are sent to the space out of the balloon in the main body box. The inside of the main body box is formed by the atmospheric gases having lowered oxygen concentration. This operation is repeated twice or three times. (I.S.)

  14. Hazardous Solvent Substitution Data System tutorial

    International Nuclear Information System (INIS)

    Twitchell, K.E.; Skinner, N.L.

    1993-07-01

    This manual is the tutorial for the Hazardous Solvent Substitution Data System (HSSDS), an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS data base contains product information, material safety data sheets, toxicity reports, usage reports, biodegradable data, product chemical element lists, and background information on solvents. HSSDS use TOPIC reg-sign to search for information based on a query defined by the user. TOPIC provides a full text retrieval of unstructured source documents. In this tutorial, a series of lessons is provided that guides the user through basic steps common to most queries performed with HSSDS. Instructions are provided for both window-based and character-based applications

  15. Packing and Disorder in Substituted Fullerenes

    KAUST Repository

    Tummala, Naga Rajesh

    2016-07-15

    Fullerenes are ubiquitous as electron-acceptor and electron-transport materials in organic solar cells. Recent synthetic strategies to improve the solubility and electronic characteristics of these molecules have translated into a tremendous increase in the variety of derivatives employed in these applications. Here, we use molecular dynamics (MD) simulations to examine the impact of going from mono-adducts to bis- and tris-adducts on the structural, cohesive, and packing characteristics of [6,6]-phenyl-C60-butyric acid methyl ester (PCBM) and indene-C60. The packing configurations obtained at the MD level then serve as input for density functional theory calculations that examine the solid-state energetic disorder (distribution of site energies) as a function of chemical substitution. The variations in structural and site-energy disorders reflect the fundamental materials differences among the derivatives and impact the performance of these materials in thin-film electronic devices.

  16. New natural product -an efficient antimicrobial applications of new newly synthesized pyrimidine derivatives by the electrochemical oxidation of hydroxyl phenol in the presence of 2-mercapto-6-(trifluoromethyl) pyrimidine-4-ol as nucleophile.

    Science.gov (United States)

    Khan, Zia Ul Haq; Khan, Amjad; Wan, Pingyu; Khan, Arif Ullah; Tahir, Kamran; Muhammad, Nawshad; Khan, Faheem Ullah; Shah, Hidayat Ullah; Khan, Zia Ullah

    2018-05-01

    Some new pyrimidine derivatives have been synthesised by electrochemical oxidation of catechol (1a) in the existence of 2-mercapto-6-(trifluoromethyl) pyrimidine-4-ol (3) as a nucleophile in aqueous solution using Cyclic Voltammetric and Controlled Potential Coulometry. The catechol has been oxidised to o-quinone through electrochemical method and participative in Michael addition reaction, leading to the development of some new pyrimidine derivatives. The products were achieved in good yield with high pureness. The mechanism of the reaction has been conformed from the Cyclic Voltammetric data and Controlled Potential Coulometry. After purification, the compounds were characterised using modern techniques. The synthesised materials were screened for antimicrobial actions using Gram positive and Gram negative strain of bacteria. These new synthesised pyrimidine derivatives showed very good antimicrobial activity.

  17. Polyphosphates substitution for zeolite to in detergents

    International Nuclear Information System (INIS)

    Restrepo V, Gloria M.; Ocampo G, Aquiles; Saldarriaga M, Carlos

    1996-01-01

    The detergents, as well as the cleaning products, contain active ingredients that are good to increase their efficiency and some of them, as the sodium Tripoli-phosphate (TPF), they have turned out to be noxious for the environment. The zeolites use in the formulation of detergents has grown substantially since they fulfill the same function of the TPF and they have been recommended ecologically as substitutes from these when not being polluting. The objective of this work is to obtain a zeolite with appropriate characteristics for its use in the formulation of detergents, reproducing those of the zeolites used industrially. The zeolite synthesis is studied 4A starting from hydro-gels of different composition, varying the operation conditions and using two raw materials: (sodium meta-silicate, commercial degree and metallic aluminum) and clay type kaolin like silica source and aluminum It is looked for to get a product of beveled cubic morphology, or spherical, with glass size between 1 and 3 microns and that it possesses good capacity of conical exchange. Since the capacity and speed of ionic exchange is influenced by the particle size, time of contact and temperature, experimentation conditions settle down to measure the exchange of ions calcium and magnesium in watery solutions that they simulate the real situation of a laundry process in the country. This way the ability of the zeolite 4A obtained to diminish the concentration of these ions in the laundry waters is evaluated and its possibilities like component in the formulation of detergents non-phosphatates. Of the synthesized zeolites, the best in agreement is chosen with chemical properties as ionic and physical exchange capacity as crystalline, particle size and color, to prepare a detergent in which the polyphosphates is substituted partial and totally for the synthesized zeolite

  18. Substituted Pyrazinecarboxamides: Synthesis and Biological Evaluation

    Directory of Open Access Journals (Sweden)

    Katarina Kralova

    2006-03-01

    Full Text Available Condensation of the corresponding chlorides of some substituted pyrazine-2-carboxylic acids (pyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 5-tert-butylpyrazine-2-carboxylic acid or 5-tert-butyl-6-chloropyrazine-2-carboxylic acid withvarious ring-substituted aminothiazoles or anilines yielded a series of amides. Thesyntheses, analytical and spectroscopic data of thirty newly prepared compounds arepresented. Structure-activity relationships between the chemical structures and the anti-mycobacterial, antifungal and photosynthesis-inhibiting activity of the evaluatedcompounds are discussed. 3,5-Bromo-4-hydroxyphenyl derivatives of substitutedpyrazinecarboxylic acid, 16-18, have shown the highest activity against Mycobacteriumtuberculosis H37Rv (54-72% inhibition. The highest antifungal effect againstTrichophyton mentagrophytes, the most susceptible fungal strain tested, was found for5-tert-butyl-6-chloro-N-(4-methyl-1,3-thiazol-2-ylpyrazine-2-carboxamide (8, MIC =31.25 μmol·mL-1. The most active inhibitors of oxygen evolution rate in spinachMolecules 2006, 11 243 chloroplasts were the compounds 5-tert-butyl-6-chloro-N-(5-bromo-2-hydroxyphenyl- pyrazine-2-carboxamide (27, IC50 = 41.9 μmol·L-1 and 5-tert-butyl-6-chloro-N-(1,3- thiazol-2-yl-pyrazine-2-carboxamide (4, IC50 = 49.5 μmol·L-1.

  19. Control of Chemical Risks by Substitution of Harmful Substances

    DEFF Research Database (Denmark)

    Jacobsen, Thomas

    1997-01-01

    Substitution of volatile, organic solvents with non-volatile, low-toxic esters of fatty acids for cleaning purposes in offset printing has successfully been implemented in several European countries. Similar substitutions in other industrial cleaning processes seem possible, especially regarding...

  20. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Science.gov (United States)

    2010-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting under...

  1. Sublattice imbalance of substitutionally doped nitrogen in graphene

    DEFF Research Database (Denmark)

    Lawlor, James A.; Gorman, Paul D.; Power, Stephen

    2014-01-01

    Motivated by the recently observed sublattice asymmetry of substitutional nitrogen impurities in CVD grown graphene, we show, in a mathematically transparent manner, that oscillations in the local density of states driven by the presence of substitutional impurities are responsible for breaking t...

  2. Maximum potential cost-savings attributable to generic substitution ...

    African Journals Online (AJOL)

    Treatment, however, can become more affordable through generic substitution. Objective: To determine the maximum potential cost-saving through generic substitution for both originator and more expensive generic items while observing the prescribing patterns of antipsychotics. Method: Antipsychotic medicine usage was ...

  3. Effect of Honey as Partial Sugar Substitute on Pasting Properties ...

    African Journals Online (AJOL)

    The effect of partial substitution of sugar with liquid honey on the pasting properties of cooked dough made from cassava-wheat composite (10:90) flour as well as the sensory preference and shelf stability of its bread was investigated. Sucrose (S) in the bread recipe formulation was substituted with honey (H) at levels 0, 10, ...

  4. Applicable technical method for freeze-substitution of high pressure ...

    African Journals Online (AJOL)

    bmshsj

    2011-11-02

    Nov 2, 2011 ... Cryo-fixation and freeze substitution followed by microscopy are commonly used sample preparation methods for visualizing the morphology of intracellular organelles. Freeze substitution is an especially important preparative step because it enables the preservation of intracellular structures in cryo-fixed.

  5. Stabilisation of the [6]-prismane structure by silicon substitution

    Indian Academy of Sciences (India)

    Asif Equbal

    effect of substitution on its mechanical properties.15–21. While the synthesis of lower prismanes (n < 6) was. *For correspondence. †Dedicated to the memory of the late Professor Charusita. Chakravarty. readily achieved,22–25 ..... The light green color in the ring indicates silicon atoms. of all Ge-substituted-benzene dimers ...

  6. Substitution as a Device of Grammatical Cohesion in English Contexts

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Hasannejad

    2012-05-01

    Full Text Available The present study set out to investigate the effect of teaching substitution as a kind of grammatical cohesion on the true identification of confusing substitution elements with cohesive or non-cohesive roles in different contexts and also the production of modal, reporting and conditional contexts through clausal substitution acquaintance. To this end, the following procedures were taken. First 120 male and female EFL students were selected from Iranshahr Azad University. Having administered the language proficiency test, researchers selected 80 students as intermediate subjects according to their TOEFL band scores. First, pretests of cohesion identification (substitution and production of modal, reporting and conditional environments were administered to both control and experimental groups. Then, the experimental group was exposed to the teaching of the above-said above-mentioned cohesive device. Finally, post-tests of substitution elements’ identification and modal, reporting and conditional contexts’ production through clausal substitution familiarity were administered. The results showed that cohesive device treatment helped students on the true identification of substitution elements. Another finding proved that EFL students might have no difficulty in learning certain rules or classification of rules and application of their clausal substitution knowledge in creating modal, reporting and conditional contexts. Our findings can have implications for the field of language learning and teaching.

  7. Effects of Dietary Substitution of Rubber Seed Cake for Groundnut ...

    African Journals Online (AJOL)

    Three hundred (300) five weeks old, Anak broilers were used in a 4-week experiment to determine the effect of dietary substitution of rubber seed cake for groundnut cake on the performance of broilers at the finisher phase. Graded levels of rubber seed cake (0, 25, 50, 75 and 100%) substituted corresponding levels of ...

  8. MOLECULAR THERMODYNAMICS IN THE DESIGN OF SUBSTITUTE SOLVENTS

    Science.gov (United States)

    The use of physical properties and fluid behavior from molecular thermodynamics can lead to better decision making in the design of substitute solvents and can greatly reduce the expense and time required to find substitutes compared to designing solvents by experiment. this pape...

  9. 76 FR 39062 - Substitution in Case of Death of Claimant

    Science.gov (United States)

    2011-07-05

    ... AFFAIRS 38 CFR Parts 3, 14, and 20 RIN 2900-AN91 Substitution in Case of Death of Claimant AGENCY: Department of Veterans Affairs. ACTION: Reopening of public comment period. SUMMARY: In response to a request... proposed rule, ``Substitution in Case of Death of Claimant'' (76 FR 8666), published in the Federal...

  10. Exploring meat substitutes: consumer experiences and contextual factors

    NARCIS (Netherlands)

    Elzerman, J.E.; Boekel, van M.A.J.S.; Luning, P.A.

    2013-01-01

    Purpose – Meat substitutes can be environmentally more sustainable alternatives to meat. However, the image of these products in The Netherlands is still low. The purpose of this paper is to explore consumers' experiences and sensory expectations of meat substitutes and the appropriateness of the

  11. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses... dye (PMN P-94-499) is subject to reporting under this section for the significant new uses described...

  12. Studies on meso-substituted free-base octamethoxyporphyrins

    Indian Academy of Sciences (India)

    Administrator

    These are characterized by 1H NMR and other spectroscopic methods. The optical absorption spectra of these meso-substituted free-base porphyrin derivatives exhibit a hypsochromic shift compared to the unsubstituted octamethoxy free-base derivative. The emission data of these meso-substituted free-base derivatives ...

  13. 40 CFR 721.10048 - Substituted anthraquinone (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted anthraquinone (generic... Specific Chemical Substances § 721.10048 Substituted anthraquinone (generic). (a) Chemical substance and... anthraquinone (PMN P-02-869) is subject to reporting under this section for the significant new uses described...

  14. 40 CFR 721.2025 - Substituted phenylimino carbamate derivative.

    Science.gov (United States)

    2010-07-01

    ... derivative. 721.2025 Section 721.2025 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.2025 Substituted phenylimino carbamate derivative. (a) Chemical... as a substituted phenylimino carbamate derivative (PMN P-91-487) is subject to reporting under this...

  15. Crystal structures of unsymmetrically mixed β-pyrrole substituted ...

    Indian Academy of Sciences (India)

    The normal-coordinate structural decomposition analysis of these structures revealed mainly saddle distortion of the macrocycle ... Unsymmetrical mixed substituted porphyrins; β-pyrrole substituted porphyrins; NSD analysis;. Hirshfeld surface ..... out-of-plane (Doop) displacement values of the macro- cycle based on the ...

  16. Maximum parsimony, substitution model, and probability phylogenetic trees.

    Science.gov (United States)

    Weng, J F; Thomas, D A; Mareels, I

    2011-01-01

    The problem of inferring phylogenies (phylogenetic trees) is one of the main problems in computational biology. There are three main methods for inferring phylogenies-Maximum Parsimony (MP), Distance Matrix (DM) and Maximum Likelihood (ML), of which the MP method is the most well-studied and popular method. In the MP method the optimization criterion is the number of substitutions of the nucleotides computed by the differences in the investigated nucleotide sequences. However, the MP method is often criticized as it only counts the substitutions observable at the current time and all the unobservable substitutions that really occur in the evolutionary history are omitted. In order to take into account the unobservable substitutions, some substitution models have been established and they are now widely used in the DM and ML methods but these substitution models cannot be used within the classical MP method. Recently the authors proposed a probability representation model for phylogenetic trees and the reconstructed trees in this model are called probability phylogenetic trees. One of the advantages of the probability representation model is that it can include a substitution model to infer phylogenetic trees based on the MP principle. In this paper we explain how to use a substitution model in the reconstruction of probability phylogenetic trees and show the advantage of this approach with examples.

  17. Exchange Rate Volatility, Currency Substitution and Monetary Policy ...

    African Journals Online (AJOL)

    This article analyses the implications of currency substitution and exchange rate volatility for monetary policy in Nigeria. It adopts the unrestricted portfolio balance model of currency substitution, incorporating exchange rate volatility within the framework of the Vector Error Correction (VEC) technique. Results from both ...

  18. Cation substitution induced blue-shift of optical band gap

    Indian Academy of Sciences (India)

    Cation substitution induced blue-shift of optical band gap in nanocrystalline Zn ( 1 − x ) Ca x O thin films deposited by sol–gel dip coating technique ... thin films giving 13.03% enhancement in theenergy gap value due to the electronic perturbation caused by cation substitution as well as deterioration in crystallinity.

  19. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Science.gov (United States)

    2010-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting under...

  20. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Science.gov (United States)

    2010-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

  1. 19 CFR 143.16 - Substitution of warehouse entry.

    Science.gov (United States)

    2010-04-01

    ... 19 Customs Duties 2 2010-04-01 2010-04-01 false Substitution of warehouse entry. 143.16 Section 143.16 Customs Duties U.S. CUSTOMS AND BORDER PROTECTION, DEPARTMENT OF HOMELAND SECURITY; DEPARTMENT... warehouse entry. The importer may substitute an entry for warehouse at any time within 1 year from the date...

  2. A Group Action Method for Construction of Strong Substitution Box

    Science.gov (United States)

    Jamal, Sajjad Shaukat; Shah, Tariq; Attaullah, Atta

    2017-06-01

    In this paper, the method to develop cryptographically strong substitution box is presented which can be used in multimedia security and data hiding techniques. The algorithm of construction depends on the action of a projective general linear group over the set of units of the finite commutative ring. The strength of substitution box and ability to create confusion is assessed with different available analyses. Moreover, the ability of resistance against malicious attacks is also evaluated. The substitution box is examined by bit independent criterion, strict avalanche criterion, nonlinearity test, linear approximation probability test and differential approximation probability test. This substitution box is equated with well-recognized substitution boxes such as AES, Gray, APA, S8, prime of residue, Xyi and Skipjack. The comparison shows encouraging results about the strength of the proposed box. The majority logic criterion is also calculated to analyze the strength and its practical implementation.

  3. Vitreous Substitutes: Old and New Materials in Vitreoretinal Surgery

    Directory of Open Access Journals (Sweden)

    Camilla Alovisi

    2017-01-01

    Full Text Available Recent developments in vitreoretinal surgery have increased the need for suitable vitreous substitutes. A successful substitute should maintain all the physical and biochemical properties of the original vitreous, be easy to manipulate, and be long lasting. Substitutes can be gaseous or liquid, both of which have associated advantages and disadvantages related to their physical properties and use. Furthermore, new surgical techniques with smaller vitreoretinal instruments have driven the use of more viscous substitutes. In this review, we analyze and discuss the most frequently used vitreous substitutes and look ahead to future alternatives. We classify these compounds based on their composition and structure, discuss their clinical use with respect to their associated advantages and disadvantages, and analyze how new vitreoretinal surgical techniques have modified their use.

  4. Vitreous Substitutes: Old and New Materials in Vitreoretinal Surgery

    Science.gov (United States)

    Panico, Claudio; Eandi, Chiara M.

    2017-01-01

    Recent developments in vitreoretinal surgery have increased the need for suitable vitreous substitutes. A successful substitute should maintain all the physical and biochemical properties of the original vitreous, be easy to manipulate, and be long lasting. Substitutes can be gaseous or liquid, both of which have associated advantages and disadvantages related to their physical properties and use. Furthermore, new surgical techniques with smaller vitreoretinal instruments have driven the use of more viscous substitutes. In this review, we analyze and discuss the most frequently used vitreous substitutes and look ahead to future alternatives. We classify these compounds based on their composition and structure, discuss their clinical use with respect to their associated advantages and disadvantages, and analyze how new vitreoretinal surgical techniques have modified their use. PMID:28785482

  5. Antimony substitution in SmFeAsO

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Daniel; Braun, Hans F. [Universitaet Bayreuth (Germany)

    2015-07-01

    In the iron based compounds structural and magnetic phase transitions can be suppressed by applying external hydrostatic pressure and superconductivity emerges. Beside hydrostatic pressure, it is possible to apply chemical pressure by the substitution of atoms in the compounds with smaller ones. Such a substitution was successful for example in LaFeAs{sub 1-x}P{sub x}O, where the parent compound shows a structural and a spin-density-wave transition and the P doped samples become superconducting. We are interested in the opposite way and substitute the As by the bigger Sb. In literature, the substitution in the La-1111 compounds was possible up to a substitution level of 40 %. With Sm, instead of La, we used a smaller rare-earth metal. We present the results obtained on polycrystalline samples characterized by Xray powder diffraction and resistivity measurements.

  6. Electrotactile and vibrotactile displays for sensory substitution systems

    Science.gov (United States)

    Kaczmarek, Kurt A.; Webster, John G.; Bach-Y-rita, Paul; Tompkins, Willis J.

    1991-01-01

    Sensory substitution systems provide their users with environmental information through a human sensory channel (eye, ear, or skin) different from that normally used or with the information processed in some useful way. The authors review the methods used to present visual, auditory, and modified tactile information to the skin and discuss present and potential future applications of sensory substitution, including tactile vision substitution (TVS), tactile auditory substitution, and remote tactile sensing or feedback (teletouch). The relevant sensory physiology of the skin, including the mechanisms of normal touch and the mechanisms and sensations associated with electrical stimulation of the skin using surface electrodes (electrotactile, or electrocutaneous, stimulation), is reviewed. The information-processing ability of the tactile sense and its relevance to sensory substitution is briefly summarized. The limitations of current tactile display technologies are discussed.

  7. Potential radiosensitizing agents. 5. 2-Substituted benzimidazole derivatives

    International Nuclear Information System (INIS)

    Gupta, R.P.; Larroquette, C.A.; Agrawal, K.C.

    1982-01-01

    A series of 2-substituted benzimidazoles and their derivatives have been synthesized and tested for their ability to selectively sensitize hypoxic Chinese hamster cells (V-79) toward the lethal effect of ionizing radiation. These compounds were prepared by reacting the 2-substituted benzimidazoles with 1,2-epoxy-3-methoxypropane in the presence of potassium carbonate. Reaction of the 2-nitro and 2-methylfonyl analogue with the epoxide also yielded a cyclized material, which was confirmed to be a benzimidazo[2,1-b]oxazole. In an attempt to increase the electron affinity, 5- or 6-nitro-2-substituted-benzimidazoles were also synthesized and then reacted with the epoxide to yield the corresponding 1-substituted derivatives. The results of the biological tests for the radiosensitizing activity of these agents against Chinese hamster cells (V-79) in culture indicated that the 2-nitro-substituted analogues were the most effective sensitizers in this series

  8. REACH-related substitution within the Danish printing industry

    DEFF Research Database (Denmark)

    Larsen, Henrik Fred; Bøg, Carsten; Markussen, Helene

    The accomplishment of the EU REACH regulation will most probably promote substitution within sectors handling a lot of different chemicals like the printing industry. With the aim of being at the cutting edge of this development the Danish EPA together with the Danish printing industry and IPU...... are running a substitution project. A major part of the work has been mapping the presence of chemicals which are potential candidates for substitution (e.g. PBT, CMR, vPvB, EDS) within the Danish printing industry. The mapping comprises a combination of a literature study and an investigation of the actual...... fulfil one or more of the criteria (e.g. CMR, EDS) for the REACH Annex XIV candidate list (authorisation). The paper presents the results of the mapping of chemical candidates and the first results of the actual substitutions. Keywords: REACH, chemicals, substitution, printing industry....

  9. Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and ...

    Indian Academy of Sciences (India)

    3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to obtain ... Keywords. Piperazine; homopiperazine; thiomorpholine; 1, 3-butadiene; E-isomers; X-ray structure. 1. Introduction .... Displacement ellipsoids are drawn at 50% probability level. temperature.

  10. Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and ...

    Indian Academy of Sciences (India)

    Herein, we report the reactions of 1, 1, 3, 4, 4-pentachloro-2-nitro-1, 3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to obtain ... Engineering Faculty, Department of Chemistry, Division of Organic Chemistry, Istanbul University, Avcilar, Istanbul, Turkey ...

  11. Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and ...

    Indian Academy of Sciences (India)

    3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to obtain ... Keywords. Piperazine; homopiperazine; thiomorpholine; 1, 3-butadiene; E-isomers; X-ray structure. 1. Introduction .... molar equivalent thiols were dissolved in ethanol. (25 mL) and added to the ...

  12. Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and ...

    Indian Academy of Sciences (India)

    Polyhalogenated-2-nitro-1, 3-butadienes are important synthetic precursors for a variety of polyfunctionalized bioactive heterocycles. Herein, we report the reactions of 1, 1, 3, 4, 4-pentachloro-2-nitro-1, 3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to ...

  13. Radiation chemistry of alternative fuel oxygenates - substituted ethers

    International Nuclear Information System (INIS)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-01-01

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

  14. Substitution site and effects on magnetism in Sr-for-Ca substituted CaBaCo4O7

    Science.gov (United States)

    Aurelio, G.; Curiale, J.; Bardelli, F.; Junqueira Prado, R.; Hennet, L.; Cuello, G.; Campo, J.; Thiaudière, D.

    2015-10-01

    Cationic substitutions in the novel magnetoelectric compound CaBaCo4O7 lead to profound changes in its magnetic and electric behaviors. In this work, we present a structural study of the isovalent substitution Sr-for-Ca in CaBaCo4O7. X-ray diffraction, as well as neutron powder diffraction experiments, are reported for a series of samples Ca1-xSrxBaCo4O7 with 0 ≤ x ≤ 0.10 . Special emphasis is given to the identification of the substitution site, as Sr has also been reported to substitute for Ba in this crystal structure. The solubility limit for Sr at the Ca site is shown to be at x ≃ 0.08 . The variation of lattice constants with Sr-doping firmly supports the Sr-for-Ca substitution. Rietveld refinements of the Sr-substituted samples are presented, and used as starting point to analyse the local structure around Sr by means of X-ray absorption spectroscopy at the Sr K-edge. Both the near-edge absorption and the extended absorption fine-structure confirm the substitution of Sr for Ca, giving definite support to the proposed nominal formula. In addition, macroscopic magnetization measurements are presented which reveal the striking effects of Sr-substitution over the magnetic landscape of this puzzling compound.

  15. Hazardous Solvent Substitution Data System reference manual

    International Nuclear Information System (INIS)

    Branham-Haar, K.A.; Twitchell, K.E.

    1993-07-01

    Concern for the environment, in addition to Federal regulation, mandate the replacement of hazardous solvents with safer cleaning agents. Manufacturers are working to produce these replacement solvents. As these products are developed, potential users need to be informed of their availability. To promote the use of these new products instead of traditional solvents, the Idaho National Engineering Laboratory (INEL) has developed the Hazardous Solvent Substitution Data System (HSSDS). The HSSDS provides a comprehensive system of information on alternatives to hazardous solvents and related subjects, and it makes that information available to solvent users, industrial hygienists, and process engineers. The HSSDS uses TOPIC reg-sign, a text retrieval system produced by Verity, Inc., to allow a user to search for information on a particular subject. TOPIC reg-sign produces a listing of the retrieved documents and allows the use to examine the documents individually and to use the information contained in them. This reference manual does not replace the comprehensive TOPIC reg-sign user documentation (available from Verity, Inc.), or the HSSDS Tutorial (available from the INEL). The purpose of this reference manual is to provide enough instruction on TOPIC reg-sign so the user may begin accessing the data contained in the HSSDS

  16. Substituted amylose matrices for oral drug delivery

    Science.gov (United States)

    Moghadam, S. H.; Wang, H. W.; Saddar El-Leithy, E.; Chebli, C.; Cartilier, L.

    2007-03-01

    High amylose corn starch was used to obtain substituted amylose (SA) polymers by chemically modifying hydroxyl groups by an etherification process using 1,2-epoxypropanol. Tablets for drug-controlled release were prepared by direct compression and their release properties assessed by an in vitro dissolution test (USP XXIII no 2). The polymer swelling was characterized by measuring gravimetrically the water uptake ability of polymer tablets. SA hydrophilic matrix tablets present sequentially a burst effect, typical of hydrophilic matrices, and a near constant release, typical of reservoir systems. After the burst effect, surface pores disappear progressively by molecular association of amylose chains; this allows the creation of a polymer layer acting as a diffusion barrier and explains the peculiar behaviour of SA polymers. Several formulation parameters such as compression force, drug loading, tablet weight and insoluble diluent concentration were investigated. On the other hand, tablet thickness, scanning electron microscope analysis and mercury intrusion porosimetry showed that the high crushing strength values observed for SA tablets were due to an unusual melting process occurring during tabletting although the tablet external layer went only through densification, deformation and partial melting. In contrast, HPMC tablets did not show any traces of a melting process.

  17. Some comments on the substituted judgement standard.

    Science.gov (United States)

    Egonsson, Dan

    2010-02-01

    On a traditional interpretation of the substituted judgement standard (SJS) a person who makes treatment decisions on behalf of a non-competent patient (e.g. concerning euthanasia) ought to decide as the patient would have decided had she been competent. I propose an alternative interpretation of SJS in which the surrogate is required to infer what the patient actually thought about these end-of-life decisions. In clarifying SJS it is also important to differentiate the patient's consent and preference. If SJS is part of an autonomy ideal of the sort found in Kantian ethics, consent seems more important than preference. From a utilitarian perspective a preference-based reading of SJS seems natural. I argue that the justification of SJS within a utilitarian framework will boil down to the question whether a non-competent patient can be said to have any surviving preferences. If we give a virtue-ethical justification of SJS the relative importance of consent and preferences depends on which virtue one stresses--respect or care. I argue that SJS might be an independent normative method for extending the patient's autonomy, both from a Kantian and a virtue ethical perspective.

  18. Substituted amylose matrices for oral drug delivery

    International Nuclear Information System (INIS)

    Moghadam, S H; Wang, H W; El-Leithy, E Saddar; Chebli, C; Cartilier, L

    2007-01-01

    High amylose corn starch was used to obtain substituted amylose (SA) polymers by chemically modifying hydroxyl groups by an etherification process using 1,2-epoxypropanol. Tablets for drug-controlled release were prepared by direct compression and their release properties assessed by an in vitro dissolution test (USP XXIII no 2). The polymer swelling was characterized by measuring gravimetrically the water uptake ability of polymer tablets. SA hydrophilic matrix tablets present sequentially a burst effect, typical of hydrophilic matrices, and a near constant release, typical of reservoir systems. After the burst effect, surface pores disappear progressively by molecular association of amylose chains; this allows the creation of a polymer layer acting as a diffusion barrier and explains the peculiar behaviour of SA polymers. Several formulation parameters such as compression force, drug loading, tablet weight and insoluble diluent concentration were investigated. On the other hand, tablet thickness, scanning electron microscope analysis and mercury intrusion porosimetry showed that the high crushing strength values observed for SA tablets were due to an unusual melting process occurring during tabletting although the tablet external layer went only through densification, deformation and partial melting. In contrast, HPMC tablets did not show any traces of a melting process

  19. The role of biomass in US industrial interfuel substitution

    International Nuclear Information System (INIS)

    Jones, Clifton T.

    2014-01-01

    The role of biomass in US industrial interfuel substitution in the industrial sector has typically been analyzed using data for the four traditional fuels of coal, oil, electricity and natural gas. However, the use of biomass as an industrial fuel in the US has grown, and now exceeds that of coal. Using data from 1960 to 2011, interfuel substitution in the US industrial sector is modeled with a dynamic linear logit model which includes biomass alongside the other four traditional fuels. Adding biomass to the model reduces somewhat the estimated own-price and cross-price elasticities for the other four fuels, while revealing that biomass and natural gas are substitute fuels. This implies that previous studies excluding biomass may have overestimated the potential for interfuel substitution, giving policy makers an inaccurate impression of the ability of carbon taxes or other environmental regulation to reduce greenhouse gas (GHG) emissions. - Highlights: • Biomass usage by the US industrial sector now exceeds coal usage. • Previous interfuel substitution studies have not included biomass as a fuel. • Linear logit model is used to examine role of biomass in interfuel substitution. • Including biomass in the model lowers estimated price elasticities for traditional fuels. • Biomass is found to be a substitute for natural gas for industrial users

  20. Substituent effects in surface-initiated ATRP of substituted styrenes

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Sampa, E-mail: ssaha@polymers.iitd.ac.in; Baker, Gregory L.

    2015-12-30

    Graphical abstract: - Highlights: • Suitably substituted styrenes can lead to rapid synthesis of uniform and thick polystyrene brushes (>100 nm in 1 h) from gold surface via surface initiated ATRP. • High growth rates were observed for styrenes substituted with electron withdrawing groups in meta/para positions. • Electron donors at meta sites show surprisingly fast growth rates, which may be due to steric inhibition of termination. • Surface polymerization rates for substituted styrenes followed the Hammett relation with ρ = 0.51, similar to conventional radical polymerization in solution. - Abstract: Surface initiated atom transfer radical polymerization (ATRP) of substituted styrenes leads to rapid synthesis of uniform and thick substituted polystyrene brushes (>100 nm in 1 h) from gold surface. High growth rates were observed for styrenes substituted with electron withdrawing groups in meta/para positions. The effects seen in surface and solution polymerizations are similar for styrenes with electron withdrawing groups, and for electron donors in ortho and para positions. However, electron donors at meta sites have surprisingly fast growth rates, which may be due to steric inhibition of termination. The overall surface polymerization rates for substituted styrenes was analyzed and found to follow the Hammett relation with ρ = 0.51. The ratio of k{sub p} to k{sub t}, is as an indicator of the likelihood that a reaction will reach high degrees of polymerization before termination.

  1. Enhanced osteoconductivity of sodium-substituted hydroxyapatite by system instability.

    Science.gov (United States)

    Sang Cho, Jung; Um, Seung-Hoon; Su Yoo, Dong; Chung, Yong-Chae; Hye Chung, Shin; Lee, Jeong-Cheol; Rhee, Sang-Hoon

    2014-07-01

    The effect of substituting sodium for calcium on enhanced osteoconductivity of hydroxyapatite was newly investigated. Sodium-substituted hydroxyapatite was synthesized by reacting calcium hydroxide and phosphoric acid with sodium nitrate followed by sintering. As a control, pure hydroxyapatite was prepared under identical conditions, but without the addition of sodium nitrate. Substitution of calcium with sodium in hydroxyapatite produced the structural vacancies for carbonate ion from phosphate site and hydrogen ion from hydroxide site of hydroxyapatite after sintering. The total system energy of sodium-substituted hydroxyapatite with structural defects calculated by ab initio methods based on quantum mechanics was much higher than that of hydroxyapatite, suggesting that the sodium-substituted hydroxyapatite was energetically less stable compared with hydroxyapatite. Indeed, sodium-substituted hydroxyapatite exhibited higher dissolution behavior of constituent elements of hydroxyapatite in simulated body fluid (SBF) and Tris-buffered deionized water compared with hydroxyapatite, which directly affected low-crystalline hydroxyl-carbonate apatite forming capacity by increasing the degree of apatite supersaturation in SBF. Actually, sodium-substituted hydroxyapatite exhibited markedly improved low-crystalline hydroxyl-carbonate apatite forming capacity in SBF and noticeably higher osteoconductivity 4 weeks after implantation in calvarial defects of New Zealand white rabbits compared with hydroxyapatite. In addition, there were no statistically significant differences between hydroxyapatite and sodium-substituted hydroxyapatite on cytotoxicity as determined by BCA assay. Taken together, these results indicate that sodium-substituted hydroxyapatite with structural defects has promising potential for use as a bone grafting material due to its enhanced osteoconductivity compared with hydroxyapatite. © 2013 Wiley Periodicals, Inc.

  2. Associations between generic substitution and patient-related factors

    DEFF Research Database (Denmark)

    Østergaard Rathe, Jette

    for Pharmacoepidemiology, Karolinska Institutet, Department of Medicine Solna, Stockholm, Sweden 3. Danish Quality Unit of General Practice, Odense, Denmark Background Generic substitution means that chemically equivalent but less expensive drugs are dispensed in place of a brand name product. Although generic medicines...... by definition are bioequivalent to their brand name counterparts there are concerns about whether generic substitution is always accompanied by clinical equivalence in terms of effectiveness and that it may cause concerns and thereby causing some skepticism towards generic substitution. There is, however...

  3. Prioritizing substitution of organic solvents in industrial cleaning processes

    DEFF Research Database (Denmark)

    Rasmussen, Pia Brunn; Jacobsen, Thomas

    1997-01-01

    A method for prioritizing the substitution of volatile organic compounds (VOC) used in industrial cleaning processes is developed. The result is a matrix, which, if all information can be obtained, gives a comprehensive description of the effects, exposure and emission of VOC, as well...... as the prospects for performing the substitution with a vegetable ester. It can be a tool for companies to decide which cleaning process has the highest demand for substitution, if there is a choice between several processes, but it may also be a tool to convince companies to use non-volatile, low-toxic cleaning...

  4. LONG TERM EVOLUTION OF BONE RECONSTRUCTION WITH BONE GRAFT SUBSTITUTES

    Directory of Open Access Journals (Sweden)

    O. V. Martynenko

    2017-06-01

    Full Text Available The review involves clinical and experimental data, constitutive modeling, and computational investigations towards an understanding on how mechanical cyclic loads for long periods of time affect damage evolution in a reconstructed bone, as well as, lifetime reduction of bone graft substitutes after advanced core decompression. The outcome of the integrated model discussed in this paper will be how damage growth in femur after advanced core decompression subjected to mechanical cyclic loading under creep and fatigue conditions may be controlled in order to optimize design and processing of bone graft substitutes, and extend lifetime of bone substitutes.

  5. Chitosan Dermal Substitute and Chitosan Skin Substitute Contribute to Accelerated Full-Thickness Wound Healing in Irradiated Rats

    Directory of Open Access Journals (Sweden)

    Abu Bakar Mohd Hilmi

    2013-01-01

    Full Text Available Wounds with full-thickness skin loss are commonly managed by skin grafting. In the absence of a graft, reepithelialization is imperfect and leads to increased scar formation. Biomaterials can alter wound healing so that it produces more regenerative tissue and fewer scars. This current study use the new chitosan based biomaterial in full-thickness wound with impaired healing on rat model. Wounds were evaluated after being treated with a chitosan dermal substitute, a chitosan skin substitute, or duoderm CGF. Wounds treated with the chitosan skin substitute showed the most re-epithelialization (33.2 ± 2.8%, longest epithelial tongue (1.62 ± 0.13 mm, and shortest migratory tongue distance (7.11 ± 0.25 mm. The scar size of wounds treated with the chitosan dermal substitute (0.13 ± 0.02 cm and chitosan skin substitute (0.16 ± 0.05 cm were significantly decreased (P<0.05 compared with duoderm (0.45 ± 0.11 cm. Human leukocyte antigen (HLA expression on days 7, 14, and 21 revealed the presence of human hair follicle stem cells and fibroblasts that were incorporated into and surviving in the irradiated wound. We have proven that a chitosan dermal substitute and chitosan skin substitute are suitable for wound healing in full-thickness wounds that are impaired due to radiation.

  6. Electrophilic-Nucleophilic Dualism of Nickel(II) toward Ni···I Noncovalent Interactions: Semicoordination of Iodine Centers via Electron Belt and Halogen Bonding via σ-Hole.

    Science.gov (United States)

    Bikbaeva, Zarina M; Ivanov, Daniil M; Novikov, Alexander S; Ananyev, Ivan V; Bokach, Nadezhda A; Kukushkin, Vadim Yu

    2017-11-06

    The nitrosoguanidinate complex [Ni{NH═C(NMe 2 )NN(O)} 2 ] (1) was cocrystallized with I 2 and sym-trifluorotriiodobenzene (FIB) to give associates 1·2I 2 and 1·2FIB. Structures of these solid species were studied by XRD followed by topological analysis of the electron density distribution within the framework of Bader's approach (QTAIM) at the M06/DZP-DKH level of theory and Hirshfeld surface analysis. Our results along with inspection of XRD (CCDC) data, accompanied by the theoretical calculations, allowed the identification of three types of Ni···I contacts. The Ni···I semicoordination of the electrophilic nickel(II) center with electron belt of I 2 was observed in 1·2I 2 , the metal-involving halogen bonding between the nucleophilic nickel(II)-d z 2 center and σ-hole of iodine center was recognized and confirmed theoretically in the structure of [FeNi(CN) 4 (IPz)(H 2 O)] n (IPz = 4-N-coordinated 2-I-pyrazine), whereas the arrangement of FIB in 1·2FIB provides a boundary case between the semicoordination and the halogen Ni···I bondings. In 1·2I 2 and 1·2FIB, noncovalent interactions were studied by variable temperature XRD detecting the expansion of noncovalent contacts with preservation of covalent bond lengths upon the temperature increase from 100 to 300 K. The nature and energies of all identified types of the Ni···I noncovalent interactions in the obtained (1·2I 2 and 1·2FIB) and in the previously reported ([FeNi(CN) 4 (IPz)(H 2 O)] n , [NiL 2 ](I 3 ) 2 ·2I 2 (L = o-phenylene-bis(dimethylphosphine), [NiL]I 2 (L = 1,4,8,11-tetra-azacyclotetradecane), Ni(en) 2 ] n [AgI 2 ] 2n (en = ethylenediamine), and [NiL](ClO 4 ) (L = 4-iodo-2-((2-(2-(2-pyridyl)ethylsulfanyl)ethylimino)methyl)-phenolate)) structures were studied theoretically. The estimated strengths of these Ni···I noncovalent contacts vary from 1.6 to 4.1 kcal/mol and, as expected, become weaker on heating. This work is the first emphasizing electrophilic-nucleophilic dualism

  7. Osseointegration of subperiosteal implants using bovine bone substitute and various membranes

    DEFF Research Database (Denmark)

    Aaboe, Merete; Schou, S.; Hjørting-Hansen, E.

    2000-01-01

    Osseointegration, subperiosteal implant, bone substitute, bovine bone, guided bone, regeneration, histology, rabbits......Osseointegration, subperiosteal implant, bone substitute, bovine bone, guided bone, regeneration, histology, rabbits...

  8. Suitability of various plant derived gelling agents as agar substitute ...

    African Journals Online (AJOL)

    Suitability of various plant derived gelling agents as agar substitute in microbiological growth media. Abdul Mateen, Shaukat Hussain, Shams Ur Rehman, Basharat Mahmood, Muhammad Aslam Khan, Abdul Rashid, Majid Sohail, Muhammad Farooq, S Jawad Ahmed Shah ...

  9. Property Model-Based Chemcal Substitution and Chemical Formulation Design

    DEFF Research Database (Denmark)

    Jhamb, Spardha Virendra; Liang, Xiaodong; Hukkerikar, Amol Shivajirao

    with environmentally benign chemicals. Additionally, the decisions taken during chemical product design also have an impact on the process and product performance and are influenced by company strategy, availability of market and government policies [2]. Hence, undoubtedly there is a need to develop a systematic...... it is desired to come up with alternative substitutes for the undesirable chemicals, the trial an error based approach will have a very large search space. This could be avoided by having predictive models coupled with the desired target properties, making the identification of these substitutes easier...... and safety) properties, and then to generate, evaluate and identify candidates that can replace them. The presentation will discuss the general methodology for chemical substitution, which caters to different problem definitions depending on the reason for substitution. The associated property modeling tools...

  10. Modified broken rice starch as fat substitute in sausages

    Directory of Open Access Journals (Sweden)

    Valéria Maria Limberger

    2011-09-01

    Full Text Available The demand for low-fat beef products has led the food industry to use fat substitutes such as modified starch. About 14% of broken rice is generated during processing. Nevertheless, this by-product contains high levels of starch; being therefore, great raw material for fat substitution. This study evaluated the applicability of chemically and physically modified broken rice starch as fat substitute in sausages. Extruded and phosphorylated broken rice was used in low-fat sausage formulation. All low-fat sausages presented about 55% reduction in the fat content and around 28% reduction in the total caloric value. Fat replacement with phosphorylated and extruded broken rice starch increased the texture acceptability of low-fat sausages, when compared to low-fat sausages with no modified broken rice. Results suggest that modified broken rice can be used as fat substitute in sausage formulations, yielding lower caloric value products with acceptable sensory characteristics.

  11. Long term substitution treatment (maintenance treatment of opioid dependent persons

    Directory of Open Access Journals (Sweden)

    Wirl, Charlotte

    2007-03-01

    Full Text Available Health political background: Methadone substitution treatment in Germany is introduced in 1988 in the framework of a scientific pilot study in North Rhein Westphalia. Recent statistics show that by now a broad offer of substitution treatment exists. From 1 June 2002 to 31 December 2003 113,000 substitution treatments have been recorded as being started of which around 56,000 have been recorded as ongoing treatments by 1 December 2003. Scientific background: Substitution treatment (treatment of opioid-dependent persons using substitution substances is one part of addiction treatment. Its goals are harm reduction and the stabilisation of opioid dependent persons. Integration of opioid-dependent persons in a treatment-setting, reduction of consumption of psychoactive substances, reduction of risk behaviour (primarily related to infectious diseases, decrease of mortality and improvements concerning the social, psychic and physic situation are seen as a success of substitution treatment as maintenance therapy. Research questions: The aim of this HTA report is to investigate which indicators can be used to evaluate the effectiveness of substitution treatment. Based on these indicators an evaluation of the medical, social and economical benefit of substitution treatment - also in relation to abstinence oriented treatment - is carried out. Methods: A systematic literature search was performed in 31 international databases which yielded 2451 articles with publication date between 1995 and February 2005. Results: After a twofold selection process 32 publications were included for assessment and 276 publications were used as background literature. Despite serious restrictions due to selection bias and dropout in most studies focusing on substitution treatment, reduction of consumption of illegal opioids, reduction of risk behaviour, criminal behaviour, mortality and incidence of HIV can be seen as an empirically proven success of substitution treatment

  12. Industrialization in Sub-Saharan Africa and import substitution policy

    Directory of Open Access Journals (Sweden)

    Ana Paula F. Mendes

    2014-03-01

    Full Text Available This article aims to contribute to the understanding of the process of import substitution in Sub-Saharan Africa. The process of industrialization in Sub-Saharan Africa occurred in two phases: a first step, even very early during the colonial regime began around the 1920s and ended in the late forties; a second phase of industrialization began in the late fifties and gained momentum in the sixties, when import substitution was implemented more widely. Although these countries were the last to embark on the strategy of import substitution, they followed the same steps of Latin American countries, and as the structural domestic and external constraints were too strong, the failure of the policy of import substitution arrived early and the negative impact on these economies had a greater magnitude.

  13. Factors Affecting the Form of Substitute Family Care

    Directory of Open Access Journals (Sweden)

    Monika Chrenková

    2015-11-01

    Full Text Available Recently, the system of care for endangered children has changed from the institutional as well as legislative point of view. In one of the partial areas of ongoing changes, research activities realised within the Students’ Grant Competition called The Factors Affecting the Form of Substitute Family Care are being focused. We deal with this topic because various forms of substitute family care are distinguished in the Czech Republic, where children are placed for various reasons, but we do not know the correct context of such placements. The main aim of the realised research was to find out the frequency of choosing a given form of placing children in substitute family care according to followed variables. The research sample of the quantitative research was consisted of children placed in one of the forms of substitute family care in the Moravian-Silesian region.

  14. Computational Modeling of Degradation of Substituted Benzyltrimethyl Ammonium: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Long, H.; Pivovar, B. S.

    2014-09-01

    The degradation of cations on the alkaline exchange membranes is the major challenge for alkaline membrane fuel cells. In this paper, we investigated the degradation barriers by density functional theory for substituted benzyltrimethyl ammonium (BTMA+) cations, which is one of the most commonly used cations for alkaline exchange membranes. We found that substituted cations with electron-releasing substituent groups at meta-position of the benzyl ring could result in improved degradation barriers. However, after investigating more than thirty substituted BTMA+ cations with ten different substituent groups, the largest improvement of degradation barriers is only 1.6 kcal/mol. This implies that the lifetime of alkaline membrane fuel cells could increase from a few months to a few years by using substituted BTMA+ cations, an encouraging but still limited improvement for real-world applications.

  15. Performance of chicken broilers fed with diets substituted with ...

    African Journals Online (AJOL)

    Performance of chicken broilers fed with diets substituted with mulberry leaf powder. Carlina Freddie Simol, Andrew Alek Tuen, Humrawali Hazid Ahmad Khan, John Keen Chubo, Patricia Jie Hung King, Kian Huat Ong ...

  16. The Substitutability Concept: A Need for Further Development

    Science.gov (United States)

    Christensen, James E.; Yoesting, Dean R.

    1977-01-01

    The possibility that participants in sport and games of a similar nature will find satisfaction in substituting one type of recreation for another is a possible factor to consider in planning and managing recreation facilities. (JD)

  17. Macroporous synthetic hydroxyapatite bioceramics for bone substitute applications

    CSIR Research Space (South Africa)

    Thomas, ME

    1999-08-01

    Full Text Available An improved strategy is described for the manufacture of macroporous hydroxyapatite bioceramics for bone substitute applications. This is based on a modified fugitive phase technique, which allows production of relatively open, high-strength devices...

  18. Weak preservation of local neutral substitution rates across mammalian genomes

    Directory of Open Access Journals (Sweden)

    Karro John E

    2009-05-01

    Full Text Available Abstract Background The rate at which neutral (non-functional bases undergo substitution is highly dependent on their location within a genome. However, it is not clear how fast these location-dependent rates change, or to what extent the substitution rate patterns are conserved between lineages. To address this question, which is critical not only for understanding the substitution process but also for evaluating phylogenetic footprinting algorithms, we examine ancestral repeats: a predominantly neutral dataset with a significantly higher genomic density than other datasets commonly used to study substitution rate variation. Using this repeat data, we measure the extent to which orthologous ancestral repeat sequences exhibit similar substitution patterns in separate mammalian lineages, allowing us to ascertain how well local substitution rates have been preserved across species. Results We calculated substitution rates for each ancestral repeat in each of three independent mammalian lineages (primate – from human/macaque alignments, rodent – from mouse/rat alignments, and laurasiatheria – from dog/cow alignments. We then measured the correlation of local substitution rates among these lineages. Overall we found the correlations between lineages to be statistically significant, but too weak to have much predictive power (r2 5%. These correlations were found to be primarily driven by regional effects at the scale of several hundred kb or larger. A few repeat classes (e.g. 7SK, Charlie8, and MER121 also exhibited stronger conservation of rate patterns, likely due to the effect of repeat-specific purifying selection. These classes should be excluded when estimating local neutral substitution rates. Conclusion Although local neutral substitution rates have some correlations among mammalian species, these correlations have little predictive power on the scale of individual repeats. This indicates that local substitution rates have changed

  19. Protein substitute for children and adults with phenylketonuria.

    Science.gov (United States)

    Yi, Sarah H L; Singh, Rani H

    2015-02-27

    Phenylketonuria is an inherited metabolic disorder characterised by an absence or deficiency of the enzyme phenylalanine hydroxylase. The aim of treatment is to lower blood phenylalanine concentrations to the recommended therapeutic range to prevent developmental delay and support normal growth. Current treatment consists of a low-phenylalanine diet in combination with a protein substitute which is free from or low in phenylalanine. Guidance regarding the use, dosage, and distribution of dosage of the protein substitute over a 24-hour period is unclear, and there is variation in recommendations among treatment centres. This is an update of a Cochrane review first published in 2005, and previously updated in 2008. To assess the benefits and adverse effects of protein substitute, its dosage, and distribution of dose in children and adults with phenylketonuria who are adhering to a low-phenylalanine diet. We searched the Cochrane Cystic Fibrosis and Genetic Disorders Group Trials Register which consists of references identified from comprehensive electronic database searches and hand searches of relevant journals and abstract books of conference proceedings. We also contacted manufacturers of the phenylalanine-free and low-phenylalanine protein substitutes for any data from published and unpublished randomised controlled trials.Date of the most recent search of the Group's Inborn Errors of Metabolism Trials Register: 03 April 2014. All randomised or quasi-randomised controlled trials comparing: any dose of protein substitute with no protein substitute; an alternative dosage; or the same dose, but given as frequent small doses throughout the day compared with the same total daily dose given as larger boluses less frequently. Both authors independently extracted data and assessed trial quality. Three trials (69 participants) are included in this review. One trial investigated the use of protein substitute in 16 participants, while a further two trials investigated the

  20. Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes.

    Science.gov (United States)

    Reeves, Ryan D; Phelps, Alicia M; Raimbach, William A T; Schomaker, Jennifer M

    2017-07-07

    Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.

  1. Self-assembled nanoparticles of dextrin substituted with hexadecanethiol

    OpenAIRE

    Gonçalves, Catarina; Martins, J. A. R.; Gama, F. M.

    2007-01-01

    The amphiphilic molecule dextrin-VA-SC16 (dexC16) was synthesized and studied in this work. DexC16 has a hydrophilic dextrin backbone with grafted acrylate groups (VA) substituted with hydrophobic 1- exadecanethiol (C16). A versatile synthetic method was developed allowing control of the dextrin degree of substitution with the hydrophobic chains (DSC16, number of alkyl chains per 100 dextrin glucopyranoside residues). Materials with different DSC16 were prepared and characterized using 1H ...

  2. Economic substitution for US wheat food use by class

    OpenAIRE

    Marsh, Thomas L.

    2005-01-01

    Wheat for food use is conceptualised as an input into flour production and demand is derived from an industry profit function to quantify price responsiveness and economic substitutability across wheat classes. Price and substitution elasticities are estimated for hard red winter, hard red spring, soft red wheat, soft white winter and durum wheat. In general, hard red winter and spring wheat varieties are much more responsive to their own price than are soft wheat varieties and durum wheat. S...

  3. Laser ablation of Bi-substituted gadolinium iron garnet films

    International Nuclear Information System (INIS)

    Watanabe, N.; Hayashida, K.; Kawano, K.; Higuchi, K.; Ohkoshi, M.; Tsushima, K.

    1995-01-01

    Bi-substituted gadolinium iron garnet films were deposited by laser ablation. The composition, the structure and the magnetic properties of the films were found to be strongly dependent both on the compositions of the targets and on the pressure of oxygen. The highest values of Bi-substitution up to x=1.44 with uniform composition were obtained, after annealing in air. ((orig.))

  4. Perspective on the substitution of electricity for oil

    International Nuclear Information System (INIS)

    De Guise, Yvon.

    1981-06-01

    The prospects for substitution of electricity for oil are discussed. Current oil use in Canada and abroad is reviewed along with studies giving projections of future use. The author shows that electricity is in a position to adequately substitute for oil in most situations. While electricity comprised 34 percent of Canadian primary energy supply in 1979, it is expected to increase to 50 percent in 2000

  5. Anthropogenic areas as incidental substitutes for original habitat.

    Science.gov (United States)

    Martínez-Abraín, Alejandro; Jiménez, Juan

    2016-06-01

    One speaks of ecological substitutes when an introduced species performs, to some extent, the ecosystem function of an extirpated native species. We suggest that a similar case exists for habitats. Species evolve within ecosystems, but habitats can be destroyed or modified by natural and human-made causes. Sometimes habitat alteration forces animals to move to or remain in a suboptimal habitat type. In that case, the habitat is considered a refuge, and the species is called a refugee. Typically refugee species have lower population growth rates than in their original habitats. Human action may lead to the unintended generation of artificial or semiartificial habitat types that functionally resemble the essential features of the original habitat and thus allow a population growth rate of the same magnitude or higher than in the original habitat. We call such areas substitution habitats and define them as human-made habitats within the focal species range that by chance are partial substitutes for the species' original habitat. We call species occupying a substitution habitat adopted species. These are 2 new terms in conservation biology. Examples of substitution habitats are dams for European otters, wheat and rice fields for many steppeland and aquatic birds, and urban areas for storks, falcons, and swifts. Although substitution habitats can bring about increased resilience against the agents of global change, the conservation of original habitat types remains a conservation priority. © 2016 Society for Conservation Biology.

  6. Characterization of hair follicle development in engineered skin substitutes.

    Directory of Open Access Journals (Sweden)

    Penkanok Sriwiriyanont

    Full Text Available Generation of skin appendages in engineered skin substitutes has been limited by lack of trichogenic potency in cultured postnatal cells. To investigate the feasibility and the limitation of hair regeneration, engineered skin substitutes were prepared with chimeric populations of cultured human keratinocytes from neonatal foreskins and cultured murine dermal papilla cells from adult GFP transgenic mice and grafted orthotopically to full-thickness wounds on athymic mice. Non-cultured dissociated neonatal murine-only skin cells, or cultured human-only skin keratinocytes and fibroblasts without dermal papilla cells served as positive and negative controls respectively. In this study, neonatal murine-only skin substitutes formed external hairs and sebaceous glands, chimeric skin substitutes formed pigmented hairs without sebaceous glands, and human-only skin substitutes formed no follicles or glands. Although chimeric hair cannot erupt readily, removal of upper skin layer exposed keratinized hair shafts at the skin surface. Development of incomplete pilosebaceous units in chimeric hair corresponded with upregulation of hair-related genes, LEF1 and WNT10B, and downregulation of a marker of sebaceous glands, Steroyl-CoA desaturase. Transepidermal water loss was normal in all conditions. This study demonstrated that while sebaceous glands may be involved in hair eruption, they are not required for hair development in engineered skin substitutes.

  7. A study of photon interaction parameters in lung tissue substitutes

    Directory of Open Access Journals (Sweden)

    H C Manjunatha

    2014-01-01

    Full Text Available The study of photon interaction with different composite materials has become a topic of prime importance for radiation physicists. Some parameters of dosimetric interest are the mass attenuation coefficient, effective atomic number, and electron density; these help in the basic understanding of photon interactions with composite materials. The photon interaction parameters such as mass attenuation coefficient (μ/ρ, effective atomic number (Z eff , and effective electron density (N el must be identical for the phantom material and their tissue. In the present study, we have evaluated the photon interaction parameters such as (μ/ρ, Z eff and N el of 13 lung tissue substitutes. The variations of these parameters of lung tissue substitutes with photon energy are graphically represented. The photon interaction parameters of lung tissue substitutes are compared with that of lung tissue. The variation of photon interaction parameters of the studied lung tissue substitutes is similar that of the lung. Logically, it can be shown that Alderson lung is good substitute for lung than the other substitutes.

  8. A study of photon interaction parameters in lung tissue substitutes.

    Science.gov (United States)

    Manjunatha, H C

    2014-04-01

    The study of photon interaction with different composite materials has become a topic of prime importance for radiation physicists. Some parameters of dosimetric interest are the mass attenuation coefficient, effective atomic number, and electron density; these help in the basic understanding of photon interactions with composite materials. The photon interaction parameters such as mass attenuation coefficient (μ/ρ), effective atomic number (Zeff), and effective electron density (N el) must be identical for the phantom material and their tissue. In the present study, we have evaluated the photon interaction parameters such as (μ/ρ), Z eff and N el of 13 lung tissue substitutes. The variations of these parameters of lung tissue substitutes with photon energy are graphically represented. The photon interaction parameters of lung tissue substitutes are compared with that of lung tissue. The variation of photon interaction parameters of the studied lung tissue substitutes is similar that of the lung. Logically, it can be shown that Alderson lung is good substitute for lung than the other substitutes.

  9. Introducing a Hydrogen-Bond Donor into a Weakly Nucleophilic Brønsted Base: Alkali Metal Hexamethyldisilazides (MHMDS, M=Li, Na, K, Rb and Cs) with Ammonia.

    Science.gov (United States)

    Neufeld, Roman; Michel, Reent; Herbst-Irmer, Regine; Schöne, Ralf; Stalke, Dietmar

    2016-08-22

    Alkali metal 1,1,1,3,3,3-hexamethyldisilazide (MHMDSs) are one of the most utilised weakly nucleophilic Brønsted bases in synthetic chemistry and especially in natural product synthesis. Like lithium organics, they aggregate depending on the employed donor solvents. Thus, they show different reactivity and selectivity as a function of their aggregation and solvation state. To date, monomeric LiHMDS with monodentate donor bases was only characterised in solution. Since the first preparation of LiHMDS in 1959 by Wannagat and Niederprüm, all efforts to crystallise monomeric LiHMDS in the absence of chelating ligands failed. Herein, we present ammonia adducts of LiHMDS, NaHMDS, KHMDS, RbHMDS and CsHMDS with unprecedented aggregation motifs: 1) The hitherto missing monomeric key compound in the LiHMDS aggregation architectures. Monomeric crystal structures of trisolvated LiHMDS (1) and NaHMDS (2), showing unique intermolecular hydrogen bonds, 2) the unprecedented tetrasolvated KHMDS (3) and RbHMDS (4) dimers and 3) the disolvated CsHMDS (5) dimer with very close intermolecular Si-CH3 ⋅⋅⋅Cs s-block "agostic" interactions have been prepared and characterised by single-crystal X-ray structure analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Promoting and Tuning Porosity of Flexible Ether-Linked Phthalazinone-Based Covalent Triazine Frameworks Utilizing Substitution Effect for Effective CO2 Capture.

    Science.gov (United States)

    Yuan, Kuanyu; Liu, Cheng; Zong, Lishuai; Yu, Guipeng; Cheng, Shengli; Wang, Jinyan; Weng, Zhihuan; Jian, Xigao

    2017-04-19

    Five porous ether-linked phthalazinone-based covalent triazine frameworks (PHCTFs) were successfully constructed via ionothermal polymerizations from flexible dicyano monomers containing asymmetric, twisted, and N-heterocyclic phthalazinone structure. All the building blocks could be easily prepared by simple and low-cost aromatic nucleophilic substitution reactions, showing the large-scale application potential of thermal stable phthalazinone structure in constructing porous materials. Generally, the flexible building blocks are avoided to prevent the networks from collapsing in constructing high surface area porous materials. Our experimental results revealed that the introduction of the substituents can effectively decrease the probability of the network interpenetration from the longer struts and the intermolecular/intramolecular intercalation from the increased degree of conformation freedom in the flexible ether-linkage, the BET surface areas of PHCTFs increasing from 676 to 1270 m 2 g -1 . Meanwhile, the effects of introducing different sizes (methyl or phenyl group) and amounts (one or two) of substituents on the porosities of the target polymer networks were also investigated in detail. The high CO 2 adsorption capacity of 10.3 wt % (273 K, 1 bar) can be ascribed to the strong affinity of the electron-rich N,O-containing networks with CO 2 . Excitingly, PHCTF-5 demonstrates the high CO 2 /N 2 selectivity up to 138 (273 K, 1 bar), according to the ideal adsorbed solution theory (IAST) for the higher proportion of V micro accompanied the electron-rich heteroatoms characteristic. Such high CO 2 adsorption capacity and good separation properties are superior to those of many other microporous organic polymers. These properties along with easily up-scalable synthesis make porous PHCTFs promising candidates applied in gas sorption and separation field.

  11. Cannabis as a substitute for alcohol and other drugs

    Directory of Open Access Journals (Sweden)

    Reiman Amanda

    2009-12-01

    Full Text Available Abstract Background Substitution can be operationalized as the conscious choice to use one drug (legal or illicit instead of, or in conjunction with, another due to issues such as: perceived safety; level of addiction potential; effectiveness in relieving symptoms; access and level of acceptance. This practice of substitution has been observed among individuals using cannabis for medical purposes. This study examined drug and alcohol use, and the occurrence of substitution among medical cannabis patients. Methods Anonymous survey data were collected at the Berkeley Patient's Group (BPG, a medical cannabis dispensary in Berkeley, CA. (N = 350 The sample was 68% male, 54% single, 66% White, mean age was 39; 74% have health insurance (including MediCal, 41% work full time, 81% have completed at least some college, 55% make less than $40,000 a year. Seventy one percent report having a chronic medical condition, 52% use cannabis for a pain related condition, 75% use cannabis for a mental health issue. Results Fifty three percent of the sample currently drinks alcohol, 2.6 was the average number of drinking days per week, 2.9 was the average number of drinks on a drinking occasion. One quarter currently uses tobacco, 9.5 is the average number of cigarettes smoked daily. Eleven percent have used a non-prescribed, non OTC drug in the past 30 days with cocaine, MDMA and Vicodin reported most frequently. Twenty five percent reported growing up in an abusive or addictive household. Sixteen percent reported previous alcohol and/or drug treatment, and 2% are currently in a 12-step or other recovery program. Forty percent have used cannabis as a substitute for alcohol, 26% as a substitute for illicit drugs and 66% as a substitute for prescription drugs. The most common reasons given for substituting were: less adverse side effects (65%, better symptom management (57%, and less withdrawal potential (34% with cannabis. Conclusion The substitution of one

  12. Fine structure study on low concentration zinc substituted hydroxyapatite nanoparticles

    International Nuclear Information System (INIS)

    Hu, Wei; Ma, Jun; Wang, Jianglin; Zhang, Shengmin

    2012-01-01

    The fine structure of zinc substituted hydroxyapatite was studied using experimental analysis and first-principles calculations. The synthetic hydroxyapatite nanoparticles containing low Zn concentration show rod-like morphology. The crystallite sizes and unit-cell volumes tended to decrease with the increased Zn concentration according to X-ray diffraction patterns. The Zn K-edge X-ray absorption spectra and fitting results suggest that the hydroxyapatite doped with 0.1 mole% zinc is different in the zinc coordination environments compared with that containing more zinc. The density function theory calculations were performed on zinc substituted hydroxyapatite. Two mechanisms included replacing calcium by zinc and inserting zinc along the hydroxyl column and were investigated, and the related substitution energies were calculated separately. It is found that the substitution energies are negative and lowest for inserting zinc between the two oxygen atoms along the hydroxyl column (c-axis). Combined with the spectral analysis, it is suggested that the inserting mechanism is favored for low concentration zinc substituted hydroxyapatite. Highlights: ► We investigate the fine structure of hydroxyapatite with low content of Zn. ► XANES spectra are similar but a little different at low zinc content. ► Zinc ions influence hydroxyapatite crystal formation and lattice parameters. ► Formation energies are calculated according to plane-wave density function theory. ► Low content of zinc prefers to locate at hydroxyl column in hydroxyapatite lattice.

  13. Characteristics of Magnetic Properties of Substituted Hexagonal Ferrites

    Directory of Open Access Journals (Sweden)

    Vladimir Jancarik

    2006-01-01

    Full Text Available The samples of barium hexaferrite BaFe12-2x(Me1Me2xO19 with x from 0.0 to 0.6 were prepared by variousmethods. The cationic preference of mainly divalent Me1 = Zn, Co, Ni, Sn ions and tetravalent Me2 = Ti, Zr, Ir, Sn, Ru ionsand their combinations in substituted Ba ferrites was investigated. The substitutions were performed to reduce the grain sizeand high magnetic uniaxial anisotropy field of the M-type Ba ferrite without affecting the magnetic polarisation. The goal isto reach the properties of ferrite proper for high-density magnetic recording and microwave absorption devices. Magneticproperties were determined as a function of the substitution level x. The specific saturation magnetic polarisation Js–m andremanence Js–rincreased with small x due to the substitution of non-magnetic and less magnetic ions in 4f1 and 4f2 sites. Thesteep decrease of coercivity Hc with increasing x may be caused by the Co2+ preference of 4f2 site and Ti4+or Zr4+ions preference of 2b and slightly in 4f1 sites. The temperature coefficient of the coercivity TKHc was very low (0.01kA.m-1.°C-1for the Co-Zr substitutions and positive for the rest of samples.

  14. A test of the substitution-habitat hypothesis in amphibians.

    Science.gov (United States)

    Martínez-Abraín, Alejandro; Galán, Pedro

    2017-12-08

    Most examples that support the substitution-habitat hypothesis (human-made habitats act as substitutes of original habitat) deal with birds and mammals. We tested this hypothesis in 14 amphibians by using percentage occupancy as a proxy of habitat quality (i.e., higher occupancy percentages indicate higher quality). We classified water body types as original habitat (no or little human influence) depending on anatomical, behavioral, or physiological adaptations of each amphibian species. Ten species had relatively high probabilities (0.16-0.28) of occurrence in original habitat, moderate probability of occurrence in substitution habitats (0.11-0.14), and low probability of occurrence in refuge habitats (0.05-0.08). Thus, the substitution-habitat hypothesis only partially applies to amphibians because the low occupancy of refuges could be due to the negligible human persecution of this group (indicating good conservation status). However, low occupancy of refuges could also be due to low tolerance of refuge conditions, which could have led to selective extinction or colonization problems due to poor dispersal capabilities. That original habitats had the highest probabilities of occupancy suggests amphibians have a good conservation status in the region. They also appeared highly adaptable to anthropogenic substitution habitats. © 2017 Society for Conservation Biology.

  15. Import Substitution as a Factor of Regional Economic Growth

    Directory of Open Access Journals (Sweden)

    Sukhanova Irina Fedorovna

    2014-11-01

    Full Text Available The current state of import substitution in Russia is considered. The authors’ definition is given to the concept of import substitution. The features of short-term and longterm strategies of import substitution are opened. The authors prove the need of diversification of the directions of foreign economic activity by reorientation of the foreign trade communications of Russia to the markets of the countries of CIS, the customs union and CES as well as the countries of the Asia Pacific region. The reasons of growth of import deliveries of foodstuff are opened. The comparative analysis of food consumption level in Russia is conducted. The food coefficients dependence on the most important food are calculated. The comparative analysis of productive indicators of domestic agricultural production with similar indicators of the foreign states is made. The strategies of import substitution for domestic agriculture taking into account its specifics and production potential, is offered. The assessment of potential of import substitution of Saratov region is presented. The priority actions on ensuring food security and growth of economy of the region are offered.

  16. Synthesis, characterization and investigation of the spectroscopic properties of novel peripherally 2,3,5-trimethylphenoxy substituted Cu and Co phthalocyanines, the computational and experimental studies of the 4-(2,3,5-trimethylphenoxyphthalonitrile

    Directory of Open Access Journals (Sweden)

    Nesuhi Akdemir

    2016-11-01

    Full Text Available 4-(2,3,5-trimethylphenoxyphthalonitrile (3 was firstly prepared via aromatic nucleophilic substitution reaction and characterized by FT-IR, mass spectrometry, 1H and 13C NMR techniques. The molecular structure of the compound (3 was optimized using Density Functional Theory (DFT/B3LYP method with 6-311G(d,p basis set in the ground state. The molecular geometric parameters which were obtained by X-ray single crystal diffraction method and the spectral results were compared with computed bond lengths and angles, vibrational frequencies and 1H, 13C NMR chemical shifts values of the compound (3. Also, Cu(II and Co(II phthalocyanines were synthesized by the treatment of dinitrile derivative with anhydrous CuCl2 or CoCl2 under N2 atmosphere in dry n-pentanol at 140oC. The new compounds have been determined by elemental analysis, FT-IR and electronic absorption. The UV-Vis spectra of the Cu(II and Co(II phthalocyanines were recorded with different concentration in THF and also with different solvents as DMF, DMSO, DCM, CHCl3, toluene.

  17. Boryl- and Silyl-Substituted Mixed Sandwich Compounds of Scandium.

    Science.gov (United States)

    Braunschweig, Holger; Damme, Alexander; Dück, Klaus; Krummenacher, Ivo; Paprocki, Valerie; Radacki, Krzysztof; Ramler, Jacqueline; Schiller, Carl; Schneider, Christoph

    2018-02-16

    An improved, one-pot synthesis of the linear sandwich compound [Sc(η 5 -C 5 H 5 )(η 8 -C 8 H 8 )] is presented. The synthetic procedure is amenable to boryl- and silyl-substituted cyclopentadienyl and cyclooctatetraenyl ligands, thereby yielding the first functionalized derivatives. We found that the synthesis of the silyl-substituted mixed sandwich complexes produces higher yields when the ligand exchange is carried out stepwise, by isolating the intermediate trimethylsilylated half-sandwich complex [Sc(η 8 -C 8 H 7 SiMe 3 )Cl(THF)] (THF=tetrahydrofuran). The molecular structures of the parent complex, as well as of its mono-boryl-substituted derivatives, have been determined by single-crystal X-ray diffraction. In addition, the optical and electrochemical properties of the mixed sandwich complexes are reported. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Pesticide Substitution: Combining Food Safety with Environmental Quality

    DEFF Research Database (Denmark)

    Fantke, Peter

    2015-01-01

    % by defining adequate substitution scenarios. Comprehensive scenarios need to also consider worker and environmental burden, and information on crop rotation, pest pressure, environmental conditions, application costs and efficacy. Such scenarios help to increase food safety and more sustainable use......Various pesticides are authorized for use on agricultural food crops. Despite regulatory risk assessments aiming at ensuring consumer and environmental safety, pesticides contribute to human and environmental impacts. Guidance is needed to optimize pesticide use practice and minimize human...... and environmental exposure. Comparative pesticide substitution scenarios are presented to address this need. In a case study on wheat, different pesticides have been compared with respect to their substitution potential with focus on human health. Results demonstrate that health impacts can be reduced up to 99...

  19. Caviar substitute produced from roes of rainbow trout (Oncorhynchus mykiss

    Directory of Open Access Journals (Sweden)

    Thaís Moron Machado

    2016-04-01

    Full Text Available The caviar substitute is obtained from processed fish roe, resulting in a product similar to the authentic caviar, prepared with sturgeon roe. The objective of this study was to develop a caviar substitute from roes of rainbow trout, Oncorhynchus mykiss. Four treatments were tested and we followed the steps of saline wash, drain, immersion in saline solution containing lactic acid for pH adjustment (4.3 to 4.5, salt addition (1.5 or 3%, traditional pasteurization or fast heat treatment, cooling and storage (0 to 4°C. The products were subjected to the physical, chemical, microbiological and sensory analyses and showed stability and safety for consumption up to 180 days in storage under refrigeration (0 to 4°C. Consumers showed preference for product containing 1.5% NaCl and subjected to fast heat treatment. The results suggest that caviar substitute developed with rainbow trout roes presents potential to production.

  20. Fibrous growth of strontium substituted hydroxyapatite and its drug release

    International Nuclear Information System (INIS)

    Suganthi, R.V.; Elayaraja, K.; Joshy, M.I. Ahymah; Chandra, V. Sarath; Girija, E.K.; Kalkura, S. Narayana

    2011-01-01

    The effect of strontium on the crystallization of helical ribbon of hydroxyapatite (HAp) was investigated by single diffusion technique in silica gel matrix at 27 deg. C and physiological pH. Fibers of HAp were obtained on addition of strontium. The length of the HAp fibers, were found to decrease as the strontium substitution increases. The presence of strontium ion increased the crystallinity as well as crystallite size of HAp. The strontium substituted HAp (Sr-HAp) has similar stoichiometry to that of biological apatite. Sr-HAp was found to have increased surface area (35%) compared to control. Further, strontium substitution leads to an enhancement of in vitro bioactivity. The cumulative in-vitro amoxicillin drug release in phosphate buffer solution (PBS, pH 7.2) showed a prolonged release profile for Sr-HAp.

  1. Fibrous growth of strontium substituted hydroxyapatite and its drug release

    Energy Technology Data Exchange (ETDEWEB)

    Suganthi, R.V.; Elayaraja, K.; Joshy, M.I. Ahymah; Chandra, V. Sarath [Crystal Growth Centre, Anna University, Chennai 600 025 (India); Girija, E.K. [Department of Physics, Periyar University, Salem 636 011 (India); Kalkura, S. Narayana, E-mail: kalkura@yahoo.com [Crystal Growth Centre, Anna University, Chennai 600 025 (India)

    2011-04-08

    The effect of strontium on the crystallization of helical ribbon of hydroxyapatite (HAp) was investigated by single diffusion technique in silica gel matrix at 27 deg. C and physiological pH. Fibers of HAp were obtained on addition of strontium. The length of the HAp fibers, were found to decrease as the strontium substitution increases. The presence of strontium ion increased the crystallinity as well as crystallite size of HAp. The strontium substituted HAp (Sr-HAp) has similar stoichiometry to that of biological apatite. Sr-HAp was found to have increased surface area (35%) compared to control. Further, strontium substitution leads to an enhancement of in vitro bioactivity. The cumulative in-vitro amoxicillin drug release in phosphate buffer solution (PBS, pH 7.2) showed a prolonged release profile for Sr-HAp.

  2. Synthesis of Randomly Substituted Anionic Cyclodextrins in Ball Milling.

    Science.gov (United States)

    Jicsinszky, László; Caporaso, Marina; Calcio Gaudino, Emanuela; Giovannoli, Cristina; Cravotto, Giancarlo

    2017-03-19

    A number of influencing factors mean that the random substitution of cyclodextrins (CD) in solution is difficult to reproduce. Reaction assembly in mechanochemistry reduces the number of these factors. However, lack of water can improve the reaction outcomes by minimizing the reagent's hydrolysis. High-energy ball milling is an efficient, green and simple method for one-step reactions and usually reduces degradation and byproduct formation. Anionic CD derivatives have successfully been synthesized in the solid state, using a planetary ball mill. Comparison with solution reactions, the solvent-free conditions strongly reduced the reagent hydrolysis and resulted in products of higher degree of substitution (DS) with more homogeneous DS distribution. The synthesis of anionic CD derivatives can be effectively performed under mechanochemical activation without significant changes to the substitution pattern but the DS distributions were considerably different from the products of solution syntheses.

  3. Synthesis of Randomly Substituted Anionic Cyclodextrins in Ball Milling

    Directory of Open Access Journals (Sweden)

    László Jicsinszky

    2017-03-01

    Full Text Available A number of influencing factors mean that the random substitution of cyclodextrins (CD in solution is difficult to reproduce. Reaction assembly in mechanochemistry reduces the number of these factors. However, lack of water can improve the reaction outcomes by minimizing the reagent’s hydrolysis. High-energy ball milling is an efficient, green and simple method for one-step reactions and usually reduces degradation and byproduct formation. Anionic CD derivatives have successfully been synthesized in the solid state, using a planetary ball mill. Comparison with solution reactions, the solvent-free conditions strongly reduced the reagent hydrolysis and resulted in products of higher degree of substitution (DS with more homogeneous DS distribution. The synthesis of anionic CD derivatives can be effectively performed under mechanochemical activation without significant changes to the substitution pattern but the DS distributions were considerably different from the products of solution syntheses.

  4. Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

    Directory of Open Access Journals (Sweden)

    Satoru Mori

    2017-10-01

    Full Text Available Phthalocyanines and subphthalocyanines are attracting attention as functional dyes that are applicable to organic solar cells, photodynamic therapy, organic electronic devices, and other applications. However, phthalocyanines are generally difficult to handle due to their strong ability to aggregate, so this property must be controlled for further applications of phthalocyanines. On the other hand, trifluoroethoxy-substituted phthalocyanines are known to suppress aggregation due to repulsion of the trifluoroethoxy group. Furthermore, the electronic characteristics of phthalocyanines are significantly changed by the strong electronegativity of fluorine. Therefore, it is expected that trifluoroethoxy-substituted phthalocyanines can be applied to new industrial fields. This review summarizes the synthesis and application of trifluoroethoxy-substituted phthalocyanine and subphthalocyanine derivatives.

  5. Selected polyethylene glycols as DOP substitutes. Addendum 1

    International Nuclear Information System (INIS)

    Gerber, B.V.

    1981-01-01

    The recommendation is made that Polyethylene glycol (PEG) 400 be considered as a substitute for DOP in aerosol generators producing a polydisperse distribution for testing the integrity of filters and for testing respirator fit. Further, the recommendation is made that pentaethylene glycol (PTAEG) and possibly hexaethylene glycol be considered as a substitute for DOP in aerosol generators thermally producing monodisperse aerosol for quality acceptance tests according tu US federal specifications and standards. The toxicology data base available on the polyethylene glycol family of chemical compounds is discussed and the conclusion is drawn that the probability of approval and acceptance as a non-hazardous substance in the filter and filter media test role is high. Data and analysis supporting PTAEG performance equivalent to DOP in the filter and filter media test role are given or referenced. Cost and availability of the substitute materials is discussed. Conclusions based on the present data and information are given and recommendations for further work are made

  6. Cost comparison of femoral head banking versus bone substitutes.

    Science.gov (United States)

    Leung, Hon-Bong; Fok, Margaret Woon-Man; Chow, Lorraine Chi-Yan; Yen, Chi-Hung

    2010-04-01

    To compare the costs of femoral head banking versus bone substitutes. Records of femoral head banking from 1998 to 2008 were reviewed. The cost of allogenic cancellous bone graft was calculated by estimating the direct expenditure of femoral head procurement, screening tests, and storage, and then divided by the amount of bone harvested. 326 females and 141 males (mean age, 80.3 years) donated 470 femoral heads. Each transplantable femoral head costs US$978. Each gram of transplantable allogenic bone graft costs US$86, compared with US$9 to 26 per gram for commercially available bone substitutes. Compared with bone substitutes, femoral head banking in Hong Kong was less economical. Unless allografts yield superior outcomes, harvesting femoral heads for general usage (such as filling bone voids for fresh fractures) is not justified from a financial perspective, especially in banks dedicated to procuring bone from femoral heads only.

  7. Fish mislabelling in France: substitution rates and retail types

    Directory of Open Access Journals (Sweden)

    Julien Bénard-Capelle

    2015-01-01

    Full Text Available Market policies have profound implications for consumers as well as for the management of resources. One of the major concerns in fish trading is species mislabelling: the commercial name used does not correspond to the product, most often because the product is in fact a cheaper or a more easily available species. Substitution rates depend heavily on species, some often being sold mislabelled while others rarely or never mislabelled. Rates also vary largely depending on countries. In this study, we analyse the first market-wide dataset collected for France, the largest sea food market in Europe, for fish species substitution. We sequenced and analysed 371 samples bearing 55 commercial species names, collected in fishmonger shops, supermarkets and restaurants; the largest dataset assembled to date in an European country. Sampling included fish fillets, both fresh and frozen, and prepared meals. We found a total of 14 cases of mislabelling in five species: bluefin tuna, cod, yellowfin tuna, sole and seabream, setting the overall substitution rate at 3.7% CI [2.2–6.4], one of the lowest observed for comparable surveys with large sampling. We detected no case of species mislabelling among the frozen fillets or in industrially prepared meals, and all the substitutions were observed in products sold in fishmongers shops or restaurants. The rate of mislabelling does not differ between species, except for bluefin tuna. Despite a very small sample size (n = 6, the rate observed for this species (83.3% CI [36–99] stands in sharp contrast with the low substitution rate observed for the other substituted species. In agreement with studies from other countries, this work shows that fish mislabelling can vary greatly within a country depending on the species. It further suggests that more efforts should be directed to the control of high value species like bluefin tuna.

  8. Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

    Science.gov (United States)

    Alkorta, Ibon; Legon, Anthony C

    2017-10-23

    It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N₂, CO, HC≡CH, CH₂=CH₂, C₃H₆, PH₃, H₂S, HCN, H₂O, H₂CO and NH₃) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H₂O, F₂, Cl₂, Br₂, ClF, BrCl, H₃SiF, H₃GeF, F₂CO, CO₂, N₂O, NO₂F, PH₂F, AsH₂F, SO₂, SeO₂, SF₂, and SeF₂) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol -1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

  9. Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds

    Directory of Open Access Journals (Sweden)

    Ibon Alkorta

    2017-10-01

    Full Text Available It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3 and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2 can be represented to good approximation by means of the equation D e = c ′ N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ′ is a constant, conveniently chosen to have the value 1.00 kJ mol−1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1 the hydrogen bond; (2 the halogen bond; (3 the tetrel bond; (4 the pnictogen bond; and (5 the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

  10. Exfoliation and thermal transformations of Nb-substituted layered titanates

    DEFF Research Database (Denmark)

    Song, H.; Sjåstad, Anja O.; Fjellvåg, Helmer

    2011-01-01

    Single-layer Nb-substituted titanate nanosheets of ca. 1 nm thickness were obtained by exfoliating tetrabutylammonium (TBA)-intercalated Nb-substituted titanates in water. AFM images and turbidity measurements reveal that the exfoliated nanosheets crack and corrugate when sonicated. Upon heating...... factors for increasing the transformation temperatures for conversion of the nanosheets to anatase and finally into rutile. It is further tempting to link the delay in crystallization to morphology limitations originating from the nanosheets. The present work shows that layered Nb-titanates...

  11. Bioactivity And Bone Formation In Silicon-Substituted Hydroxyapatite

    Directory of Open Access Journals (Sweden)

    Ulvan Ozad

    2012-06-01

    Full Text Available Bioactivity and successful bone formation in silicon-substituted hydroxyapatite bone grafts were investigated by using scanning electron microscopy and electron dispersive x-ray spectroscopy. Areas of bone formation have been detected in scanning electron microscopy; and, arranged lamellar collagen has been observed. 20.8% average carbon content rise has been detected between bone graft and the produced bone; and, this has been confirmed to be a gradual increase throughout the interphase. Obvious bone formation and maturation were observed in the samples. Carbon content gradually increased from bone graft to the bone formed, confirming formation of new bone and dissociation of silicon-substituted bone graft.

  12. Synthesis and biological evaluation of 2-substituted benzimidazole derivatives

    Directory of Open Access Journals (Sweden)

    Gurusamy Mariappan

    2015-09-01

    Full Text Available A novel series of 2-substituted benzimidazole derivatives (3a–3j were synthesized by the reaction of 2-chloro methyl benzimidazole with substituted primary aromatic amines. All the compounds were characterized by UV, IR, 1H NMR, mass spectral data and CHN elemental analysis. The synthesized derivatives were screened for analgesic and anti-inflammatory activities. All the compounds showed significant effect at 100 mg/kg p.o. and the experimental data are statistically significant at p < 0.01 level.

  13. Researcher’s Perspective of Substitution Method on Text Steganography

    Science.gov (United States)

    Zamir Mansor, Fawwaz; Mustapha, Aida; Azah Samsudin, Noor

    2017-08-01

    The linguistic steganography studies are still in the stage of development and empowerment practices. This paper will present several text steganography on substitution methods based on the researcher’s perspective, all scholar paper will analyse and compared. The objective of this paper is to give basic information in the substitution method of text domain steganography that has been applied by previous researchers. The typical ways of this method also will be identified in this paper to reveal the most effective method in text domain steganography. Finally, the advantage of the characteristic and drawback on these techniques in generally also presented in this paper.

  14. Activation of rhenium(I) toward substitution in fac-[Re(N,O'-Bid)(CO)3(HOCH3)] by Schiff-base bidentate ligands (N,O'-Bid).

    Science.gov (United States)

    Brink, Alice; Visser, Hendrik G; Roodt, Andreas

    2013-08-05

    A series of fac-[Re(N,O'-Bid)(CO)3(L)] (N,O'-Bid = monoanionic bidentate Schiff-base ligands with N,O donor atoms; L = neutral monodentate ligand) has been synthesized, and the methanol substitution reactions have been investigated. The complexes were characterized by NMR, IR, and UV-vis spectroscopy. X-ray crystal structures of the compounds fac-[Re(Sal-mTol)(CO)3(HOCH3)], fac-[Re(Sal-pTol)(CO)3(HOCH3)], fac-[Re(Sal-Ph)(CO)3(HOCH3)], and fac-[Re(Sal-Ph)(CO)3(Py)] (Sal-mTol = 2-(m-tolyliminomethyl)phenolato; Sal-pTol = 2-(p-tolyliminomethyl)phenolato; Sal-Ph = 2-(phenyliminomethyl)phenolato; Py = pyridine) are reported. Significant activation for the methanol substitution is induced by the use of the N,O bidentate ligand as manifested by the second order rate constants, with limiting kinetics being observed for the first time. Rate constants (25 °C) (k1 or k3) and activation parameters (ΔHk‡, kJ mol(-1); ΔSk‡, J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(Sal-mTol)(CO)3(HOCH3)] 3-chloropyridine: (k1) 2.33 ± 0.01 M(-1) s(-1); 85.1 ± 0.6, 48 ± 2; fac-[Re(Sal-mTol)(CO)3(HOCH3)] pyridine: (k1) 1.29 ± 0.02 M(-1) s(-1); 92 ± 2, 66 ± 7; fac-[Re(Sal-mTol)(CO)3(HOCH3)] 4-picoline: (k1) 1.27 ± 0.05 M(-1) s(-1); 88 ± 2, 53 ± 6; (k3) 3.9 ± 0.03 s(-1); 78 ± 8, 30 ± 27; (kf) 1.7 ± 0.02 M(-1) s(-1); 86 ± 2, 49 ± 6; fac-[Re(Sal-mTol)(CO)3(HOCH3)] DMAP (k3) 1.15 ± 0.02 s(-1); 88 ± 2, 52 ± 7. An interchange dissociative mechanism is proposed.

  15. Porcine wound models for skin substitution and burn treatment.

    NARCIS (Netherlands)

    Middelkoop, E.; Bogaerdt, A.J. van den; Lamme, E.N.; Hoekstra, M.J.; Brandsma, K.; Ulrich, M.M.

    2004-01-01

    Skin regeneration is an important field of tissue engineering. Especially in larger burns and chronic wounds, present treatments are insufficient in preventing scar formation and promoting healing. Initial screening of potentially interesting products for skin substitution is usually done by in

  16. An environmentally benign one pot synthesis of substituted ...

    Indian Academy of Sciences (India)

    Instance of Plagiarism in Journal of Chemical Sci- ences and withdrawal of published article. The Journal of Chemical Sciences office received a complaint from an alert reader to the effect that the paper 'An environmentally benign one pot syn- thesis of substituted quinolines catalysed by fluo- roboric acid based ionic ...

  17. Stereochemistry of substitution at trico-ordinate phosphorus

    DEFF Research Database (Denmark)

    Nielsen, John; Dahl, Otto

    1984-01-01

    and 31P) from reactant and product diastereoisomers have been assigned, and the stereo-chemistry of the substitution reactions have been determined by 31P n.m.r. monitoring. The outcome varies from complete inversion to complete lack of stereoselectivity. During the initial stages many of the non...

  18. Report on the first government-funded opioid substitution ...

    African Journals Online (AJOL)

    Background. Although pharmacological opioid substitution treatment (OST) is a well-established treatment modality for heroin addiction, it is a relatively recent introduction in low- and middle-income countries. Objective. To report on a pilot OST programme initiated in 2013 that was the only public-funded programme in ...

  19. Investigation on applicability of substitute beam-column frame for ...

    African Journals Online (AJOL)

    ... of the sway frame moment magnification provision for the design of slender reinforced concrete columns in sway frames according to EBCS 2: 1995. A special feature of the moment magnification method in EBCS 2: 1995 is the introduction of the concept of substitute frame for the determination of the storey buckling load.

  20. Iron-substituted AB5-type MH electrode

    Indian Academy of Sciences (India)

    substituted AB5-type MH electrode. SUMITA SRIVASTAVAa,∗ and R K UPADHYAYAb. aDepartment of Physics, Government P.G. College, Uttarkashi 249 193, India. bDepartment of Physics, Government P.G. College, Rishikesh 249 201, India.