WorldWideScience

Sample records for bond formation reactions

  1. C—C bond formation in the intramolecular Diels-Alder reaction of triene amides

    Directory of Open Access Journals (Sweden)

    Abdelilah Benallou

    2018-02-01

    Full Text Available The mechanism nature of the intramolecular Diels–Alder reaction has been performed; and thus, the changes of C—C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C—C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2—C3 σ bond while the second stage aims for C1—C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

  2. C-C bond formation in the intramolecular Diels-Alder reaction of triene amides.

    Science.gov (United States)

    Benallou, Abdelilah; El Alaoui El Abdallaoui, Habib; Garmes, Hocine

    2018-02-01

    The mechanism nature of the intramolecular Diels-Alder reaction has been performed; and thus, the changes of C-C bond forming/breaking along IRC are characterized in this study. Conceptual DFT analyses of the most favorable adduct fused/exo shows that the flux electronic will take place from diene to dienophile moiety. Moreover, ELF topological analysis based on the electron density predicts that C-C bond is formed by the coupling of two pseudoradical centers generated at the most significant atoms of the molecules. However, C2 vs C3, also C1 and C4 interaction comes mainly from the global electron density transfer which takes place along the reaction. Two- stage one-step is the proposed mechanism of this reaction, the first stage aims for the formation of C2-C3 σ bond while the second stage aims for C1-C4 σ bond formation. Interestingly, the observed asynchronicity of this IMDA reaction due principally to the asymmetric reorganization of electron density at the most attractive centers.

  3. Boron-Based Catalysts for C-C Bond-Formation Reactions.

    Science.gov (United States)

    Rao, Bin; Kinjo, Rei

    2018-05-02

    Because the construction of the C-C bond is one of the most significant reactions in organic chemistry, the development of an efficient strategy has attracted much attention throughout the synthetic community. Among various protocols to form C-C bonds, organoboron compounds are not just limited to stoichiometric reagents, but have also made great achievements as catalysts because of the easy modification of the electronic and steric impacts on the boron center. This review presents recent developments of boron-based catalysts applied in the field of C-C bond-formation reactions, which are classified into four kinds on the basis of the type of boron catalyst: 1) highly Lewis acidic borane, B(C 6 F 5 ) 3 ; 2) organoboron acids, RB(OH) 2 , and their ester derivatives; 3) borenium ions, (R 2 BL)X; and 4) other miscellaneous kinds. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Formation of porous surface layers in reaction bonded silicon nitride during processing

    Science.gov (United States)

    Shaw, N. J.; Glasgow, T. K.

    1979-01-01

    Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

  5. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  6. Ab initio computational study of –N-C and –O-C bonding formation : functional group modification reaction based chitosan

    Science.gov (United States)

    Siahaan, P.; Salimah, S. N. M.; Sipangkar, M. J.; Hudiyanti, D.; Djunaidi, M. C.; Laksitorini, M. D.

    2018-04-01

    Chitosan application in pharmaceutics and cosmeceutics industries is limited by its solubility issue. Modification of -NH2 and -OH fuctional groups of chitosan by adding carboxyl group has been shown to improve its solubility and application. Attempt to synthesize carboxymethyl chitosan (CMC) from monocloroacetic acid (MCAA) has been done prior this report. However no information is available wether –OH (-O-C bonding formation) or -NH2 (-N-C bonding formation) is the preference for - CH2COOH to attach. In the current study, the reaction mechanism between chitosan and MCAA reactants into carboxymethyl chitosan (CMC) was examined by computational approach. Dimer from of chitosan used as a molecular model in calculation All the molecular structure involved in the reaction mechanism was optimized by ab initio computational on the theory and basis set HF/6-31G(d,p). The results showed that the - N-C bonding formation via SN2 than the -O-C bonding formation via SN2 which have activation energy 469.437 kJ/mol and 533.219 kJ/mol respectively. However, the -O-C bonding formation more spontaneous than the -N-C bonding formation because ΔG the formation of O-CMC-2 reaction is more negative than ΔG of formation N-CMC-2 reaction is -4.353 kJ/mol and -1.095 kJ/mol respectively. The synthesis of N,O-CMC first forms -O-CH2COOH, then continues to form -NH-CH2COOH. This information is valuable to further optimize the reaction codition for CMC synthesis.

  7. Bonded exciplex formation: electronic and stereoelectronic effects.

    Science.gov (United States)

    Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P; Farid, Samir; Farid, Ramy S; Gould, Ian R

    2008-12-18

    As recently proposed, the singlet-excited states of several cyanoaromatics react with pyridine via bonded-exciplex formation, a novel concept in photochemical charge transfer reactions. Presented here are electronic and steric effects on the quenching rate constants, which provide valuable support for the model. Additionally, excited-state quenching in poly(vinylpyridine) is strongly inhibited both relative to that in neat pyridine and also to conventional exciplex formation in polymers, consistent with a restrictive orientational requirement for the formation of bonded exciplexes. Examples of competing reactions to form both conventional and bonded exciplexes are presented, which illustrate the delicate balance between these two processes when their reaction energetics are similar. Experimental and computational evidence is provided for the formation of a bonded exciplex in the reaction of the singlet excited state of 2,6,9,10-tetracyanoanthracene (TCA) with an oxygen-substituted donor, dioxane, thus expanding the scope of bonded exciplexes.

  8. Reaction-bonded silicon nitride

    International Nuclear Information System (INIS)

    Porz, F.

    1982-10-01

    Reaction-bonded silicon nitride (RBSN) has been characterized. The oxidation behaviour in air up to 1500 0 C and 3000 h and the effects of static and cyclic oxidation on room-temperature strength have been studied. (orig./IHOE) [de

  9. Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

    Science.gov (United States)

    Plaga, W; Frank, R; Knappe, J

    1988-12-15

    Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

  10. CS Bond formation by

    Indian Academy of Sciences (India)

    2017-02-02

    Feb 2, 2017 ... a thiol substituent at position-2 of the quinazoline ring. ... coupling reactions represent great contribution to the recent growth of organic synthesis.2 ... Difficulties in C-S ...... Experimental Advances (Amsterdam: Elsevier) 19; (b).

  11. Formation of cyclobutanones by the photolytic reaction of (CO)/sub 5/Cr/double bond/C(OMe)Me with electron-rich olefins

    Energy Technology Data Exchange (ETDEWEB)

    Sierra, M.A.; Hegedus, L.S.

    1989-03-15

    Recent research has centered on the development of useful organic synthetic methodology based on the photolytic reactions of chromium Fischer carbene complexes, particularly in regards to the development of new /beta/-lactam syntheses. In the course of these studies it became evident that photolysis of chromium-carbene complexes resulted in the reversible production of chromium-ketene complexes, by a photochemically driven CO insertion into the chromium-carbene carbon double bond and that this unstable intermediate was responsible for /beta/-lactam formation.

  12. Ab initio computational study of reaction mechanism of peptide bond formation on HF/6-31G(d,p) level

    Science.gov (United States)

    Siahaan, P.; Lalita, M. N. T.; Cahyono, B.; Laksitorini, M. D.; Hildayani, S. Z.

    2017-02-01

    Peptide plays an important role in modulation of various cell functions. Therefore, formation reaction of the peptide is important for chemical reactions. One way to probe the reaction of peptide synthesis is a computational method. The purpose of this research is to determine the reaction mechanism for peptide bond formation on Ac-PV-NH2 and Ac-VP-NH2 synthesis from amino acid proline and valine by ab initio computational approach. The calculations were carried out by theory and basis set HF/6-31G(d,p) for four mechanisms (path 1 to 4) that proposed in this research. The results show that the highest of the rate determining step between reactant and transition state (TS) for path 1, 2, 3, and 4 are 163.06 kJ.mol-1, 1868 kJ.mol-1, 5685 kJ.mol-1, and 1837 kJ.mol-1. The calculation shows that the most preferred reaction of Ac-PV-NH2 and Ac-VP-NH2 synthesis from amino acid proline and valine are on the path 1 (initiated with the termination of H+ in proline amino acid) that produce Ac-PV-NH2.

  13. Analysis of Disulfide Bond Formation

    NARCIS (Netherlands)

    Braakman, Ineke; Lamriben, Lydia; van Zadelhoff, Guus; Hebert, Daniel N.

    2017-01-01

    In this unit, protocols are provided for detection of disulfide bond formation in cultures of intact cells and in an in vitro translation system containing isolated microsomes or semi-permeabilized cells. First, the newly synthesized protein of interest is biosynthetically labeled with radioactive

  14. Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

    Science.gov (United States)

    Sad, María E; Neurock, Matthew; Iglesia, Enrique

    2011-12-21

    This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

  15. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou

    2016-06-01

    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  16. Reaction kinetics of bond rotations in graphene

    KAUST Repository

    Skowron, Stephen T.; Koroteev, Victor O.; Baldoni, Matteo; Lopatin, Sergei; Zurutuza, Amaia; Chuvilin, Andrey; Besley, Elena

    2016-01-01

    The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

  17. Reaction kinetics of bond rotations in graphene

    KAUST Repository

    Skowron, Stephen T.

    2016-04-12

    The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

  18. Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions.

    Science.gov (United States)

    Leckie, Stuart M; Harkness, Gavin J; Clarke, Matthew L

    2014-10-09

    As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole.

  19. Effect of Pressurizing during Compaction and Sintering on the Formation of Reaction-Bonded SiC–Ti{sub 3}SiC{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sun-Han; Jung, Yang-Il; Rhee, Young-Woo; Park, Dong-Jun; Park, Jung-Hwan; Park, Jeong-Yong; Kim, Hyun-Gil; Koo, Yang-Hyun [LWR Fuel Technology Division, KAERI, Daejeon (Korea, Republic of)

    2016-05-15

    A reaction-bonded SiC-Ti{sub 3}SiC{sub 2} ceramic composite was produced for use in a ceramic-metal composite cladding tube. The diffusion reaction between TiC and Si was investigated with respect to process pressure. The mole-fraction of TiC and Si was controlled to be 3:2 to obtain a Ti{sub 3}SiC{sub 2} phase in the ceramic composite. Sintering was conducted at 1450 °C where TiC particles could react with melted Si. SiC ceramic composites consisting of Ti{sub 3}SiC{sub 2} and TiSi{sub 2} matrix phases were obtained. The formation of the constituent phases was strongly related to the processing pressure. The number of second phases in the SiC-Ti{sub 3}SiC{sub 2} composite was controlled by adjusting the processing pressure. When the powder compacts were not pressurized, no Ti{sub 3}SiC{sub 2} phase was formed. However, the Ti{sub 3}SiC{sub 2} phase was formed under pressurizing during compaction and/or sintering. The higher the pressure the higher the purity of SiC-Ti{sub 3}SiC{sub 2}. The dual-phased SiC-Ti{sub 3}SiC{sub 2} composite, however, revealed the decreased resistance to high-temperature oxidation. It is suggested that the incorporation of TiSi{sub 2} in the composite increases the oxidation resistance as well as mechanical property.

  20. Pressure bonding molybdenum alloy (TZM) to reaction-bonded silicon nitride

    International Nuclear Information System (INIS)

    Huffsmith, S.A.; Landingham, R.L.

    1978-01-01

    Topping cycles could boost the energy efficiencies of a variety of systems by using what is now waste heat. One such topping cycle uses a ceramic helical expander and would require that a reaction-bonded silicon nitride (RBSN) rotor be bonded to a shaft of TZM (Mo-0.5 wt % Ti-0.08 wt % Zr). Coupon studies show that TZM can be bonded to RBSN at 1300 0 C and 69 MPa if there is an interlayer of MoSi 2 . A layer of finely ground (10 μm) MoSi 2 facilitates bond formation and provides a thicker bond interface. The hardness and grain structure of the TZM and RBSN were not affected by the temperature and pressure required to bond the coupons

  1. Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

    Science.gov (United States)

    Mencos, Alejandro; Krim, Lahouari

    2018-06-01

    We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

  2. tri-n-butyltin hydride-mediated radical reaction of a 2-iodobenzamide: formation of an unexpected carbon-tin bond

    International Nuclear Information System (INIS)

    Oliveira, Marcelo T.; Alves, Rosemeire B.; Cesar, Amary; Prado, Maria Auxiliadora F.; Alves, Ricardo J.; Queiroga, Carla G.; Santos, Leonardo S.; Eberlin, Marcos N.

    2007-01-01

    The tri-n-butyltin hydride-mediated reaction of methyl 2,3-di-O-benzyl-4-O-trans-cinnamyl- 6-deoxy-6-(2-iodobenzoylamino)-α-D-galactopyranoside afforded an unexpected aryltributyltin compound. The structure of this new tetraorganotin(IV) product has been elucidated by 1 H, 13 C NMR spectroscopy, COSY and HMQC experiments and electrospray ionization mass spectrometry (ESI-MS). The formation of this new compound via a radical coupling reaction and a radical addition-elimination process is discussed. (author)

  3. Nonperfect synchronization of bond-forming and bond-rupturing processes in the reaction H + H2 → H2 + H

    International Nuclear Information System (INIS)

    Chandra, A.K.; Rao, V.S.

    1996-01-01

    The simplest prototypical hydrogen transfer reaction, i.e., H + H 2 → H 2 + H, is studied by the quantum-mechanical ab initio methods. Results reveal that during this reaction free valence which almost equals the square of the spin density develops on the migrating hydrogen atom. Bond orders are calculated using Mayer's formalism. Both the variations of bond orders and bond lengths along the reaction path are examined. This analysis reveals that the bond formation and bond cleavage processes in this reaction are not perfectly synchronous. The bond clevage process is slightly more advanced on the reaction path. 38 refs., 6 figs., 2 tabs

  4. Photoinitiated reactions in weakly bonded complexes

    International Nuclear Information System (INIS)

    Wittig, C.

    1993-01-01

    This paper discusses photoinitiated reactions in weakly bonded binary complexes in which the constituents are only mildly perturbed by the intermolecular bond. Such complexes, with their large zero point excursions, set the stage for events that occur following electronic excitation of one of the constituents. This can take several forms, but in all cases, entrance channel specificity is imposed by the character of the complex as well as the nature of the photoinitiation process. This has enabled us to examine aspects of bimolecular processes: steric effects, chemical branching ratios, and inelastic scattering. Furthermore, monitoring reactions directly in the time domain can reveal mechanisms that cannot be inferred from measurements of nascent product excitations. Consequently, we examined several systems that had been studied previously by our group with product state resolution. With CO 2 /HI, in which reaction occurs via a HOCO intermediate, the rates agree with RRKM predictions. With N 2 O/HI, the gas phase single collision reaction yielding OH + N 2 has been shown to proceed mainly via an HNNO intermediate that undergoes a 1,3-hydrogen shift to the OH + N 2 channel. With complexes, ab initio calculations and high resolution spectroscopic studies of analogous systems suggest that the hydrogen, while highly delocalized, prefers the oxygen to the nitrogen. We observe that OH is produced with a fast risetime (< 250 fs) which can be attributed to either direct oxygen-side attack or rapid HNNO decomposition and/or a termolecular contribution involving the nearby iodine

  5. Reactions of sigma-bonded organochromium(III)complexes

    International Nuclear Information System (INIS)

    Leslie, J.P. II.

    1975-12-01

    Three projects were carried out, each dealing with the kinetics and mechanism of reactions of sigma-bonded organochromium(III) complexes of the form (H 2 O) 5 CrR 2+ . Part I describes the kinetics of the reaction of dichloromethylchromium(III) ion with chromium(II) ion in aqueous acid. Part II deals with the radioexchange of 4-pyridinomethylchromium(III) ion with 51 Cr 2+ and the kinetics of formation of the organochromium species at 55 0 in 1 M H + . Part III deals with the reactions of Hg 2+ and CH 3 Hg + with a series of (H 2 O) 5 CrR 2+ complexes, in which R is an aliphatic alkyl group, a haloalkyl group, or an aralkyl group

  6. Insertion reactions into Pd[bond]O and Pd[bond]N bonds: preparation of alkoxycarbonyl, carbonato, carbamato, thiocarbamate, and thioureide complexes of palladium(II).

    Science.gov (United States)

    Ruiz, José; Martínez, M Teresa; Florenciano, Félix; Rodríguez, Venancio; López, Gregorio; Pérez, José; Chaloner, Penny A; Hitchcock, Peter B

    2003-06-02

    Mononuclear palladium hydroxo complexes of the type [Pd(N[bond]N)(C(6)F(5))(OH)] [(N[bond]N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N[bond]N)(C(6)F(5))(acetone)]ClO(4) with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)Me)]. Similar alkoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)R)] (N[bond]N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or (i)Pr) are obtained when [Pd(N[bond]N)(C(6)F(5))Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N[bond]N)(C(6)F(5))(OH)] (N[bond]N = bipy or Me(2)bipy) with CO(2), in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N[bond]N)(C(6)F(5))Pd(mu-eta(2)-CO(3))Pd(C(6)F(5))(N[bond]N)]. Complexes [Pd(N[bond]N)(C(6)F(5))(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N[bond]N)(C(6)F(5))[SC(OR)NPh

  7. Solvent Induced Disulfide Bond Formation in 2,5-dimercapto-1,3,4-thiadiazole

    OpenAIRE

    Palanisamy Kalimuthu; Palraj Kalimuthu; S. Abraham John

    2007-01-01

    Disulfide bond formation is the decisive event in the protein folding to determine the conformation and stability of protein. To achieve this disulfide bond formation in vitro, we took 2,5-dimercapto-1,3,4-thiadiazole (DMcT) as a model compound. We found that disulfide bond formation takes place between two sulfhydryl groups of DMcT molecules in methanol. UV-Vis, FT-IR and mass spectroscopic as well as cyclic voltammetry were used to monitor the course of reaction. We proposed a mechanism for...

  8. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    Science.gov (United States)

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  9. Disulphide bond formation in food protein aggregation and gelation

    NARCIS (Netherlands)

    Visschers, R.W.; Jongh, de H.H.J.

    2005-01-01

    In this short review we discuss the role of cysteine residues and cystine bridges for the functional aggregation of food proteins. We evaluate how formation and cleavage of disulphide bonds proceeds at a molecular level, and how inter- and intramolecular disulfide bonds can be detected and modified.

  10. Spur Reaction Model of Positronium Formation

    DEFF Research Database (Denmark)

    Mogensen, O. E.

    1974-01-01

    A new model of positronium (Ps) formation is proposed. Positronium is assumed to be formed by a reaction between a positron and an electron in the positron spur. Ps formation must compete with electron‐ion recombination and electron or positron reactions with solvent molecules and scavenger...

  11. Te(II)/Te(IV) Mediated C-N Bond Formation on 2,5-Diphenyltellurophene and a Reassignment of the Product from the Reaction of PhI(OAc)2 with 2 TMS-OTf.

    Science.gov (United States)

    Aprile, Antonino; Iversen, Kalon J; Wilson, David J D; Dutton, Jason L

    2015-05-18

    We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant [PhI(4-DMAP)2](2+). Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought.

  12. Formation of a hydrogen-bonded barbiturate [2]-rotaxane.

    Science.gov (United States)

    Tron, Arnaud; Thornton, Peter J; Rocher, Mathias; Jacquot de Rouville, Henri-Pierre; Desvergne, Jean-Pierre; Kauffmann, Brice; Buffeteau, Thierry; Cavagnat, Dominique; Tucker, James H R; McClenaghan, Nathan D

    2014-03-07

    Interlocked structures containing the classic Hamilton barbiturate binding motif comprising two 2,6-diamidopyridine units are reported for the first time. Stable [2]-rotaxanes can be accessed either through hydrogen-bonded preorganization by a barbiturate thread followed by a Cu(+)-catalyzed "click" stoppering reaction or by a Cu(2+)-mediated Glaser homocoupling reaction.

  13. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

  14. Bond-selective control of a gas-surface reaction

    Science.gov (United States)

    Killelea, Daniel R.

    The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

  15. Formation of Irreversible H-bonds in Cellulose Materials

    Science.gov (United States)

    Umesh P. Agarwal; Sally A. Ralph; Rick S. Reiner; Nicole M. Stark

    2015-01-01

    Understanding of formation of irreversible Hbonds in cellulose is important in a number of fields. For example, fields as diverse as pulp and paper and enzymatic saccharification of cellulose are affected. In the present investigation, the phenomenon of formation of irreversible H-bonds is studied in a variety of celluloses and under two different drying conditions....

  16. Bite angle effects of diphosphines in C-C and C-X bond forming cross coupling reactions

    NARCIS (Netherlands)

    Birkholz, M.N.; Freixa, Z.; van Leeuwen, P.W.N.M.

    2009-01-01

    Catalytic reactions of C-C and C-X bond formation are discussed in this critical review with particular emphasis on cross coupling reactions catalyzed by palladium and wide bite angle bidentate diphosphine ligands. Especially those studies have been collected that allow comparison of the ligand bite

  17. In-situ determination of amine/epoxy and carboxylic/epoxy exothermic heat of reaction on surface of modified carbon nanotubes and structural verification of covalent bond formation

    Science.gov (United States)

    Neves, Juliana C.; de Castro, Vinícius G.; Assis, Ana L. S.; Veiga, Amanda G.; Rocco, Maria Luiza M.; Silva, Glaura G.

    2018-04-01

    An effective nanofiller-matrix interaction is considered crucial to produce enhanced nanocomposites. Nevertheless, there is lack of experiments focused in the direct measurement of possible filler-matrix covalent linkage, which was the main goal of this work for a carbon nanotube (CNT)/epoxy system. CNT were functionalized with oxygenated (ox) functions and further with triethylenetetramine (TETA). An in-situ determination methodology of epoxy-CNTs heat of reaction was developed by Differential Scanning Calorimetry (DSC). Values of -(8.7 ± 0.4) and -(6.0 ± 0.6) J/g were observed for epoxy with CNT-ox and CNT-TETA, respectively. These results confirm the occurrence of covalent bonds for both functionalized CNTs, a very important information due to the literature generally disregard this possibility for oxygenated functions. The higher value obtained for CNT-ox can be attributed to a not complete amidation and to steric impediments in the CNT-TETA structure. The modified CNTs produced by DSC experiments were then characterized by X-Ray Photoelectron Spectroscopy, Transmission Electron Microscopy and Thermogravimetry, which confirmed the covalent linkage. This characterization methodology can be used to verify the occurrence of covalent bonds in various nanocomposites with a quantitative evaluation, providing data for better understanding of the role of CNT functional groups and for tailoring its interface with polymers.

  18. Optimal control of bond selectivity in unimolecular reactions

    International Nuclear Information System (INIS)

    Shi Shenghua; Rabitz, H.

    1991-01-01

    The optimal control theory approach to designing optimal fields for bond-selective unimolecular reactions is presented. A set of equations for determining the optimal fields, which will lead to the achievement of the objective of bond-selective dissociation is developed. The numerical procedure given for solving these equations requires the repeated calculation of the time propagator for the system with the time-dependent Hamiltonian. The splitting approximation combined with the fast Fourier transform algorithm is used for computing the short time propagator. As an illustrative example, a model linear triatomic molecule is treated. The model system consists of two Morse oscillators coupled via kinetic coupling. The magnitude of the dipoles of the two Morse oscillators are the same, the fundamental frequencies are almost the same, but the dissociation energies are different. The rather demanding objective under these conditions is to break the stronger bond while leaving the weaker one intact. It is encouraging that the present computational method efficiently gives rise to the optimal field, which leads to the excellent achievement of the objective of bond selective dissociation. (orig.)

  19. Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

    Science.gov (United States)

    Fox, D. S.

    1994-01-01

    Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

  20. Investigations of Reactive Carbohydrates in Glycosidic Bond Formation and Degradation

    DEFF Research Database (Denmark)

    Heuckendorff, Mads

    The overall objective of the research described in this thesis was to explore the field of glycosidic bond formation and degradation. In more detail, the objective was to do further research in the field of highly reactive glycosyl donors. New ways of making highly reactive donors were explored...

  1. Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

    Science.gov (United States)

    Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

    2018-02-16

    A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Carbon-sulfur bond formation by reductive elimination of gold(iii) thiolates.

    Science.gov (United States)

    Currie, Lucy; Rocchigiani, Luca; Hughes, David L; Bochmann, Manfred

    2018-04-10

    Whereas the reaction of the gold(iii) pincer complex (C^N^C)AuCl with 1-adamantyl thiol (AdSH) in the presence of base affords (C^N^C)AuSAd, the same reaction in the absence of base leads to formation of aryl thioethers as the products of reductive elimination of the Au-C and Au-S ligands (C^N^C = dianion of 2-6-diphenylpyridine or 2-6-diphenylpyrazine). Although high chemical stability is usually taken as a characteristic of pincer complexes, results show that thiols are capable of cleaving one of the pincer Au-C bonds. This reaction is not simply a function of S-H acidity, since no cleavage takes place with other more acidic X-H compounds, such as carbazole, amides, phenols and malonates. The reductive C-S elimination follows a second-order rate law, -d[1a]/dt = k[1a][AdSH]. Reductive elimination is enabled by displacement of the N-donor by thiol; this provides the conformational flexibility necessary for C-S bond formation to occur. Alternatively, reductive C-S bond formation can be induced by reaction of pre-formed thiolates (C^N^C)AuSR with a strong Brønsted acid, followed by addition of SMe2 as base. On the other hand, treatment of (C^N^C)AuR (R = Me, aryl, alkynyl) with thiols under similar conditions leads to selective C-C rather than C-S bond formation. The reaction of (C^N^C)AuSAd with H+ in the absence of a donor ligand affords the thiolato-bridged complex [{(C^N-CH)Au(μ-SAd)}2]2+ which was crystallographically characterised.

  3. Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

    International Nuclear Information System (INIS)

    Hoang, Michelle V; Chung, Hyun-Joong; Elias, Anastasia L

    2016-01-01

    Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm −1 ) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ∼0.2 N mm −1 (method 1) and  >0.3 N mm −1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication. (paper)

  4. Ductile mode grinding of reaction-bonded silicon carbide mirrors.

    Science.gov (United States)

    Dong, Zhichao; Cheng, Haobo

    2017-09-10

    The demand for reaction-bonded silicon carbide (RB-SiC) mirrors has escalated recently with the rapid development of space optical remote sensors used in astronomy or Earth observation. However, RB-SiC is difficult to machine due to its high hardness. This study intends to perform ductile mode grinding to RB-SiC, which produces superior surface integrity and fewer subsurface damages, thus minimizing the workload of subsequent lapping and polishing. For this purpose, a modified theoretical model for grain depth of cut of grinding wheels is presented, which correlates various processing parameters and the material characteristics (i.e., elastic module) of a wheel's bonding matrix and workpiece. Ductile mode grinding can be achieved as the grain depth of cut of wheels decreases to be less than the critical cut depth of workpieces. The theoretical model gives a roadmap to optimize the grinding parameters for ductile mode grinding of RB-SiC and other ultra-hard brittle materials. Its feasibility was validated by experiments. With the optimized grinding parameters for RB-SiC, the ductile mode grinding produced highly specular surfaces (with roughness of ∼2.2-2.8  nm Ra), which means the material removal mechanism of RB-SiC is dominated by plastic deformation rather than brittle fracture. Contrast experiments were also conducted on fused silica, using the same grinding parameters; this produced only very rough surfaces, which further validated the feasibility of the proposed model.

  5. Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

    Science.gov (United States)

    Kabbani, Mohamad A.

    In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

  6. Role of hydrogen bonds in the reaction mechanism of chalcone isomerase.

    Science.gov (United States)

    Jez, Joseph M; Bowman, Marianne E; Noel, Joseph P

    2002-04-23

    In flavonoid, isoflavonoid, and anthocyanin biosynthesis, chalcone isomerase (CHI) catalyzes the intramolecular cyclization of chalcones into (S)-flavanones with a second-order rate constant that approaches the diffusion-controlled limit. The three-dimensional structures of alfalfa CHI complexed with different flavanones indicate that two sets of hydrogen bonds may possess critical roles in catalysis. The first set of interactions includes two conserved amino acids (Thr48 and Tyr106) that mediate a hydrogen bond network with two active site water molecules. The second set of hydrogen bonds occurs between the flavanone 7-hydroxyl group and two active site residues (Asn113 and Thr190). Comparison of the steady-state kinetic parameters of wild-type and mutant CHIs demonstrates that efficient cyclization of various chalcones into their respective flavanones requires both sets of contacts. For example, the T48A, T48S, Y106F, N113A, and T190A mutants exhibit 1550-, 3-, 30-, 7-, and 6-fold reductions in k(cat) and 2-3-fold changes in K(m) with 4,2',4'-trihydroxychalcone as a substrate. Kinetic comparisons of the pH-dependence of the reactions catalyzed by wild-type and mutant enzymes indicate that the active site hydrogen bonds contributed by these four residues do not significantly alter the pK(a) of the intramolecular cyclization reaction. Determinations of solvent kinetic isotope and solvent viscosity effects for wild-type and mutant enzymes reveal a change from a diffusion-controlled reaction to one limited by chemistry in the T48A and Y106F mutants. The X-ray crystal structures of the T48A and Y106F mutants support the assertion that the observed kinetic effects result from the loss of key hydrogen bonds at the CHI active site. Our results are consistent with a reaction mechanism for CHI in which Thr48 polarizes the ketone of the substrate and Tyr106 stabilizes a key catalytic water molecule. Hydrogen bonds contributed by Asn113 and Thr190 provide additional

  7. Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

    2014-12-08

    A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

    KAUST Repository

    Chen, Shuli

    2013-09-17

    Phenylbis(phenylethynyl)phosphane PhP(C≡CPh)2 coordinates regiospecifically to the α-methyl-chiral ortho-platinated and -palladated naphthylamine units at the positions trans to the nitrogen donors. The P→Pt coordination bond is kinetically inert, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine ring. No intramolecular insertion reaction occurred. In contrast to its palladium analogue, the ortho-platinated ring is not reactive towards coordinated PhP(C≡CPh)2, although it can promote the Pd-C bond insertion reaction. However, despite the high kinetic stability of the P→Pt coordination, the organoplatinum unit is a noticeably weaker activator than its organopalladium counterpart. The chirality of the reacting ortho-metallated naphthylamine ligand exhibited high stereochemical influence on the formation of the new stereogenic phosphorus center during the course of these C-C bond-formation reactions. The coordination chemistry and the absolute stereochemistry of the dimetallic products were determined by single-crystal X-ray crystallographic analysis. The asymmetric monoinsertion of PhP(C≡CPh)2 coordinated to a cyclometallated N,N-dimethyl naphthyl/benzylamine template into the Pd-C bonds of N,N-dimethylnaphthylamine palladacycles has been demonstrated for the synthesis of a variety of new P-stereogenic homo- or heterodimetallic complexes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Pomarole, Julien; Thérien, Marie-Ève; Benhassine, Yasmine; Beaulieu, Samuel; Legault, Claude Y; Paquin, Jean-François

    2013-05-03

    It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

  10. Formation of RNA phosphodiester bond by histidine-containing dipeptides

    DEFF Research Database (Denmark)

    Wieczorek, Rafal; Dörr, Mark; Chotera, Agata

    2013-01-01

    A new scenario for prebiotic formation of nucleic acid oligomers is presented. Peptide catalysis is applied to achieve condensation of activated RNA monomers into short RNA chains. As catalysts, L-dipeptides containing a histidine residue, primarily Ser-His, were used. Reactions were carried out...... in self-organised environment, a water-ice eutectic phase, with low concentrations of reactants. Incubation periods up to 30 days resulted in the formation of short oligomers of RNA. During the oligomerisation, an active intermediate (dipeptide-mononucleotide) is produced, which is the reactive species...... by a transamination mechanism. Because peptides are much more likely products of spontaneous condensation than nucleotide chains, their potential as catalysts for the formation of RNA is interesting from the origin-of-life perspective. Finally, the formation of the dipeptide-mononucleotide intermediate and its...

  11. Intermolecular Formation of Two C−C Bonds across Olefins Enabled by Boron-Based Relay Strategies

    Czech Academy of Sciences Publication Activity Database

    Hidasová, Denisa; Jahn, Ullrich

    2017-01-01

    Roč. 56, č. 33 (2017), s. 9656-9658 ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : 1,2- metal ate rearrangement * C−C bond formation * radical reactions * transition metal catalysis * vinyl boronates Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 11.994, year: 2016

  12. Simultaneous bond degradation and bond formation during phenol-formaldehyde curing with wood

    Science.gov (United States)

    Daniel J. Yelle; John Ralph

    2016-01-01

    Bonding of wood using phenol–formaldehyde adhesive develops highly durable bonds. Phenol– formaldehyde is believed to form primary bonds with wood cell wall polymers (e.g., lignin). However, it is unclear how this adhesive interacts and bonds to lignin. Through wood solubilisation methodologies, earlywood and latewood bonded assemblies were characterized using two-...

  13. Surface Reconstruction-Induced Coincidence Lattice Formation Between Two-Dimensionally Bonded Materials and a Three-Dimensionally Bonded Substrate

    NARCIS (Netherlands)

    Boschker, Jos E.; Momand, Jamo; Bragaglia, Valeria; Wang, Ruining; Perumal, Karthick; Giussani, Alessandro; Kooi, Bart J.; Riechert, Henning; Calarco, Raffaella

    Sb2Te3 films are used for studying the epitaxial registry between two-dimensionally bonded (2D) materials and three-dimensional bonded (3D) substrates. In contrast to the growth of 3D materials, it is found that the formation of coincidence lattices between Sb2Te3 and Si(111) depends on the geometry

  14. Physics of positronium acceptor complex formation reactions

    International Nuclear Information System (INIS)

    Gangopadhyay, Debarshi; Ganguly, Bichitra Nandi; Mukherjee, Tapas; Dutta-Roy, Binayak

    2002-01-01

    Positronium (P s ) reaction rates (κ) with weak Acceptors (Ac) leading to the formation of Ps-Ac complexes show several interesting features: non-monotonic temperature dependence of κ(departing from the usual Arrhenius behaviour), considerable variability of κ with respect to different solvents, and anomalies in response to external pressure at ambient temperature. The object of this work is to explain all these phenomena using a remarkably simple bubble model (the widely used model for the pick-off component of ortho-positronium decay in liquids), which has been revisited several times in the context and as a result smooth diffuse boundary of the bubble was suggested that yields reasonable agreement of the experimental data. The contractile force on the bubble relies much on the surface tension of the liquid, through our calculation the notion of critical surface tension emerges and enables us to explain the experimental observations satisfactorily. (author)

  15. Liquid phase diffusion bonding of A1070 by using metal formate coated Zn sheet

    Science.gov (United States)

    Ozawa, K.; Koyama, S.; shohji, I.

    2017-05-01

    Aluminium alloy have high strength and easily recycle due to its low melting point. Therefore, aluminium is widely used in the manufacturing of cars and electronic devices. In recent years, the most common way for bonding aluminium alloy is brazing and friction stir welding. However, brazing requires positional accuracy and results in the formation of voids by the flax residue. Moreover, aluminium is an excellent heat radiating and electricity conducting material; therefore, it is difficult to bond together using other bonding methods. Because of these limitations, liquid phase diffusion bonding is considered to the suitable method for bonding aluminium at low temperature and low bonding pressure. In this study, the effect of metal formate coating processing of zinc surface on the bond strength of the liquid phase diffusion bonded interface of A1070 has been investigated by SEM observation of the interfacial microstructures and fractured surfaces after tensile test. Liquid phase diffusion bonding was carried out under a nitrogen gas atmosphere at a bonding temperature of 673 K and 713 K and a bonding load of 6 MPa (bonding time: 15 min). As a result of the metal formate coating processing, a joint having the ultimate tensile strength of the base aluminium was provided. It is hypothesized that this is because metallic zinc is generated as a result of thermal decomposition of formate in the bonded interface at lower bonding temperatures.

  16. Al/Ni metal intermetallic composite produced by accumulative roll bonding and reaction annealing

    International Nuclear Information System (INIS)

    Mozaffari, A.; Hosseini, M.; Manesh, H. Danesh

    2011-01-01

    Highlights: → Al/Ni metallic composites produced by accumulative roll bonding were heat treated at different temperatures and periods, to investigate the effect of reaction annealing on the structure and mechanical properties. → Based on the annealing conditions, various intermetallic phases were formed. The structure and composition of the composites were detected by SEM and XRD techniques. → The strength of the initial metallic composite can be improved due to the formation of the hard intermetallic phases, by the heat treatment process. - Abstract: In this research, Al/Ni multilayers composites were produced by accumulative roll bonding and then annealed at different temperatures and durations. The structure and mechanical properties of the fabricated metal intermetallic composites (MICs) were investigated. Scanning electron microscopy and X-ray diffraction analyses were used to evaluate the structure and composition of the composite. The Al 3 Ni intermetallic phase is formed in the Al/Ni interface of the samples annealed at 300 and 400 deg. C. When the temperature increased to 500 deg. C, the Al 3 Ni 2 phase was formed in the composite structure and grew, while the Al 3 Ni and Al phases were simultaneously dissociated. At these conditions, the strength of MIC reached the highest content and was enhanced by increasing time. At 600 deg. C, the AlNi phase was formed and the mechanical properties of MIC were intensively degraded due to the formation of structural porosities.

  17. Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

    Science.gov (United States)

    Corbin, Joshua R; Schomaker, Jennifer M

    2017-04-13

    Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

  18. On the importance of hydrogen bonding in the promotion of Diels-Alder reactions of unactivated aldehydes: a computational study

    Science.gov (United States)

    Chemouri, Hafida; Mekelleche, Sidi Mohamed

    2014-03-01

    The kinetic solvent effects on the Diels-Alder (DA) reaction of N,N-dimethylamino-3-trimethylsilyl butadiene with p-anisaldehyde are studied by density functional calculations at the B3LYP/6-31C(d) level of theory. Experimentally, it has been found that the acceleration of this reaction is not due to the increase of the polarity of the solvent but it is rather due to hydrogen bonding (HB). Intrinsic reaction coordinate calculations combined with electron localisation function analysis show that this reaction follows a one-step two-stage mechanism with a highly asynchronous sigma bond formation process. The calculations, performed using an explicit solvent model based on the coordination of the carbonyl group with one molecule of the solvent, show a considerable decrease of the activation energy when going from the gas phase (ɛ = 1) to solution phase and this diminution is found to be more important in isopropyl alcohol (ɛ = 18.3) in comparison with acetonitrile (ɛ = 37.5). Our calculations also show that the acceleration of this DA reaction is due to the increase of the electrophilicity power of the solvated carbonyl compound and consequently the increase of the polarity of the reaction in the presence of protic solvents. The obtained results put in evidence the relevance of HB in the promotion of DA reactions of unactivated ketones as experimentally expected.

  19. {alpha}-Man monolayer formation via Si-C bond formation and protein recognition

    Energy Technology Data Exchange (ETDEWEB)

    Funato, Koji [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Shirahata, Naoto [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Miura, Yoshiko, E-mail: miuray@jaist.ac.j [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

    2009-11-30

    An acetylenyl-terminated saccharide was synthesized and the thin layer formation on the hydrogen-terminated silicon was investigated. The acetylenyl-terminated saccharide was synthesized by the condensation reaction of hexynoic acid and p-aminophenyl saccharide. This was reacted with hydrogen-terminated silicon (Si-H) by a photochemical reaction. The resulting saccharide modified substrate was analyzed by ellipsometry and X-ray photoelectron spectroscopy, which showed the formation of a uniform monolayer. The surface's ability to recognize proteins was analyzed by fluorescent microscopy, and showed specific interactions with sugar recognition proteins.

  20. Persistent local chemical bonds in intermetallic phase formation

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Yanwen [Key Laboratory for Liquid–Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Bian, Xiufang, E-mail: xfbian@sdu.edu.cn [Key Laboratory for Liquid–Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Qin, Xubo [Key Laboratory for Liquid–Solid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Zhang, Shuo; Huang, Yuying [Shanghai Synchrotron Radiation Facilities, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204 (China)

    2014-05-01

    We found a direct evidence for the existence of the local chemical Bi–In bonds in the BiIn{sub 2} melt. These bonds are strong and prevail, dominating the structure evolution of the intermetallic clusters. From the local structure of the melt-quenched BiIn{sub 2} ribbon, the chemical Bi–In bonds strengthen compared with those in the equilibrium solidified alloy. The chemical bonds in BiIn{sub 2} melt retain to solid during a rapid quenching process. The results suggest that the intermetallic clusters in the melt evolve into the as-quenched intermetallic phase, and the intermetallic phase originates from the chemical bonds between unlike atoms in the melt. The chemical bonds preserve the chemical ordered clusters and dominate the clusters evolution.

  1. Diels-Alder reactions in water : Enforced hydrophobic interaction and hydrogen bonding

    NARCIS (Netherlands)

    Engberts, Jan B.F.N.

    1995-01-01

    Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

  2. DIELS-ALDER REACTIONS IN WATER - ENFORCED HYDROPHOBIC INTERACTION AND HYDROGEN-BONDING

    NARCIS (Netherlands)

    Engberts, J.B.F.N.

    Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

  3. Cycloaddition Reaction of Hydrogen-Bonded Zn(II)

    Indian Academy of Sciences (India)

    Solid-state Photochemical [2+2] Cycloaddition Reaction of ... and free bpe and lattice water molecules shows face-to-face, π ··· π stacking of two of the four free bpe molecules with coordinated .... were decanted and dried in air. [Yield: 0.068 g ...

  4. Construction of Eight-Membered Carbocycles with Trisubstituted Double Bonds Using the Ring Closing Metathesis Reaction

    Directory of Open Access Journals (Sweden)

    Motoo Tori

    2010-06-01

    Full Text Available Medium sized carbocycles are particularly difficult to synthesize. Ring closing metathesis reactions (RCM have recently been applied to construct eight-membered carbocycles, but trisubstituted double bonds in the eight-membered rings are more difficult to produce using RCM reactions. In this review, model examples and our own results are cited and the importance of the preparation of suitably designed precursors is discussed. Examples of RCM reactions used in the total synthesis of natural products are also outlined.

  5. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  6. Amide Bond Formation Assisted by Vicinal Alkylthio Migration in Enaminones: Metal- and CO-Free Synthesis of α,β-Unsaturated Amides.

    Science.gov (United States)

    Liu, Zhuqing; Huang, Fei; Wu, Ping; Wang, Quannan; Yu, Zhengkun

    2018-05-18

    Amide bond formation is one of the most important transformations in organic synthesis, drug development, and materials science. Efficient construction of amides has been among the most challenging tasks for organic chemists. Herein, we report a concise methodology for amide bond (-CONH-) formation assisted by vicinal group migration in alkylthio-functionalized enaminones (α-oxo ketene N, S-acetals) under mild conditions. Simple treatment of such enaminones with PhI(OAc) 2 at ambient temperature in air afforded diverse multiply functionalized α,β-unsaturated amides including β-cyclopropylated acrylamides, in which a wide array of functional groups such as aryl, (hetero)aryl, alkenyl, and alkyl can be conveniently introduced to a ketene moiety. The reaction mechanism was investigated by exploring the origins of the amide oxygen and carbon atoms as well as isolation and structural characterization of the reaction intermediates. The amide bond formation reactions could also be efficiently performed under solventless mechanical milling conditions.

  7. Importance of mother-infant communication for social bond formation in mammals.

    Science.gov (United States)

    Okabe, Shota; Nagasawa, Miho; Mogi, Kazutaka; Kikusui, Takefumi

    2012-06-01

    Mother-infant bonding is a universal relationship of all mammalian species. Here, we describe the role of reciprocal communication between mother and infant in the formation of bonding for several mammalian species. Mother-infant bond formation is reinforced by various social cues or stimuli, including communicative signals, such as odor and vocalizations, or tactile stimuli. The mother also develops cross-modal sensory recognition of the infant, during bond formation. Many studies have indicated that the oxytocin neural system plays a pivotal role in bond formation by the mother; however, the underlying neural mechanisms for infants have not yet been clarified. The comparative understanding of cognitive functions of mother and infants may help us understand the biological significance of mother-infant communication in mammalian species. © 2012 The Authors. Animal Science Journal © 2012 Japanese Society of Animal Science.

  8. Pressure-assisted reaction bonding between W and Si80Ge20 alloy with Ni as the interlayer

    International Nuclear Information System (INIS)

    Xu, Y.; Laabs, F.C.; Beaudry, B.J.; Gschneidner, K.A. Jr.

    1991-01-01

    The conditions and reaction mechanism of W/Ni/Si 80 Ge 20 hot-press bonding have been studied. It was found that a Ni/Si 80 Ge 20 bond can be formed using low pressure, 19.6 MPa, in the temperature range between 780 and 900 degree C in a short time. The kinetics follows a parabolic pattern, suggesting it is a diffusion-controlled process. The activation energy is 2.7 eV and the parabolic rate constant is given by K P = 4.0 x 10 14 exp(-3.2x10 4 /T) (μm 2 /min). The bonding interface has a multilayered structure. A phenomenological mechanism of the bonding formation has been proposed based on scanning electron microscopy observations and energy dispersive spectroscopy. The cracking problem due to thermal stress is discussed based on Oxx's equation. It was found that bonds free from cracks in the Si 80 Ge 20 alloy are formed when the Ni consumption (as measured by the thickness of the nickel layer) is sufficiently small ( 4 . As an interlayer, nickel can join the tungsten sheet and the Si 80 Ge 20 together. It has been also demonstrated that a thin nickel layer formed by vapor deposition on a tungsten sheet may be used as the interlayer in place of nickel sheet

  9. Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.

    Science.gov (United States)

    Kumatabara, Yusuke; Kaneko, Shiho; Nakata, Satoshi; Shirakawa, Seiji; Maruoka, Keiji

    2016-08-05

    A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

    Science.gov (United States)

    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

    2016-08-19

    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

  11. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.

    2013-12-01

    Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

  12. Interfacial Reaction Characteristics and Mechanical Properties of Welding-brazing Bonding Between AZ31B Magnesium Alloy and PRO500 Ultra-high Strength Steel

    Directory of Open Access Journals (Sweden)

    CHEN Jian-hua

    2017-11-01

    Full Text Available Experiments were carried out with TIG welding-brazing of AZ31B magnesium alloy to PRO500 steel using TIG arc as heat source. The interfacial reaction characteristics and mechanical properties of the welding-brazing bonding were investigated. The results show that an effective bonding is achieved between AZ31B magnesium alloy and PRO500 steel by using TIG welding-brazing method. Some spontaneous oxidation reactions result in the formation of a transition zone containing AlFe3 phase with rich oxide. The micro-hardness value of the interfacial transition zone is between that of the AZ31B and the PRO500. Temper softening zone appears due to the welding thermal cycle nearby the bonding position in the interface. A higher heat input makes an increase of the brittle phases and leads to an obvious decrease of the bonding strength.

  13. Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation.

    Science.gov (United States)

    Wang, Guangtong; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi

    2014-02-18

    A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

  14. Covalently Bonded Chitosan on Graphene Oxide via Redox Reaction

    Directory of Open Access Journals (Sweden)

    Víctor M. Castaño

    2013-03-01

    Full Text Available Carbon nanostructures have played an important role in creating a new field of materials based on carbon. Chemical modification of carbon nanostructures through grafting has been a successful step to improve dispersion and compatibility in solvents, with biomolecules and polymers to form nanocomposites. In this sense carbohydrates such as chitosan are extremely valuable because their functional groups play an important role in diversifying the applications of carbon nanomaterials. This paper reports the covalent attachment of chitosan onto graphene oxide, taking advantage of this carbohydrate at the nanometric level. Grafting is an innovative route to modify properties of graphene, a two-dimensional nanometric arrangement, which is one of the most novel and promising nanostructures. Chitosan grafting was achieved by redox reaction using different temperature conditions that impact on the morphology and features of graphene oxide sheets. Transmission Electron Microscopy, Fourier Transform Infrared, Raman and Energy Dispersive spectroscopies were used to study the surface of chitosan-grafted-graphene oxide. Results show a successful modification indicated by the functional groups found in the grafted material. Dispersions of chitosan-grafted-graphene oxide samples in water and hexane revealed different behavior due to the chemical groups attached to the graphene oxide sheet.

  15. High Charge Mobility of a Perylene Bisimide Dye with Hydrogen-bond Formation Group

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A perylene bisimide dye covalently bonded with a hydrogen-bond formation group of 1,3, 5-triazine-2, 4-diamine has been synthesized. Its casting films show a charge carrier mobility over 10-3 cm2/Vs, which is in the range of the highest values found for other promising charge transport materials suitable for solution processable technique.

  16. The formation reaction of calcium hexa-aluminate

    International Nuclear Information System (INIS)

    Tuganova, S.Kh.; Sirajiddinov, N.A.

    1990-01-01

    The formation reaction of CaAl 12 O 19 at interaction of calcium oxide and aluminium in solid form has been studied. Some physical-chemical characteristics of calcium hexa-aluminate are given. (author)

  17. Adhesives with wood materials : bond formation and performance

    Science.gov (United States)

    Charles R. Frihart; Christopher G. Hunt

    2010-01-01

    Adhesive bonding of wood plays an increasing role in the forest products industry and is a key factor for efficiently utilizing our timber resource. The main use of adhesives is in the manufacture of building materials, including plywood, oriented strandboard, particleboard, fiberboard, structural composite lumber, doors, windows and frames, and factory-laminated wood...

  18. Molecular and ionic hydrogen bond formation in fluorous solvents.

    Science.gov (United States)

    O'Neal, Kristi L; Weber, Stephen G

    2009-01-08

    There are only a few studies of noncovalent association in fluorous solvents and even fewer that are quantitative. A full understanding, particularly of stoichiometry and binding strength of noncovalent interactions in fluorous solvents could be very useful in improved molecular-receptor-based extractions, advancements in sensor technologies, crystal engineering, and supramolecular chemistry. This work investigates hydrogen bonding between heterocyclic bases and a perfluoropolyether with a terminal carboxylic acid group (Krytox 157FSH (1)), chiefly in FC-72 (a mixture of perfluorohexanes). In particular, we were interested in whether or not proton transfer occurs, and if so, under what conditions in H-bonded complexes. Continuous variations experiments show that in FC-72 weaker bases (pyrazine, pyrimidine, and quinazoline) form 1:1 complexes with 1, whereas stronger bases (quinoline, pyridine, and isoquinoline) form 1:3 complexes. Ultraviolet and infrared spectral signatures reveal that the 1:1 complexes are molecular (B.HA) whereas the 1:3 complexes are ionic (BH+.A-HAHA). Infrared spectra of 1:3 ionic complexes are discussed in detail. Literature and experimental data on complexes between N-heterocyclic bases and carboxylic acids in a range of solvents are compiled to compare solvent effects on proton transfer. Polar solvents support ionic hydrogen bonds at a 1:1 mol ratio. In nonpolar organic solvents, ionic hydrogen bonds are only observed in complexes with 1:2 (base/acid) stoichiometries. In fluorous solvents, a larger excess of acid, 1:3, is necessary to facilitate proton transfer in hydrogen bonds between carboxylic acids and the bases studied.

  19. Reaction sintering of a clay-containing silicon nitride bonded silicon carbide refractory

    International Nuclear Information System (INIS)

    Swenser, S.P.; Cheng, Y.B.

    1998-01-01

    Aspects of the reaction sequence for the reaction bonding of a cast refractory, which in the green state was composed of 79 wt-% SiC grit, 16 wt-% Si powder and 5 wt-% clay were established. As it was fired up to 1600 deg C in flowing N 2 (g), weight gains were noted and phase evolution was monitored by X-ray diffraction. However, details of the reaction sequence were not determined directly from this material because several reaction-bonding processes occurred simultaneously. Reaction features were ascertained by contrasting the weight changes and phase evolution in the refractory with those observed during reaction-bonding of (a) Si and clay without the SiC and (b) SiC and clay without the Si. In addition to silicon nitridation and the development of sialon phases by silicothermal and carbothermal reduction-nitridation processes, indirect evidence suggested that α-Si 3 N 4 formed by the carbothermal reduction-nitridation (CRN) of SiO(g). Copyright (1998) Australasian Ceramic Society

  20. Pattern formation in reaction diffusion systems with finite geometry

    International Nuclear Information System (INIS)

    Borzi, C.; Wio, H.

    1990-04-01

    We analyze the one-component, one-dimensional, reaction-diffusion equation through a simple inverse method. We confine the system and fix the boundary conditions as to induce pattern formation. We analyze the stability of those patterns. Our goal is to get information about the reaction term out of the preknowledgment of the pattern. (author). 5 refs

  1. Formation of flavour compounds in the Maillard reaction

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2006-01-01

    This paper discusses the importance of the Maillard reaction for food quality and focuses on flavour compound formation. The most important classes of Maillard flavour compounds are indicated and it is shown where they are formed in the Maillard reaction. Some emphasis is given on the kinetics of

  2. The relationship of microstructure and temperature to fracture mechanics parameters in reaction bonded silicon nitride

    International Nuclear Information System (INIS)

    Jennings, H.M.; Dalgleish, B.J.; Pratt, P.L.

    1978-01-01

    The development of physical properties in reaction bonded silicon nitride has been investigated over a range of temperatures and correlated with microstructure. Fracture mechanics parameters, elastic moduli, strength and critical defect size have been determined. The nitrided microstructure is shown to be directly related to these observed properties and these basic relationships can be used to produce material with improved properties. (orig.) [de

  3. Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

    KAUST Repository

    Chen, Shuli; Chiew, Jun Xuan; Pullarkat, Sumod A.; Li, Yongxin; Leung, Pak Hing

    2013-01-01

    , whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine

  4. Studying Chemical Reactions, One Bond at a Time, with Single Molecule AFM Techniques

    Science.gov (United States)

    Fernandez, Julio M.

    2008-03-01

    The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule

  5. Covalent-Bond Formation via On-Surface Chemistry.

    Science.gov (United States)

    Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

    2017-05-02

    In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

    International Nuclear Information System (INIS)

    Wang, Qiang; Gao, Jun; Zhang, Dongju; Liu, Chengbu

    2015-01-01

    Highlights: • We theoretical studied peptide bond formation reaction mechanism with two water molecules. • The first water molecule can decrease the reaction barriers by forming hydrogen bonds. • The water molecule mediated three-proton transfer mechanism is the favorable mechanism. • Our calculation supports the two-step and eight membered ring mechanism. - Abstract: The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9′ and H15′ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome

  7. A novel approach for a C-11C bond formation: synthesis of 17α-([11C]prop-1-ynyl)-3-methoxy-3,17β-estradiol

    International Nuclear Information System (INIS)

    Wuest, F.; Zessin, J.

    2002-01-01

    A novel method for a 11 C-C bond formation was developed, employing a cross-coupling reaction between a terminal acetylene and [ 11 C]methyl iodide. The method was used for the synthesis of 17α-([ 11 C]prop-1-ynyl)-3-methoxy-3,17β-estadiol. (orig.)

  8. Phase formation at bonded vanadium and stainless steel interfaces

    International Nuclear Information System (INIS)

    Summers, T.S.E.

    1992-01-01

    The interface between vanadium bonded to stainless steel was studies to determine whether a brittle phase formed during three joining operations. Inertia friction welds between V and 21-6-9 stainless steel were examined using TEM. In the as-welded condition, a continuous, polygranular intermetallic layer about 0.25 μm thick was present at the interface. This layer grew to about 50 μm thick during heat treatment at 1000 degrees C for two hours. Analysis of electron diffraction patterns confirmed that this intermetallic was the ω phase. The interface between vanadium and type 304, SANDVIK SAF 2205, and 21-6-9 stainless steel bonded by a co-extrusion process had intermetallic particles at the interface in the as-extruded condition. Heat treatment at 1000 degrees C for two hours caused these particles to grow into continuous layers in all three cases. Based on the appearance, composition and hardness of this interfacial intermetallic, it was also concluded to be ω phase. Bonding V to type 430 stainless steel by co-extrusion caused V-rich carbides to form at the interface due to the higher concentration of C in the type 430 than in the other stainless steels investigated. The carbide particles initially present grew into a continuous layer during a two-hour heat treatment at 1000 degrees C. Co-hipping 21-6-9 stainless steel tubing with V rod resulted in slightly more concentric specimens than the co-extruded ones, but a continuous layer of the ω phase formed during the hipping operation. This brittle layer could initiate failure during subsequent forming operations. The vanadium near the stainless steel interface in the co-extruded and co-hipped tubing in some cases was harder than before heat treatment. It was concluded that this hardening was due to thermal straining during cooling following heat treatment and that thermal strains might present a greater problem than seen here when longer tubes are used in actual applications

  9. Carbon-Carbon and Carbon-Heteroatom Bonds Formation and ...

    Indian Academy of Sciences (India)

    IAS Admin

    NH2. Page 3. 3. Cross-Dehydrogenative Coupling. Directed C-H Activation. Page 4. N. N. Me. N. N. Me. OH. O. Telmisartan. Treatment of high blood pressure. Examples of Biologically Important Benzofuzed Azoles. 4. Page 5. Advantages. • Wide Substrate Scope. • Mild Reaction Conditions. • Atom Economical. Drawbacks.

  10. Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian

    2014-01-01

    The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well-known aqueous...... reaction mechanism. The energy barrier of the catalyzed amidation reaction is approximately 40 kJ mol(-1) lower than the non-catalyzed amidation reaction. At least partially this can be explained by a hydrogen bond from the amine to the π-electrons of the thiophenol, stabilizing the transition state...

  11. Preventing disulfide bond formation weakens non-covalent forces among lysozyme aggregates.

    Directory of Open Access Journals (Sweden)

    Vijay Kumar Ravi

    Full Text Available Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescence anisotropy, atomic force microscopy and single-molecule force spectroscopy to quantify the size, morphology and non-covalent interaction forces among the aggregates, respectively. These measurements were performed under conditions when disulfide bond formation was allowed (control and alternatively when it was prevented by alkylation of free thiols using iodoacetamide. Blocking disulfide bond formation affected growth but not growth kinetics of aggregates which were ∼50% reduced in volume, flatter in vertical dimension and non-fibrillar in comparison to control. Interestingly, single-molecule force spectroscopy data revealed that preventing disulfide bond formation weakened the non-covalent interaction forces among monomers in the aggregate by at least ten fold, thereby stalling their growth and yielding smaller aggregates in comparison to control. We conclude that while constrained protein chain dynamics in correctly disulfide bonded amyloidogenic proteins may protect them from venturing into partial folded conformations that can trigger entry into aggregation pathways, aberrant disulfide bonds in non-amyloidogenic proteins (like HEWL on the other hand, may strengthen non-covalent intermolecular forces among monomers and promote their aggregation.

  12. Effect of hot isostatic pressing on reaction-bonded silicon nitride

    Science.gov (United States)

    Watson, G. K.; Moore, T. J.; Millard, M. L.

    1984-01-01

    Specimens of nearly theoretical density have been obtained through the isostatic hot pressing of reaction-bonded silicon nitride under 138 MPa of pressure for two hours at 1850, 1950, and 2050 C. An amorphous phase that is introduced by the hot isostatic pressing partly accounts for the fact that while room temperature flexural strength more than doubles, the 1200 C flexural strength increases significantly only after pressing at 2050 C.

  13. EXFOR Systems Manual Nuclear reaction Data Exchange Format

    International Nuclear Information System (INIS)

    McLane, V.

    2000-01-01

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format

  14. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    Energy Technology Data Exchange (ETDEWEB)

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  15. Fluctuation-Induced Pattern Formation in a Surface Reaction

    DEFF Research Database (Denmark)

    Starke, Jens; Reichert, Christian; Eiswirth, Markus

    2006-01-01

    Spontaneous nucleation, pulse formation, and propagation failure have been observed experimentally in CO oxidation on Pt(110) at intermediate pressures ($\\approx 10^{-2}$mbar). This phenomenon can be reproduced with a stochastic model which includes temperature effects. Nucleation occurs randomly...... due to fluctuations in the reaction processes, whereas the subsequent damping out essentially follows the deterministic path. Conditions for the occurence of stochastic effects in the pattern formation during CO oxidation on Pt are discussed....

  16. Formation of phosphonates and pyrophosphates in the reactions of ...

    Indian Academy of Sciences (India)

    Bu-4-Me-C6H2O)2P(O)]2O (8) could be isolated, although the reaction mixture showed several other compounds in the phosphorus NMR. A possible pathway for the formation of phosphonate salts is proposed. The X-ray crystal structures of 4, ...

  17. Evolution of the chemical bonding nature and electrode activity of indium selenide upon the composite formation with graphene nanosheets

    International Nuclear Information System (INIS)

    Oh, Seung Mi; Lee, Eunsil; Adpakpang, Kanyaporn; Patil, Sharad B.; Park, Mi Jin; Lim, Young Soo; Lee, Kyu Hyoung; Kim, Jong-Young; Hwang, Seong-Ju

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • In 4 Se 2.85 @graphene nanocomposite is easily prepared by high energy mechanical milling process. • The bond covalency of In 4 Se 2.85 is notably changed upon the composite formation with graphene. • In 4 Se 2.85 @graphene nanocomposite shows promising anode performance for lithium ion battery. -- Abstract: Evolution of the chemical bonding nature and electrochemical activity of indium selenide upon the composite formation with carbon species is systematically investigated. Nanocomposites of In 4 Se 2.85 @graphene and In 4 Se 2.85 @carbon-black are synthesized via a solid state reaction between In and Se elements, and the following high energy mechanical milling of In 4 Se 2.85 with graphene and carbon-black, respectively. The high energy mechanical milling (HEMM) of In 4 Se 2.85 with carbon species gives rise to a decrease of particle size with a significant depression of the crystallinity of In 4 Se 2.85 phase. In contrast to the composite formation with carbon-black, that with graphene induces a notable decrease of (In−Se) bond covalency, underscoring significant chemical interaction between graphene and In 4 Se 2.85 . Both the nanocomposites of In 4 Se 2.85 @graphene and In 4 Se 2.85 @carbon-black show much better anode performance for lithium ion batteries with larger discharge capacity and better cyclability than does the pristine In 4 Se 2.85 material, indicating the beneficial effect of composite formation on the electrochemical activity of indium selenide. Between the present nanocomposites, the electrode performance of the In 4 Se 2.85 @graphene nanocomposite is superior to that of the In 4 Se 2.85 @carbon-black nanocomposite, which is attributable to the weakening of (In−Se) bonds upon the composite formation with graphene as well as to the better mixing between In 4 Se 2.85 and graphene. The present study clearly demonstrates that the composite formation with graphene has strong influence

  18. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

    Science.gov (United States)

    George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

    2016-12-01

    The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

  19. Synthesis of 1,2,4-Triazoles via Oxidative Heterocyclization: Selective C-N Bond Over C-S Bond Formation.

    Science.gov (United States)

    Gogoi, Anupal; Guin, Srimanta; Rajamanickam, Suresh; Rout, Saroj Kumar; Patel, Bhisma K

    2015-09-18

    The higher propensity of C-N over C-S bond forming ability was demonstrated, through formal C-H functionalization during the construction of 4,5-disubstituted 1,2,4-triazole-3-thiones from arylidenearylthiosemicarbazides catalyzed by Cu(II). However, steric factors imparted by the o-disubstituted substrates tend to change the reaction path giving thiodiazole as the major or an exclusive product. Upon prolonging the reaction time, the in situ generated thiones are transformed to 4,5-disubstituted 1,2,4-triazoles via a desulfurization process. Two classes of heterocycles viz. 4,5-disubstituted 1,2,4-triazole-3-thiones and 4,5-disubstituted 1,2,4-triazoles can be synthesized from arylidenearylthiosemicarbazides by simply adjusting the reaction time. Desulfurization of 1,2,4-triazole-3-thiones is assisted by thiophilic Cu to provide 1,2,4-triazoles with concomitant formation of CuS and polynuclear sulfur anions as confirmed from scanning electron microscope and energy dispersive X-ray spectroscopy measurements. A one-pot synthesis of an antimicrobial compound has been successfully achieved following this strategy.

  20. Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

    Science.gov (United States)

    Liu, Chengwei; Szostak, Michal

    2017-05-29

    The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Absolute rate constants for the reaction of hypochlorous acid with protein side chains and peptide bonds

    DEFF Research Database (Denmark)

    Pattison, D I; Davies, Michael Jonathan

    2001-01-01

    , absolute second-order rate constants for the reactions of HOCl with protein side chains, model compounds, and backbone amide (peptide) bonds have been determined at physiological pH values. The reactivity of HOCl with potential reactive sites in proteins is summarized by the series: Met (3.8 x 10(7) M(-1......Hypochlorous acid (HOCl) is a potent oxidant, which is produced in vivo by activated phagocytes. This compound is an important antibacterial agent, but excessive or misplaced production has been implicated in a number of human diseases, including atherosclerosis, arthritis, and some cancers....... Proteins are major targets for this oxidant, and such reaction results in side-chain modification, backbone fragmentation, and cross-linking. Despite a wealth of qualitative data for such reactions, little absolute kinetic data is available to rationalize the in vitro and in vivo data. In this study...

  2. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Science.gov (United States)

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  3. Designing new catalytic C-C and C-N bond formations promoted by organoactinides

    International Nuclear Information System (INIS)

    Eisen, M.S.; Straub, T.; Haskel, A.

    1998-01-01

    Organoactinides of the type Cp 2 * AcMe 2 (Cp * =C 5 Me 5 ; Ac=Th; U) are active catalytic precursors for the oligomerization of terminal alkynes HC≡CR (R=alkyl, aryl, SiMe 3 ). The regioselectivity and the extent of oligomerization depend strongly on the alkyne substituent R, whereas the catalytic reactivity is similar for both organoactinides. Reaction with tert-butylacetylene yields regioselectively the E-2,4-disubstituted 1-buten-3-yne dimer whereas trimethylsilylacetylene is regioselective trimerized to the E,E-1,4,6-tris(trimethylsilyl)-1,3-hexa diene-5-yne, with small amounts (3-5%) of the corresponding E-2,4-disubstituted 1-buten-3-yne dimer. Oligomerization with less bulky alkyl and aryl substituted alkynes produces a mixture of higher oligomers with no regioselectivity. Using the Cp 2 * ThMe 2 catalyst, we have recently developed a strategic method to control the extent and in some cases the regioselectivity of the catalyzed oligomerization of nonbulky terminal alkynes to dimers and/or trimers. The metallocene catalytic precursors ensure the selective synthesis of small oligomers by the addition of specific amines. Catalytic ''tailoring'' to dimer and trimers can be achieved by using small or bulky amines, respectively. Kinetic and mechanistic data for the controlling experiments argue that the turnover-limiting step involves the acetylide actinide complex formation with the rapid insertion of the alkyne and protonolysis by the amine. The analog Cp 2 * UMe 2 in the presence of primary amines induce the selective C-N bond formation, producing enamines which are tautomerized to the corresponding imines. (orig.)

  4. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... in the intrinsic fluorescence. Inter conversion between the two redox states could thus be followed in vitro as well as in vivoby non- invasive fluorimetric measurements. The 1.5 Angstrom crystal structure of the oxidized protein revealed a disulfide bond- induced distortion of the beta -barrel, as well...... the physiological range for redox-active cysteines. In the cytoplasm of Escherichia coli, the protein was a sensitive probe for the redox changes that occur upon disruption of the thioredoxin reductive pathway....

  5. EXFOR systems manual: Nuclear reaction data exchange format

    International Nuclear Information System (INIS)

    McLane, V.

    1996-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. In addition to storing the data and its bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine)

  6. Reaction-assisted diffusion bonding of TiAl alloy to steel

    Energy Technology Data Exchange (ETDEWEB)

    Simões, S., E-mail: ssimoes@fe.up.pt [CEMUC, Department of Metallurgical and Materials Engineering, University of Porto, R. Dr. Roberto Frias, 4200-465 Porto (Portugal); Viana, F. [CEMUC, Department of Metallurgical and Materials Engineering, University of Porto, R. Dr. Roberto Frias, 4200-465 Porto (Portugal); Ramos, A.S.; Vieira, M.T. [CEMUC, Department of Mechanical Engineering, University of Coimbra, R. Luís Reis Santos, 3030-788 Coimbra (Portugal); Vieira, M.F. [CEMUC, Department of Metallurgical and Materials Engineering, University of Porto, R. Dr. Roberto Frias, 4200-465 Porto (Portugal)

    2016-03-01

    The dissimilar joining of TiAl to AISI 310 stainless steel by a reaction-assisted diffusion bonding process, using Ni/Al nanolayers as an interlayer, was investigated in the present work. The Ni and Al alternated nanolayers were deposited by d.c. magnetron sputtering onto the base materials, with a bilayer thickness of 14 nm. Joining experiments were performed at 800 °C for 60 min with compressive stress of 25 and 50 MPa. The effectiveness of the interlayer on the bonding process was assessed by microstructural characterization of the interface and by mechanical tests. Diffusion bonded joints were characterized by scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM) and analyzed by energy dispersive X-ray spectroscopy (EDS) in SEM and TEM and Fast Fourier Transform (FFT). The thickness of the interface region, together with its microstructural and mechanical characteristics, is affected by the use of Ni/Al multilayers; which promote joints with lower hardness values, closer to the values of the base materials, and exhibit higher shear strength. - Highlights: • Dissimilar joining by a reaction-assisted diffusion bonding were studied. • Ni/Al nanolayers allows join TiAl to steel in less demanding processing conditions. • The microstructural and mechanical characterization of the joints were investigated. • The fracture occurring in the TiAl base material attests to the sound joining. • Shear strength value decreases for joints with base materials without nanolayers.

  7. Formation of metal-F bonds during frictional sliding : Influence of water and applied load

    NARCIS (Netherlands)

    Shen, J. T.; Pei, Y. T.; De Hosson, J. Th. M.

    2016-01-01

    Effects of water lubrication and applied load on the formation of PTFE transfer films and metal-F bonds during sliding when PTFE filled composites sliding against steel and Al2O3 are investigated. In water lubricated conditions, XPS analysis reveals that a thin layer of water molecules at the

  8. Ring-opening of cyclic ethers with carbon–carbon bond formation by Grignard reagents

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Holm, Torkil; Madsen, Robert

    2014-01-01

    The ring-opening of cyclic ethers with concomitant C–C bond formation was studied with a number of Grignard reagents. The transformation was performed in a sealed vial by heating to ∼160 °C in an aluminum block or at 180 °C in a microwave oven. Good yields of the product alcohols were obtained...

  9. Religion, Repulsion, and Reaction Formation: Transforming Repellent Attractions and Repulsions.

    Science.gov (United States)

    Cohen, Dov; Kim, Emily; Hudson, Nathan W

    2017-06-12

    Protestants were more likely than non-Protestants to demonstrate phenomena consistent with the use of reaction formation. Lab experiments showed that when manipulations were designed to produce taboo attractions (to unconventional sexual practices), Protestants instead showed greater repulsion. When implicitly conditioned to produce taboo repulsions (to African Americans), Protestants instead showed greater attraction. Supportive evidence from other studies came from clinicians' judgments, defense mechanism inventories, and a survey of respondent attitudes. Other work showed that Protestants who diminished and displaced threatening affect were more likely to sublimate this affect into creative activities; the present work showed that Protestants who do not or cannot diminish or displace such threatening affect instead reverse it. Traditional individual difference variables showed little ability to predict reaction formation, suggesting that the observed processes go beyond what we normally study when we talk about self-control. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  10. Buffering dissociation/formation reaction of biogenic calcium carbonate.

    Science.gov (United States)

    Ichikawa, Kazuhiko

    2007-01-01

    The oscillating stability of coral reef seawater pH has been maintained at around physiological pH values over the past 300 years (Pelejero et al., 2005). The stability mechanism of its pH has been interpreted in terms of the buffering dissolution/formation reaction of CaCO(3) as well as the proton consumption/generation reaction in CaCO(3)-saturated water. Here the pH-dependent solubility product [HCO(3)(-)][Ca(2+)] has been derived on the basis of the actual pH-dependent reactions for the atmospheric CO(2)/CO(2 (aq.))/HCO(3)(-)/CO(3)(2-)/Ca(2+)/CaCO(3) system. Overbasic pH peaks appeared between pH approximately 8 and approximately 9.5 during sodium hydroxide titration, as a result of simultaneous CaCO(3) formation and proton generation. The spontaneous and prompt water pH recovery from the acidic to the physiological range has been confirmed by the observation of acid/base time evolution, because of simultaneous CaCO(3) dissolution and proton consumption. The dissolution/formation of CaCO(3) in water at pH 7.5-9 does not take place without a proton consumption/generation reaction, or a buffering chemical reaction of HCO(3)(-)+Ca(2+)right arrow over left arrowCaCO(3)+H(+). SEM images of the CaCO(3) fragments showed that the acid water ate away at the CaCO(3) formed at physiological pH values. Natural coral reefs can thus recover the physiological pH levels of seawater from the acidic range through partial dissolution of their own skeletons.

  11. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    Energy Technology Data Exchange (ETDEWEB)

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.

    2004-11-27

    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

  12. Chemically activated formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones.

    Science.gov (United States)

    Jalan, Amrit; Allen, Joshua W; Green, William H

    2013-10-21

    Reactions of the Criegee intermediate (CI, ˙CH2OO˙) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between ˙CH2OO˙ and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48-51 kcal mol(-1) lower in energy, formed via 1,3-cycloaddition of ˙CH2OO˙ across the C=O bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O-O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

  13. Effect of strain on bond-specific reaction kinetics during the oxidation of H-terminated (111) Si

    International Nuclear Information System (INIS)

    Gokce, Bilal; Aspnes, David E.; Gundogdu, Kenan

    2011-01-01

    Although strain is used in semiconductor technology for manipulating optical, electronic, and chemical properties of semiconductors, the understanding of the microscopic phenomena that are affected or influenced by strain is still incomplete. Second-harmonic generation data obtained during the air oxidation of H-terminated (111) Si reveal the effect of compressive strain on this chemical reaction. Even small amounts of strain manipulate the reaction kinetics of surface bonds significantly, with tensile strain enhancing oxidation and compressive strain retarding it. This dramatic change suggests a strain-driven charge transfer mechanism between Si-H up bonds and Si-Si back bonds in the outer layer of Si atoms.

  14. A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

    DEFF Research Database (Denmark)

    Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

    2016-01-01

    A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

  15. Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal Propargyl Alcohols.

    Science.gov (United States)

    Lee, Kui Fun; Bai, Wei; Sung, Herman H Y; Williams, Ian D; Lin, Zhenyang; Jia, Guochen

    2018-06-07

    The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm) 3 ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph 2, C(OH)Me 2 , C(OH)HPh, C(OH)H 2 ) produced the vinylidene complexes ReI(=C=CHR)(dppm) 2 with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm) 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Reaction mechanism of the acidic hydrolysis of highly twisted amides: Rate acceleration caused by the twist of the amide bond.

    Science.gov (United States)

    Mujika, Jon I; Formoso, Elena; Mercero, Jose M; Lopez, Xabier

    2006-08-03

    We present an ab initio study of the acid hydrolysis of a highly twisted amide and a planar amide analogue. The aim of these studies is to investigate the effect that the twist of the amide bond has on the reaction barriers and mechanism of acid hydrolysis. Concerted and stepwise mechanisms were investigated using density functional theory and polarizable continuum model calculations. Remarkable differences were observed between the mechanism of twisted and planar amide, due mainly to the preference for N-protonation of the former and O-protonation of the latter. In addition, we were also able to determine that the hydrolytic mechanism of the twisted amide will be pH dependent. Thus, there is a preference for a stepwise mechanism with formation of an intermediate in the acid hydrolysis, whereas the neutral hydrolysis undergoes a concerted-type mechanism. There is a nice agreement between the characterized intermediate and available X-ray data and a good agreement with the kinetically estimated rate acceleration of hydrolysis with respect to analogous undistorted amide compounds. This work, along with previous ab initio calculations, describes a complex and rich chemistry for the hydrolysis of highly twisted amides as a function of pH. The theoretical data provided will allow for a better understanding of the available kinetic data of the rate acceleration of amides upon twisting and the relation of the observed rate acceleration with intrinsic differential reactivity upon loss of amide bond resonance.

  17. Non-statistical effects in bond fission reactions of 1,2-difluoroethane

    Science.gov (United States)

    Schranz, Harold W.; Raff, Lionel M.; Thompson, Donald L.

    1991-08-01

    A microcanonical, classical variational transition-state theory based on the use of the efficient microcanonical sampling (EMS) procedure is applied to simple bond fission in 1,2-difluoroethane. Comparison is made with results of trajectory calculations performed on the same global potential-energy surface. Agreement between the statistical theory and trajectory results for CC CF and CH bond fissions is poor with differences as large as a factor of 125. Most importantly, at the lower energy studied, 6.0 eV, the statistical calculations predict considerably slower rates than those computed from trajectories. We conclude from these results that the statistical assumptions inherent in the transition-state theory method are not valid for 1,2-difluoroethane in spite of the fact that the total intramolecular energy transfer rate out of CH and CC normal and local modes is large relative to the bond fission rates. The IVR rate is not globally rapid and the trajectories do not access all of the energetically available phase space uniformly on the timescale of the reactions.

  18. Fabrication and characterization of reaction bonded silicon carbide/carbon nanotube composites

    International Nuclear Information System (INIS)

    Thostenson, Erik T; Karandikar, Prashant G; Chou, T.-W.

    2005-01-01

    Carbon nanotubes have generated considerable excitement in the scientific and engineering communities because of their exceptional mechanical and physical properties observed at the nanoscale. Carbon nanotubes possess exceptionally high stiffness and strength combined with high electrical and thermal conductivities. These novel material properties have stimulated considerable research in the development of nanotube-reinforced composites (Thostenson et al 2001 Compos. Sci. Technol. 61 1899, Thostenson et al 2005 Compos. Sci. Technol. 65 491). In this research, novel reaction bonded silicon carbide nanocomposites were fabricated using melt infiltration of silicon. A series of multi-walled carbon nanotube-reinforced ceramic matrix composites (NT-CMCs) were fabricated and the structure and properties were characterized. Here we show that carbon nanotubes are present in the as-fabricated NT-CMCs after reaction bonding at temperatures above 1400 deg. C. Characterization results reveal that a very small volume content of carbon nanotubes, as low as 0.3 volume %, results in a 75% reduction in electrical resistivity of the ceramic composites. A 96% decrease in electrical resistivity was observed for the ceramics with the highest nanotube volume fraction of 2.1%

  19. Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly

    Science.gov (United States)

    Lundberg, Dan; Stjerndahl, Maria

    2011-01-01

    The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

  20. Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

    Science.gov (United States)

    Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

    2018-06-29

    The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

    Science.gov (United States)

    Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

    2014-07-01

    Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

  2. DNA degradation by bleomycin: evidence for 2'R-proton abstraction and for C-O bond cleavage accompanying base propenal formation

    International Nuclear Information System (INIS)

    Ajmera, S.; Wu, J.C.; Worth, L. Jr.; Rabow, L.E.; Stubbe, J.; Kozarich, J.W.

    1986-01-01

    Reaction of poly(dA-[2'S- 3 H]dU) with activated bleomycin yields [ 3 H] uracil propenal that completely retains the tritium label. In contrast, the authors have previously shown that reaction of poly(dA-[2'R- 3 H]dU) with activated bleomycin affords unlabeled uracil propenal. They have also prepared both cis- and trans-thymine propenals by chemical synthesis and have observed that the trans isomer is the exclusive product of the bleomycin reaction. Moreover, the cis isomer was found to be stable to the conditions of bleomycin-induced DNA degradation. Taken together, these results establish that the formation of trans-uracil propenal occurs via an anti-elimination mechanism with the stereospecific abstraction of the 2R proton. The question of phosphodiester bond cleavage during base propenal formation has also been addressed by the analysis of the fate of oxygen-18 in poly(dA-[3'- 18 O]dT) upon reaction with activated bleomycin. The 5'-monophosphate oligonucleotide ends produced from thymine propenal formation have been converted to inorganic phosphate by the action of alkaline phosphatase, and the phosphate has been analyzed for 18 O content by 31 P NMR spectroscopy. The oxygen-18 is retained in the inorganic phosphate, establishing that the formation of thymine propenal by activated bleomycin proceeds with C-O bond cleavage at the 3-position

  3. Thiolated polymers: evidence for the formation of disulphide bonds with mucus glycoproteins.

    Science.gov (United States)

    Leitner, Verena M; Walker, Greg F; Bernkop-Schnürch, Andreas

    2003-09-01

    Disulphide bonds between thiolated polymers (thiomers) and cysteine-rich subdomains of mucus glycoproteins are supposed to be responsible for the enhanced mucoadhesive properties of thiomers. This study set out to provide evidence for these covalent interactions using poly(acrylic acid)-cysteine conjugates of 2 and 450 kDa (PAA2-Cys, PAA450-Cys) displaying 402.5-776.0 micromol thiol groups per gram polymer. The effect of the disulphide bond breaker cysteine on thiomer-mucin disulphide bonds was monitored by (1) mucoadhesion studies and (2) rheological studies. Furthermore, (3) diffusion studies and (4) gel filtration studies were performed with thiomer-mucus mixtures. The addition of cysteine significantly (Ppolymer. Gel filtration studies showed that PAA2-Cys was able to form disulphide bonds with mucin glycoproteins resulting in an altered elution profile of the mucin/PAA2-Cys mixture in comparison to mucin alone or mucin/PAA2 mixture. According to these results, the study provides evidence for the formation of covalent bonds between thiomer and mucus glycoproteins.

  4. Corrosion Study and Intermetallics Formation in Gold and Copper Wire Bonding in Microelectronics Packaging

    Directory of Open Access Journals (Sweden)

    Christopher Breach

    2013-07-01

    Full Text Available A comparison study on the reliability of gold (Au and copper (Cu wire bonding is conducted to determine their corrosion and oxidation behavior in different environmental conditions. The corrosion and oxidation behaviors of Au and Cu wire bonding are determined through soaking in sodium chloride (NaCl solution and high temperature storage (HTS at 175 °C, 200 °C and 225 °C. Galvanic corrosion is more intense in Cu wire bonding as compared to Au wire bonding in NaCl solution due to the minimal formation of intermetallics in the former. At all three HTS annealing temperatures, the rate of Cu-Al intermetallic formation is found to be three to five times slower than Au-Al intermetallics. The faster intermetallic growth rate and lower activation energy found in this work for both Au/Al and Cu/Al as compared to literature could be due to the thicker Al pad metallization which removed the rate-determining step in previous studies due to deficit in Al material.

  5. Fragment formation in light-ion induced reactions

    International Nuclear Information System (INIS)

    Hirata, Yuichi

    2001-01-01

    The intermediate mass fragment (IMF) formation in the 12 GeV proton induced reaction on Au target is analyzed by the quantum molecular dynamics model combined with the JAM hadronic cascade model and the non-equilibrated percolation model. We show that the sideward peaked angular distribution of IMF occur in the multifragmentation at very short time scale around 20 fm/c where non-equilibrated features of the residual nucleus fluctuates the nucleon density and fragments in the repulsive Coulomb force are pushed for the sideward direction. (author)

  6. Influence of phase transition on pattern formation during catalytic reactions

    OpenAIRE

    Andrade, Roberto Fernandes Silva; Lima, D.; Cunha, F. B.

    2000-01-01

    p.434–445 We investigate the influence of the order of surface phase transitions on pattern formation during chemical reaction on mono-crystal catalysts. We use a model consisting of two partial differential equations, one of which describes the dynamics of the surface state with the help of a Ginzburg–Landau potential. Second- or first-order transitions are described by decreasing or increasing the relative value of the third-order coefficient of the potential. We concentrate on the stabi...

  7. Pattern formation in three-dimensional reaction-diffusion systems

    Science.gov (United States)

    Callahan, T. K.; Knobloch, E.

    1999-08-01

    Existing group theoretic analysis of pattern formation in three dimensions [T.K. Callahan, E. Knobloch, Symmetry-breaking bifurcations on cubic lattices, Nonlinearity 10 (1997) 1179-1216] is used to make specific predictions about the formation of three-dimensional patterns in two models of the Turing instability, the Brusselator model and the Lengyel-Epstein model. Spatially periodic patterns having the periodicity of the simple cubic (SC), face-centered cubic (FCC) or body-centered cubic (BCC) lattices are considered. An efficient center manifold reduction is described and used to identify parameter regimes permitting stable lamellæ, SC, FCC, double-diamond, hexagonal prism, BCC and BCCI states. Both models possess a special wavenumber k* at which the normal form coefficients take on fixed model-independent ratios and both are described by identical bifurcation diagrams. This property is generic for two-species chemical reaction-diffusion models with a single activator and inhibitor.

  8. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

    Science.gov (United States)

    Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

    2017-09-19

    As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

  9. Formation and hydrolysis of amide bonds by lipase A from Candida antarctica; exceptional features.

    Science.gov (United States)

    Liljeblad, Arto; Kallio, Pauli; Vainio, Marita; Niemi, Jarmo; Kanerva, Liisa T

    2010-02-21

    Various commercial lyophilized and immobilized preparations of lipase A from Candida antarctica (CAL-A) were studied for their ability to catalyze the hydrolysis of amide bonds in N-acylated alpha-amino acids, 3-butanamidobutanoic acid (beta-amino acid) and its ethyl ester. The activity toward amide bonds is highly untypical of lipases, despite the close mechanistic analogy to amidases which normally catalyze the corresponding reactions. Most CAL-A preparations cleaved amide bonds of various substrates with high enantioselectivity, although high variations in substrate selectivity and catalytic rates were detected. The possible role of contaminant protein species on the hydrolytic activity toward these bonds was studied by fractionation and analysis of the commercial lyophilized preparation of CAL-A (Cat#ICR-112, Codexis). In addition to minor impurities, two equally abundant proteins were detected, migrating on SDS-PAGE a few kDa apart around the calculated size of CAL-A. Based on peptide fragment analysis and sequence comparison both bands shared substantial sequence coverage with CAL-A. However, peptides at the C-terminal end constituting a motile domain described as an active-site flap were not identified in the smaller fragment. Separated gel filtration fractions of the two forms of CAL-A both catalyzed the amide bond hydrolysis of ethyl 3-butanamidobutanoate as well as the N-acylation of methyl pipecolinate. Hydrolytic activity towards N-acetylmethionine was, however, solely confined to the fractions containing the truncated form of CAL-A. These fractions were also found to contain a trace enzyme impurity identified in sequence analysis as a serine carboxypeptidase. The possible role of catalytic impurities versus the function of CAL-A in amide bond hydrolysis is further discussed in the paper.

  10. Origins of the Mechanochemical Coupling of Peptide Bond Formation to Protein Synthesis.

    Science.gov (United States)

    Fritch, Benjamin; Kosolapov, Andrey; Hudson, Phillip; Nissley, Daniel A; Woodcock, H Lee; Deutsch, Carol; O'Brien, Edward P

    2018-04-18

    Mechanical forces acting on the ribosome can alter the speed of protein synthesis, indicating that mechanochemistry can contribute to translation control of gene expression. The naturally occurring sources of these mechanical forces, the mechanism by which they are transmitted 10 nm to the ribosome's catalytic core, and how they influence peptide bond formation rates are largely unknown. Here, we identify a new source of mechanical force acting on the ribosome by using in situ experimental measurements of changes in nascent-chain extension in the exit tunnel in conjunction with all-atom and coarse-grained computer simulations. We demonstrate that when the number of residues composing a nascent chain increases, its unstructured segments outside the ribosome exit tunnel generate piconewtons of force that are fully transmitted to the ribosome's P-site. The route of force transmission is shown to be through the nascent polypetide's backbone, not through the wall of the ribosome's exit tunnel. Utilizing quantum mechanical calculations we find that a consequence of such a pulling force is to decrease the transition state free energy barrier to peptide bond formation, indicating that the elongation of a nascent chain can accelerate translation. Since nascent protein segments can start out as largely unfolded structural ensembles, these results suggest a pulling force is present during protein synthesis that can modulate translation speed. The mechanism of force transmission we have identified and its consequences for peptide bond formation should be relevant regardless of the source of the pulling force.

  11. Rethinking pattern formation in reaction-diffusion systems

    Science.gov (United States)

    Halatek, J.; Frey, E.

    2018-05-01

    The present theoretical framework for the analysis of pattern formation in complex systems is mostly limited to the vicinity of fixed (global) equilibria. Here we present a new theoretical approach to characterize dynamical states arbitrarily far from (global) equilibrium. We show that reaction-diffusion systems that are driven by locally mass-conserving interactions can be understood in terms of local equilibria of diffusively coupled compartments. Diffusive coupling generically induces lateral redistribution of the globally conserved quantities, and the variable local amounts of these quantities determine the local equilibria in each compartment. We find that, even far from global equilibrium, the system is well characterized by its moving local equilibria. We apply this framework to in vitro Min protein pattern formation, a paradigmatic model for biological pattern formation. Within our framework we can predict and explain transitions between chemical turbulence and order arbitrarily far from global equilibrium. Our results reveal conceptually new principles of self-organized pattern formation that may well govern diverse dynamical systems.

  12. Size effects in tin-based lead-free solder joints: Kinetics of bond formation and mechanical characteristics

    Science.gov (United States)

    Abdelhadi, Ousama Mohamed Omer

    Continuous miniaturization of microelectronic interconnects demands smaller joints with comparable microstructural and structural sizes. As the size of joints become smaller, the volume of intermetallics (IMCs) becomes comparable with the joint size. As a result, the kinetics of bond formation changes and the types and thicknesses of IMC phases that form within the constrained region of the bond varies. This dissertation focuses on investigating combination effects of process parameters and size on kinetics of bond formation, resulting microstructure and the mechanical properties of joints that are formed under structurally constrained conditions. An experiment is designed where several process parameters such as time of bonding, temperature, and pressure, and bond thickness as structural chracteristic, are varied at multiple levels. The experiment is then implemented on the process. Scanning electron microscope (SEM) is then utilized to determine the bond thickness, IMC phases and their thicknesses, and morphology of the bonds. Electron backscatter diffraction (EBSD) is used to determine the grain size in different regions, including the bulk solder, and different IMC phases. Physics-based analytical models have been developed for growth kinetics of IMC compounds and are verified using the experimental results. Nanoindentation is used to determine the mechanical behavior of IMC phases in joints in different scales. Four-point bending notched multilayer specimen and four-point bending technique were used to determine fracture toughness of the bonds containing IMCs. Analytical modeling of peeling and shear stresses and fracture toughness in tri-layer four-point bend specimen containing intermetallic layer was developed and was verified and validated using finite element simulation and experimental results. The experiment is used in conjunction with the model to calculate and verify the fracture toughness of Cu6Sn5 IMC materials. As expected two different IMC phases

  13. Peptide bond formation of alanine on silica and alumina surfaces as a catalyst

    Science.gov (United States)

    Sánchez Arenillas, M.; Mateo-Martí, E.

    2012-09-01

    Polymerization of amino acids has been important for the origin of life because the peptides may have been the first self-replicating systems. The amino acid concentrations in the oceans may have been too diluted in the early phases of the Earth. The formation of the biopolymers could have been due to the catalytic action of various minerals (such as silica or alumina). Our work is based on the comparison between alumina and silica minerals with and without prior activation of their silanol groups for the formation of peptide bonds using alanina like amino acid which it is the simplest quiral amino acid.

  14. Microwave-assisted Ullmann C-S bond formation: synthesis of the P38alpha MAPK clinical candidate VX-745.

    Science.gov (United States)

    Bagley, Mark C; Davis, Terence; Dix, Matthew C; Fusillo, Vincenzo; Pigeaux, Morgane; Rokicki, Michal J; Kipling, David

    2009-11-06

    Microwave irradiation promotes the rapid and efficient reaction of a thiophenol and aryl or heteroaryl halide using a copper or palladium catalyst and a range of ligands, depending upon substrate. Of particular utility is the use of copper(I) iodide (5 mol %) and trans-cyclohexane-1,2-diol as ligand under basic conditions and microwave irradiation to give the corresponding sulfide in high yield. This method for C-S bond formation is applied in the four-step synthesis of the clinical candidate VX-745 in 38% overall yield. The inhibitory activity of VX-745 against p38alpha MAPK is confirmed in Werner syndrome dermal fibroblasts at 1.0 microM concentration by immunoblot assay.

  15. Characteristics of chemical bond and vacancy formation in chalcopyrite-type CuInSe2 and related compounds

    International Nuclear Information System (INIS)

    Maeda, Tsuyoshi; Wada, Takahiro

    2009-01-01

    We studied characteristics of chemical bond and vacancy formation in chalcopyrite-type CuInSe 2 (CIS) by first principles calculations. The chalcopyrite-type CIS has two kinds of chemical bonds, Cu-Se and In-Se. The Cu-Se bond is a weak covalent bonding because electrons occupy both bonding and antibonding orbitals of Cu 3d and Se 4p and occupy only the bonding orbital (a 1 ) of Cu 4s and Se 4p and do not occupy the antibonding orbital (a 1 * ) of Cu 4s and Se 4p. On the other hand, the In-Se bond has a partially covalent and partially ionic character because the In 5s orbital covalently interacts with Se 4p; the In 5p orbital is higher than Se 4p and so the electron in the In 5p orbital moves to the Se 4p orbital. The average bond order of the Cu-Se and In-Se bonds can be calculated to be 1/4 and 1, respectively. The bond order of Cu-Se is smaller than that of In-Se. The characteristics of these two chemical bonds are related to the formation of Cu and In vacancies in CIS. The formation energy of the Cu vacancy is smaller than that of the In vacancy under both Cu-poor and In-poor conditions. The displacement (Δl) of the surrounding Se atoms after the formation of the Cu vacancy is smaller than the Δl after the formation of the In vacancy. The interesting and unique characteristics of CIS are discussed on the basis of the characteristics of the chemical bond. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. Formation of Me–O–Si covalent bonds at the interface between polysilazane and stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Amouzou, Dodji, E-mail: adodji@gmail.com [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium); Fourdrinier, Lionel; Maseri, Fabrizio [CRM-Group, Boulevard de Colonster, B 57, 4000 Liège (Belgium); Sporken, Robert [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, 5000 Namur (Belgium)

    2014-11-30

    Highlights: • Natural metal-oxides, hydroxides are detected on the top surface of steel substrates we tested. • Polysilazane reacts with hydroxide functional groups on steel substrates to form Cr–O–Si and Fe–O–Si covalent bonds. • Covalent bonding between steel and polysilazane at the interface was probed using spectroscopic techniques. - Abstract: In earlier works, we demonstrated the potential of polysilazane (PSZ) coatings for a use as insulating layers in Cu(In,Ga)Se{sub 2} (CIGS) solar cells prepared on steels substrates and showed a good adhesion between PSZ coatings and both AISI316 and AISI430 steels. In the present paper, spectroscopic techniques are used to elucidate the reason of such adhesion. X-ray Photoelectron Spectroscopy (XPS) was used to investigate surfaces for the two steel substrates and showed the presence of metal oxides and metal hydroxides at the top surface. XPS has been also used to probe interfaces between substrates and PSZ, and metallosiloxane (Me–O–Si) covalent bonds have been detected. These results were confirmed by Infra-Red Reflection Absorption Spectroscopy (IRRAS) analyses since vibrations related to Cr–O–Si and Fe–O–Si compounds were detected. Thus, the good adhesion between steel substrates and PSZ coatings was explained by covalent bonding through chemical reactions between PSZ precursors and hydroxide functional groups present on top surface of the two types of steel. Based on these results, an adhesion mechanism between steel substrates and PSZ coatings is proposed.

  17. Formation of the market of high-bond (junk bonds in the United States in 1970–1980 years

    Directory of Open Access Journals (Sweden)

    Moshenskyi S.Z.

    2017-03-01

    Full Text Available Market of high-yield bonds (also known as «junk bonds» began to emerge in the US in the mid-1970s and was associated with the activities of «junk bond king» Michael Milken from Drexel investment company. Junk bonds emitents are small and newly established companies which cannot get a high credit rating. Emission of high-yield (8–10 % bond was their only chance to find its place in the financial market. Michael Milken realized the potential of these bonds, which, in fact, were often quite reliable securities, and started organizing their emissions by selling junk bonds to Savings and Loan Associations and other investors. In the 1980 issue of such bonds used for aggressive corporate takeovers, which supplied the capital from junk bonds market. Some of takeovers carried out in violation of laws that led to the arrest of Michael Milken, Drexel bankruptcy and the collapse of the entire junk bonds market.

  18. Experimental investigation on material migration phenomena in micro-EDM of reaction-bonded silicon carbide

    Energy Technology Data Exchange (ETDEWEB)

    Liew, Pay Jun [Department of Mechanical Systems and Design, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku, Sendai, 980-8579 (Japan); Manufacturing Process Department, Faculty of Manufacturing Engineering, Universiti Teknikal Malaysia Melaka, Hang Tuah Jaya, 76100, Durian Tunggal, Melaka (Malaysia); Yan, Jiwang, E-mail: yan@mech.keio.ac.jp [Department of Mechanical Engineering, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama, 223-8522 (Japan); Kuriyagawa, Tsunemoto [Department of Mechanical Systems and Design, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku, Sendai, 980-8579 (Japan)

    2013-07-01

    Material migration between tool electrode and workpiece material in micro electrical discharge machining of reaction-bonded silicon carbide was experimentally investigated. The microstructural changes of workpiece and tungsten tool electrode were examined using scanning electron microscopy, cross sectional transmission electron microscopy and energy dispersive X-ray under various voltage, capacitance and carbon nanofibre concentration in the dielectric fluid. Results show that tungsten is deposited intensively inside the discharge-induced craters on the RB-SiC surface as amorphous structure forming micro particles, and on flat surface region as a thin interdiffusion layer of poly-crystalline structure. Deposition of carbon element on tool electrode was detected, indicating possible material migration to the tool electrode from workpiece material, carbon nanofibres and dielectric oil. Material deposition rate was found to be strongly affected by workpiece surface roughness, voltage and capacitance of the electrical discharge circuit. Carbon nanofibre addition in the dielectric at a suitable concentration significantly reduced the material deposition rate.

  19. Experimental investigation on material migration phenomena in micro-EDM of reaction-bonded silicon carbide

    International Nuclear Information System (INIS)

    Liew, Pay Jun; Yan, Jiwang; Kuriyagawa, Tsunemoto

    2013-01-01

    Material migration between tool electrode and workpiece material in micro electrical discharge machining of reaction-bonded silicon carbide was experimentally investigated. The microstructural changes of workpiece and tungsten tool electrode were examined using scanning electron microscopy, cross sectional transmission electron microscopy and energy dispersive X-ray under various voltage, capacitance and carbon nanofibre concentration in the dielectric fluid. Results show that tungsten is deposited intensively inside the discharge-induced craters on the RB-SiC surface as amorphous structure forming micro particles, and on flat surface region as a thin interdiffusion layer of poly-crystalline structure. Deposition of carbon element on tool electrode was detected, indicating possible material migration to the tool electrode from workpiece material, carbon nanofibres and dielectric oil. Material deposition rate was found to be strongly affected by workpiece surface roughness, voltage and capacitance of the electrical discharge circuit. Carbon nanofibre addition in the dielectric at a suitable concentration significantly reduced the material deposition rate.

  20. Surface/subsurface observation and removal mechanisms of ground reaction bonded silicon carbide

    Science.gov (United States)

    Yao, Wang; Zhang, Yu-Min; Han, Jie-cai; Zhang, Yun-long; Zhang, Jian-han; Zhou, Yu-feng; Han, Yuan-yuan

    2006-01-01

    Reaction Bonded Silicon Carbide (RBSiC) has long been recognized as a promising material for optical applications because of its unique combination of favorable properties and low-cost fabrication. Grinding of silicon carbide is difficult because of its high hardness and brittleness. Grinding often induces surface and subsurface damage, residual stress and other types of damage, which have great influence on the ceramic components for optical application. In this paper, surface integrity, subsurface damage and material removal mechanisms of RBSiC ground using diamond grinding wheel on creep-feed surface grinding machine are investigated. The surface and subsurface are studied with scanning electron microscopy (SEM) and optical microscopy. The effects of grinding conditions on surface and subsurface damage are discussed. This research links the surface roughness, surface and subsurface cracks to grinding parameters and provides valuable insights into the material removal mechanism and the dependence of grind induced damage on grinding conditions.

  1. Effect of loading rate on dynamic fracture of reaction bonded silicon nitride

    Science.gov (United States)

    Liaw, B. M.; Kobayashi, A. S.; Emery, A. F.

    1986-01-01

    Wedge-loaded, modified tapered double cantilever beam (WL-MTDCB) specimens under impact loading were used to determine the room temperature dynamic fracture response of reaction bonded silicon nitride (RBSN). The crack extension history, with the exception of the terminal phase, was similar to that obtained under static loading. Like its static counterpart, a distinct crack acceleration phase, which was not observed in dynamic fracture of steel and brittle polymers, was noted. Unlike its static counterpart, the crack continued to propagate at nearly its terminal velocity under a low dynamic stress intensity factor during the terminal phase of crack propagation. These and previously obtained results for glass and RBSN show that dynamic crack arrest under a positive dynamic stress intensity factor is unlikely in static and impact loaded structural ceramics.

  2. Nano-motion dynamics are determined by surface-tethered selectin mechanokinetics and bond formation.

    Directory of Open Access Journals (Sweden)

    Brian J Schmidt

    2009-12-01

    Full Text Available The interaction of proteins at cellular interfaces is critical for many biological processes, from intercellular signaling to cell adhesion. For example, the selectin family of adhesion receptors plays a critical role in trafficking during inflammation and immunosurveillance. Quantitative measurements of binding rates between surface-constrained proteins elicit insight into how molecular structural details and post-translational modifications contribute to function. However, nano-scale transport effects can obfuscate measurements in experimental assays. We constructed a biophysical simulation of the motion of a rigid microsphere coated with biomolecular adhesion receptors in shearing flow undergoing thermal motion. The simulation enabled in silico investigation of the effects of kinetic force dependence, molecular deformation, grouping adhesion receptors into clusters, surface-constrained bond formation, and nano-scale vertical transport on outputs that directly map to observable motions. Simulations recreated the jerky, discrete stop-and-go motions observed in P-selectin/PSGL-1 microbead assays with physiologic ligand densities. Motion statistics tied detailed simulated motion data to experimentally reported quantities. New deductions about biomolecular function for P-selectin/PSGL-1 interactions were made. Distributing adhesive forces among P-selectin/PSGL-1 molecules closely grouped in clusters was necessary to achieve bond lifetimes observed in microbead assays. Initial, capturing bond formation effectively occurred across the entire molecular contour length. However, subsequent rebinding events were enhanced by the reduced separation distance following the initial capture. The result demonstrates that vertical transport can contribute to an enhancement in the apparent bond formation rate. A detailed analysis of in silico motions prompted the proposition of wobble autocorrelation as an indicator of two-dimensional function. Insight into two

  3. Theoretical Study on the Aza-Diels-Alder Reaction Catalyzed by PHCl2 Lewis Acid via Pnicogen Bonding.

    Science.gov (United States)

    Yaghoobi, Fereshteh; Sohrabi Mahboub, Mahdi

    2018-03-15

    The reaction mechanism of the Aza-Diels-Alder (A-D-A) cycloaddition reaction between X 2 C═NNH 2 , where X = H, F, Cl, Br, and 1,3-butadiene catalyzed by a PHCl 2 Lewis acid was characterized using density functional theory calculations. The influences of various substituents of X on the studied reaction were analyzed using the activation strain model (ASM), which is also termed as the distortion-interaction model. Calculations showed that the smallest and largest values of the activation energies belong to the substituents of F and Br, respectively. The activation energy of the studied reactions was decreased within 8.6 kcal·mol -1 in the presence of PHCl 2 catalyst. Investigations showed that the pnicogen bonding is adequately capable of activating the A-D-A reaction. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis were implemented to understand the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bonds at the TS structures. Additionally, the energy decomposition analysis (EDA) based on the ETS-NOCV scheme was used to characterize the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bond. The results of the study mirror the fact that the PHCl 2 Lewis acid may be suggested as a simple suitable catalyst for experimental studies on the A-D-A reactions.

  4. Mechanism of chimera formation during the Multiple Displacement Amplification reaction

    Directory of Open Access Journals (Sweden)

    Stockwell Timothy B

    2007-04-01

    Full Text Available Abstract Background Multiple Displacement Amplification (MDA is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Results Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2–21 nucleotides (nts in the new templates. Conclusion Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications.

  5. Variational RRKM calculation of thermal rate constant for C–H bond fission reaction of nitro methane

    Directory of Open Access Journals (Sweden)

    Afshin Taghva Manesh

    2017-02-01

    Full Text Available The present work provides quantitative results for the rate constants of unimolecular C–H bond fission reactions in the nitro methane at elevated temperatures up to 2000 K. In fact, there are three different hydrogen atoms in the nitro methane. The potential energy surface for each C–H bond fission reaction of nitro methane was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C–H bond fission channel is a barrierless reaction, we have used variational RRKM theory to predict rate coefficients. By means of calculated rate coefficients at different temperatures, the Arrhenius expression of the channel over the temperature range of 100–2000 K is k(T = 5.9E19∗exp(−56274.6/T.

  6. Ester-Mediated Amide Bond Formation Driven by Wet-Dry Cycles: A Possible Path to Polypeptides on the Prebiotic Earth.

    Science.gov (United States)

    Forsythe, Jay G; Yu, Sheng-Sheng; Mamajanov, Irena; Grover, Martha A; Krishnamurthy, Ramanarayanan; Fernández, Facundo M; Hud, Nicholas V

    2015-08-17

    Although it is generally accepted that amino acids were present on the prebiotic Earth, the mechanism by which α-amino acids were condensed into polypeptides before the emergence of enzymes remains unsolved. Here, we demonstrate a prebiotically plausible mechanism for peptide (amide) bond formation that is enabled by α-hydroxy acids, which were likely present along with amino acids on the early Earth. Together, α-hydroxy acids and α-amino acids form depsipeptides-oligomers with a combination of ester and amide linkages-in model prebiotic reactions that are driven by wet-cool/dry-hot cycles. Through a combination of ester-amide bond exchange and ester bond hydrolysis, depsipeptides are enriched with amino acids over time. These results support a long-standing hypothesis that peptides might have arisen from ester-based precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Effect of Reaction Temperature on Structure, Appearance and Bonding Type of Functionalized Graphene Oxide Modified P-Phenylene Diamine

    Directory of Open Access Journals (Sweden)

    Hong-Juan Sun

    2018-04-01

    Full Text Available In this study, graphene oxides with different functionalization degrees were prepared by a facile one-step hydrothermal reflux method at various reaction temperatures using graphene oxide (GO as starting material and p-phenylenediamine (PPD as the modifier. The effects of reaction temperature on structure, appearance and bonding type of the obtained materials were investigated by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, and scanning electron microscopy (SEM. The results showed that when the reaction temperature was 10–70 °C, the GO reacted with PPD through non-covalent ionic bonds (–COO−H3+N–R and hydrogen bonds (C–OH…H2N–X. When the reaction temperature reached 90 °C, the GO was functionalized with PPD through covalent bonds of C–N. The crystal structure of products became more ordered and regular, and the interlayer spacing (d value and surface roughness increased as the temperature increased. Furthermore, the results suggested that PPD was grafted on the surface of GO through covalent bonding by first attacking the carboxyl groups and then the epoxy groups of GO.

  8. Photosynthetic water oxidation: binding and activation of substrate waters for O-O bond formation.

    Science.gov (United States)

    Vinyard, David J; Khan, Sahr; Brudvig, Gary W

    2015-01-01

    Photosynthetic water oxidation occurs at the oxygen-evolving complex (OEC) of Photosystem II (PSII). The OEC, which contains a Mn4CaO5 inorganic cluster ligated by oxides, waters and amino-acid residues, cycles through five redox intermediates known as S(i) states (i = 0-4). The electronic and structural properties of the transient S4 intermediate that forms the O-O bond are not well understood. In order to gain insight into how water is activated for O-O bond formation in the S4 intermediate, we have performed a detailed analysis of S-state dependent substrate water binding kinetics taking into consideration data from Mn coordination complexes. This analysis supports a model in which the substrate waters are both bound as terminal ligands and react via a water-nucleophile attack mechanism.

  9. Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study.

    Science.gov (United States)

    Rocchigiani, Luca; Fernandez-Cestau, Julio; Budzelaar, Peter H M; Bochmann, Manfred

    2018-06-21

    The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied by using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, by using the pincer compounds [(C^N^C)AuR] (R=C 6 F 5 , CH=CMe 2 , Me and p-C 6 H 4 X, where X=OMe, F, H, tBu, Cl, CF 3 , or NO 2 ) as starting materials (C^N^C=2,6-(4'-tBuC 6 H 3 ) 2 pyridine dianion). Protodeauration followed by addition of one equivalent SMe 2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe 2 )] + . Upon addition of a second SMe 2 pyridine is displaced, which triggers the reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl)>k(aryl)≫k(C 6 F 5 )>k(Me). Vinyl-aryl coupling is particularly fast, 1.15×10 -3  L mol -1  s -1 at 221 K, whereas both C 6 F 5 and Me couplings encountered higher barriers for the C-C bond forming step. The use of P(p-tol) 3 in place of SMe 2 greatly accelerates the C-C couplings. Computational modelling shows that in the C^N-bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. The C-C bond formation is the rate-limiting step. In the non-chelating case, reductive C(sp 2 )-C(sp 2 ) elimination from three-coordinate ions [(Ar 1 )(Ar 2 )AuL] + is almost barrier-free, particularly if L=phosphine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Extremely efficient catalysis of carbon-carbon bond formation using "click" dendrimer-stabilized palladium nanoparticles.

    Science.gov (United States)

    Astruc, Didier; Ornelas, Cátia; Diallo, Abdou K; Ruiz, Jaime

    2010-07-20

    This article is an account of the work carried out in the authors' laboratory illustrating the usefulness of dendrimer design for nanoparticle palladium catalysis. The "click" synthesis of dendrimers constructed generation by generation by 1-->3 C connectivity, introduces 1,2,3-triazolyl ligands insides the dendrimers at each generation. Complexation of the ligands by Pd(II) followed by reduction to Pd(0) forms dendrimer-stabilized Pd nanoparticles (PdNPs) that are extremely reactive in the catalysis of olefin hydrogenation and C-C bond coupling reactions. The stabilization can be outer-dendritic for the small zeroth-generation dendrimer or intra-dendritic for the larger first- and second-generation dendrimers. The example of the Miyaura-Suzuki reaction that can be catalyzed by down to 1 ppm of PdNPs with a "homeopathic" mechanism (the less, the better) is illustrated here, including catalysis in aqueous solvents.

  11. Madumycin II inhibits peptide bond formation by forcing the peptidyl transferase center into an inactive state

    Energy Technology Data Exchange (ETDEWEB)

    Osterman, Ilya A.; Khabibullina, Nelli F.; Komarova, Ekaterina S.; Kasatsky, Pavel; Kartsev, Victor G.; Bogdanov, Alexey A.; Dontsova, Olga A.; Konevega, Andrey L.; Sergiev, Petr V.; Polikanov, Yury S. (InterBioScreen); (UIC); (MSU-Russia); (Kurchatov)

    2017-05-13

    The emergence of multi-drug resistant bacteria is limiting the effectiveness of commonly used antibiotics, which spurs a renewed interest in revisiting older and poorly studied drugs. Streptogramins A is a class of protein synthesis inhibitors that target the peptidyl transferase center (PTC) on the large subunit of the ribosome. In this work, we have revealed the mode of action of the PTC inhibitor madumycin II, an alanine-containing streptogramin A antibiotic, in the context of a functional 70S ribosome containing tRNA substrates. Madumycin II inhibits the ribosome prior to the first cycle of peptide bond formation. It allows binding of the tRNAs to the ribosomal A and P sites, but prevents correct positioning of their CCA-ends into the PTC thus making peptide bond formation impossible. We also revealed a previously unseen drug-induced rearrangement of nucleotides U2506 and U2585 of the 23S rRNA resulting in the formation of the U2506•G2583 wobble pair that was attributed to a catalytically inactive state of the PTC. The structural and biochemical data reported here expand our knowledge on the fundamental mechanisms by which peptidyl transferase inhibitors modulate the catalytic activity of the ribosome.

  12. Identification of the formation of metal-vinylidene interfacial bonds of alkyne-capped platinum nanoparticles by isotopic labeling.

    Science.gov (United States)

    Hu, Peiguang; Chen, Limei; Deming, Christopher P; Bonny, Lewis W; Lee, Hsiau-Wei; Chen, Shaowei

    2016-10-07

    Stable platinum nanoparticles were prepared by the self-assembly of 1-dodecyne and dodec-1-deuteroyne onto bare platinum colloid surfaces. The nanoparticles exhibited consistent core size and optical properties. FTIR and NMR measurements confirmed the formation of Pt-vinylidene (Pt[double bond, length as m-dash]C[double bond, length as m-dash]CH-) interfacial linkages rather than Pt-acetylide (Pt-C[triple bond, length as m-dash]C-) and platinum-hydride (Pt-H) bonds.

  13. Bridging and bonding interactions in higher education: social capital and students’ academic and professional identity formation

    Science.gov (United States)

    Jensen, Dorthe H.; Jetten, Jolanda

    2015-01-01

    It is increasingly recognized that graduates’ achievements depend in important ways on their opportunities to develop an academic and a professional identity during their studies. Previous research has shown that students’ socio-economic status (SES) and social capital prior to entering university affects their ability to obtain these identities in higher education. However, what is less well understood is whether social capital that is built during university studies shapes identity development, and if so, whether the social capital gained during university years impacts on academic and professional identity differently. In a qualitative study, we interviewed 26 Danish and 11 Australian university students about their social interaction experiences, their opportunities to develop bonding capital as well as bridging capital, and their academic and professional identity. Findings show that while bonding social capital with co-students facilitated academic identity formation, such social capital does not lead to professional identity development. We also found that the development of bridging social capital with educators facilitated students’ professional identity formation. However, bonding social capital among students stood in the way of participating in bridging interaction with educators, thereby further hindering professional identity formation. Finally, while students’ parental background did not affect the perceived difficulty of forming professional identity, there was a tendency for students from lower SES backgrounds to be more likely to make internal attributions while those from higher SES backgrounds were more likely to make external attributions for the failure to develop professional identity. Results point to the importance of creating opportunities for social interaction with educators at university because this facilitates the generation of bridging social capital, which, in turn, is essential for students’ professional identity

  14. Bridging and bonding interactions in higher education: social capital and students' academic and professional identity formation.

    Science.gov (United States)

    Jensen, Dorthe H; Jetten, Jolanda

    2015-01-01

    It is increasingly recognized that graduates' achievements depend in important ways on their opportunities to develop an academic and a professional identity during their studies. Previous research has shown that students' socio-economic status (SES) and social capital prior to entering university affects their ability to obtain these identities in higher education. However, what is less well understood is whether social capital that is built during university studies shapes identity development, and if so, whether the social capital gained during university years impacts on academic and professional identity differently. In a qualitative study, we interviewed 26 Danish and 11 Australian university students about their social interaction experiences, their opportunities to develop bonding capital as well as bridging capital, and their academic and professional identity. Findings show that while bonding social capital with co-students facilitated academic identity formation, such social capital does not lead to professional identity development. We also found that the development of bridging social capital with educators facilitated students' professional identity formation. However, bonding social capital among students stood in the way of participating in bridging interaction with educators, thereby further hindering professional identity formation. Finally, while students' parental background did not affect the perceived difficulty of forming professional identity, there was a tendency for students from lower SES backgrounds to be more likely to make internal attributions while those from higher SES backgrounds were more likely to make external attributions for the failure to develop professional identity. Results point to the importance of creating opportunities for social interaction with educators at university because this facilitates the generation of bridging social capital, which, in turn, is essential for students' professional identity development.

  15. An Erbium-Based Bifuctional Heterogeneous Catalyst: A Cooperative Route Towards C-C Bond Formation

    Directory of Open Access Journals (Sweden)

    Manuela Oliverio

    2014-07-01

    Full Text Available Heterogeneous bifuctional catalysts are multifunctional synthetic catalysts enabling efficient organic transformations by exploiting two opposite functionalities without mutual destruction. In this paper we report the first Er(III-based metallorganic heterogeneous catalyst, synthesized by post-calcination MW-assisted grafting and modification of the natural aminoacid L-cysteine. The natural acid–base distance between sites was maintained to assure the cooperation. The applicability of this new bifunctional heterogeneous catalyst to C-C bond formation and the supposed mechanisms of action are discussed as well.

  16. Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds

    Energy Technology Data Exchange (ETDEWEB)

    Vereshchagin, L.I.; Kuznetsova, N.I.; Kirillova, L.P.; Shcherbakov, V.V.; Sukhanov, G.T.; Gareev, G.A.

    1987-01-01

    When 4-nitro-1,2,3-triazole is alkylated, a mixture of N1- and N2-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.

  17. Competition of electron transfer, dissociation, and bond-forming reactions in collisions of CO22+ with neutral CO2

    Czech Academy of Sciences Publication Activity Database

    Ricketts, Claire; Schröder, Detlef; Roithová, Jana; Schwarz, H.; Thissen, R.; Dutuit, O.; Žabka, Ján; Herman, Zdeněk; Price, S. D.

    2008-01-01

    Roč. 10, č. 33 (2008), s. 5135-5143 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : carbon dioxide * bond -forming reactions * dications Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.064, year: 2008

  18. Insights into the Diels-Alder Reaction between 3-Vinylindoles and Methyleneindolinone without and with the Assistance of Hydrogen-Bonding Catalyst Bisthiourea: Mechanism, Origin of Stereoselectivity, and Role of Catalyst.

    Science.gov (United States)

    Yan, Chao-Xian; Yang, Fan; Yang, Xing; Zhou, Da-Gang; Zhou, Pan-Pan

    2017-03-17

    The Diels-Alder reaction between 3-vinylindoles and methyleneindolinone can proceed both under catalyst-free conditions and with bisthiourea as the catalyst. The reaction with bisthiourea is much faster and results in higher stereoselectivity of the product. The reaction mechanism, origin of stereoselectivity, and role of the catalyst were elaborated based on quantum mechanical calculations and theoretical methods of reactivity indices, NCI, QTAIM, and distortion/interaction models. In the uncatalyzed reaction, the two C-C bonds that are formed undergo conversion from noncovalent to covalent bonding via a concerted asynchronous mechanism. The weak intermolecular interactions formed in the transition state play important roles. The difference between the interaction and distortion energies is responsible for the stereoselectivity. In the catalyzed reaction, bisthiourea induces both the diene and dienophile to approach it via weak intermolecular interactions, which greatly lowers the energy barrier of the reaction and leads to the product with excellent stereoselectivity. The possible pathways of this reaction were explored, which suggested that the formation of the two C-C bonds goes through either a stepwise or concerted asynchronous mechanism. These results detail the reaction mechanism and shed light on both the significant role of the bisthiourea catalyst and the origin of stereoselectivity for this type of Diels-Alder reaction and related ones.

  19. Synthesis of Reusable Silica Nanosphere-Supported Pt(IV Complex for Formation of Disulfide Bonds in Peptides

    Directory of Open Access Journals (Sweden)

    Xiaonan Hou

    2017-02-01

    Full Text Available Some peptide-based drugs, including oxytocin, vasopressin, ziconotide, pramlintide, nesiritide, and octreotide, contain one intramolecular disulfide bond. A novel and reusable monodispersed silica nanosphere-supported Pt(IV complex (SiO2@TPEA@Pt(IV; TPEA: N-[3-(trimethoxysilylpropyl]ethylenediamine was synthesized via a four-step procedure and was used for the formation of intramolecular disulfide bonds in peptides. Transmission electron microscopy (TEM and chemical mapping results for the Pt(II intermediates and for SiO2@TPEA@Pt(IV show that the silica nanospheres possess a monodisperse spherical structure and contain uniformly-distributed Si, O, C, N, Cl, and Pt. The valence state of Pt on the silica nanospheres was characterized by X-ray photoelectron spectroscopy (XPS. The Pt(IV loaded on SiO2@TPEA@Pt(IV was 0.15 mmol/g, as determined by UV-VIS spectrometry. The formation of intramolecular disulfides in six dithiol-containing peptides of variable lengths by the use of SiO2@TPEA@Pt(IV was investigated, and the relative oxidation yields were determined by high-performance liquid chromatography (HPLC. In addition, peptide 1 (Ac-CPFC-NH2 was utilized to study the reusability of SiO2@TPEA@Pt(IV. No significant decrease in the relative oxidation yield was observed after ten reaction cycles. Moreover, the structure of SiO2@TPEA@Pt(IV after being used for ten cycles was determined to be similar to its initial one, demonstrating the cycling stability of the complex.

  20. Dissecting the role of disulfide bonds on the amyloid formation of insulin

    International Nuclear Information System (INIS)

    Li, Yang; Gong, Hao; Sun, Yue; Yan, Juan; Cheng, Biao; Zhang, Xin; Huang, Jing; Yu, Mengying; Guo, Yu; Zheng, Ling; Huang, Kun

    2012-01-01

    Highlights: ► We dissect how individual disulfide bond affects the amyloidogenicity of insulin. ► A controlled reduction system for insulin is established in this study. ► Disulfide breakage is associated with unfolding and increased amyloidogenicity. ► Breakage of A6-A11 is associated with significantly increased cytotoxicity. ► Analogs without A6-A11 have a higher potency to form high order toxic oligomers. -- Abstract: Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6 > INS-3 > INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7-B7 induced more unfolding of the insulin structure and a higher amyloidogenicity than breakage of A6-A11, but breakage of A6

  1. Formation of III–V-on-insulator structures on Si by direct wafer bonding

    International Nuclear Information System (INIS)

    Yokoyama, Masafumi; Iida, Ryo; Ikku, Yuki; Kim, Sanghyeon; Takenaka, Mitsuru; Takagi, Shinichi; Takagi, Hideki; Yasuda, Tetsuji; Yamada, Hisashi; Ichikawa, Osamu; Fukuhara, Noboru; Hata, Masahiko

    2013-01-01

    We have studied the formation of III–V-compound-semiconductors-on-insulator (III–V-OI) structures with thin buried oxide (BOX) layers on Si wafers by using developed direct wafer bonding (DWB). In order to realize III–V-OI MOSFETs with ultrathin body and extremely thin body (ETB) InGaAs-OI channel layers and ultrathin BOX layers, we have developed an electron-cyclotron resonance (ECR) O 2 plasma-assisted DWB process with ECR sputtered SiO 2 BOX layers and a DWB process based on atomic-layer-deposition Al 2 O 3 (ALD-Al 2 O 3 ) BOX layers. It is essential to suppress micro-void generation during wafer bonding process to achieve excellent wafer bonding. We have found that major causes of micro-void generation in DWB processes with ECR-SiO 2 and ALD-Al 2 O 3 BOX layers are desorption of Ar and H 2 O gas, respectively. In order to suppress micro-void generation in the ECR-SiO 2 BOX layers, it is effective to introduce the outgas process before bonding wafers. On the other hand, it is a possible solution for suppressing micro-void generation in the ALD-Al 2 O 3 BOX layers to increase the deposition temperature of the ALD-Al 2 O 3 BOX layers. It is also another possible solution to deposit ALD-Al 2 O 3 BOX layers on thermally oxidized SiO 2 layers, which can absorb the desorption gas from ALD-Al 2 O 3 BOX layers. (invited paper)

  2. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2015-01-01

    Full Text Available Succinimide formation from aspartic acid (Asp residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe as a model compound, we propose the possibility that acetic acid (AA, which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  3. Acetic acid can catalyze succinimide formation from aspartic acid residues by a concerted bond reorganization mechanism: a computational study.

    Science.gov (United States)

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-01-12

    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  4. Adaptable liquid crystal elastomers with transesterification-based bond exchange reactions.

    Science.gov (United States)

    Hanzon, Drew W; Traugutt, Nicholas A; McBride, Matthew K; Bowman, Christopher N; Yakacki, Christopher M; Yu, Kai

    2018-02-14

    Adaptable liquid crystal elastomers (LCEs) have recently emerged to provide a new and robust method to program monodomain LCE samples. When a constant stress is applied with active bond exchange reactions (BERs), polymer chains and mesogens gradually align in the strain direction. Mesogen alignment is maintained after removing the BER stimulus (e.g. by lowering the temperature) and the programmed LCE samples exhibit free-standing two-way shape switching behavior. Here, a new adaptable main-chain LCE system was developed with thermally induced transesterification BERs. The network combines the conventional properties of LCEs, such as an isotropic phase transition and soft elasticity, with the dynamic features of adaptable network polymers, which are malleable to stress relaxation due to the BERs. Polarized Fourier transform infrared measurements confirmed the alignment of polymer chains and mesogens after strain-induced programming. The influence of the creep stress, temperature, and time on the strain amplitude of two-way shape switching was examined. The LCE network demonstrates an innovative feature of reprogrammability, where the reversible shape-switching memory of programmed LCEs is readily deleted by free-standing heating as random BERs disrupt the mesogen alignment, so LCEs are reprogrammed after returning to the polydomain state. Due to the dynamic nature of the LCE network, it also exhibits a surface welding effect and can be fully dissolved in the organic solvent, which might be utilized for green and sustainable recycling of LCEs.

  5. Investigation of thermal conductivity and oxidation behaviour of reaction bonded aluminum nitride (RBAN) ceramics

    International Nuclear Information System (INIS)

    Salahi, E; Moztarzadeh, F.; Margoosian, V.; Heinrich, J. G.

    2003-01-01

    AlN samples have been produced by reaction bonding process using AlN and aluminum powders as starting materials. Different aluminum nitride and aluminum powders ratios were mixed in ethanol media, dried, isostatically and nitrided in (N 2 )atmosphere. Results showed that conversion of to AlN depends strongly on the amount of aluminum starting powder and decreased with increasing after a maximum at 25 Al wt %. Changing the particle size and morphology of the aluminum starting powder leads to change in the conversion ratio and microstructure of RBAN ceramics. Typical scanning electron micrographs of RBAN sample indicating primary and secondary aluminum nitride morphology and pore structure. The oxidation behavior of RABN samples showed the weight gain depends on the average particle size, morphology and amount of Al in starting mixture and pore structure. Samples have been manufactured with equi-axed morphology of Al starting powder have thermal conductivity higher than the samples have been manufactured with flake-like morphology. These differences were directly related to the different microstructure of RBAN samples

  6. In vivo biofilm formation on stainless steel bonded retainers during different oral health-care regimens.

    Science.gov (United States)

    Jongsma, Marije A; van der Mei, Henny C; Atema-Smit, Jelly; Busscher, Henk J; Ren, Yijin

    2015-03-23

    Retention wires permanently bonded to the anterior teeth are used after orthodontic treatment to prevent the teeth from relapsing to pre-treatment positions. A disadvantage of bonded retainers is biofilm accumulation on the wires, which produces a higher incidence of gingival recession, increased pocket depth and bleeding on probing. This study compares in vivo biofilm formation on single-strand and multi-strand retention wires with different oral health-care regimens. Two-centimetre wires were placed in brackets that were bonded to the buccal side of the first molars and second premolars in the upper arches of 22 volunteers. Volunteers used a selected toothpaste with or without the additional use of a mouthrinse containing essential oils. Brushing was performed manually. Regimens were maintained for 1 week, after which the wires were removed and the oral biofilm was collected to quantify the number of organisms and their viability, determine the microbial composition and visualize the bacteria by electron microscopy. A 6-week washout period was employed between regimens. Biofilm formation was reduced on single-strand wires compared with multi-strand wires; bacteria were observed to adhere between the strands. The use of antibacterial toothpastes marginally reduced the amount of biofilm on both wire types, but significantly reduced the viability of the biofilm organisms. Additional use of the mouthrinse did not result in significant changes in biofilm amount or viability. However, major shifts in biofilm composition were induced by combining a stannous fluoride- or triclosan-containing toothpaste with the mouthrinse. These shifts can be tentatively attributed to small changes in bacterial cell surface hydrophobicity after the adsorption of the toothpaste components, which stimulate bacterial adhesion to the hydrophobic oil, as illustrated for a Streptococcus mutans strain.

  7. Moisture distribution measurements in adhesive-bonded composites using the D (3He,p)4 He reaction

    International Nuclear Information System (INIS)

    Schulte, R.L.; Deiasi, R.J.

    1981-01-01

    Adhesive bonding of composite materials for many aircraft components offers a distinct advantage in weight and cost reduction compared to similar structures that have been joined by riveting. However, the long term performance of adhesive-bonded components depends on the degree and rate of moisture absorption by the adhesive in the service environment. To investigate the rate and the mechanism of water transport in adhesive-bonded composite materials, a nuclear reaction analysis method based on the D( 3 He,p) 4 He reaction is used to measure the moisture distributions. Samples of graphite/epoxy composite materials were bonded with an epoxy adhesive and isothermally conditioned in a controlled D 2 O environment at 70% relative humidity and 77 0 C for various exposure times. The moisture profiles were measured along the adhesive (adhesive scan) as well as through the thickness of the bonded joint (transverse scan). The dimensions of the probing beam were 125 μm x 125 μm for the adhesive scan and 25 μ x 200 μm for the transverse scan. Absolute deuterium concentrations were determined by comparison of the proton yield from the composite/adhesive to that from reference standards. Calculations from diffusion models of water transport based on parameters determined from bulk measurement techniques are compared to the measured profile and the agreement indicates that classical Fickian diffusion describes the transport of moisture in these materials

  8. The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions

    Science.gov (United States)

    Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo

    2018-02-01

    Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

  9. Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

    Science.gov (United States)

    Zhang, Chun; Feng, Peng; Jiao, Ning

    2013-10-09

    The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

  10. Interfacial micromorphological differences in hybrid layer formation between water- and solvent-based dentin bonding systems.

    Science.gov (United States)

    Gregoire, Geneviève L; Akon, Bernadette A; Millas, Arlette

    2002-06-01

    Many dentin bonding systems of different compositions, and in particular containing different solvents, have been introduced to the market. Their effect on the quality of the interface requires clarification by means of comparative trials. This study investigated micromorphological differences in hybrid layer formation with a variety of commercially available water- or solvent-based dentin bonding products and their recommended compomers. Five bonding systems were used on groups of 10 teeth each as follows: group I, acetone-based system used with 36% phosphoric acid; group II, a different acetone-based system containing nano-sized particles for filler loading and used with a non-rinsing conditioner containing maleic acid; group III, the acetone-based system of group II used with 36% phosphoric acid (the only difference in the treatment for groups II and III was the acid etching system); group IV, a mixed-solvent-based system (water/ethanol) used with 37% phosphoric acid; and group V, a water-based system used with 37% phosphoric acid. Each bonding system was covered with the recommended compomer. Class I occlusal preparations were made in extracted teeth and restored with one of the above systems. Five specimens of each group were studied with optical microscopy after staining. Scanning electron microscopy was used to examine the interface of the bonding system/dentin of the other 5 teeth in each group. The optical microscopy measurements were made with a 10 x 10 reticle. A micron mark with scale was used for the scanning electron microscope. All measurements were made in microm. The following criteria were used to define a good interface: absence of voids between the different parts of the interface, uniformity of the hybrid layer, good opening of the tubuli orifices, and tag adherence to the tubuli walls. Morphological differences were found at the interface depending on dentin treatment and adhesive composition. The acetone-containing systems were associated

  11. Un-catalyzed peptide bond formation between two monomers of glycine, alanine, serine, threonine, and aspartic acid in gas phase: a density functional theory study

    Science.gov (United States)

    Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K.

    2016-05-01

    In the present report, un-catalyzed peptide bond formation between two monomers of glycine (Gly), alanine (Ala), serine (Ser), threonine (Thr), and aspartic acid (Asp) has been investigated in gas phase via two steps reaction mechanism and concerted mechanism at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. The peptide bond is formed through a nucleophilic reaction via transition states, TS1 and TS2 in stepwise mechanism. The TS1 reveals formation of a new C-N bond while TS2 illustrate the formation of C=O bond. In case of concerted mechanism, C-N bond is formed by a single four-centre transition state (TS3). The energy barrier is used to explain the involvement of energy at each step of the reaction. The energy barrier (20-48 kcal/mol) is required for the transformation of reactant state R1 to TS1 state and intermediate state I1 to TS2 state. The large value of energy barrier is explained in terms of distortion and interaction energies for stepwise mechanism. The energy barrier of TS3 in concerted mechanism is very close to the energy barrier of the first transition state (TS1) of the stepwise mechanism for the formation of Gly-Gly and Ala-Ala di- peptide. However, in case of Ser-Ser, Thr-Thr and Asp-Asp di-peptide, the energy barrier of TS3 is relatively high than that of the energy barrier of TS1 calculated at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. In both the mechanisms, the value of energy barrier calculated at B3LYP/6-31G(d,p) level of theory is greater than that of the value calculated at M062X/6-31G(d,p) level of theory.

  12. Intra- and inter-subunit disulfide bond formation is nonessential in adeno-associated viral capsids.

    Directory of Open Access Journals (Sweden)

    Nagesh Pulicherla

    Full Text Available The capsid proteins of adeno-associated viruses (AAV have five conserved cysteine residues. Structural analysis of AAV serotype 2 reveals that Cys289 and Cys361 are located adjacent to each other within each monomer, while Cys230 and Cys394 are located on opposite edges of each subunit and juxtaposed at the pentamer interface. The Cys482 residue is located at the base of a surface loop within the trimer region. Although plausible based on molecular dynamics simulations, intra- or inter-subunit disulfides have not been observed in structural studies. In the current study, we generated a panel of Cys-to-Ser mutants to interrogate the potential for disulfide bond formation in AAV capsids. The C289S, C361S and C482S mutants were similar to wild type AAV with regard to titer and transduction efficiency. However, AAV capsid protein subunits with C230S or C394S mutations were prone to proteasomal degradation within the host cells. Proteasomal inhibition partially blocked degradation of mutant capsid proteins, but failed to rescue infectious virions. While these results suggest that the Cys230/394 pair is critical, a C394V mutant was found viable, but not the corresponding C230V mutant. Although the exact nature of the structural contribution(s of Cys230 and Cys394 residues to AAV capsid formation remains to be determined, these results support the notion that disulfide bond formation within the Cys289/361 or Cys230/394 pair appears to be nonessential. These studies represent an important step towards understanding the role of inter-subunit interactions that drive AAV capsid assembly.

  13. Spectroscopic investigation and computational analysis of charge transfer hydrogen bonded reaction between 3-aminoquinoline with chloranilic acid in 1:1 stoichiometric ratio

    Science.gov (United States)

    Al-Ahmary, Khairia M.; Alenezi, Maha S.; Habeeb, Moustafa M.

    2015-10-01

    Charge transfer hydrogen bonded reaction between the electron donor (proton acceptor) 3-aminoquinoline with the electron acceptor (proton donor) chloranilic acid (H2CA) has been investigated experimentally and theoretically. The experimental work included the application of UV-vis spectroscopy to identify the charge transfer band of the formed complex, its molecular composition as well as estimating its formation constants in different solvent included acetonitrile (AN), methanol (MeOH), ethanol (EtOH) and chloroform (CHL). It has been recorded the presence of new absorption bands in the range 500-550 nm attributing to the formed complex. The molecular composition of the HBCT complex was found to be 1:1 (donor:acceptor) in all studied solvents based on continuous variation and photometric titration methods. In addition, the calculated formation constants from Benesi-Hildebrand equation recorded high values, especially in chloroform referring to the formation of stable HBCT complex. Infrared spectroscopy has been applied for the solid complex where formation of charge and proton transfer was proven in it. Moreover, 1H and 13C NMR spectroscopies were used to characterize the formed complex where charge and proton transfers were reconfirmed. Computational analysis included the use of GAMESS computations as a package of ChemBio3D Ultr12 program were applied for energy minimization and estimation of the stabilization energy for the produced complex. Also, geometrical parameters (bond lengths and bond angles) of the formed HBCT complex were computed and analyzed. Furthermore, Mullikan atomic charges, molecular potential energy surface, HOMO and LUMO molecular orbitals as well as assignment of the electronic spectra of the formed complex were presented. A full agreement between experimental and computational analysis has been found especially in the existence of the charge and proton transfers and the assignment of HOMO and LUMO molecular orbitals in the formed complex as

  14. Processing development for ceramic structural components: the influence of a presintering of silicon on the final properties of reaction bonded silicon nitride. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    1982-03-01

    The influence of a presintering of silicon on the final properties of reaction bonded silicon nitride has been studied using scanning electron and optical microscopy, x-ray diffraction analysis, 4 pt. bend test, and mecury intrusion porosimetry. It has been shown that presintering at 1050/sup 0/C will not affect the final nitrided properties. At 1200/sup 0/C, the oxide layer is removed, promoting the formation of B-phase silicon nitride. Presintering at 1200/sup 0/C also results in compact weight loss due to the volatilization of silicon, and the formation of large pores which severely reduce nitrided strength. The development of the structure of sintered silicon compacts appears to involve a temperature gradient, with greater sintering observed near the surface.

  15. Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2013-01-01

    Simple and versatile routes to the functionalization of uranyl-derived U"V-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}_2(L)] and [{(py)_3LiOUO}(OUOSiMe_3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py)_2][(OUO)(N'')_3](N''=N(SiMe_3)_2) with the polypyrrolic macrocycle H_4L or the mononuclear uranyl (VI) Pacman complex [UO_2(py)(H_2L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}_2(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)_3] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO)_2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli

    Directory of Open Access Journals (Sweden)

    Hatahet Feras

    2010-09-01

    Full Text Available Abstract Background The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Results Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3 pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Conclusions Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory.

  17. New conception in the theory of chemical bonding; the role of core and valence atomic orbitals in formation of chemical bonds

    International Nuclear Information System (INIS)

    Kostikova, G.P.; Kostikov, Yu.P.; Korol'kov, D.V.

    1986-01-01

    An analysis of x-ray photoelectron spectra leads to a simple and consistent conception in the theory of chemical bonding, which satisfies (unlike the simple MO-LCAO theory) the virial theorem and defines the roles of the core and valence atomic orbitals in the formation of chemical bonds. Its essence is clear from the foregoing: the exothermic effects of the formation of complexes are caused by the lowering of the energies of the core levels of the central atoms with simultaneous small changes in the energies of the core levels of the ligands despite the significant destabilization of the delocalized valence MO's in comparison to the orbital energies of the corresponding free atoms. In order to confirm these ideas, they recorded the x-ray photoelectron spectra of the valence region and the inner levels of single-crystal silicon carbide, silicon, and graphite

  18. HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

    International Nuclear Information System (INIS)

    Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

    2004-01-01

    We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

  19. Unusual C-C bond cleavage in the formation of amine-bis(phenoxy) group 4 benzyl complexes: Mechanism of formation and application to stereospecific polymerization

    KAUST Repository

    Gowda, Ravikumar R.

    2014-08-11

    Group 4 tetrabenzyl compounds MBn4 (M = Zr, Ti), upon protonolysis with an equimolar amount of the tetradentate amine-tris(phenol) ligand N[(2,4-tBu2C6H2(CH 2)OH]3 in toluene from -30 to 25 °C, unexpectedly lead to amine-bis(phenoxy) dibenzyl complexes, BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn2 (M = Zr (1), Ti (2)) in 80% (1) and 75% (2) yields. This reaction involves an apparent cleavage of the >NCH2-ArOH bond (loss of the phenol in the ligand) and formation of the >NCH 2-CH2Bn bond (gain of the benzyl group in the ligand). Structural characterization of 1 by X-ray diffraction analysis confirms that the complex formed is a bis(benzyl) complex of Zr coordinated by a newly derived tridentate amine-bis(phenoxy) ligand arranged in a mer configuration in the solid state. The abstractive activation of 1 and 2 with B(C6F 5)3·THF in CD2Cl2 at room temperature generates the corresponding benzyl cations {BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn(THF)}+[BnB(C6F5) 3]- (M = Zr (3), Ti, (4)). These cationic complexes, along with their analogues derived from (imino)phenoxy tri- and dibenzyl complexes, [(2,6-iPr2C6H3)N=C(3,5- tBu2C6H2)O]ZrBn3 (5) and [2,4-Br2C6H2(O)(6-CH2(NC 5H9))CH2N=CH(2-adamantyl-4-MeC 6H2O)]ZrBn2 (6), have been found to effectively polymerize the biomass-derived renewable β-methyl-α-methylene- γ-butyrolactone (βMMBL) at room temperature into the highly stereoregular polymer PβMMBL with an isotacticity up to 99% mm. A combined experimental and DFT study has yielded a mechanistic pathway for the observed unusual C-C bond cleavage in the present protonolysis reaction between ZrBn4 and N[(2,4-tBu2C 6H2(CH2)OH]3 for the formation of complex 1, which involves the benzyl radical and the Zr(III) species, resulting from thermal and photochemical decomposition of ZrBn4, followed by a series of reaction sequences consisting of protonolysis, tautomerization, H-transfer, oxidation, elimination, and radical coupling. © 2014 American Chemical Society.

  20. Effect of hydroxyl bond formation on the adhesion improvement of a polyethylene copper thin film system

    International Nuclear Information System (INIS)

    Camacho, M.; Blantocas, G.; Ramos, H.

    2009-01-01

    Formation of hydroxyl bonds on the surface of a gas plasma treated high density polyethylene (HDPE) sheets significantly enhanced the adhesion strength of the polyethylene copper thin film system. Surface treatments using oxygen gas plasmas at varying plasma parameters are applied in this study to identify the most effective plasma parameters that would promote the best adhesion strength. Analysis of gas plasma adulterated HDPE sheets showed best enhancement of polyethylene copper adhesion after an oxygen gas plasma treatment for 60 minutes at 5mA discharge current. Scanning Electron Microscopy Analysis, Fourier Transform Infrared Spectroscopy and Adhesion measurements using Pull out Force Analysis were used to measure the changes in the surface chemistry and surface topology of the HDPE sheets. (author)

  1. Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR)

    Energy Technology Data Exchange (ETDEWEB)

    Roth, Justine P. [Johns Hopkins Univ., Baltimore, MD (United States)

    2015-03-03

    Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR) Research during the project period focused primarily on mechanisms of water oxidation by structurally defined transition metal complexes. Competitive oxygen isotope fractionation of water, mediated by oxidized precursors or reduced catalysts together with ceric, Ce(IV), ammonium nitrate in aqueous media, afforded oxygen-18 kinetic isotope effects (O-18 KIEs). Measurement, calculation, and interpretation of O-18 KIEs, described in the accompanying report has important ramifications for the production of electricity and solar hydrogen (as fuel). The catalysis division of BES has acknowledged that understanding mechanisms of transition metal catalyzed water oxidation has major ramifications, potentially leading to transformation of the global economy and natural environment in years to come. Yet, because of program restructuring and decreased availability of funds, it was recommended that the Solar Photochemistry sub-division of BES would be a more appropriate parent program for support of continued research.

  2. Isotopic studies of trans- and cis-HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures

    Energy Technology Data Exchange (ETDEWEB)

    McCarthy, Michael C., E-mail: mccarthy@cfa.harvard.edu; Martinez, Oscar; Crabtree, Kyle N.; Martin-Drumel, Marie-Aline [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138, USA and School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, Massachusetts 02138 (United States); McGuire, Brett A. [National Radio Astronomy Observatory, Charlottesville, Virginia 22901 (United States); Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138, USA and School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, Massachusetts 02138 (United States); Stanton, John F. [Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712-0165 (United States)

    2016-03-28

    HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO{sub 2} reaction represents the final step for the production of CO{sub 2} in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans-HOCO can be produced almost equally well from either OH + CO or H + CO{sub 2} in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO{sub 2}. Using isotopically labelled precursors, the OH + C{sup 18}O reaction predominately yields HOC{sup 18}O for both isomers, but H{sup 18}OCO is observed as well, typically at the level of 10%-20% that of HOC{sup 18}O; the opposite propensity is found for the {sup 18}OH + CO reaction. DO + C{sup 18}O yields similar ratios between DOC{sup 18}O and D{sup 18}OCO as those found for OH + C{sup 18}O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO{sub 2}, which, at the high pressure of our gas expansion, can readily occur. The large {sup 13}C Fermi-contact term (a{sub F}) for trans- and cis-HO{sup 13}CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers.

  3. Bond-forming reactions of dications with molecules: A computational and experimental study of the mechanisms for the formation of HCF.sub.2./sub..sup.+./sup. from CF.sub.3./sub..sup.2+./sup. and H.sub.2./sub

    Czech Academy of Sciences Publication Activity Database

    Lambert, N.; Kaltsoyannis, N.; Price, S. D.; Žabka, Ján; Herman, Zdeněk

    2006-01-01

    Roč. 110, č. 9 (2006), s. 2898-2905 ISSN 1089-5639 Grant - others:European Union Network(GB) RTN1-1999-00254; U.K.s EPSRC for computing resources(GB) GR/506233/01 Institutional research plan: CEZ:AV0Z40400503 Keywords : charge-transfer reactions * cross-section data * ab-initio * atmospheric reaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.047, year: 2006

  4. Identification and cloning of an NADPH-dependent hydroxycinnamoyl-CoA double bond reductase involved in dihydrochalcone formation in Malus×domestica Borkh.

    Science.gov (United States)

    Ibdah, Mwafaq; Berim, Anna; Martens, Stefan; Valderrama, Andrea Lorena Herrera; Palmieri, Luisa; Lewinsohn, Efraim; Gang, David R

    2014-11-01

    The apple tree (Malus sp.) is an agriculturally and economically important source of food and beverages. Many of the health beneficial properties of apples are due to (poly)phenolic metabolites that they contain, including various dihydrochalcones. Although many of the genes and enzymes involved in polyphenol biosynthesis are known in many plant species, the specific reactions that lead to the biosynthesis of the dihydrochalcone precursor, p-dihydrocoumaroyl-CoA (3), are unknown. To identify genes involved in the synthesis of these metabolites, existing genome databases of the Rosaceae were screened for apple genes with significant sequence similarity to Arabidopsis alkenal double bond reductases. Herein described are the isolation and characterization of a Malus hydroxycinnamoyl-CoA double bond reductase, which catalyzed the NADPH-dependent reduction of p-coumaroyl-CoA and feruloyl-CoA to p-dihydrocoumaroyl-CoA and dihydroferuloyl-CoA, respectively. Its apparent Km values for p-coumaroyl-CoA, feruloyl-CoA and NADPH were 96.6, 92.9 and 101.3μM, respectively. The Malus double bond reductase preferred feruloyl-CoA to p-coumaroyl-CoA as a substrate by a factor of 2.1 when comparing catalytic efficiencies in vitro. Expression analysis of the hydroxycinnamoyl-CoA double bond reductase gene revealed that its transcript levels showed significant variation in tissues of different developmental stages, but was expressed when expected for involvement in dihydrochalcone formation. Thus, the hydroxycinnamoyl-CoA double bond reductase appears to be responsible for the reduction of the α,β-unsaturated double bond of p-coumaroyl-CoA, the first step of dihydrochalcone biosynthesis in apple tissues, and may be involved in the production of these compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Deuterium secondary isotope kinetic effects in imine formation reactions

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1986-01-01

    The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

  6. Investigations on organolead compounds V. Lead---lead bond cleavage reactions of hexaphenyldilead

    NARCIS (Netherlands)

    Willemsens, L.C.; Kerk, G.J.M. van der

    1968-01-01

    It has been shown that a number of nucleophilic and weakly electrophilic reagents (organolithium and organomagnesium compounds, metallic lithium, potassium permanganate, sodium ethoxide, diaryl disulphides, sulphur, ozone, hypochlorous acid and iodine/iodide) selectively cleave the lead---lead bond

  7. Experimental and theoretical investigation of the production of cations containing C-N bonds in the reaction of benzene with atomic nitrogen ions

    International Nuclear Information System (INIS)

    Di Stefano, Marco; Rosi, Marzio; Sgamellotti, Antonio; Ascenzi, Daniela; Bassi, Davide; Franceschi, Pietro; Tosi, Paolo

    2003-01-01

    In the last few years, astronomical spectra have revealed the presence of aromatic and polyaromatic molecules in extraterrestrial environments, near carbon stars, in molecular clouds and meteorites. Moreover, the recent observation of benzene in interstellar space has noticeably increased the interest in the entire class of molecules and in their chemical behavior. In this work, we have investigated the reaction between the benzene molecule and the atomic nitrogen cation and, in particular, the mechanisms by which the reactants are converted into cationic products containing at least one C-N bond, according to the general scheme C 6 H 6 +N + →H m C n N + +C x H y . We have measured the energy dependence of the cross section in a guided ion beam tandem mass spectrometer. Relevant stationary points of the potential energy surface have been studied by using the density functional theory hybrid functional B3LYP with the 6-31G* basis set. Thermochemical calculations, and the comparison with experimental results, allow us to distinguish between exoergic and endoergic processes and to obtain a detailed description of the reaction mechanisms. We show that aromatic hydrocarbons may be converted into organic-nitrogen compounds via the insertion of N + into the benzene ring and the formation of C-N bonds from C-C ring reactants

  8. Stereoelectronic control in peptide bond formation. Ab initio calculations and speculations on the mechanism of action of serine proteases.

    Science.gov (United States)

    Gorenstein, D G; Taira, K

    1984-01-01

    Ab initio molecular orbital calculations have been performed on the reaction profile for the addition/elimination reaction between ammonia and formic acid, proceeding via a tetrahedral intermediate: NH3 + HCO2H----H2NCH(OH)2----NH2CHO + H2O. Calculated transition state energies for the first addition step of the reaction revealed that a lone pair on the oxygen of the OH group, which is antiperiplanar to the attacking nitrogen, stabilized the transition state by 3.9 kcal/mol, thus supporting the hypothesis of stereoelectronic control for this reaction. In addition, a secondary, counterbalancing stereoelectronic effect stabilizes the second step, water elimination, transition state by 3.1 kcal/mol if the lone pair on the leaving water oxygen is not antiperiplanar to the C-N bond. The best conformation for the transition states was thus one with a lone pair antiperiplanar to the adjacent scissile bond and also one without a lone-pair orbital on the scissile bond oxygen or nitrogen antiperiplanar to the adjacent polar bond. The significance of these stereoelectronic effects for the mechanism of action of serine proteases is discussed. PMID:6394065

  9. Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2013-07-29

    Simple and versatile routes to the functionalization of uranyl-derived U{sup V}-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}{sub 2}(L)] and [{(py)_3LiOUO}(OUOSiMe{sub 3})(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py){sub 2}][(OUO)(N''){sub 3}](N''=N(SiMe{sub 3}){sub 2}) with the polypyrrolic macrocycle H{sub 4}L or the mononuclear uranyl (VI) Pacman complex [UO{sub 2}(py)(H{sub 2}L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}{sub 2}(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr){sub 3}] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO){sub 2}(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

    KAUST Repository

    Alsam, Amani Abdu

    2017-03-14

    Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

  11. Bifunctional RuII -Complex-Catalysed Tandem C-C Bond Formation: Efficient and Atom Economical Strategy for the Utilisation of Alcohols as Alkylating Agents.

    Science.gov (United States)

    Roy, Bivas Chandra; Chakrabarti, Kaushik; Shee, Sujan; Paul, Subhadeep; Kundu, Sabuj

    2016-12-12

    Catalytic activities of a series of functional bipyridine-based Ru II complexes in β-alkylation of secondary alcohols using primary alcohols were investigated. Bifunctional Ru II complex (3 a) bearing 6,6'-dihydroxy-2,2'-bipyridine (6DHBP) ligand exhibited the highest catalytic activity for this reaction. Using significantly lower catalyst loading (0.1 mol %) dehydrogenative carbon-carbon bond formation between numerous aromatic, aliphatic and heteroatom substituted alcohols were achieved with high selectivity. Notably, for the synthesis of β-alkylated secondary alcohols this protocol is a rare one-pot strategy using a metal-ligand cooperative Ru II system. Remarkably, complex 3 a demonstrated the highest reactivity compared to all the reported transition metal complexes in this reaction. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Early biofilm formation and the effects of antimicrobial agents on orthodontic bonding materials in a parallel plate flow chamber

    NARCIS (Netherlands)

    Chin, Yeen; Busscher, HJ; Evans, R; Noar, J; Pratten, J

    Decalcification is a commonly recognized complication of orthodontic treatment with fixed appliances. A technology, based on a parallel plate flow chamber, was developed to investigate early biofilm formation of a strain of Streptococcus sanguis on the surface of four orthodontic bonding materials:

  13. Bond Formation in Diatomic Transition Metal Hydrides: Insights from the Analysis of Domain-Averaged Fermi Holes

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Ponec, Robert

    2013-01-01

    Roč. 113, č. 2 (2013), s. 102-111 ISSN 0020-7608 R&D Projects: GA ČR GA203/09/0118 Institutional support: RVO:67985858 Keywords : transition metal hydrides * bond formation * analysis of domain averaged Fermi holes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.166, year: 2013

  14. Extraordinary Mechanism of the Diels-Alder Reaction: Investigation of Stereochemistry, Charge Transfer, Charge Polarization, and Biradicaloid Formation.

    Science.gov (United States)

    Sexton, Thomas; Kraka, Elfi; Cremer, Dieter

    2016-02-25

    The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA (Unified Reaction Valley Approach) by 300% compared to previous studies. For the first time, the pre- and postchemical steps of the reaction are analyzed at the same level of theory as the actual chemical processes utilizing the path curvature and its decomposition into internal coordinate or curvilinear coordinate components. A first smaller charge transfer to the dienophile facilitates the rotation of gauche butadiene into its cis form. The actual chemical processes are initiated by a second larger charge transfer to the dienophile that facilitates pyramidalization of the reacting carbon centers, bond equalization, and biradicaloid formation of the reactants. The transition state is aromatically stabilized and moved by five path units into the entrance channel in line with the Hammond-Leffler postulate. The pseudorotation of the boat form into the halfchair of cyclohexene is analyzed. Predictions are made for the Diels-Alder reaction based on a 11-phase mechanism obtained by the URVA analysis.

  15. Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

    Science.gov (United States)

    Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

    2014-05-02

    Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

  16. Organoruthenium (II) complexes produced by insertion reactions of substituted olefins into a hydrido-ruthenium bond

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, Katsuma; Sasada, Yoko; Kitamura, Tsuneyuki [Nagasaki Univ. (Japan)

    1980-04-01

    Dimethyl fumarate, 2-vinylpyridine, and acrylonitrile insert into a H-Ru bond of (RuClH(CO)(PPh/sub 3/)/sub 3/) (1) to yield new substituted alkylruthenium(II) complexes. Methyl sorbate also reacted with 1 to give a new substituted eta/sup 3/-allylruthenium(II) complex.

  17. Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress

    Directory of Open Access Journals (Sweden)

    Tyo Keith EJ

    2012-03-01

    Full Text Available Abstract Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor or a larger protein (α-amylase. Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a degradation of protein/recycling amino acids, (b overall transcription/translation repression, and (c oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases.

  18. Soil aggregate formation: the role of wetting-drying cycles in the genesis of interparticle bonding

    Science.gov (United States)

    Albalasmeh, Ammar; Ghezzehei, Teamrat

    2013-04-01

    Soil structure influences many soil properties including aeration, water retention, drainage, bulk density, and resistance to erosion and indirectly influences most biological and chemical processes that occur in and around soil. In nature, soil is continually exposed to wetting (e.g., rainfall and diffusive flow) and drying (e.g., evaporation, diffusive flow and plant uptake). These natural wetting and drying cycles of soils are physical events that profoundly affect the development of soil structure, aggregate stability, carbon (C) flux and mineralization. We hypothesize that drying of capillary water transports suspended and/or dissolved cementing agents toward inter-particle contacts and eventually deposits part of the colloidal mass forming inter-particle bonds. Here, we will show the role of wetting and drying cycles on soil aggregation and stabilization and how these cycles transport and deposit organic cementing agents at the inter-particle contact. We found that aggregates of sand and silt particles can be formed by subjecting loose particles to wetting-drying cycles in the presence of dilute solutions of organic matter that mimic root or microbial exudates. Moreover, majority of the organic matter was deposited in the contact region between the sand particles, where the water accumulates during drying. The model predictions and aggregate stability measurements are supported by scanning electron micrographs that clearly show the process of aggregate formation.

  19. Highly Efficient Fumed Silica Nanoparticles for Peptide Bond Formation: Converting Alanine to Alanine Anhydride.

    Science.gov (United States)

    Guo, Chengchen; Jordan, Jacob S; Yarger, Jeffery L; Holland, Gregory P

    2017-05-24

    In this work, thermal condensation of alanine adsorbed on fumed silica nanoparticles is investigated using thermal analysis and multiple spectroscopic techniques, including infrared (IR), Raman, and nuclear magnetic resonance (NMR) spectroscopies. Thermal analysis shows that adsorbed alanine can undergo thermal condensation, forming peptide bonds within a short time period and at a lower temperature (∼170 °C) on fumed silica nanoparticle surfaces than that in bulk (∼210 °C). Spectroscopic results further show that alanine is converted to alanine anhydride with a yield of 98.8% during thermal condensation. After comparing peptide formation on solution-derived colloidal silica nanoparticles, it is found that fumed silica nanoparticles show much better efficiency and selectivity than solution-derived colloidal silica nanoparticles for synthesizing alanine anhydride. Furthermore, Raman spectroscopy provides evidence that the high efficiency for fumed silica nanoparticles is likely related to their unique surface features: the intrinsic high population of strained ring structures present at the surface. This work indicates the great potential of fumed silica nanoparticles in synthesizing peptides with high efficiency and selectivity.

  20. EXFOR Basics. A short guide to the neutron reaction data exchange format

    International Nuclear Information System (INIS)

    McLane, V.; NUCLEAR DATA CENTER NETWORK

    2000-01-01

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data

  1. Reactions of phenols and alcohols over thoria: mechanism of ether formation

    International Nuclear Information System (INIS)

    Karuppannasamy, S.; Narayanan, K.; Pillai, C.N.

    1980-01-01

    The dehydration of phenols and alkylation of phenols by alcohols over thoria were studied at 400 to 500 0 C and atmospheric pressure. Phenol and cresols, when dehydrated gave diaryl ethers as main products. With para-substituted phenols such as p-methoxy, p-t-butyl, p-chloro, and p-nitrophenol no ether formation was noticed. All the reactions were accompanied by considerable amount of coke formation. Alkylation of phenols by alcohols gave a mixture of O- and C-alkylated products under the same reaction conditions. O-alkylation and C-alkylation are parallel reactions. The mechanistic aspects of the reactions are discussed. 3 figures, 3 tables

  2. N-nitrosodimethylamine (NDMA) formation during ozonation of N,N-dimethylhydrazine compounds: Reaction kinetics, mechanisms, and implications for NDMA formation control.

    Science.gov (United States)

    Lim, Sungeun; Lee, Woongbae; Na, Soyoung; Shin, Jaedon; Lee, Yunho

    2016-11-15

    Compounds with N,N-dimethylhydrazine moieties ((CH 3 ) 2 N-N-) form N-nitrosodimethylamine (NDMA) during ozonation, but the relevant reaction chemistry is hitherto poorly understood. This study investigated the reaction kinetics and mechanisms of NDMA formation during ozonation of unsymmetrical dimethylhydrazine (UDMH) and daminozide (DMZ) as structural model N,N-dimethylhydrazine compounds. The reaction of ozone with these NDMA precursor compounds was fast, and k O3 at pH 7 was 2 × 10 6  M -1  s -1 for UDMH and 5 × 10 5  M -1  s -1 for DMZ. Molar NDMA yields (i.e., Δ[NDMA]/Δ[precursor] × 100) were 84% and 100% for UDMH and DMZ, respectively, determined at molar ozone dose ratio ([O 3 ] 0 /[precursor] 0 ) of ≥4 in the presence of tert-butanol as hydroxyl radical (OH) scavenger. The molar NDMA yields decreased significantly in the absence of tert-butanol, indicating OH formation and its subsequent reaction with the parent precursors forming negligible NDMA. The k OH at pH 7 was 4.9 × 10 9  M -1  s -1 and 3.4 × 10 9  M -1  s -1 for UDMH and DMZ, respectively. Reaction mechanisms are proposed in which an ozone adduct is formed at the nitrogen next to N,N-dimethylamine which decomposes via homolytic and heterolytic cleavages of the -N + -O-O-O - bond, forming NDMA as a final product. The heterolytic cleavage pathway explains the significant OH formation via radical intermediates. Overall, significant NDMA formation was found to be unavoidable during ozonation or even O 3 /H 2 O 2 treatment of waters containing N,N-dimethylhydrazine compounds due to their rapid reaction with ozone forming NDMA with high yield. Thus, source control or pre-treatment of N,N-dimethylhydrazine precursors and post-treatment of NDMA are proposed as the mitigation options. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Heterogeneous-catalytic redox reactions in nitrate - formate systems

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

    2000-01-01

    It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

  4. Alcali-silica reactions: Mechanisms for crack formations

    DEFF Research Database (Denmark)

    Goltermann, Per

    2006-01-01

    Alkali-silica reactions (ASR) are found all over the world and cause a large number of damage, which have lead to different sets of requirements in the different countries for the aggregates, the cements and the admixtures. One of the reasons for the damage and the different requirements is that ......Alkali-silica reactions (ASR) are found all over the world and cause a large number of damage, which have lead to different sets of requirements in the different countries for the aggregates, the cements and the admixtures. One of the reasons for the damage and the different requirements...... is that the mechanical behavior of the ASR has not been fully investigated, although the chemical aspects of ASR have been dealt with in depth. This paper presents a unified, mechanical explanation of the ASR damage mechanism, covering the relevant aspects of the diffusion model; the stress-variations in the aggregate...

  5. Biofilm formation on stainless steel and gold wires for bonded retainers in vitro and in vivo and their susceptibility to oral antimicrobials

    NARCIS (Netherlands)

    Jongsma, Marije A.; Pelser, Floris D. H.; van der Mei, Henny C.; Atema-Smit, Jelly; van de Belt-Gritter, Betsy; Busscher, Henk J.; Ren, Yijin

    OBJECTIVE: Bonded retainers are used in orthodontics to maintain treatment result. Retention wires are prone to biofilm formation and cause gingival recession, bleeding on probing and increased pocket depths near bonded retainers. In this study, we compare in vitro and in vivo biofilm formation on

  6. The initial step of silicate versus aluminosilicate formation in zeolite synthesis: a reaction mechanism in water with a tetrapropylammonium template

    KAUST Repository

    Trinh, Thuat T.

    2012-01-01

    The initial step for silicate and aluminosilicate condensation is studied in water in the presence of a realistic tetrapropylammonium template under basic conditions. The model corresponds to the synthesis conditions of ZSM5. The free energy profile for the dimer formation ((OH) 3Si-O-Si-(OH) 2O - or [(OH) 3Al-O-Si-(OH) 3] -) is calculated with ab initio molecular dynamics and thermodynamic integration. The Si-O-Si dimer formation occurs in a two-step manner with an overall free energy barrier of 75 kJ mol -1. The first step is associated with the Si-O bond formation and results in an intermediate with a five-coordinated Si, and the second one concerns the removal of the water molecule. The template is displaced away from the Si centres upon dimer formation, and a shell of water molecules is inserted between the silicate and the template. The main effect of the template is to slow down the backward hydrolysis reaction with respect to the condensation one. The Al-O-Si dimer formation first requires the formation of a metastable precursor state by proton transfer from Si(OH) 4 to Al(OH) 4 - mediated by a solvent molecule. It then proceeds through a single step with an overall barrier of 70 kJ mol -1. The model with water molecules explicitly included is then compared to a simple calculation using an implicit continuum model for the solvent. The results underline the importance of an explicit and dynamical treatment of the water solvent, which plays a key role in assisting the reaction. © the Owner Societies 2012.

  7. Visible Light Driven Nanosecond Bromide Oxidation by a Ru Complex with Subsequent Br-Br Bond Formation.

    Science.gov (United States)

    Li, Guocan; Ward, William M; Meyer, Gerald J

    2015-07-08

    Visible light excitation of [Ru(deeb)(bpz)2](2+) (deeb = 4,4'-diethylester-2,2'-bipyridine; bpz = 2,2'-bipyrazine), in Br(-) acetone solutions, led to the formation of Br-Br bonds in the form of dibromide, Br2(•-). This light reactivity stores ∼1.65 eV of free energy for milliseconds. Combined (1)H NMR, UV-vis and photoluminescence measurements revealed two distinct mechanisms. The first involves diffusional quenching of the excited state by Br(-) with a rate constant of (8.1 ± 0.1) × 10(10) M(-1) s(-1). At high Br(-) concentrations, an inner-sphere pathway is dominant that involves the association of Br(-), most likely with the 3,3'-H atoms of a bpz ligand, before electron transfer from Br(-) to the excited state, ket = (2.5 ± 0.3) × 10(7) s(-1). In both mechanisms, the direct photoproduct Br(•) subsequently reacts with Br(-) to yield dibromide, Br(•) + Br(-) → Br2(•-). Under pseudo-first-order conditions, this occurs with a rate constant of (1.1 ± 0.4) × 10(10) M(-1) s(-1) that was, within experimental error, the same as that measured when Br(•) were generated with ultraviolet light. Application of Marcus theory to the sensitized reaction provided an estimate of the Br(•) formal reduction potential E(Br(•)/Br(-)) = 1.22 V vs SCE in acetone, which is about 460 mV less positive than the accepted value in H2O. The results demonstrate that Br(-) oxidation by molecular excited states can be rapid and useful for solar energy conversion.

  8. Hydrogen bonds in the vicinity of the special pair of the bacterial reaction center probed by hydrostatic high-pressure absorption spectroscopy.

    Science.gov (United States)

    Kangur, Liina; Jones, Michael R; Freiberg, Arvi

    2017-12-01

    Using the native bacteriochlorophyll a pigment cofactors as local probes, we investigated the response to external hydrostatic high pressure of reaction center membrane protein complexes from the photosynthetic bacterium Rhodobacter sphaeroides. Wild-type and engineered complexes were used with a varied number (0, 1 or 2) of hydrogen bonds that bind the reaction center primary donor bacteriochlorophyll cofactors to the surrounding protein scaffold. A pressure-induced breakage of hydrogen bonds was established for both detergent-purified and membrane-embedded reaction centers, but at rather different pressures: between 0.2 and 0.3GPa and at about 0.55GPa, respectively. The free energy change associated with the rupture of the single hydrogen bond present in wild-type reaction centers was estimated to be equal to 13-14kJ/mol. In the mutant with two symmetrical hydrogen bonds (FM197H) a single cooperative rupture of the two bonds was observed corresponding to an about twice stronger bond, rather than a sequential rupture of two individual bonds. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. STUDY OF REACTION SEQUENCES FOR FORMATION OF SOLID ...

    African Journals Online (AJOL)

    31 déc. 2012 ... phase intermédiaire PbTiO3 et la formation de PZT à 800 °C. ... matériau céramique de type PZT de formule chimique: 0,48PbZrO3-0 .... (ATG) relative au mélange par un changement de perte visible équivalente à 3%.

  10. Ultraclean Si/Si interface formation by surface preparation and direct bonding in ultrahigh vacuum

    DEFF Research Database (Denmark)

    Hermansson, Karin; Grey, Francois; Bengtsson, Stefan

    1998-01-01

    Silicon surfaces have been cleaned and bonded in ultrahigh vacuum, at a pressure in the 10(-10) Torr range. The bonded interfaces show extremely low contamination levels as measured by secondary ion mass spectroscopy. Nevertheless, a potential barrier could be detected at the interface by spreading...

  11. In vivo biofilm formation on stainless steel bonded retainers during different oral health-care regimens

    NARCIS (Netherlands)

    Jongsma, Marije A.; van der Mei, Henny C.; Atema-Smit, Jelly; Busscher, Henk I.; Ren, Yijin

    2015-01-01

    Retention wires permanently bonded to the anterior teeth are used after orthodontic treatment to prevent the teeth from relapsing to pre-treatment positions. A disadvantage of bonded retainers is biofilm accumulation on the wires, which produces a higher incidence of gingival recession, increased

  12. Sequential C-Si Bond Formations from Diphenylsilane: Application to Silanediol Peptide Isostere Precursors

    DEFF Research Database (Denmark)

    Nielsen, Lone; Skrydstrup, Troels

    2008-01-01

    and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows...

  13. Synthetic Methods for Ester Bond Formation and Conformational Analysis of Ester-Containing Carbohydrates

    Science.gov (United States)

    Hackbusch, Sven

    This dissertation encompasses work related to synthetic methods for the formation of ester linkages in organic compounds, as well as the investigation of the conformational influence of the ester functional group on the flexibility of inter-saccharide linkages, specifically, and the solution phase structure of ester-containing carbohydrate derivatives, in general. Stereoselective reactions are an important part of the field of asymmetric synthesis and an understanding of their underlying mechanistic principles is essential for rational method development. Here, the exploration of a diastereoselective O-acylation reaction on a trans-2-substituted cyclohexanol scaffold is presented, along with possible reasons for the observed reversal of stereoselectivity dependent on the presence or absence of an achiral amine catalyst. In particular, this work establishes a structure-activity relationship with regard to the trans-2-substituent and its role as a chiral auxiliary in the reversal of diastereoselectivity. In the second part, the synthesis of various ester-linked carbohydrate derivatives, and their conformational analysis is presented. Using multidimensional NMR experiments and computational methods, the compounds' solution-phase structures were established and the effect of the ester functional group on the molecules' flexibility and three-dimensional (3D) structure was investigated and compared to ether or glycosidic linkages. To aid in this, a novel Karplus equation for the C(sp2)OCH angle in ester-linked carbohydrates was developed on the basis of a model ester-linked carbohydrate. This equation describes the sinusoidal relationship between the C(sp2)OCH dihedral angle and the corresponding 3JCH coupling constant that can be determined from a J-HMBC NMR experiment. The insights from this research will be useful in describing the 3D structure of naturally occurring and lab-made ester-linked derivatives of carbohydrates, as well as guiding the de novo-design of

  14. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias

    2014-01-01

    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  15. C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): dimerizations, 3 + 2 cyclization, and nucleophilic attack; transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (di-(2-pyridyl-methyl)-amide)).

    Science.gov (United States)

    Frazier, Brenda A; Williams, Valerie A; Wolczanski, Peter T; Bart, Suzanne C; Meyer, Karsten; Cundari, Thomas R; Lobkovsky, Emil B

    2013-03-18

    Molecular orbital analysis depicts the CNC(nb) backbone of the smif (1,3-di-(2-pyridyl)-2-azaallyl) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)2} (1) to [{(Me3Si)2N}Fe]2(μ-κ(3),κ(3)-N,py2-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me2(o)Me2smif)FeN(SiMe3)2 (8) provides a route to [{(Me3Si)2N}Fe]2(μ-κ(4),κ(4)-N,py2,C-((b)Me,(b)CH2,(o)Me2(smif)H))2 (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN(SiMe3)2]2 (11), and the collateral discovery of alkyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)2(THF) as an effective catalyst. Nucleophilic attack by (smif)2Fe (13) on (t)BuNCO and (2,6-(i)Pr2C6H3)NCO afforded (RNHCO-smif)2Fe (14a, R = (t)Bu; 14b, 2,6-(i)PrC6H3). Calculations suggested that (dpma)2Fe (15) would favorably lose dihydrogen to afford (smif)2Fe (13). H2-transfer to alkynes, olefins, imines, PhN═NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

  16. Oxidation effects on the mechanical properties of SiC fiber-reinforced reaction-bonded silicon nitride matrix composites

    Science.gov (United States)

    Bhatt, Ramakrishna T.

    1989-01-01

    The room temperature mechanical properties of SiC fiber reinforced reaction bonded silicon nitride composites were measured after 100 hrs exposure at temperatures to 1400 C in nitrogen and oxygen environments. The composites consisted of approx. 30 vol percent uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The results indicate that composites heat treated in a nitrogen environment at temperatures to 1400 C showed deformation and fracture behavior equivalent to that of the as-fabricated composites. Also, the composites heat treated in an oxidizing environment beyond 400 C yielded significantly lower tensile strength values. Specifically in the temperature range from 600 to 1000 C, composites retained approx. 40 percent of their as-fabricated strength, and those heat treated in the temperatures from 1200 to 1400 C retained 70 percent. Nonetheless, for all oxygen heat treatment conditions, composite specimens displayed strain capability beyond the matrix fracture stress; a typical behavior of a tough composite.

  17. Formation of N-nitrosodimethylamine (NDMA) from reaction of monochloramine: a new disinfection by-product.

    Science.gov (United States)

    Choi, Junghoon; Valentine, Richard L

    2002-02-01

    Studies have been conducted specifically to investigate the hypothesis that N-nitrosodimethylamine (NDMA) can be produced by reactions involving monochloramine. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed from the reaction between DMA and monochloramine indicating that it should be considered a potential disinfection by-product. The formation of NDMA increased with increased monochloramine concentration and showed maximum in yield when DMA was varied at fixed monochloramine concentrations. The mass spectra of the NDMA formed from DMA and 15N isotope labeled monochloramine (15NH2Cl) showed that the source of one of the nitrogen atoms in the nitroso group in NDMA was from monochloramine. Addition of 0.05 and 0.5 mM of preformed monochloramine to a secondarily treated wastewater at pH 7.2 also resulted in the formation of 3.6 and 111 ng/L of NDMA, respectively, showing that this is indeed an environmentally relevant NDMA formation pathway. The proposed NDMA formation mechanism consists of (i) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (ii) the oxidation of UDMH by monochloramine to NDMA, and (iii) the reversible chlorine transfer reaction between monochloramine and DMA which is parallel to (i). We conclude that reactions involving monochloramine in addition to classical nitrosation reactions are potentially important pathways for NDMA formation.

  18. Quasifission in heavy and superheavy element formation reactions

    International Nuclear Information System (INIS)

    Hinde, D.J.; Dasgupta, M.; Jeung, D.Y.; Mohanto, G.; Prasad, E.; Simenel, C.; Walshe, J.; Wahkle, A.; Williams, E.; Carter, I.P.; Cook, K.J.; Kalkal, Sunil; Rafferty, D.C.; Rietz, R. du; Simpson, E.C.; David, H.M.; Düllmann, Ch.E.; Khuyagbaatar, J.

    2016-01-01

    Superheavy elements are created in the laboratory by the fusion of two heavy nuclei. The large Coulomb repulsion that makes superheavy elements decay also makes the fusion process that forms them very unlikely. Instead, after sticking together for a short time, the two nuclei usually come apart, in a process called quasifission. Mass-angle distributions give the most direct information on the characteristics and time scales of quasifission. A systematic study of carefully chosen mass-angle distributions has provided information on the global trends of quasifission. Large deviations from these systematics reveal the major role played by the nuclear structure of the two colliding nuclei in determining the reaction outcome, and thus implicitly in hindering or favouring superheavy element production.

  19. Spectroscopic Identification of the Au-C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold.

    Science.gov (United States)

    Guo, Limin; Ma, Lipo; Zhang, Yelong; Cheng, Xun; Xu, Ye; Wang, Jin; Wang, Erkang; Peng, Zhangquan

    2016-11-08

    Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self-assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar) n , which can be further degraded to a monolayer of Au-Ar-S - by electrochemical cleavage of the S-S moieties within the multilayer. By conducting an in situ surface-enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au-C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au-C bond being intrinsically stronger than the Au-S bond for a given phenylthiolate compound by ca. 0.4 eV.

  20. Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O-O Bond Formation Pathways by Different Aggregation Patterns.

    Science.gov (United States)

    Yang, Bing; Jiang, Xin; Guo, Qing; Lei, Tao; Zhang, Li-Ping; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

    2016-05-17

    The oxidation of water to molecular oxygen is the key step to realize water splitting from both biological and chemical perspective. In an effort to understand how water oxidation occurs on a molecular level, a large number of molecular catalysts have been synthesized to find an easy access to higher oxidation states as well as their capacity to make O-O bond. However, most of them function in a mixture of organic solvent and water and the O-O bond formation pathway is still a subject of intense debate. Herein, we design the first amphiphilic Ru-bda (H2 bda=2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts (WOCs) of formula [Ru(II) (bda)(4-OTEG-pyridine)2 ] (1, OTEG=OCH2 CH2 OCH2 CH2 OCH3 ) and [Ru(II) (bda)(PySO3 Na)2 ] (2, PySO3 (-) =pyridine-3-sulfonate), which possess good solubility in water. Dynamic light scattering (DLS), scanning electron microscope (SEM), critical aggregation concentration (CAC) experiments and product analysis demonstrate that they enable to self-assemble in water and form the O-O bond through different routes even though they have the same bda(2-) backbone. This work illustrates for the first time that the O-O bond formation pathway can be regulated by the interaction of ancillary ligands at supramolecular level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

    Science.gov (United States)

    Stinson, Craig A; Xia, Yu

    2016-06-21

    Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

  2. On the Mechanism of the Copper-Mediated C-S Bond Formation in the Intramolecular Disproportionation of Imine Disulfides

    Czech Academy of Sciences Publication Activity Database

    Rokob, Tibor András; Rulíšek, Lubomír; Šrogl, Jiří; Révész, Agnes; Zins, Emilie-Laure; Schröder, Detlef

    2011-01-01

    Roč. 50, č. 20 (2011), s. 9968-9979 ISSN 0020-1669 R&D Projects: GA MŠk LC512 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : collision-induced dissociation * DFT calculations * C-S bond formation * Cu(I) catalysis * infrared multiphoton spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.601, year: 2011

  3. Skeletal Diversity in Combinatorial Fashion: A New Format for the Castagnoli-Cushman Reaction.

    Science.gov (United States)

    Lepikhina, Anastasia; Dar'in, Dmitry; Bakulina, Olga; Chupakhin, Evgeny; Krasavin, Mikhail

    2017-11-13

    A new format for the Castagnoli-Cushman reaction of structurally diverse dicarboxylic acids, amines, and aldehydes in the presence of acetic anhydride as dehydrating agent is described. The reaction is distinctly amenable to parallel format: the combinatorial array of 180 reactions delivered 157 products of >85% purity without chromatographic purification (of this number, 143 compounds had >94% purity). The new method offers a convenient preparation of the skeletally and peripherally diverse, lead- and druglike γ- and δ-lactam carboxylic acids with high diastereoselectivity in combinatorial fashion.

  4. Supercritical carbon dioxide versus toluene as reaction media in silica functionalisation: Synthesis and characterisation of bonded aminopropyl silica intermediate.

    Science.gov (United States)

    Ashu-Arrah, Benjamin A; Glennon, Jeremy D

    2017-06-09

    This research reports supercritical carbon dioxide versus toluene as reaction media in silica functionalisation for use in liquid chromatography. Bonded aminopropyl silica (APS) intermediates were prepared when porous silica particles (Exsil-pure, 3μm) were reacted with 3-aminopropyltriethoxysilane (3-APTES) or N,N-dimethylaminopropyltrimethoxysilane (DMAPTMS) using supercritical carbon dioxide (sc-CO 2 ) and toluene as reaction media. Covalent bonding to silica was confirmed using elemental microanalysis (CHN), thermogravimetric analysis (TGA), zeta potential (ξ), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, scanning electron microscopy (SEM) and solid-state nuclear magnetic resonance (CP/MAS NMR) spectroscopy. The results demonstrate that under sc-CO 2 conditions of 100°C/414bar in a substantial reduced time of 3h, the surface coverage of APS (evaluated from%C obtained from elemental analysis) prepared with APTES (%C: 8.03, 5.26μmol/m -2 ) or DMAPTES (%C: 5.12, 4.58μmol/m 2 ) is somewhat higher when compared to organic based reactions under reflux in toluene at a temperature of 110°C in 24h with APTES (%C: 7.33, 4.71μmol/m 2 ) and DMAPTMS (%C: 4.93, 4.38μmol/m 2 ). Zeta potential measurements revealed a change in electrostatic surface charge from negative values for bare Exsil-pure silica to positive for functionalised APS materials indicating successful immobilization of the aminosilane onto the surface of silica. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

    Science.gov (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

    2018-02-01

    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  6. The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

    Science.gov (United States)

    Jaisi, Deb P.; Eberl, Dennis D.; Dong, Hailiang; Kim, Jinwook

    2011-01-01

    The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65°C) were the most favorable conditions for the formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

  7. Determination of Double Bond Positions in Polyunsaturated Fatty Acids Using the Photochemical Paternò-Büchi Reaction with Acetone and Tandem Mass Spectrometry.

    Science.gov (United States)

    Murphy, Robert C; Okuno, Toshiaki; Johnson, Christopher A; Barkley, Robert M

    2017-08-15

    The positions of double bonds along the carbon chain of methylene interrupted polyunsaturated fatty acids are unique identifiers of specific fatty acids derived from biochemical reactions that occur in cells. It is possible to obtain direct structural information as to these double bond positions using tandem mass spectrometry after collisional activation of the carboxylate anions of an acetone adduct at each of the double bond positions formed by the photochemical Paternò-Büchi reaction with acetone. This reaction can be carried out by exposing a small portion of an inline fused silica capillary to UV photons from a mercury vapor lamp as the sample is infused into the electrospray ion source of a mass spectrometer. Collisional activation of [M - H] - yields a series of reverse Paternò-Büchi reaction product ions that essentially are derived from cleavage of the original carbon-carbon double bonds that yield an isopropenyl carboxylate anion corresponding to each double bond location. Aldehydic reverse Paternò-Büchi product ions are much less abundant as the carbon chain length and number of double bonds increase. The use of a mixture of D 0 /D 6 -acetone facilitates identification of these double bonds indicating product ions as shown for arachidonic acid. If oxygen is present in the solvent stream undergoing UV photoactivation, ozone cleavage ions are also observed without prior collisional activation. This reaction was used to determine the double bond positions in a 20:3 fatty acid that accumulated in phospholipids of RAW 264.7 cells cultured for 3 days.

  8. Diels-Alder Reactions in Water. Effects of Hydrophobicity and Hydrogen Bonding

    NARCIS (Netherlands)

    Otto, Sijbren; Blokzijl, Wilfried; Engberts, Jan B.F.N.

    1994-01-01

    In order to check whether the activated complex for the Diels-Alder reactions of 5-substituted 1,4-naphthoquinones with cyclopentadiene is more polar in water than in other solvents, we have determined the substituent effects in seven different solvents. The substituent effects gradually decrease

  9. Dynamical hindrance to compound nucleus formation in heavy ion reactions

    International Nuclear Information System (INIS)

    Blocki, J.; Feldmeier, H.; Swiatecki, W.J.

    1987-01-01

    A large number of dynamical trajectories corresponding to colliding nuclei, as represented by an idealized, sharp-surfaced liquid-drop model with one-body dissipation are examined. The objective was to delineate quantitatively, within this model, the behaviour of the extra-extra-push energy E XX in its dependence on the mass /or charge/ numbers of the colliding nuclei. Qualitatively, the results are as anticipated on the basis of earlier studies: the appearance of a dynamical limitation on compound nucleus formation beyond a certain threshold locus in the A 1 . A 2 plane, with the energy E XX rising smoothly but rapidly beyond the threshold. The reduction of the two-dimensional function E XX /A 1 ,A 2 / to a one-dimensional function of a mean fissility x m appears possible as a rough approximation. As expected, the mean fissility x and the entrance channel fissility x 0 . The optimum choice appears to be one in which x is given about twice the weight of x 0

  10. Optimization of Si–C reaction temperature and Ge thickness in C-mediated Ge dot formation

    Energy Technology Data Exchange (ETDEWEB)

    Satoh, Yuhki, E-mail: yu-ki@ecei.tohoku.ac.jp; Itoh, Yuhki; Kawashima, Tomoyuki; Washio, Katsuyoshi

    2016-03-01

    To form Ge dots on a Si substrate, the effect of thermal reaction temperature of sub-monolayer C with Si (100) was investigated and the deposited Ge thickness was optimized. The samples were prepared by solid-source molecular beam epitaxy with an electron-beam gun for C sublimation and a Knudsen cell for Ge evaporation. C of 0.25 ML was deposited on Si (100) at a substrate temperature of 200 °C, followed by a high-temperature treatment at the reaction temperature (T{sub R}) of 650–1000 °C to create Si–C bonds. Ge equivalent to 2 to 5 nm thick was subsequently deposited at 550 °C. Small and dense dots were obtained for T{sub R} = 750 °C but the dot density decreased and the dot diameter varied widely in the case of lower and higher T{sub R}. A dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge deposition equivalent to 3 to 5 nm thick and a standard deviation of dot diameter was the lowest of 10 nm for 5 nm thick Ge. These results mean that C-mediated Ge dot formation was strongly influenced not only by the c(4 × 4) reconstruction condition through the Si–C reaction but also the relationship between the Ge deposition thickness and the exposed Si (100)-(2 × 1) surface area. - Highlights: • The effect of Si–C reaction temperature on Ge dot formation was investigated. • Small and dense dots were obtained for T{sub R} = 750 °C. • The dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge = 3 to 5 nm. • The standard deviation of dot diameter was the lowest of 10 nm at Ge = 5 nm.

  11. EXFOR basics: A short guide to the nuclear reaction data exchange format

    International Nuclear Information System (INIS)

    McLane, V.

    1996-07-01

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear data compilation centers. This format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The exchange format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine). The data presently included in the EXFOR exchange include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle induced reaction data, a selected compilation of photon-induced reaction data

  12. Formation of Conjugated Double Bonds to Induce Polystyrene Conductivity by using Different Concentrations of Methoxo-Oxo Bis (8-Quinolyloxo Vanadium (V

    Directory of Open Access Journals (Sweden)

    Basim Mohamad Hasan

    2017-02-01

    Full Text Available The effect of different concentrations of additive compound methoxo–oxo bis (8-quinolyloxo vanadium (v on formation of conjugated double bonds as part of photo transformation of polystyrene has been investigated. The UV-Vis spectrophotometery has been used in this work. The results are show that additive concentrations applied increase the formation of conjugated double bond as compared with polystyrene. In this study methoxo – oxo bis (8-quinolyloxo vanadium (v indicates great activity to enhance the conductivity of polystyrene by formation of conjugated double bonds.

  13. Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

    Science.gov (United States)

    Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

    2016-07-01

    For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

  14. Thermal effects on the mechanical properties of SiC fibre reinforced reaction-bonded silicon nitride matrix composites

    Science.gov (United States)

    Bhatt, R. T.; Phillips, R. E.

    1990-01-01

    The elevated temperature four-point flexural strength and the room temperature tensile and flexural strength properties after thermal shock were measured for ceramic composites consisting of 30 vol pct uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The elevated temperature strengths were measured after 15 min of exposure in air at temperatures to 1400 C. Thermal shock treatment was accomplished by heating the composite in air for 15 min at temperatures to 1200 C and then quenching in water at 25 C. The results indicate no significant loss in strength properties either at temperature or after thermal shock when compared with the strength data for composites in the as-fabricated condition.

  15. Dynamics of Plug Formation in a Circular Cylinder Under Low Bond Number Conditions: Experiment and Simulation

    Science.gov (United States)

    Hallaby, Ghazi; Kizito, John P.

    2016-08-01

    The goal of the current study is to investigate the dynamics of two phase interface under a low Bond number condition. Silicone oil is injected into a cylinder under a Bond number of about 0.47 via a side tube forming a T-junction with the former. The time evolution of the interface of silicon oil in a cylinder is captured using a high speed camera. The volume at which the plug is formed is then determined using an image processing tool to analyze the captured images. A numerical simulation is carried out where fluid is injected into a cylinder, under a less than unity Bond number condition, via a side tube. Numerical and experimental results are then compared.

  16. Cross-Dehydrogenative Coupling Reactions Between P(O)-H and X-H (X = S, N, O, P) Bonds.

    Science.gov (United States)

    Hosseinian, Akram; Farshbaf, Sepideh; Fekri, Leila Zare; Nikpassand, Mohammad; Vessally, Esmail

    2018-05-26

    P(O)-X (X = S, N, O, P) bond-containing compounds have extensive application in medicinal chemistry, agrochemistry, and material chemistry. These useful organophosphorus compounds also have many applications in organic synthesis. In light of the importance of titled compounds, there is continuing interest in the development of synthetic methods for P(O)-X bonds construction. In the last 4 years, the direct coupling reaction of P(O)-H compounds with thiols, alcohols, and amines/amides has received much attention because of the atom-economic character. This review aims to give an overview of new developments in cross-dehydrogenative coupling reactions between P(O)-H and X-H (X = S, N, O, P) bonds, with special emphasis on the mechanistic aspects of the reactions.

  17. Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

    Science.gov (United States)

    Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

    2016-07-14

    We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

  18. Elementary Steps of Syngas Reactions on Mo2C(001): Adsorption Thermochemistry and Bond Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Medford, Andrew

    2012-02-16

    Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo{sub 2}C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorption energy scaling relations and Broensted-Evans-Polanyi relationships are established and used to place Mo{sub 2}C into the context of transition metal surfaces. The results indicate that the surface termination is a complex function of reaction conditions and kinetics. It is predicted that the surface will be covered by either C{sub 2}H{sub 2} or O depending on conditions. Comparisons to transition metals indicate that the Mo-terminated Mo{sub 2}C(001) surface exhibits carbon reactivity similar to transition metals such as Ru and Ir, but is significantly more reactive towards oxygen.

  19. Role of the Disulfide Bond in Prion Protein Amyloid Formation: A Thermodynamic and Kinetic Analysis.

    Science.gov (United States)

    Honda, Ryo

    2018-02-27

    Prion diseases are associated with the structural conversion of prion protein (PrP) to a β-sheet-rich aggregate, PrP Sc . Previous studies have indicated that a reduction of the disulfide bond linking C179 and C214 of PrP yields an amyloidlike β-rich aggregate in vitro. To gain mechanistic insights into the reduction-induced aggregation, here I characterized how disulfide bond reduction modulates the protein folding/misfolding landscape of PrP, by examining 1) the equilibrium stabilities of the native (N) and aggregated states relative to the unfolded (U) state, 2) the transition barrier separating the U and aggregated states, and 3) the final structure of amyloidlike misfolded aggregates. Kinetic and thermodynamic experiments revealed that disulfide bond reduction decreases the equilibrium stabilities of both the N and aggregated states by ∼3 kcal/mol, without changing either the amyloidlike aggregate structure, at least at the secondary structural level, or the transition barrier of aggregation. Therefore, disulfide bond reduction modulates the protein folding/misfolding landscape by entropically stabilizing disordered states, including the U and transition state of aggregation. This also indicates that the equilibrium stability of the N state, but not the transition barrier of aggregation, is the dominant factor determining the reduction-induced aggregation of PrP. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  20. Reaction heats and bond strengths based on a series of lectures given to postgraduate students at the University of Keele, 1960

    CERN Document Server

    Mortimer, C T

    1962-01-01

    Reaction Heats and Bond Strengths presents the variations in the heats of particular types of reaction. This book covers a variety of topics, including the hydrogenation and polymerization of olefinic compounds, the dissociation of organic and organo-metallic compounds, and the molecular-addition compounds. Organized into 10 chapters, this book begins with an overview of the concept of bond energy that can be very useful where a comparison is being made between two dissimilar molecules. This text then examines the strain in cyclopropane and cyclobutane, which is largely a result of angular str

  1. Suzuki-Miyaura cross-coupling reactions in aqueous media: Green and sustainable syntheses of biaryls

    KAUST Repository

    Polshettiwar, Vivek; Decottignies, Audrey; Len, Christophe; Fihri, Aziz

    2010-01-01

    Carbon-carbon cross-coupling reactions are among the most important processes in organic chemistry, and Suzuki-Miyaura reactions are among the most widely used protocols for the formation of carbon-carbon bonds. These reactions are generally

  2. The interaction of reaction-bonded silicon carbide and inconel 600 with a nickel-based brazing alloy

    Science.gov (United States)

    McDermid, J. R.; Pugh, M. D.; Drew, R. A. L.

    1989-09-01

    The objective of the present research was to join reaction-bonded silicon carbide (RBSC) to INCONEL 600 (a nickel-based superalloy) for use in advanced heat engine applications using either direct brazing or composite interlayer joining. Direct brazing experiments employed American Welding Society (AWS) BNi-5, a commercial nickel-based brazing alloy, as a filler material; composite interlayers consisted of intimate mixtures of α-SiC and BNi-5 powders. Both methods resulted in the liquid filler metal forming a Ni-Si liquid with the free Si in the RBSC, which, in turn, reacted vigorously with the SiC component of the RBSC to form low melting point constituents in both starting materials and Cr carbides at the metal-ceramic interface. Using solution thermodynamics, it was shown that a Ni-Si liquid of greater than 60 at. pct Ni will decompose a-SiC at the experimental brazing temperature of 1200 ‡C; these calculations are consistent with the experimentally observed composition profiles and reaction morphology within the ceramic. It was concluded that the joining of RBSC to INCONEL 600 using a nickel-based brazing alloy is not feasible due to the inevitability of the filler metal reacting with the ceramic, degrading the high-temperature properties of the base materials.

  3. A novel metal-to-metal bonding process through in-situ formation of Ag nanoparticles using Ag2O microparticles

    International Nuclear Information System (INIS)

    Hirose, Akio; Tatsumi, Hiroaki; Takeda, Naoya; Akada, Yusuke; Ogura, Tomo; Ide, Eiichi; Morita, Toshiaki

    2009-01-01

    The metal-to-metal bonding has been successfully achieved via the bonding process using Ag metallo-organic nanoparticles at a bonding temperature of around 300-, which can be alternative to the current microsoldering in electronics assembly using high-temperature solders. However, further reduction of bonding temperature and/or bonding pressure is needed. In the present research, a novel bonding process through in-situ formation of Ag nanoparticles instead of the filler material of the Ag metallo-organic nanoparticles has been developed. The Ag nanoparticles can form by the reduction of Ag 2 O particles. In this study, the Ag 2 O particles were mixed with triethylene glycol as a reducing agent to form a paste for bonding. The Au coated cylindrical specimens were bonded using the paste. The Ag nanoparticles formed at around 130 to 160 through the reduction process of Ag2O particles with triethylene glycol. The Ag nanoparticles were immediately sintered each other due to a great surface energy per volume. A transmission electron microscope observation revealed that the sintered Ag metallurgically bonded to the Au substrate at around 160 and a dense Ag layer formed after further heating. The tensile strength of the joint bonded at 250 under a bonding pressure of 5MPa was around 60MPa

  4. Chemical-Reaction-Controlled Phase Separated Drops: Formation, Size Selection, and Coarsening

    Science.gov (United States)

    Wurtz, Jean David; Lee, Chiu Fan

    2018-02-01

    Phase separation under nonequilibrium conditions is exploited by biological cells to organize their cytoplasm but remains poorly understood as a physical phenomenon. Here, we study a ternary fluid model in which phase-separating molecules can be converted into soluble molecules, and vice versa, via chemical reactions. We elucidate using analytical and simulation methods how drop size, formation, and coarsening can be controlled by the chemical reaction rates, and categorize the qualitative behavior of the system into distinct regimes. Ostwald ripening arrest occurs above critical reaction rates, demonstrating that this transition belongs entirely to the nonequilibrium regime. Our model is a minimal representation of the cell cytoplasm.

  5. Formation and reactions of radical cations of substituted benzenes in aqueous media

    International Nuclear Information System (INIS)

    Holcman, J.

    1977-08-01

    Radical cations of anisole, methylated benzenes, ethylbenzene, isopropylbenzene, tert-butylbenzene and N,N-dimethylaniline were studied in aqueous media by pulse radiolytic technique. Absorption spectra and reaction kinetics of the radical cations were recorded. The radical cations are formed from the corresponding OH adducts by the elimination of OH - , either by a simple dissociation or by an acid catalyzed reaction. The rate constants of the formation of the radical cations and their reactions with water, OH - and Fe 2+ , or the reaction of a proton loss, were measured. The rate constants for the reaction with water and OH - , together with the rate constants for the dissociation of the OH adducts, are correlated with the ionization potential of the parent compound. These correlations offer a possibility of predicting the acid-base properties of radical cations of substituted benzenes, or the estimation of their ionization potential. (author)

  6. EXFOR systems manual: Nuclear reaction data exchange format. Revision 97/1

    International Nuclear Information System (INIS)

    McLane, V.

    1997-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Center Network. In addition to storing the data and its' bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility rather than optimization of data processing in order to meet the diverse needs of the nuclear reaction data centers. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine)

  7. Gas to liquid to solid transition in halogen hot atom chemistry. 6. Product formation routes and chemical selectivity of high energy iodine reactions with butyne isomers

    International Nuclear Information System (INIS)

    Garmestani, S.K.; Firouzbakht, M.L.; Rack, E.P.

    1979-01-01

    Reactions of recoil produced iodine-128 with isomers of butyne were studied in gaseous, high pressure, and condensed phase conditions, with rare gas additives and in the presence and absence of radical scavengers (I 2 and O 2 ). It was found that recoil iodine-128 reactions were initiated by thermal electronically excited I + species for both 1-butyne and 2-butyne systems. While the diverse and complex nature of the reactions cannot be explained by simple chemical parameters, comparisons among the alkyne systems demonstrate preferential attack of iodine at the triple bond resulting, mainly, in electronically excited intermediates. A comparison of the various product formation routes results in the characterization of general traits common to the alkynes. 6 figures, 4 tables

  8. Probability of conductive bond formation in a percolating network of nanowires with fusible tips

    Science.gov (United States)

    Rykaczewski, Konrad; Wang, Robert Y.

    2018-03-01

    Meeting the heat dissipation demands of microelectronic devices requires development of polymeric composites with high thermal conductivity. This property is drastically improved by percolation networks of metallic filler particles that have their particle-to-particle contact resistances reduced through thermal or electromagnetic fusing. However, composites with fused metallic fillers are electrically conductive, which prevents their application within the chip-board and the inter-chip gaps. Here, we propose that electrically insulating composites for these purposes can be achieved by the application of fusible metallic coatings to the tips of nanowires with thermally conductive but electrically insulating cores. We derive analytical models that relate the ratio of the coated and total nanowire lengths to the fraction of fused, and thus conductive, bonds within percolating networks of these structures. We consider two types of materials for these fusible coatings. First, we consider silver-like coatings, which form only conductive bonds when contacting the silver-like coating of another nanowire. Second, we consider liquid metal-like coatings, which form conductive bonds regardless of whether they contact a coated or an uncoated segment of another nanowire. These models were validated using Monte Carlo simulations, which also revealed that electrical short-circuiting is highly unlikely until most of the wire is coated. Furthermore, we demonstrate that switching the tip coating from silver- to liquid metal-like materials can double the fraction of conductive bonds. Consequently, this work provides motivation to develop scalable methods for fabrication of the hybrid liquid-coated nanowires, whose dispersion in a polymer matrix is predicted to yield highly thermally conductive but electrically insulating composites.

  9. Bond breaking and bond making in tetraoxygen: analysis of the O2(X3Sigma(g)-) + O2(X3Sigma(g)-) O4 reaction using the electron pair localization function.

    Science.gov (United States)

    Scemama, Anthony; Caffarel, Michel; Ramírez-Solís, Alejandro

    2009-08-06

    We study the nature of the electron pairing at the most important critical points of the singlet potential energy surface of the 2O2 O4 reaction and its evolution along the reaction coordinate using the electron pair localization function (EPLF) [Scemama, A.; Chaquin, P.; Caffarel, M. J. Chem. Phys. 2004, 121, 1725]. To do that, the 3D topology of the EPLF calculated with quantum Monte Carlo (at both variational and fixed-node-diffusion Monte Carlo levels) using Hartree-Fock, multiconfigurational CASSCF, and explicitly correlated trial wave functions is analyzed. At the O4 equilibrium geometry the EPLF analysis reveals four equivalent covalent bonds and two lone pairs on each oxygen atom. Along the reaction path toward dissociation it is found that the two oxygen-oxygen bonds are not broken simultaneously but sequentially, and then the lone pairs are rearranged. In a more general perspective, the usefulness of the EPLF as a unique tool to analyze the topology of electron pairing in nontrivial chemical bonding situations as well as to visualize the major steps involved in chemical reactivity is emphasized. In contrast with most standard schemes to reveal electron localization (atoms in molecules, electron localization function, natural bond orbital, etc.), the newly introduced EPLF function gives a direct access to electron pairings in molecules.

  10. Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

    DEFF Research Database (Denmark)

    Rasmussen, Jonas Stensgaard; Barsberg, Søren Talbro; Venås, Thomas Mark

    2014-01-01

    In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation...... of ether linkages between lignin and titanium coupling agent. In the present work, changes were found in the attenuated total reflectance-Fourier transform IR (ATR-FTIR) spectra of lignin and wood mixed with silane, and titanium coupling agents, and to a lesser extent for a zirconium coupling agent...

  11. Fused-Ring Formation by an Intramolecular "Cut-and-Sew" Reaction between Cyclobutanones and Alkynes.

    Science.gov (United States)

    Deng, Lin; Jin, Likun; Dong, Guangbin

    2018-03-01

    The development of a catalytic intramolecular "cut-and-sew" transformation between cyclobutanones and alkynes to construct cyclohexenone-fused rings is described herein. The challenge arises from the need for selective coupling at the more sterically hindered proximal position, and can be addressed by using an electron-rich, but less bulky, phosphine ligand. The control experiment and 13 C-labelling study suggest that the reaction may start with cleavage of the less hindered distal C-C bond of cyclobutanones, followed by decarbonylation and CO reinsertion to enable Rh insertion at the more hindered proximal position. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Reactivity of the parent amido complexes of iridium with olefins: C-NH2 bond formation versus C-H activation.

    Science.gov (United States)

    Mena, Inmaculada; García-Orduña, Pilar; Polo, Víctor; Lahoz, Fernando J; Casado, Miguel A; Oro, Luis A

    2017-08-29

    Herein we report on the different chemical reactivity displayed by two mononuclear terminal amido compounds depending on the nature of the coordinated diene. Hence, treatment of amido-bridged iridium complexes [{Ir(μ-NH 2 )(tfbb)} 3 ] (1; tfbb = tetrafluorobenzobarrelene) with dppp (dppp = bis(diphenylphosphane)propane) leads to the rupture of the amido bridges forming the mononuclear terminal amido compound [Ir(NH 2 )(dppp)(tfbb)] (3) in the first stage. On changing the reaction conditions, the formation of a C-NH 2 bond between the amido moiety and the coordinated diene is observed and a new dinuclear complex [{Ir(1,2-η 2 -4-κ-C 12 H 8 F 4 N)(dppp)} 2 (μ-dppp)] (4) has been isolated. On the contrary, the diiridium amido-bridged complex [{Ir(μ-NH 2 )(cod)} 2 ] (2; cod = 1,5-cyclooctadiene) in the presence of dppb (dppb = bis(diphenylphosphane)butane) allows the isolation of a mononuclear complex [Ir(1,2,3-η 3 -6-κ-C 8 H 10 )H(dppb)] (5), as a consequence of the extrusion of ammonia. The monitoring of the reaction of 2 with dppb (and dppp) allowed us to detect terminal amido complexes [Ir(NH 2 )(P-P)(cod)] (P-P = dppb (6), dppp (7)) in solution, as confirmed by an X-ray analysis of 7. Complex 7 was observed to evolve into hydrido species 5 at room temperature. DFT studies showed that C-H bond activation occurs through the deprotonation of one methylene fragment of the cod ligand by the highly basic terminal amido moiety instead of C-H oxidative addition to the Ir(i) center.

  13. A quantum-chemical validation about the formation of hydrogen bonds and secondary interactions in intermolecular heterocyclic systems

    Directory of Open Access Journals (Sweden)

    Boaz Galdino Oliveira

    2009-08-01

    Full Text Available We have performed a detailed theoretical study in order to understand the charge density topology of the C2H4O···C2H2 and C2H4S···C2H2 heterocyclic hydrogen-bonded complexes. Through the calculations derived from Quantum Theory of Atoms in Molecules (QTAIM, it was observed the formation of hydrogen bonds and secondary interactions. Such analysis was performed through the determination of optimized geometries at B3LYP/6-31G(d,p level of theory, by which is that QTAIM topological operators were computed, such as the electronic density ρ(r, Laplacian Ñ2ρ(r, and ellipticity ε. The examination of the hydrogen bonds has been performed through the measurement of ρ(r, Ñ2ρ(r and ε between (O···H—C and (S···H—C, whereas the secondary interaction between axial hydrogen atoms Hα and carbon of acetylene. In this insight, it was verified the existence of secondary interaction only in C2H4S···C2H2 complex because its structure is propitious to form multiple interactions.

  14. Effects of online advertising format and persuasion knowledge on audience reactions

    NARCIS (Netherlands)

    Tutaj, K.; van Reijmersdal, E.A.

    2012-01-01

    In an experiment (N = 99), effects of subtle and prominent online advertising formats, respectively sponsored content and banner ads, on audience reactions toward the advertisement are tested. In addition, the role of several persuasion knowledge elements such as understanding of persuasive intent

  15. In-situ X-ray diffraction : a useful tool to investigate hydride-formation reactions

    NARCIS (Netherlands)

    Notten, P.H.L.; Daams, J.L.C.; Veirman, de A.E.M.; Staals, A.A.

    1994-01-01

    A high-pressure X-ray diffraction (XRD) cell has been designed which allowed us to study simultaneously hydrogen absorption/desorption isotherms and XRD powder diffraction patterns on (de)hydrided intermetallic compounds. The hydride formation reaction was investigated in the case of LaNi5 under

  16. Toward a Kinetic Model for Acrylamide Formation in a Glucose-Asparagine Reaction System

    NARCIS (Netherlands)

    Knol, J.J.; Loon, W.A.M.; Linssen, J.P.H.; Ruck, A.L.; Boekel, van M.A.J.S.

    2005-01-01

    A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different tempera-tures (120-200 C) at pH 6.8. Besides the reactants, acrylamide, fructose, and melanoidins were quantified after

  17. Study of reaction sequences for formation of solid solution: 0,48 ...

    African Journals Online (AJOL)

    ... of a low concentration of ions forming the perovskite structure PZT (Pb2+, Zr4+ et Ti4+) by other ions (Zn2+, Cr3+ et Sb+5 in our study) alters the reaction sequences training of the solid solution PZT and especially the formation of intermediate phase. Keywords: PZT / Calcination / TGA / DTA / RX / Piezoelectric Ceramics ...

  18. Formation of amorphous Ti-50at.%Pt by solid state reactions during mechanical alloying

    CSIR Research Space (South Africa)

    Mahlatji, ML

    2013-10-01

    Full Text Available Mechanical alloying of an equiatomic mixture of crystalline elemental powders of Ti and Pt in a high-energy ball mill results in formation of an amorphous alloy by solid-state reactions. Mechanical alloying was carried out in an argon atmosphere...

  19. Suppression of interfacial voids formation during silane (SiH4)-based silicon oxide bonding with a thin silicon nitride capping layer

    Science.gov (United States)

    Lee, Kwang Hong; Bao, Shuyu; Wang, Yue; Fitzgerald, Eugene A.; Seng Tan, Chuan

    2018-01-01

    The material properties and bonding behavior of silane-based silicon oxide layers deposited by plasma-enhanced chemical vapor deposition were investigated. Fourier transform infrared spectroscopy was employed to determine the chemical composition of the silicon oxide films. The incorporation of hydroxyl (-OH) groups and moisture absorption demonstrates a strong correlation with the storage duration for both as-deposited and annealed silicon oxide films. It is observed that moisture absorption is prevalent in the silane-based silicon oxide film due to its porous nature. The incorporation of -OH groups and moisture absorption in the silicon oxide films increase with the storage time (even in clean-room environments) for both as-deposited and annealed silicon oxide films. Due to silanol condensation and silicon oxidation reactions that take place at the bonding interface and in the bulk silicon, hydrogen (a byproduct of these reactions) is released and diffused towards the bonding interface. The trapped hydrogen forms voids over time. Additionally, the absorbed moisture could evaporate during the post-bond annealing of the bonded wafer pair. As a consequence, defects, such as voids, form at the bonding interface. To address the problem, a thin silicon nitride capping film was deposited on the silicon oxide layer before bonding to serve as a diffusion barrier to prevent moisture absorption and incorporation of -OH groups from the ambient. This process results in defect-free bonded wafers.

  20. Electron Reorganization in Allowed and Forbidden Reactions: Multicenter Bond Indices as a Measure of Aromaticity and/or Anti-aromaticity in Transition States of Pericyclic Electrocyclizations

    Czech Academy of Sciences Publication Activity Database

    Mandado, M.; Ponec, Robert

    2009-01-01

    Roč. 22, č. 12 (2009), s. 1225-1232 ISSN 0894-3230 R&D Projects: GA ČR GA203/09/0118 Institutional research plan: CEZ:AV0Z40720504 Keywords : pericycli reactions * aromaticity * multicenter bond indices Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.602, year: 2009

  1. A cascade of acid-promoted C-O bond cleavage and redox reactions: from oxa-bridged benzazepines to benzazepinones.

    Science.gov (United States)

    Zhang, Yuewei; Yang, Fengzhi; Zheng, Lianyou; Dang, Qun; Bai, Xu

    2014-12-05

    A sequence of C-O bond cleavage and redox reactions in oxa-bridged azepines was realized under acid promoted conditions. This protocol provides an atom-economical and straightforward approach to access benzo[b]azepin-5(2H)-ones in high yields. The formal synthesis of tolvaptan was achieved by exploiting this new transformation.

  2. Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

    KAUST Repository

    Elshewy, Ahmed M.

    2013-01-01

    linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts

  3. Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

    KAUST Repository

    Yang, Wenguo; Tan, Davin; Lee, Richmond; Li, Lixin; Pan, Yuanhang; Huang, Kuo-Wei; Tan, Choonhong; Jiang, Zhiyong

    2012-01-01

    Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E

  4. Interstellar hydrogen bonding

    Science.gov (United States)

    Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

    2018-06-01

    This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

  5. Mechanisms for the reactions of group 10 transition metal complexes with metal-group 14 element bonds, Bbt(Br)E═M(PCy3)2 (E = C, Si, Ge, Sn, Pb; M = Pd and Pt).

    Science.gov (United States)

    Liao, Wei-Hung; Ho, Pei-Yun; Su, Ming-Der

    2013-02-04

    The electronic structures of the Bbt(Br)E═M(PCy(3))(2) (E = C, Si, Ge, Sn, Pb and M = Pt, Pd) complexes and their potential energy surfaces for the formation and water addition reactions were studied using density functional theory (B3LYP/LANL2DZ). The theoretical evidence suggests that the bonding character of the E═M double bond between the six valence-electron Bbt(Br)E: species and the 14 valence-electron (PCy(3))(2)M complexes has a predominantly high s-character. That is, on the basis of the NBO, this theoretical study indicates that the σ-donation from the E element to the M atom prevails. Also, theoretical computations suggest that the relative reactivity decreases in the order: Bbt(Br)C═M(PCy(3))(2) > Bbt(Br)Si═M(PCy(3))(2) > Bbt(Br)Ge═M(PCy(3))(2) > Bbt(Br)Sn═M(PCy(3))(2) > Bbt(Br)Pb═M(PCy(3))(2), irrespective of whether M = Pt or M = Pd is chosen. Namely, the greater the atomic weight of the group 14 atom (E), the larger is the atomic radius of E and the more stable is its Bbt(Br)E═M(PCy(3))(2) doubly bonded species toward chemical reactions. The computational results show good agreement with the available experimental observations. The theoretical results obtained in this work allow a number of predictions to be made.

  6. Pore-scale studies of multiphase flow and reaction involving CO2 sequestration in geologic formations

    Science.gov (United States)

    Kang, Q.; Wang, M.; Lichtner, P. C.

    2008-12-01

    In geologic CO2 sequestration, pore-scale interfacial phenomena ultimately govern the key processes of fluid mobility, chemical transport, adsorption, and reaction. However, spatial heterogeneity at the pore scale cannot be resolved at the continuum scale, where averaging occurs over length scales much larger than typical pore sizes. Natural porous media, such as sedimentary rocks and other geological media encountered in subsurface formations, are inherently heterogeneous. This pore-scale heterogeneity can produce variabilities in flow, transport, and reaction processes that take place within a porous medium, and can result in spatial variations in fluid velocity, aqueous concentrations, and reaction rates. Consequently, the unresolved spatial heterogeneity at the pore scale may be important for reactive transport modeling at the larger scale. In addition, current continuum models of surface complexation reactions ignore a fundamental property of physical systems, namely conservation of charge. Therefore, to better understand multiphase flow and reaction involving CO2 sequestration in geologic formations, it is necessary to quantitatively investigate the influence of the pore-scale heterogeneity on the emergent behavior at the field scale. We have applied the lattice Boltzmann method to simulating the injection of CO2 saturated brine or supercritical CO2 into geological formations at the pore scale. Multiple pore-scale processes, including advection, diffusion, homogeneous reactions among multiple aqueous species, heterogeneous reactions between the aqueous solution and minerals, ion exchange and surface complexation, as well as changes in solid and pore geometry are all taken into account. The rich pore scale information will provide a basis for upscaling to the continuum scale.

  7. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Science.gov (United States)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-09-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  8. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Energy Technology Data Exchange (ETDEWEB)

    Fedorenko, S. G. [Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk (Russian Federation); Burshtein, A. I. [Weizmann Institute of Science, 76100, Rehovot (Israel)

    2014-09-21

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  9. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    International Nuclear Information System (INIS)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-01-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics

  10. Formation of hydrogen bonds precedes the rate-limiting formation of persistent structure in the folding of ACBP

    DEFF Research Database (Denmark)

    Teilum, K; Kragelund, B B; Knudsen, J

    2000-01-01

    A burst phase in the early folding of the four-helix two-state folder protein acyl-coenzyme A binding protein (ACBP) has been detected using quenched-flow in combination with site-specific NMR-detected hydrogen exchange. Several of the burst phase structures coincide with a structure consisting...... of eight conserved hydrophobic residues at the interface between the two N and C-terminal helices. Previous mutation studies have shown that the formation of this structure is rate limiting for the final folding of ACBP. The burst phase structures observed in ACBP are different from the previously reported...

  11. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  12. Multifunctional Hydrogel with Good Structure Integrity, Self-Healing, and Tissue-Adhesive Property Formed by Combining Diels-Alder Click Reaction and Acylhydrazone Bond.

    Science.gov (United States)

    Yu, Feng; Cao, Xiaodong; Du, Jie; Wang, Gang; Chen, Xiaofeng

    2015-11-04

    Hydrogel, as a good cartilage tissue-engineered scaffold, not only has to possess robust mechanical property but also has to have an intrinsic self-healing property to integrate itself or the surrounding host cartilage. In this work a double cross-linked network (DN) was designed and prepared by combining Diels-Alder click reaction and acylhydrazone bond. The DA reaction maintained the hydrogel's structural integrity and mechanical strength in physiological environment, while the dynamic covalent acylhydrazone bond resulted in hydrogel's self-healing property and controlled the on-off switch of network cross-link density. At the same time, the aldehyde groups contained in hydrogel further promote good integration of the hydrogel to surrounding tissue based on aldehyde-amine Schiff-base reaction. This kind of hydrogel has good structural integrity, autonomous self-healing, and tissue-adhesive property and simultaneously will have a good application in tissue engineering and tissue repair field.

  13. Advanced multivariate data analysis to determine the root cause of trisulfide bond formation in a novel antibody–peptide fusion

    Science.gov (United States)

    Goldrick, Stephen; Holmes, William; Bond, Nicholas J.; Lewis, Gareth; Kuiper, Marcel; Turner, Richard

    2017-01-01

    ABSTRACT Product quality heterogeneities, such as a trisulfide bond (TSB) formation, can be influenced by multiple interacting process parameters. Identifying their root cause is a major challenge in biopharmaceutical production. To address this issue, this paper describes the novel application of advanced multivariate data analysis (MVDA) techniques to identify the process parameters influencing TSB formation in a novel recombinant antibody–peptide fusion expressed in mammalian cell culture. The screening dataset was generated with a high‐throughput (HT) micro‐bioreactor system (AmbrTM 15) using a design of experiments (DoE) approach. The complex dataset was firstly analyzed through the development of a multiple linear regression model focusing solely on the DoE inputs and identified the temperature, pH and initial nutrient feed day as important process parameters influencing this quality attribute. To further scrutinize the dataset, a partial least squares model was subsequently built incorporating both on‐line and off‐line process parameters and enabled accurate predictions of the TSB concentration at harvest. Process parameters identified by the models to promote and suppress TSB formation were implemented on five 7 L bioreactors and the resultant TSB concentrations were comparable to the model predictions. This study demonstrates the ability of MVDA to enable predictions of the key performance drivers influencing TSB formation that are valid also upon scale‐up. Biotechnol. Bioeng. 2017;114: 2222–2234. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. PMID:28500668

  14. Control of reactivity and regioselectivity for on-surface dehydrogenative aryl-aryl bond formation

    Czech Academy of Sciences Publication Activity Database

    Kocić, N.; Liu, X.; Chen, S.; Decurtins, S.; Krejčí, Ondřej; Jelínek, Pavel; Repp, J.; Liu, S.

    2016-01-01

    Roč. 138, č. 17 (2016), s. 5585-5593 ISSN 0002-7863 R&D Projects: GA ČR(CZ) GC14-16963J Institutional support: RVO:68378271 Keywords : on-surface reaction * AFM * DFT * metal-organic coordination Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.858, year: 2016

  15. Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space.

    Science.gov (United States)

    Gamez-Garcia, Victoria G; Galano, Annia

    2017-10-05

    A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

  16. Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

    Energy Technology Data Exchange (ETDEWEB)

    Moradi, Christopher P.; Douberly, Gary E., E-mail: douberly@uga.edu [Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556 (United States); Xie, Changjian; Guo, Hua [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Kaufmann, Matin [Department of Physical Chemistry II, Ruhr-University Bochum, D-44801 Bochum (Germany)

    2016-04-28

    Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3} is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.

  17. Can Dietary Polyphenols Prevent the Formation of Toxic Compounds from Maillard Reaction?

    Science.gov (United States)

    Del Turco, Serena; Basta, Giuseppina

    2016-01-01

    Polyphenols are functional compounds in edible vegetable and food such as tea, coffee and red wine and increasing evidence demonstrates a positive link between consumption of polyphenol-rich foods and disease prevention. In this review we have focused on the current knowledge of the potential anti-glycation effects of polyphenols, particularly in regard to their influence on Maillard reaction, a non-enzymatic reaction between amino acids and reducing sugars that contributes to the production of toxic compounds, mainly reactive carbonyl species, advanced glycation end-products (AGEs) and other toxicants. The Maillard reaction occurs in the human body during hyperglycemic condition, but it is well known as browning reaction in thermally processed foods and it is responsible for flavor and toxicant formation. Dietary polyphenols can have anti-glycation effects and actively participate in Maillard reaction, mitigating the AGE formation and the heat-induced production of toxic compounds. In a time in which the role of a healthy diet in the prevention of chronic diseases is welcome and the borderline between food and medicine is becoming very thin, an improved mechanistic knowledge of how polyphenols can function to reduce harmful and unhealthy substances is mandatory.

  18. Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void

    International Nuclear Information System (INIS)

    Shan, Tzu-Ray; Thompson, Aidan P

    2014-01-01

    We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO 2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N 2 and H 2 O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

  19. Char and coke formation as unwanted side reaction of the hydrothermal biomass gasification

    Energy Technology Data Exchange (ETDEWEB)

    Karayildirim, T. [Department of Chemistry, Science Faculty, Ege University, Bornova-Izmir (Turkey); Sinag, A. [Department of Chemistry, Science Faculty, Ankara University, Besevler-Ankara (Turkey); Kruse, A. [Institut fuer Technische Chemie CPV, Forschungszentrum Karlsruhe GmbH, Karlsruhe (Germany)

    2008-11-15

    The hydrothermal biomass gasification is a promising technology to produce hydrogen and/or methane from wet biomass with a water content of {>=}80 % (g/g). In the process, the coke formation usually is very low, but already low amounts may cause problems like, e.g., fouling in the heat exchanger. To learn more about the product formation, the results of the hydrothermal treatment (at 400,500,600 C and 1 h) of different biomass feedstocks (artichoke stalk, pinecone, sawdust, and cellulose as model biomass) in a microreactor are compared. The gas composition and the total organic carbon content of the aqueous phase were determined after reaction. The gas formation rises with increasing temperature. The formation of carbon deposits and their characterization has been investigated by scanning electron microscopy (SEM). The variation of the solid morphology during the hydrothermal conversion is discussed based on chemical pathways occurring during hydrothermal biomass degradation. (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  20. Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

    Science.gov (United States)

    Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

    2000-12-01

    Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

  1. How the shape of an H-bonded network controls proton-coupled water activation in HONO formation.

    Science.gov (United States)

    Relph, Rachael A; Guasco, Timothy L; Elliott, Ben M; Kamrath, Michael Z; McCoy, Anne B; Steele, Ryan P; Schofield, Daniel P; Jordan, Kenneth D; Viggiano, Albert A; Ferguson, Eldon E; Johnson, Mark A

    2010-01-15

    Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)-bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

  2. Heat-induced whey protein isolate fibrils: Conversion, hydrolysis, and disulphide bond formation

    NARCIS (Netherlands)

    Bolder, S.G.; Vasbinder, A.; Sagis, L.M.C.; Linden, van der E.

    2007-01-01

    Fibril formation of individual pure whey proteins and whey protein isolate (WPI) was studied. The heat-induced conversion of WPI monomers into fibrils at pH 2 and low ionic strength increased with heating time and protein concentration. Previous studies, using a precipitation method, size-exclusion

  3. Organoactinides-new type of catalysts for carbon-silicon bond formation

    International Nuclear Information System (INIS)

    Dash, Aswini K.; Wang, Ji.Q.; Wang, Jiaxi; Gourevich, Ilya; Eisen, Moris S.

    2002-01-01

    Organoactinide complexes of the type Cp 2 * AnMe 2 (An=Th, U) have been found to be efficient catalysts for the hydrosilylation of terminal alkynes. The chemoselectivity and regiospecificity of the reactions depend strongly on the nature of the catalyst, the nature of the alkyne, the silane substituents, the ratio between the silane and alkyne, the solvent and the reaction temperature. The hydrosilylation reaction of the terminal alkynes with PhSiH 3 at room temperature produces the trans-vinylsilane as the major product along with the silylalkyne and the corresponding alkene. At higher temperatures the cis-vinylsilane and the double hydrosilylated alkene, in which the two silicon moieties are connected at the same carbon atom, are also obtained. Replacing the pentamethylcyclopentadienyl ligand by the bridge ligation [Me 2 SiCp'' 2 ] 2- 2[Li] + (Cp''=C 5 Me 4 ) affords the synthesis of ansa-Me 2 SiCp'' 2 ThBu 2 , which was found to react extremely fast for the hydrosilylation of terminal alkynes or alkenes with PhSiH 3 . Besides the rapidity of the processes using the bridge organoactinide, as compared to Cp * 2 ThMe 2 , the chemo- and regio-selectivity of the products were increased allowing the production of only the trans-vinylsilane and the 1-silylated alkane for the hydrosilylation of alkyne and alkene, respectively. (author)

  4. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    Energy Technology Data Exchange (ETDEWEB)

    Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

  5. Kinetics of contrail particles formation and heterogeneous reactions on such particles

    Energy Technology Data Exchange (ETDEWEB)

    Kogan, M.N.; Butkovsky, A.V.; Erofeev, A.I.; Freedlender, O.G.; Makashev, N.K. [Central Aerohydrodynamic Inst., Zhukovsky (Russian Federation)

    1997-12-31

    The research of impact of aircraft emissions upon the atmosphere is very complex and difficult problem. More than two decades of intensive investigations of the problem of ozone decay do not permit to make definite conclusions. Many important problems still remain unsolved in the aircraft/atmosphere interaction: engine, nozzle, jet, jet/vortex system interaction, vortex breakdown, contrail formation, meso-scale and global processes, their effects on climate. The particles formation and heterogeneous reactions play an important role in some of these processes. These problems are discussed. (author) 11 refs.

  6. Kinetics of contrail particles formation and heterogeneous reactions on such particles

    Energy Technology Data Exchange (ETDEWEB)

    Kogan, M N; Butkovsky, A V; Erofeev, A I; Freedlender, O G; Makashev, N K [Central Aerohydrodynamic Inst., Zhukovsky (Russian Federation)

    1998-12-31

    The research of impact of aircraft emissions upon the atmosphere is very complex and difficult problem. More than two decades of intensive investigations of the problem of ozone decay do not permit to make definite conclusions. Many important problems still remain unsolved in the aircraft/atmosphere interaction: engine, nozzle, jet, jet/vortex system interaction, vortex breakdown, contrail formation, meso-scale and global processes, their effects on climate. The particles formation and heterogeneous reactions play an important role in some of these processes. These problems are discussed. (author) 11 refs.

  7. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  8. Formation of Broensted acids sites in the reaction of cyclohexanol on NaCeY zeolites

    International Nuclear Information System (INIS)

    Vogt, O.; Nattich, M.; Datka, J.; Gil, B.

    2002-01-01

    This study was undertaken to elucidate why the catalytic activity of NaCeY in cyclohexanol reactions carried out in a pulse reactor increases with the pulse number. We studied therefore the effect of cyclohexanol and also of ethanol and water on catalytic activity NaCeY (of exchange degrees 36 and 72%) in cyclohexanol reactions: isomerization and disproportionation. We also studied the reaction of cyclohexanol and water with NaCeY zeolite by IR spectroscopy. Our results evidenced that new Broensted acid sites were formed by the reaction of cyclohexanol and water. This was shown by IR spectroscopy: the increase of Si-O 1 H-Al band 3638 cm -1 and in increase of ammonium ions band (upon ammonia adsorption). The new sites were formed by hydrolysis of Ce 3+ ions with water introduced in a pulse, or produced by dehydration of cyclohexanol catalyzed by acid sites. Formation of new Broensted acid sites resulted in an increase of catalytic activity of NaCeY in cyclohexane reaction as observed in this study and also in cyclohexanol reactions. (author)

  9. EXFOR basics. A short guide to the nuclear reaction data exchange format

    International Nuclear Information System (INIS)

    McLane, Victoria

    2000-01-01

    EXFOR is the agreed exchange format for the transmission of experimental nuclear reaction data between national and international nuclear data centers for the benefit of nuclear data users in all countries. This report is intended as a guide to data users. For a complete guide to the EXFOR system see: EXFOR Systems Manual, IAEA-NDS-207 (BNL-NCS-63330-00/04-Rev.) (author)

  10. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms

    DEFF Research Database (Denmark)

    Rasmussen, Helena; Sørensen, Hanne R.; Meyer, Anne S.

    2014-01-01

    , several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes......The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5......-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes...

  11. Formation, separation and detection of evaporation residues produced in complete fusion reactions

    CERN Document Server

    Sagaidak, R N

    2015-01-01

    Some aspects of formation, separation and detection of evaporation residues (ERs) produced in complete fusion reactions induced by accelerated heavy ions are considered. These reactions allow to obtain heavy neutron-deficient nuclei and to study their properties. The statistical model analysis of the production cross sections for these nuclei obtained in a wide range of their neutron numbers allows to trace the changes in their macroscopic properties such as fission barriers. The fusion probability of massive projectile and target nuclei is of interest. Empirical estimates of this value allow to verify the predictions of theoretical models for the optimal ways of synthesis of unknown nuclei. Some peculiarities in the separation and detection of ERs in experiments are briefly considered by the example of the Ra ERs produced in the 12 C+Pb reactions. The reliable cross sections for ERs produced in very asymmetric projectile-target combination, such as 12 C+Pb, are important for the em...

  12. Heterogeneous reactions and aerosol formation in flue gas cleaning by electron beam

    International Nuclear Information System (INIS)

    Baumann, W.; Jordan, S.; Leichsenring, C.H.; Maetzing, H.; Paur, H.R.; Schikarski, W.

    1990-08-01

    The electron beam dry scrubbing process is a simultaneous method for the removal of SO 2 and NO x from flue gas. By electron irradiation radicals (OH, O 2 H, O) are formed from the main flue gas components which oxidize NO x and SO 2 into the acids HNO 3 and H 2 SO 4 . These are then neutralized by the injection of NH 3 . A submicron aerosol consisting of ammonium salts is formed which is filtered from the offgas. The main pathways of the gas phase chemistry and product formation have been elucidated by experimental and theoretical studies. Back reactions which occur in the gas and the particle phase limit the energy efficiency of the process. By recirculation of irradiated gas into the reaction vessel (multiple irradiation) a significant improvement of removal yields was obtained. This enhancement of the energy efficiency requires the removal of products between the irradiation steps. Studies show that the material balance is complete. Deficits in the N and S balance of the process are due to the additional formation of molecular nitrogen and the deposition of ammonium sulfate in the ducts. Aerosol formation participates only with 30% in the material balance. The remaining 70% of the product are formed by surface reactions in the filter cake (40%) and in the ducts (30%). (orig.) With 38 figs., 29 tabs [de

  13. A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase

    International Nuclear Information System (INIS)

    Lyubimov, Artem Y.; Chen, Lin; Sampson, Nicole S.; Vrielink, Alice

    2009-01-01

    The importance of active-site electrostatics for oxidative and reductive half-reactions in a redox flavoenzyme (cholesterol oxidase) have been investigated by a combination of biochemistry and atomic resolution crystallography. A detailed examination of active-site dynamics demonstrates that the oxidation of substrate and the re-oxidation of the flavin cofactor by molecular oxygen are linked by a single active-site asparagine. Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3β-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH⋯π interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k cat . Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0 Å resolution) reveals significant perturbations in the active site. As predicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH⋯π interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered

  14. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn

    2012-06-01

    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  15. Formation of nitrogen complexes when [Ru(NH3)5H2O]2+ ion reaction with diazo-acetic ester and aromatic salts of diazonium

    International Nuclear Information System (INIS)

    Shur, V.B.; Tikhonova, I.A.; Vol'pin, M.E.

    1978-01-01

    A possibility of formation of nitrogen complexes during transition metal compound interaction with aliphatic and aromatic diazo compounds is studied. It is shown that at the interaction of [Ru(NH 3 ) 5 H 2 O] 2+ with diazo-acetic ester in water (pH7) at 20 deg, quick splitting of the CN-bond in the ester molecule takes place with the formation of [Ru(NH 3 ) 5 N 2 ] 2+ and [(NH 3 ) 5 RuN 2 Ru(NH 3 ) 5 ] 4+ (NRRN) nitrogen complexes. The sum yield of complexes comprises 86% taking into acount diazo-acetic ester. Aromatic salts of diazonium, n-O 3 SC 6 H 4 N 2 and p-quinone diazide react with the [Ru(NH 3 ) 5 H 2 O] 2+ excess forming NRRN (the yield equals 40-53%). The reaction mechanism is discussed

  16. Advanced multivariate data analysis to determine the root cause of trisulfide bond formation in a novel antibody-peptide fusion.

    Science.gov (United States)

    Goldrick, Stephen; Holmes, William; Bond, Nicholas J; Lewis, Gareth; Kuiper, Marcel; Turner, Richard; Farid, Suzanne S

    2017-10-01

    Product quality heterogeneities, such as a trisulfide bond (TSB) formation, can be influenced by multiple interacting process parameters. Identifying their root cause is a major challenge in biopharmaceutical production. To address this issue, this paper describes the novel application of advanced multivariate data analysis (MVDA) techniques to identify the process parameters influencing TSB formation in a novel recombinant antibody-peptide fusion expressed in mammalian cell culture. The screening dataset was generated with a high-throughput (HT) micro-bioreactor system (Ambr TM 15) using a design of experiments (DoE) approach. The complex dataset was firstly analyzed through the development of a multiple linear regression model focusing solely on the DoE inputs and identified the temperature, pH and initial nutrient feed day as important process parameters influencing this quality attribute. To further scrutinize the dataset, a partial least squares model was subsequently built incorporating both on-line and off-line process parameters and enabled accurate predictions of the TSB concentration at harvest. Process parameters identified by the models to promote and suppress TSB formation were implemented on five 7 L bioreactors and the resultant TSB concentrations were comparable to the model predictions. This study demonstrates the ability of MVDA to enable predictions of the key performance drivers influencing TSB formation that are valid also upon scale-up. Biotechnol. Bioeng. 2017;114: 2222-2234. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

  17. Catalytic diastereoselective tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts by C-C bond cleavage

    KAUST Repository

    Yang, Wenguo

    2012-02-08

    Through the cleavage of the C-C bond, the first catalytic tandem conjugate addition-elimination reaction of Morita-Baylis-Hillman C adducts has been presented. Various S N2′-like C-, S-, and P-allylic compounds could be obtained with exclusive E configuration in good to excellent yields. The Michael product could also be easily prepared by tuning the β-C-substituent group of the α-methylene ester under the same reaction conditions. Calculated relative energies of various transition states by DFT methods strongly support the observed chemoselectivity and diastereoselectivity. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  18. The origin of enantioselectivity in the l-threonine-derived phosphine-sulfonamide catalyzed aza-Morita-Baylis-Hillman reaction: Effects of the intramolecular hydrogen bonding

    KAUST Repository

    Lee, Richmond

    2013-01-01

    l-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity. © 2013 The Royal Society of Chemistry.

  19. Hydrogen-bond-driven electrophilic activation for selectivity control: scope and limitations of fluorous alcohol-promoted selective formation of 1,2-disubstituted benzimidazoles and mechanistic insight for rationale of selectivity.

    Science.gov (United States)

    Chebolu, Rajesh; Kommi, Damodara N; Kumar, Dinesh; Bollineni, Narendra; Chakraborti, Asit K

    2012-11-16

    Hydrogen-bond-driven electrophilic activation for selectivity control during competitive formation of 1,2-disubstituted and 2-substituted benzimidazoles from o-phenylenediamine and aldehydes is reported. The fluorous alcohols trifluoroethanol and hexafluoro-2-propanol efficiently promote the cyclocondensation of o-phenylenediamine with aldehydes to afford selectively the 1,2-disubstituted benzimidazoles at rt in short times. A mechanistic insight is invoked by NMR, mass spectrometry, and chemical studies to rationalize the selectivity. The ability of the fluorous alcohols in promoting the reaction and controlling the selectivity can be envisaged from their better hydrogen bond donor (HBD) abilities compared to that of the other organic solvents as well as of water. Due to the better HBD values, the fluorous alcohols efficiently promote the initial bisimine formation by electrophilic activation of the aldehyde carbonyl. Subsequently the hydrogen-bond-mediated activation of the in situ-formed bisimine triggers the rearrangement via 1,3-hydride shift to form the 1,2-disubstituted benzimidazoles.

  20. Bond-specific reaction kinetics during the oxidation of (111) Si: Effect of n-type doping

    International Nuclear Information System (INIS)

    Gokce, B.; Aspnes, D. E.; Lucovsky, G.; Gundogdu, K.

    2011-01-01

    It is known that a higher concentration of free carriers leads to a higher oxide growth rate in the thermal oxidation of silicon. However, the role of electrons and holes in oxidation chemistry is not clear. Here, we report real-time second-harmonic-generation data on the oxidation of H-terminated (111)Si that reveal that high concentrations of electrons increase the chemical reactivity of the outer-layer Si-Si back bonds relative to the Si-H up bonds. However, the thicknesses of the natural oxides of all samples stabilize near 1 nm at room temperature, regardless of the chemical kinetics of the different bonds.

  1. The Cosmic-Chemical Bond: Chemistry from the Big Bang to Planet Formation

    Science.gov (United States)

    Williams, D. A.; Hartquist, T. W.

    2013-01-01

    Introducing astrochemistry to a wide audience, this book describes how molecules formed in chemical reactions occur in a range of environments in interstellar and circumstellar space, from shortly after the Big Bang up to the present epoch. Stressing that chemistry in these environments needs to be "driven", it helps identify these drivers and the various chemical networks that operate giving rise to signature molecules that enable the physics of the region to be better understood. The book emphasises, in a non-mathematical way, the chemistry of the Milky Way Galaxy and its planet-forming regions, describes how other galaxies may have rather different chemistries and shows how chemistry was important even in the Early Universe when most of the elements had yet to be formed. This book will appeal to anyone with a general interest in chemistry, from students to professional scientists working in interdisciplinary areas and non-scientists fascinated by the evolving and exciting story of chemistry in the cosmos.

  2. An unusual cysteine VL87 affects the antibody fragment conformations without interfering with the disulfide bond formation.

    Science.gov (United States)

    Attallah, Carolina; Aguilar, María Fernanda; Garay, A Sergio; Herrera, Fernando E; Etcheverrigaray, Marina; Oggero, Marcos; Rodrigues, Daniel E

    2017-10-01

    The Cys residues are almost perfectly conserved in all antibodies. They contribute significantly to the antibody fragment stability. The relevance of two natural contiguous Cys residues of an anti-recombinant human-follicle stimulation hormone (rhFSH) in a format of single-chain variable fragment (scFv) was studied. This scFv contains 5 Cys residues: V H 22 and V H 92 in the variable heavy chain (V H ) and V L 23, V L 87 and V L 88 in the variable light chain (V L ). The influence of two unusual contiguous Cys at positions V L 87 and V L 88 was studied by considering the wild type fragment and mutant variants: V L -C88S, V L -C87S, V L -C87Y. The analysis was carried out using antigen-binding ability measurement by indirect specific ELISA and a detailed molecular modeling that comprises homology methods, long molecular dynamics simulations and docking. We found that V L -C87 affected the antibody fragment stability without interfering with the disulfide bond formation. The effect of mutating the V L -C87 by a usual residue at this position like Tyr caused distant structural changes at the V H region that confers a higher mobility to the V H -CDR2 and V H -CDR3 loops improving the scFv binding to the antigen. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Dispersion-corrected first-principles calculation of terahertz vibration, and evidence for weak hydrogen bond formation

    Science.gov (United States)

    Takahashi, Masae; Ishikawa, Yoichi; Ito, Hiromasa

    2013-03-01

    A weak hydrogen bond (WHB) such as CH-O is very important for the structure, function, and dynamics in a chemical and biological system WHB stretching vibration is in a terahertz (THz) frequency region Very recently, the reasonable performance of dispersion-corrected first-principles to WHB has been proven. In this lecture, we report dispersion-corrected first-principles calculation of the vibrational absorption of some organic crystals, and low-temperature THz spectral measurement, in order to clarify WHB stretching vibration. The THz frequency calculation of a WHB crystal has extremely improved by dispersion correction. Moreover, the discrepancy in frequency between an experiment and calculation and is 10 1/cm or less. Dispersion correction is especially effective for intermolecular mode. The very sharp peak appearing at 4 K is assigned to the intermolecular translational mode that corresponds to WHB stretching vibration. It is difficult to detect and control the WHB formation in a crystal because the binding energy is very small. With the help of the latest intense development of experimental and theoretical technique and its careful use, we reveal solid-state WHB stretching vibration as evidence for the WHB formation that differs in respective WHB networks The research was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grant No. 22550003).

  4. Formation of nitrogen-containing compounds during microwave pyrolysis of microalgae: Product distribution and reaction pathways.

    Science.gov (United States)

    Huang, Feng; Tahmasebi, Arash; Maliutina, Kristina; Yu, Jianglong

    2017-12-01

    The formation of nitrogen-containing compounds in bio-oil during microwave pyrolysis of Chlorella and Spirulina microalgae has been investigated in this study. Activated carbon (AC) and magnetite (Fe 3 O 4 ) were used as microwave receptors during microwave pyrolysis experiments. It has been found that the use of Fe 3 O 4 increased the total yield of bio-oil. The use of different microwave receptors did not seem to have affected the total yield of nitrogen-containing compounds in the bio-oil. However, Fe 3 O 4 promoted the formation of nitrogen-containing aliphatics, thereby reducing the formation of nitrogen-containing aromatics. The use of AC promoted the dehydration reactions during amino acid decomposition, thereby enhancing the formation of nitrogen-containing aromatics during pyrolysis. From the gas chromatography-mass spectrometry (GC-MS) analysis results, the major high-value nitrogen-containing compounds in the pyrolysis bio-oil of Chlorella and Spirulina were identified as indole and dodecamide. The formation mechanisms of nitrogen-containing compounds were proposed and discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry

    Science.gov (United States)

    Aprea, Eugenio; Biasioli, Franco; Carlin, Silvia; Märk, Tilmann D.; Gasperi, Flavia

    2008-08-01

    The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control. Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices. Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks.

  6. Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Elimelech, Orian [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel; Liu, Jing [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Plonka, Anna M. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Frenkel, Anatoly I. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Banin, Uri [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel

    2017-07-19

    Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.

  7. Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

    Science.gov (United States)

    Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

    2014-11-20

    Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

  8. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C4H5, from reaction of C(3Pj) with propylene, C3H6 (X1A)

    International Nuclear Information System (INIS)

    Kaiser, R.I.; Stranges, D.; Bevsek, H.M.; Lee, Y.T.; Suits, A.G.

    1997-01-01

    The reaction between ground state carbon atoms and propylene, C 3 H 6 , was studied at average collision energies of 23.3 and 45.0 kJmol -1 using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C 4 H 5 at m/e=53 were recorded. Forward-convolution fitting of the data yields a maximum energy release as well as angular distributions consistent with the formation of methylpropargyl radicals. Reaction dynamics inferred from the experimental results suggest that the reaction proceeds on the lowest 3 A surface via an initial addition of the carbon atom to the π-orbital to form a triplet methylcyclopropylidene collision complex followed by ring opening to triplet 1,2-butadiene. Within 0.3 endash 0.6 ps, 1,2-butadiene decomposes through carbon endash hydrogen bond rupture to atomic hydrogen and methylpropargyl radicals. The explicit identification of C 4 H 5 under single collision conditions represents a further example of a carbon endash hydrogen exchange in reactions of ground state carbon with unsaturated hydrocarbons. This versatile machine represents an alternative pathway to build up unsaturated hydrocarbon chains in combustion processes, chemical vapor deposition, and in the interstellar medium. copyright 1997 American Institute of Physics

  9. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  10. A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation.

    Science.gov (United States)

    Li, Cheng-An; Ji, Wei; Qu, Jian; Jing, Su; Gao, Fei; Zhu, Dun-Ru

    2018-05-22

    The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a greener alternative organic solvent has been developed. The PEG-400/5 system can achieve 99% targeted yield with a mild reaction temperature and short reaction time. After the isolation of the products by extraction with diethyl ether, this PEG-400/cluster system could be easily recycled. Spectroscopic studies elucidate a stepwise mechanism: firstly, proton-coupled electron transfer (PCET) involving the transfer of an electron from Cu+ and a proton from imidazole results in the formation of a labile penta-coordinated Cu2+ and aryl radical; the following effective electron transfer from the ferrocene unit reduces Cu2+ and forms the target product; finally, the ferrocenium unit is reduced by the I- anion. The merits of this eco-friendly synthesis are the efficient utilization of reagents and easy recyclability.

  11. OH+ Formation in the Low-temperature O+(4S) + H2 Reaction

    Science.gov (United States)

    Kovalenko, Artem; Dung Tran, Thuy; Rednyk, Serhiy; Roučka, Štěpán; Dohnal, Petr; Plašil, Radek; Gerlich, Dieter; Glosík, Juraj

    2018-04-01

    Formation of OH+ in collisions of ground-state O+(4S) ions with normal H2 has been studied using a variable temperature 22-pole RF ion trap. From 300 to 30 K the measured reaction rate coefficient is temperature-independent, with a small decrease toward 15 K. The recent wave packet calculation predicts a slightly steeper temperature dependence. The rate coefficients at 300 and 15 K are almost the same, (1.4 ± 0.3) × 10‑9 cm3 s‑1 and (1.3 ± 0.3) × 10‑9 cm3 s‑1, respectively. The influence of traces of the two metastable ions, O+(2D) and O+(2P), has been examined by monitoring the H+ products of their reactions with H2, as well as by chemically probing them with N2 reactant gas.

  12. Dichotomous-noise-induced pattern formation in a reaction-diffusion system

    Science.gov (United States)

    Das, Debojyoti; Ray, Deb Shankar

    2013-06-01

    We consider a generic reaction-diffusion system in which one of the parameters is subjected to dichotomous noise by controlling the flow of one of the reacting species in a continuous-flow-stirred-tank reactor (CSTR) -membrane reactor. The linear stability analysis in an extended phase space is carried out by invoking Furutzu-Novikov procedure for exponentially correlated multiplicative noise to derive the instability condition in the plane of the noise parameters (correlation time and strength of the noise). We demonstrate that depending on the correlation time an optimal strength of noise governs the self-organization. Our theoretical analysis is corroborated by numerical simulations on pattern formation in a chlorine-dioxide-iodine-malonic acid reaction-diffusion system.

  13. Formation of quinones, indanones and furans by the reaction of molybdenum carbene complexes with alkynes

    International Nuclear Information System (INIS)

    Doetz, K.H.; Larbig, H.

    1992-01-01

    (Alkoxy)carbene complexes of molybdenum react with terminal alkynes to give carbene annulation of cycloaddition products, the skeleton of which depends on the carbene substitution pattern and the alkyne used. (CO) 5 Mo=C(OMe)-p-tol undergoes carbene annulation upon reaction with trimethylsilylacetylene leading to naphthoquinone after oxidative work-up. Similar products are obtained from (CO) 5 Mo=C(OMe)2-furyl and hex-1-yne or oct-1-yne. The reaction of these alkynes results in the formation of indanones as five-membered annulation products. In the presence of 3.3-dimethylbut-1-yne the (phenyl) carbene ligands act as a C 1 -synthon, which is incorporated into the furan cycloaddition products

  14. Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    Gelencsér

    2005-01-01

    Full Text Available In a simple conceptual cloud-aerosol model the mass of secondary organic aerosol (SOA that may be formed in multiphase reaction in an idealized scenario involving two cloud cycles separated with a cloud-free period is evaluated. The conditions are set to those typical of continental clouds, and each parameter used in the model calculations is selected as a mean of available observational data of individual species for which the multiphase SOA formation route has been established. In the idealized setting gas and aqueous-phase reactions are both considered, but only the latter is expected to yield products of sufficiently low volatility to be retained by aerosol particles after the cloud dissipates. The key variable of the model is the Henry-constant which primarily determines how important multiphase reactions are relative to gas-phase photooxidation processes. The precursor considered in the model is assumed to already have some affinity to water, i.e. it is a compound having oxygen-containing functional group(s. As a principal model output an aerosol yield parameter is calculated for the multiphase SOA formation route as a function of the Henry-constant, and has been found to be significant already above H~103 M atm-1. Among the potential precursors that may be eligible for this mechanism based on their Henry constants, there are a suite of oxygenated compounds such as primary oxidation products of biogenic and anthropogenic hydrocarbons, including, for example, pinonaldehyde. Finally, the analogy of multiphase SOA formation to in-cloud sulfate production is exploited.

  15. Study on the kinetics of gel formation in the radiation crosslinking reaction

    International Nuclear Information System (INIS)

    Wang Mingjun; Liu Yuming

    1988-01-01

    From the kinetic equation of gel formation obtained by the authors, the mechanism of gel formation may be interpreted clearly as follows: (1) When the degree of crosslinking q g , the system is sol and the crosslinking reaction is only carried out between the sol molecules. (q g is the gel point). (2) When q=q g , there exists a beginning point where the gel is coexisted with the sol, and the system is still sol, and the crosslinking reaction is still carried out between the sol molecules. (3) When q>q g , the crosslinking reaction exceeds the gel point and the gel is coexisted with the sol. The kinetic equation shows clearly that the transformation from sol into gel is caused by crosslinking reaction of the uncrosslinked chain units between the sol and gel molecules. As a result the sol molecules are transformed into the gel molecules gradually, and the sol fraction is reduced. When the chain units P-barw(s)S(1-s)dq in sol are crosslinked with gel, the sol fraction in the system is reduced ds (where P-barw(s) is a function of the radiation dose and s is sol frection). The degree of crosslinking per unit dose (q 0 ) is a reduced function of dose (R). The equation for calculating its value for every irradiation dose is obtained. After knowing the correlation between P-bar W(s) vs R and q 0 vs R, the distribution of gel and sol in the process of radiation crosslinking can be discussed as well

  16. Assessment of the potential for ammonium nitrate formation and reaction in Tank 241-SY-101

    International Nuclear Information System (INIS)

    Pederson, L.R.; Bryan, S.A.

    1994-08-01

    Two principal scenarios by which ammonium nitrate may be formed were considered: (a) precipitation of ammonium nitrate in the waste, and (b) ammonium nitrate formation via the gas phase reaction of ammonia and nitrogen dioxide. The first of these can be dismissed because ammonium ions, which are necessary for ammonium nitrate precipitation, can exist only in negligibly small concentrations in strongly alkaline solutions. Gas phase reactions between ammonia, nitrogen dioxide, and water vapor in the gas phase represent the most likely means by which ammonium nitrate aerosols could be formed in Tank 241-SY-101. Predicted ammonium nitrate formation rates are largely controlled by the concentration of nitrogen dioxide. This gas has not been detected among those gases vented from the wastes using Fourier Transform Infrared Spectrometry (FTIR) or mass spectrometry. While detection limits for nitrogen dioxide have not been established experimentally, the maximum concentration of nitrogen dioxide in the gas phase in Tank 241-SY-101 was estimated at 0.1 ppm based on calculations using the HITRAN data base and on FTIR spectra of gases vented from the wastes. At 50 C and with 100 ppm ammonia also present, less than one gram of ammonium nitrate per year is estimated to be formed in the tank. To date, ammonium nitrate has not been detected on HEPA filters in the ventilation system, so any quantity that has been formed in the tank must be quite small, in good agreement with rate calculations. The potential for runaway exothermic reactions involving ammonium nitrate in Tank 241-SY-101 is minimal. Dilution by non-reacting waste components, particularly water, would prevent hazardous exothermic reactions from occurring within the waste slurry, even if ammonium nitrate were present. 41 refs

  17. Fragment formation in GeV-energy proton and light heavy-ion induced reactions

    International Nuclear Information System (INIS)

    Murakami, T.; Haga, M.; Haseno, M.

    2002-01-01

    We have investigated similarities and differences among the fragment formation processes in GeV-energy light-ion and light heavy-ion induced reactions. We have newly measured inclusive and exclusive energy spectra of intermediate mass fragments (3 ≤ Z ≤ 30; IMFs) for 8-GeV 16 O and 20 Ne and 12-GeV 20 Ne induced target multifragmentations (TMFs) in order to compare them with those previously measured for 8- and 12-GeV proton induced TMFs. We fond noticeable difference in their spectrum shapes and magnitudes but all of them clearly indicate the existence of sideward-peaked components, indicating fragment formations are mainly dictated not by a incident energy per nucleon but by a total energy of the projectile. (author)

  18. Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

    Science.gov (United States)

    Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

    2010-11-01

    We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

  19. Study of Reaction of Curium Oxy-Compound Formation in Molten Chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Osipenko, A.G.; Mayorshin, A.A.; Bychkov, A.V. [Dimitrovgrad-10, Ulyanovsk region, 433510 (Russian Federation)

    2008-07-01

    The method of potentiometric titration using oxygen sensors with solid electrolyte membrane was applied for the study of the interaction of curium cations with oxygen anions in the molten alkali metal chlorides in the temperature range of 450-850 C degrees depending on oxy-acidity of the environment. Assumptions were made concerning ion and phase composition of the obtained high-temperature compounds and chemical reactions taking place in the melts. This scheme assumes that as the basicity of the melt increases, initially the formation of soluble curium oxychlorides takes place in the melt (presumably CmO{sup -}) that is followed by formation of solid CmOCl and finally sesquioxide Cm{sub 2}O{sub 3}. Basic thermodynamic values were calculated for the resultant curium oxy-compounds.

  20. Study on the formation of fission isomer via 232Th + α reaction

    International Nuclear Information System (INIS)

    Vianna, D.M.

    1982-01-01

    The formation of fission isomer through 232 Th+α reaction is studied using the distance-recoil method, employing policarbonate MAKROFOL detector. The total isomeric half-life measured has the value T 1/2 = 0.23 ± 0.03 ns and an ratio of formation of isomeric fission relative to prompt fission(σ i /σ p =0.75x10 -5 ). According to the energy of incident particle (Eα = 28 MeV), the cross-sections presented in the literature and the low value found for the total isomeric half-life, we attribute these half-life value to the 234 U isomer (even-even nucleus). The results were compared with those existent in the literature (La69, E170, Re70, Wo70, Po70, Br71) for this isomer. (author) [pt

  1. Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

    Science.gov (United States)

    Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

    2018-04-01

    In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize

  2. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  3. Correlation between Gas Bubble Formation and Hydrogen Evolution Reaction Kinetics at Nanoelectrodes.

    Science.gov (United States)

    Chen, Qianjin; Luo, Long

    2018-04-17

    We report the correlation between H 2 gas bubble formation potential and hydrogen evolution reaction (HER) activity for Au and Pt nanodisk electrodes (NEs). Microkinetic models were formulated to obtain the HER kinetic information for individual Au and Pt NEs. We found that the rate-determining steps for the HER at Au and Pt NEs were the Volmer step and the Heyrovsky step, respectively. More interestingly, the standard rate constant ( k 0 ) of the rate-determining step was found to vary over 2 orders of magnitude for the same type of NEs. The observed variations indicate the HER activity heterogeneity at the nanoscale. Furthermore, we discovered a linear relationship between bubble formation potential ( E bubble ) and log( k 0 ) with a slope of 125 mV/decade for both Au and Pt NEs. As log ( k 0 ) increases, E bubble shifts linearly to more positive potentials, meaning NEs with higher HER activities form H 2 bubbles at less negative potentials. Our theoretical model suggests that such linear relationship is caused by the similar critical bubble formation condition for Au and Pt NEs with varied sizes. Our results have potential implications for using gas bubble formation to evaluate the HER activity distribution of nanoparticles in an ensemble.

  4. MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

  5. Formation of a dinuclear copper(II) complex through the cleavage of CBond' name='Single-Bond' value='Single-Bond'/>N bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    Energy Technology Data Exchange (ETDEWEB)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia); Kassim, Mohammad B. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor, Malaysia and Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor (Malaysia)

    2014-09-03

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl}Bond' name='Single-Bond' value='Single-Bond'/>N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

  6. VIRGIN2007, Calculates Un-collided Neutron Flux and Neutron Reactions from Transmission in ENDF Format

    International Nuclear Information System (INIS)

    2007-01-01

    1 - Description of program or function: VIRGIN calculates un-collided flux and reactions due to transmission of a mono-directional beam of neutrons through any thickness of material. In order to simulate an experimental measurement the results are given as integrals over energy tally groups (as opposed to point-wise in energy). IAEA0932/10: This version include the updates up to January 30, 2007. Changes in ENDF/B-VII Format and procedures, as well as the evaluations themselves, make it impossible for versions of the ENDF/B pre-processing codes earlier than PREPRO 2007 (2007 Version) to accurately process current ENDF/B-VII evaluations. The present code can handle all existing ENDF/B-VI evaluations through release 8, which will be the last release of ENDF/B-VI. Modifications from previous versions: Virgin VERS. 2007-1 (Jan. 2007): checked against all ENDF/B-VII; increased in-core page size from 60,000 to 240,000. 2 - Method of solution: By taking the ratio of reactions to flux in each group an equivalent spatially dependent group averaged cross section is calculated. 3 - Restrictions on the complexity of the problem: The evaluated data must be in the ENDF/B format. However it must be linear-linear interpolable in energy-cross section between tabulated points. Since only cross sections (file 3) are used, this program will work on any version of ENDF/B

  7. Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds.

    Science.gov (United States)

    Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders

    2011-04-13

    Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

  8. Chemically fixed p-n heterojunctions for polymer electronics by means of covalent B-F bond formation

    Science.gov (United States)

    Hoven, Corey V.; Wang, Huiping; Elbing, Mark; Garner, Logan; Winkelhaus, Daniel; Bazan, Guillermo C.

    2010-03-01

    Widely used solid-state devices fabricated with inorganic semiconductors, including light-emitting diodes and solar cells, derive much of their function from the p-n junction. Such junctions lead to diode characteristics and are attained when p-doped and n-doped materials come into contact with each other. Achieving bilayer p-n junctions with semiconducting polymers has been hindered by difficulties in the deposition of thin films with independent p-doped and n-doped layers. Here we report on how to achieve permanently fixed organic p-n heterojunctions by using a cationic conjugated polyelectrolyte with fluoride counteranions and an underlayer composed of a neutral conjugated polymer bearing anion-trapping functional groups. Application of a bias leads to charge injection and fluoride migration into the neutral layer, where irreversible covalent bond formation takes place. After the initial charging and doping, one obtains devices with no delay in the turn on of light-emitting electrochemical behaviour and excellent current rectification. Such devices highlight how mobile ions in organic media can open opportunities to realize device structures in ways that do not have analogies in the world of silicon and promise new opportunities for integrating organic materials within technologies now dominated by inorganic semiconductors.

  9. INVESTIGATING THE fFORMATION OF INTERMETALLIC COMPOUNDS AND THE VARIATION OF BOND STRENGTH BETWEEN Al-Cu LAYERS AFTER ANNEALING IN PRESENCE OF NICKEL BETWEEN LAYERS

    Directory of Open Access Journals (Sweden)

    A. Shabani

    2016-06-01

    Full Text Available In the present study, the effect of post-rolling annealing heat treatment on the formation of intermetallic compounds between Al-Cu strips, in the presence of nickel coating on the Cu strips, was investigated. In addition, the effect of post-rolling annealing and intermetallic compounds on the bond strength of Al-Cu strips was evaluated. In order to prepare samples, Cu strips were coated with nickel by electroplating process. After surface preparing, Cu strips were placed between two Al strips and roll bonded. This method is used for producing Al-Ni-Cu composites. Then the samples were annealed at 773K for 2 h. The formation of intermetallic compounds was studied using energy dispersive spectroscopy (EDS and X-ray diffraction (XRD. Also, in order to investigate bond strength of Al-Cu after post-rolling annealing heat treatment, samples were produced using nickel powder and nickel coating. Then bond strength of strips was investigated using peeling test. The results revealed that by post-rolling annealing of layers, the bond strength between Al-Cu strips decreases dramatically.

  10. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya; Raj, Abhijeet; Chung, Suk-Ho

    2015-01-01

    and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics

  11. Emotional reactions of different interface formats: Comparing digital and traditional board games

    Directory of Open Access Journals (Sweden)

    Yu-Min Fang

    2016-03-01

    Full Text Available Some games provide both traditional board games and digital versions at the same time in the market. Why the rise of virtual games has not forced traditional physical board games to disappear? Do traditional physical games evoke different emotional reactions and interpersonal relationships? This article explored the subjects’ preferences toward traditional and digital versions of the same game and investigated social interaction while playing games. Based on Norman’s three emotional design levels—visceral, behavioral, and reflective levels—this study examined players’ satisfaction degree. This study also applied Positive and Negative Affect Schedule to measure subjects’ emotional reactions. Monopoly and Jenga games were selected as stimuli. A total of 77 subjects received tests of three different interface formats (physical, desktop, and tablet and then filled out the questionnaire. The findings successfully evidenced the significant differences between digital and traditional board games. The statistical results indicated that satisfaction degrees of digital games declined in visceral, behavioral, and reflective levels. Traditional games not only evoked users’ stronger emotional reactions but also received higher preferences. Traditional games could improve interpersonal relationships as well.

  12. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

    KAUST Repository

    Wu, Junjun; Khaled, Fathi; Ning, Hongbo; Ma, Liuhao; Farooq, Aamir; Ren, Wei

    2017-01-01

    We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  13. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

    KAUST Repository

    Wu, Junjun

    2017-08-03

    We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  14. Radiation induced Maillard reactions (the kinetic of colour formation during heating)

    International Nuclear Information System (INIS)

    Tegota, A.; Bachman, S.

    1998-01-01

    The results are presented of the investigation of the effect of ionizing radiation from 60 Co on the acceleration of the Maillard reactions in a model system containing an aqueous solution of fructose (F) at 0.03 mol/dm 3 and alanine (Ala) at 0.01 mol/dm 3 . Solutions of F/Ala irradiated with 5 to 30 kGy at a dose rate 1.4 Gy/s were then heated for a few hours at different temperatures: 400, 600, 800, and 1000 deg C. The colour intensity of the solutions was measured via their absorbance at 450 nm. The reaction constant estimates increased with increasing radiation dose and temperature. The activation energy of colour development determined over the range of 600 deg C to 1000 deg C decreased with dose from 70.6 kJ/mol for 5 kGy to 60.7 kJ/mol for 30 kGy. The results confirmed the formation of carbonyl products from fructose radiolysis and their participation in the acceleration of the non-enzymatic browning reactions. The aldehyde products formed from the amino acids as a result of the Strecker degradation are responsible for the formation of odour typical of the Maillard reaction during heating. The changes in the F and Ala concentrations during irradiation of the solutions were proportional to the radiation dose. The radiation yield of fructose and alanine decomposition was G = 2.6 and 0.22, respectively. In the irradiated solutions of F/Ala, serine has been found, which has not been mentioned so far as a product of alanine radiolysis. The study demonstrates the influence of radiation and acceleration of the Maillard reaction during subsequent heating at 400 deg C up to 1000 deg C of systems containing reducing sugars and amino acids. It should be taken under consideration in the studies on introducing radiation technology of food products preservation connected with further thermal treatment

  15. Prompt HO2 formation following the reaction of OH with aromatic compounds under atmospheric conditions.

    Science.gov (United States)

    Nehr, Sascha; Bohn, Birger; Wahner, Andreas

    2012-06-21

    The secondary formation of HO(2) radicals following OH + aromatic hydrocarbon reactions in synthetic air under normal pressure and temperature was investigated in the absence of NO after pulsed production of OH radicals. OH and HO(x) (=OH + HO(2)) decay curves were recorded using laser-induced fluorescence after gas-expansion. The prompt HO(2) yields (HO(2) formed without preceding NO reactions) were determined by comparison to results obtained with CO as a reference compound. This approach was recently introduced and applied to the OH + benzene reaction and was extended here for a number of monocyclic aromatic hydrocarbons. The measured HO(2) formation yields are as follows: toluene, 0.42 ± 0.11; ethylbenzene, 0.53 ± 0.10; o-xylene, 0.41 ± 0.08; m-xylene, 0.27 ± 0.06; p-xylene, 0.40 ± 0.09; 1,2,3-trimethylbenzene, 0.31 ± 0.06; 1,2,4-trimethylbenzene, 0.37 ± 0.09; 1,3,5-trimethylbenzene, 0.29 ± 0.08; hexamethylbenzene, 0.32 ± 0.08; phenol, 0.89 ± 0.29; o-cresol, 0.87 ± 0.29; 2,5-dimethylphenol, 0.72 ± 0.12; 2,4,6-trimethylphenol, 0.45 ± 0.13. For the alkylbenzenes HO(2) is the proposed coproduct of phenols, epoxides, and possibly oxepins formed in secondary reactions with O(2). In most product studies the only quantified coproducts were phenols whereas only a few studies reported yields of epoxides. Oxepins have not been observed so far. Together with the yields of phenols from other studies, the HO(2) yields determined in this work set an upper limit to the combined yields of epoxides and oxepins that was found to be significant (≤0.3) for all investigated alkylbenzenes except m-xylene. For the hydroxybenzenes the currently proposed HO(2) coproducts are dihydroxybenzenes. For phenol and o-cresol the determined HO(2) yields are matching the previously reported dihydroxybenzene yields, indicating that these are the only HO(2) forming reaction channels. For 2,5-dimethylphenol and 2,4,6-trimethylphenol no complementary product studies are available.

  16. Sub-barrier quasifission in heavy element formation reactions with deformed actinide target nuclei

    Science.gov (United States)

    Hinde, D. J.; Jeung, D. Y.; Prasad, E.; Wakhle, A.; Dasgupta, M.; Evers, M.; Luong, D. H.; du Rietz, R.; Simenel, C.; Simpson, E. C.; Williams, E.

    2018-02-01

    Background: The formation of superheavy elements (SHEs) by fusion of two massive nuclei is severely inhibited by the competing quasifission process. Low excitation energies favor SHE survival against fusion-fission competition. In "cold" fusion with spherical target nuclei near 208Pb, SHE yields are largest at beam energies significantly below the average capture barrier. In "hot" fusion with statically deformed actinide nuclei, this is not the case. Here the elongated deformation-aligned configurations in sub-barrier capture reactions inhibits fusion (formation of a compact compound nucleus), instead favoring rapid reseparation through quasifission. Purpose: To determine the probabilities of fast and slow quasifission in reactions with prolate statically deformed actinide nuclei, through measurement and quantitative analysis of the dependence of quasifission characteristics at beam energies spanning the average capture barrier energy. Methods: The Australian National University Heavy Ion Accelerator Facility and CUBE fission spectrometer have been used to measure fission and quasifission mass and angle distributions for reactions with projectiles from C to S, bombarding Th and U target nuclei. Results: Mass-asymmetric quasifission occurring on a fast time scale, associated with collisions with the tips of the prolate actinide nuclei, shows a rapid increase in probability with increasing projectile charge, the transition being centered around projectile atomic number ZP=14 . For mass-symmetric fission events, deviations of angular anisotropies from expectations for fusion fission, indicating a component of slower quasifission, suggest a similar transition, but centered around ZP˜8 . Conclusions: Collisions with the tips of statically deformed prolate actinide nuclei show evidence for two distinct quasifission processes of different time scales. Their probabilities both increase rapidly with the projectile charge. The probability of fusion can be severely

  17. Evaluation of maillard reaction variables and their effect on heterocyclic amine formation in chemical model systems.

    Science.gov (United States)

    Dennis, Cara; Karim, Faris; Smith, J Scott

    2015-02-01

    Heterocyclic amines (HCAs), highly mutagenic and potentially carcinogenic by-products, form during Maillard browning reactions, specifically in muscle-rich foods. Chemical model systems allow examination of in vitro formation of HCAs while eliminating complex matrices of meat. Limited research has evaluated the effects of Maillard reaction parameters on HCA formation. Therefore, 4 essential Maillard variables (precursors molar concentrations, water amount, sugar type, and sugar amounts) were evaluated to optimize a model system for the study of 4 HCAs: 2-amino-3-methylimidazo-[4,5-f]quinoline, 2-amino-3-methylimidazo[4,5-f]quinoxaline, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, and 2-amino-3,4,8-trimethyl-imidazo[4,5-f]quinoxaline. Model systems were dissolved in diethylene glycol, heated at 175 °C for 40 min, and separated using reversed-phase liquid chromatography. To define the model system, precursor amounts (threonine and creatinine) were adjusted in molar increments (0.2/0.2, 0.4/0.4, 0.6/0.6, and 0.8/0.8 mmol) and water amounts by percentage (0%, 5%, 10%, and 15%). Sugars (lactose, glucose, galactose, and fructose) were evaluated in several molar amounts proportional to threonine and creatinine (quarter, half, equi, and double). The precursor levels and amounts of sugar were significantly different (P < 0.05) in regards to total HCA formation, with 0.6/0.6/1.2 mmol producing higher levels. Water concentration and sugar type also had a significant effect (P < 0.05), with 5% water and lactose producing higher total HCA amounts. A model system containing threonine (0.6 mmol), creatinine (0.6 mmol), and glucose (1.2 mmol), with 15% water was determined to be the optimal model system with glucose and 15% water being a better representation of meat systems. © 2015 Institute of Food Technologists®

  18. Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

    Science.gov (United States)

    Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

    2016-02-04

    A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

  19. Bond cleavage reactions of the bridge structure in coal in the presence of hydrogen donating compounds; Suiso kyoyosei kagobutsu sonzaika deno sekitanchu no kakyo kozo no kairetsu hanno

    Energy Technology Data Exchange (ETDEWEB)

    Bando, N.; Kidena, K.; Murata, S.; Nomura, M. [Osaka University, Osaka (Japan). Faculty of Engineering

    1996-10-28

    In this paper, bond cleavage reactions are discussed in relation to the softening and solubilization of coal. Were used 9,10-dihydroanthracene (DHA) and 9,10-dihydrophenanthrene (DHP) as models of hydrogen donating compounds in coal, and bibenzyl, 1,2-diethane, benzylphenylether, and 1,5-dibenzylnaphthalene were used as models of bridge structure compounds. They were compared mutually, as to reactivity of coal against DHA and DHP. For the homolytic cleavage of bridges, DHA with excellent radical supplement performance provided excellent hydrogen donating performance. While, for the ipso-position cleavage of bridges, it was found that DHP can act as an effective hydrogen donor. For the reaction between coal and hydrogenated aromatic compounds, cleavage of relatively weak bonds, such as ether linkage and dimethylene linkage, occurred at about 380{degree}C, and hydrogen from DHA or DHP was consumed. On the other hand, the results suggested that the cleavage reaction at ipso-position affected by hydrogen donating solvent is also important at temperature range around 420{degree}C. 2 refs., 3 figs., 1 tab.

  20. Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

    Science.gov (United States)

    Zhou, Tian

    Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

  1. Morphological effects of single-layer graphene oxide in the formation of covalently bonded polypyrrole composites using intermediate diisocyanate chemistry

    International Nuclear Information System (INIS)

    Whitby, Raymond L. D.; Korobeinyk, Alina; Mikhalovsky, Sergey V.; Fukuda, Takahiro; Maekawa, Toru

    2011-01-01

    Single-layer graphene oxide (SLGO) possesses carboxylic and hydroxyl groups suitable for reactions with aliphatic or aromatic diisocyanate molecules. TEM analysis reveals that aliphatic diisocyanate molecules caused SLGO to scroll into star-like formations, whereas aromatic diisocyanate molecules retained SGLO in a flat-sheet morphology. TGA confirms the stabilisation of the formed urea and urethane groups on SLGO, but the onset of sheet pyrolysis occurs at a lower temperature due to isocyanate reactions with anhydride and epoxide groups embedded in the sheet. Pendant isocyanate groups act as bridging units to facilitate the attachment of pyrrole molecules, which are then used as anchor sites for the covalent polymerisation of pyrrole to polypyrrole (PPy). The use of FeCl 3 as the polymerisation catalyst generated both covalent and free PPy, but also iron hydroxide nanoparticles were observed decorating the SLGO surface. When using ammonium persulfate as a catalyst and dodecylbenzenesulfonate as a dopant, free PPy could be removed under treatment with solvents to leave a purely covalent system. Discrete regions of SLGO were observed decorated with nanoparticles of PPy along the edge or across the surface of individual sheets. It was found that the flexibility of the SLGO sheet and the type of diisocyanate used directly affected the electrical resistance of the final composite.

  2. Unravelling the kinetics of the formation of acrylamide in the Maillard reaction of fructose and asparagine by multiresponse modelling

    NARCIS (Netherlands)

    Knol, J.J.; Linssen, J.P.H.; Boekel, van M.A.J.S.

    2010-01-01

    A kinetic model for the formation of acrylamide in a fructose–asparagine reaction system at initial pH 5.5 is proposed, based on an approach called multiresponse kinetic modelling. The formation of acetic acid and formic acid from the degradation of fructose and its isomer glucose was included in

  3. FLUID EVOLUTION AND MINERAL REACTIONS DURING SHEAR ZONE FORMATION AT NUSFJORD, LOFOTEN, NORWAY (Invited)

    Science.gov (United States)

    Kullerud, K.

    2009-12-01

    At Nusfjord in Lofoten, Norway, three 0.3 - 3 m thick shear zones occur in a gabbro-anorthosite. During deformation, the shear zones were infiltrated by a hydrous fluid enriched in Cl. In the central parts of the shear zones, fluid-rock interaction resulted in complete break-down of the primary mafic silicates. Complete hydration of these minerals to Cl-free amphibole and biotite suggests that the hydrous fluid was present in excess during deformation in these parts of the shear zones. Along the margins of the shear zones, however, the igneous mafic silicates (Cpx, Bt, Opx) were only partly overgrown by hydrous minerals. Here, Cl-enriched minerals (Amph, Bt, Scp, Ap) can be observed. Amphibole shows compositions covering the range 0.1 - 4.0 wt % Cl within single thin sections. Mineral textures and extreme compositional variations of the Cl-bearing minerals indicate large chemical gradients of the fluid phase. Relics of primary mafic silicates and compositionally zoned reaction coronas around primary mafic silicates suggest that the free fluid was totally consumed before the alteration of the primary phases were completed. The extreme variations in the Cl-content of amphibole are inferred to monitor a gradual desiccation of the Cl-bearing grain-boundary fluid during fluid-mineral reactions accordingly: 1) The first amphibole that formed during the reactions principally extracted water from the fluid, resulting in a slight increase in the Cl content of the fluid. 2) Continued amphibole-forming reactions resulted in gradual consumption of the free fluid phase, principally by extracting water from the fluid, resulting in an increase in its Cl-content. Higher Cl-content of the fluid resulted in higher Cl-content of the equilibrium amphibole. 3) The most Cl-enriched amphibole (4 wt % Cl) formed in equilibrium with the last volumes of the grain-boundary fluid, which had evolved to a highly saline solution. Mineral reactions within a 1-2 thick zone of the host rock along

  4. Investigations of structure, bonding, and reactions of radiation-induced free radicals in the solid state using electron spin resonance spectroscopy

    International Nuclear Information System (INIS)

    Hudson, R.L.

    1978-01-01

    Electron spin resonance spectroscopy (ESR) has been used to study the structure, bonding, and reactions of several types of free radicals produced by γ irradiation of solids at 77K. Well-defined spectral patterns and the use of photolysis and annealing treatments assisted the analyses and interpretations. The radical anion BF 3 - was generated and identified unequivocally in a matrix of tetramethylsilane at 77K. Both the ESR data and theoretical calculations support a pyramidal structure with a bond angle of about 110 0 . The present experiments showed that BF 3 - has ESR parameters consistent with those of the isoelectronic radicals CF 3 , NF 3 + , and F 2 NO. γ irradiation of polycrystalline trimethyl borate at 77K gave an ESR spectrum which was assigned to the dimer radical anion [(MeO) 3 B.B(OMe) 3 ] - . Radical anions of dialkyl carbonates were observed for the first time and found to undergo a β-scission reaction to produce alkyl radicals. This free radical reaction is unusual in that it proceeds both thermally and photochemically. For the dimethyl carbonate radical anion, 13 C parameters were obtained from a 13 C enriched sample. The photolysis of trapped radicals in γ irradiated carboxylic esters, RC(O)OR', was studied by ESR spectroscopy and two different reactions were characterized. Two hypervalent silicon radical anions were prepared and examined in SI(OCH 3 ) 4 . The results of the present work thus represent the first complete sets of data on the silicon 3s and 3p spin densities for such species. The first PL 3 - radical anion was prepared by the γ irradiation of crystalline trimethylphosphite, and identified through its photolysis reactions and from the results of radiation chemical experiments

  5. Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3 and Ammonia (NH3 Donor-Acceptor Complex

    Directory of Open Access Journals (Sweden)

    Dulal C. Ghosh

    2004-09-01

    Full Text Available The formation of the F3B–NH3 supermolecule by chemical interaction of its fragment parts, BF3 and NH3, and the dynamics of internal rotation about the ‘B–N’ bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF3 becomes more acidic and NH3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the ‘B–N’ bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule

  6. Discovery of Amadori-Type Conjugates in a Peptide Maillard Reaction and Their Corresponding Influence on the Formation of Pyrazines.

    Science.gov (United States)

    Zou, Tingting; Liu, Jianbin; Song, Huanlu; Liu, Ye

    2018-05-10

    Knowledge of the role of peptides in the Maillard reaction is rather limited. In this study, peptide Maillard reaction model systems were established. Volatile and nonvolatile MRPs (Maillard reaction products) were investigated by GC-O-MS and LC-MS. Carbohydrate module labeling (CAMOLA) experiments were performed to elucidate the carbon skeleton of these compounds. Results showed that the peptide reaction system generated more pyrazines than the free amino acid group. Several new Amadori-type conjugates were identified as novel Maillard reaction products that could greatly influence the formation of pyrazines. Our work suggested anew mechanism involving these Amadori-type conjugates and subsequent investigation revealed that the conjugates could be important intermediate products in the reaction between dicarbonyl and dipeptide. Our findings demonstrate anew pyrazine generation mechanism in the dipeptide Maillard reaction. We found that a dipeptide Maillard reaction system generated more pyrazines than a reaction system composed of free amino acids. New cross-linked peptide-sugar compounds were identified and found to impact the formation of pyrazines. The results of this study may help in the preparation of thermal reaction flavors using enzymatically hydrolyzed vegetable/animal proteins, which contain a considerable amount of peptides, as one of the major reactants. © 2018 Institute of Food Technologists®.

  7. Hydrogen bonding between the QB site ubisemiquinone and Ser-L223 in the bacterial reaction centre – a combined spectroscopic and computational perspective^

    OpenAIRE

    Martin, Erik; Baldansuren, Amgalanbaatar; Lin, Tzu-Jen; Samoilova, Rimma I.; Wraight, Colin A.; Dikanov, Sergei A.; O’Malley, Patrick J.

    2012-01-01

    In the QB site of the Rba. sphaeroides photosynthetic reaction centre the donation of a hydrogen bond from the hydroxyl group of Ser-L223 to the ubisemiquinone formed after the first flash is debatable. In this study we use a combination of spectroscopy and quantum mechanics/molecular mechanics (QM/MM) calculations to comprehensively explore this topic. We show that ENDOR, ESEEM and HYSCORE spectroscopic differences between the mutant L223SA and the wild type sample (WT) are negligible, indic...

  8. Density functional computational studies on the glucose and glycine Maillard reaction: Formation of the Amadori rearrangement products

    Science.gov (United States)

    Jalbout, Abraham F.; Roy, Amlan K.; Shipar, Abul Haider; Ahmed, M. Samsuddin

    Theoretical energy changes of various intermediates leading to the formation of the Amadori rearrangement products (ARPs) under different mechanistic assumptions have been calculated, by using open chain glucose (O-Glu)/closed chain glucose (A-Glu and B-Glu) and glycine (Gly) as a model for the Maillard reaction. Density functional theory (DFT) computations have been applied on the proposed mechanisms under different pH conditions. Thus, the possibility of the formation of different compounds and electronic energy changes for different steps in the proposed mechanisms has been evaluated. B-Glu has been found to be more efficient than A-Glu, and A-Glu has been found more efficient than O-Glu in the reaction. The reaction under basic condition is the most favorable for the formation of ARPs. Other reaction pathways have been computed and discussed in this work.0

  9. On the nature of the olefination reaction involving ditungsten hexaalkoxides and aldehydes or ketones

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, M.H.; Huffman, J.C.; Lucas, E.A.; Sousa, A.; Streib, W.E. [Indiana Univ., Bloomington, IN (United States)

    1992-03-25

    Reductive coupling of aldehydes and ketones to olefins under the action of ditungsten hexaalkoxides was investigated. In these reactions, reductive cleavage of the aldehyde or ketone carbonyl is followed by formation of the olefinic C-C bond and breaking of the carbonyl C-O bond of the second aldehyde or ketone. Observations concerning the initial C-O bond cleavage and subsequent C-C bond formation are presented. 10 refs., 4 figs.

  10. Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

    Science.gov (United States)

    Larksarp, C; Sellier, O; Alper, H

    2001-05-18

    The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.

  11. Formation of intermediate structures during the thermal transformation of lignin. 5. Contribution of the reactions of formation and recombination of paramagnetic centres

    Energy Technology Data Exchange (ETDEWEB)

    Domburg, G E; Skripchenko, T N

    1982-01-01

    ESR spectra were determined for samples of softwood (spruce) lignin and hardwood (aspen or birch) lignin at 20-400 degrees C and after cooling to 20 degrees C. Results provide evidence for a change from low-temperature to high-temperature reactions at 300-350 degrees C (higher in hardwoods than softwoods) associated with increased formation and recombination of paramagnetic centres (free radicals). A scheme is presented for the sequence of reactions leading to charcoal formation over the temperature range 100-500 degrees C.

  12. Reaction of iminopropadienones with amines: mechanistic explanations of zwitterionic intermediate, ketene and ketenimine formation.

    Science.gov (United States)

    Koch, Rainer; Finnerty, Justin J; Bruhn, Torsten; Borget, Fabien; Wentrup, Curt

    2008-09-25

    The complex reaction of thermally generated iminopropadienones with amines in the gas phase and upon matrix deposition and its varying product composition is investigated using density functional theory. In the high energy gas phase addition a single amine molecule reacts readily with iminopropadienone with the decisive step being a 1,3-hydrogen shift and activation barriers of at least 100 kJ/mol. In accordance with the experiment, the formation of ketenes is favored. In the condensed phase of an amine matrix, the utilization of amine dimers both as reagents and as explicit solvents lowers the activation energy required to a feasible 20-30 kJ/mol and predicts ketenimines as the main products, as observed experimentally.

  13. Formation of barium strontium titanate powder by solid state reaction using different calcination temperatures

    International Nuclear Information System (INIS)

    Teoh Wah Tzu; Ahmad Fauzi Mohd Noor; Zainal Arifin Ahmad

    2002-01-01

    The unique electrical properties of large permittivity in Barium Strontium Titanate have been widely used to make capacitors; it can be produced by solid state reaction. In this study, the mixture of Barium Carbonate, Strontium Carbonate and Titanium Dioxide was calcined at 500 degree C, 1000 degree C, 1100 degree C , 1150 degree C, 1200 degree C, 1250 degree C and 1300 degree C. The results of the phases change in each stage were investigated via X ay Diffraction. The results show that the formation of Barium Strontium Titanate started at 1100 degree C with the presence of other phases. The mixture is fully reacted to form Barium Strontium Titanate at 1150 degree C. Only Barium Strontium Titanate was formed as the calcination temperature was set higher. (Author)

  14. Fuel-sodium reaction product formation in breached mixed-oxide fuel

    International Nuclear Information System (INIS)

    Bottcher, J.H.; Lambert, J.D.B.; Strain, R.V.; Ukai, S.; Shibahara, S.

    1988-01-01

    The run-beyond-cladding-breach (RBCB) operation of mixed-oxide LMR fuel pins has been studied for six years in the Experimental Breeder Reactor-II (EBR-II) as part of a joint program between the US Department of Energy and the Power Reactor and Nuclear Fuel Development Corporation of Japan. The formation of fuel-sodium reaction product (FSRP), Na 3 MO 4 , where M = U/sub 1-y/Pu/sub y/, in the outer fuel regions is the major phenomenon governing RBCB behavior. It increases fuel volume, decreases fuel stoichiometry, modifies fission-product distributions, and alters thermal performance of a pin. This paper describes the morphology of Na 3 MO 4 observed in 5.84-mm diameter pins covering a variety of conditions and RBCB times up to 150 EFPD's. 8 refs., 1 fig

  15. On determination of enthalpies of complex formation reactions by means of temperature coefficient of complexing degree

    International Nuclear Information System (INIS)

    Povar, I.G.

    1995-01-01

    Equations describing the relation between temperature coefficient of ∂lnα/∂T complexing degree and the sum of changes in the enthalpy of complex formation of the composition M m L n δH mn multiplied by the weight coefficients k mm , are presented. A method to determine changes in the enthalpy of certain ΔH mm reactions from ∂lnα/∂T derivatives has been suggested. The best approximating equation from lnα/(T) dependence has been found. Errors of thus determined δH mm values are estimated and the results of calculation experiment for the system In 3+ -F - are provided. 10 refs., 2 figs., 3 tabs

  16. Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

    Science.gov (United States)

    Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

    2017-10-24

    Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

  17. Microstructure of Reaction Zone Formed During Diffusion Bonding of TiAl with Ni/Al Multilayer

    Science.gov (United States)

    Simões, Sónia; Viana, Filomena; Koçak, Mustafa; Ramos, A. Sofia; Vieira, M. Teresa; Vieira, Manuel F.

    2012-05-01

    In this article, the characterization of the interfacial structure of diffusion bonding a TiAl alloy is presented. The joining surfaces were modified by Ni/Al reactive multilayer deposition as an alternative approach to conventional diffusion bonding. TiAl substrates were coated with alternated Ni and Al nanolayers. The nanolayers were deposited by dc magnetron sputtering with 14 nm of period (bilayer thickness). Joining experiments were performed at 900 °C for 30 and 60 min with a pressure of 5 MPa. Cross sections of the joints were prepared for characterization of their interfaces by scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), high resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD). Several intermetallic compounds form at the interface, assuring the bonding of the TiAl. The interface can be divided into three distinct zones: zone 1 exhibits elongated nanograins, very small equiaxed grains are observed in zone 2, while zone 3 has larger equiaxed grains. EBSD analysis reveals that zone 1 corresponds to the intermetallic Al2NiTi and AlNiTi, and zones 2 and 3 to NiAl.

  18. Modeling the formation of N-nitrosodimethylamine (NDMA) from the reaction of natural organic matter (NOM) with monochloramine.

    Science.gov (United States)

    Chen, Zhuo; Valentine, Richard L

    2006-12-01

    This paper presents mechanistic studies on the formation of NDMA, a newly identified chloramination disinfection byproduct, from reactions of monochloramine with natural organic matter. A kinetic model was developed to validate proposed reactions and to predict NDMA formation in chloraminated water during the time frame of 1-5 days. This involved incorporating NDMA formation reactions into an established comprehensive model describing the oxidation of humic-type natural organic matter by monochloramine. A rate-limiting step involving the oxidation of NOM is theorized to control the rate of NDMA formation which is assumed to be proportional to the rate of NOM oxidized by monochloramine. The applicability of the model to describe NDMA formation in the presence of three NOM sources over a wide range in water quality (i.e., pH, DOC, and ammonia concentrations) was evaluated. Results show that with accurate measurement of monochloramine demand for a specific supply, NDMA formation could be modeled over an extended range of experimental conditions by considering a single NOM source-specific value of thetaNDMA, a stoichiometric coefficient relating the amount of NDMA produced to the amount of NOM oxidized, and several kinetic parameters describing NOM oxidation. Furthermore, the oxidation of NOM is the rate-limiting step governing NDMA formation. This suggests that NDMA formation over a 1-5 day time frame may be estimated from information on the chloramine or free chlorine demand of the NOM and the source-specific linear relationship between this demand and NDMA formation. Although the proposed model has not yet been validated for shorter time periods that may better characterize the residence time in some distribution systems, the improved understanding of the important reactions governing NDMA formation and the resulting model should benefit the water treatment industry as a tool in developing strategies that minimize NDMA formation.

  19. Reaction pathway towards formation of cobalt single chain magnets and nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Balaji, G.; Desilva, Rohini M.; Palshin, V. [Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States); Desilva, N. [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Palmer, G. [Department of Biochemistry and Cell Biology, Rice University, MS 140, 6100 Main street, Houston, TX 77251 (United States); Kumar, Challa S.S.R., E-mail: ckumar1@lsu.ed [Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States)

    2010-03-15

    With the advent of molecular magnets the quest for suitable high density magnetic storage materials has fuelled further research in this area. Here in this report, we present a detailed mechanistic investigation of thermal decomposition of cyclopentadienyl cobalt [CoCp(CO){sub 2}] precursor where Cp is the cyclopentadienyl moiety. The reaction revealed the formation of cobalt nanoparticles (Co-NPs) through an isolable reaction intermediate characterized as a Single Chain Magnet (SCM), [Co(Cp){sub 2}]{sub 2}CoCl{sub 4} (1). The SQUID magnetic measurements showed the presence of very strong antiferromagnetic interactions between Co{sup 2+} ions. The zero-field cooled (ZFC) and field cooled (FC) magnetization curves branch out below 5 K and there is evidence for frequency dependent complex susceptibility along with a maximum observed around 2.5 K. The optical studies indicated that the Co{sup 2+} d-d transition is influenced by the polarity of the solvents. The cobalt nanoparticles (Co-NPs) were obtained, either directly from 1 or from its precursor. They are spherical in shape with a mean size 15 nm, have fcc crystal structure and were found to be ferromagnetic at room temperature.

  20. Formation of early and advanced Maillard reaction products correlates to the ripening of cheese.

    Science.gov (United States)

    Spanneberg, Robert; Salzwedel, Grit; Glomb, Marcus A

    2012-01-18

    The present study deals with the characterization of the ripening of cheese. A traditional German acid curd cheese was ripened under defined conditions at elevated temperature, and protein and amino acid modifications were investigated. Degree of proteolysis and analysis of early [Amadori compound furosine (6)] and advanced [N(ε)-carboxymethyllysine (4), N(ε)-carboxyethyllysine (5)] Maillard reaction products confirmed the maturation to proceed from the rind to the core of the cheese. Whereas 6 was decreased, 4 and 5 increased over time. Deeper insight into the Maillard reaction during the ripening of cheese was achieved by the determination of selected α-dicarbonyl compounds. Especially methylglyoxal (2) showed a characteristic behavior during storage of the acid curd cheese. Decrease of this reactive structure was directly correlated to the formation of 5. To extend the results of experimental ripening to commercial cheeses, different aged Gouda types were investigated. Maturation times of the samples ranged from 6 to 8 weeks (young) to more than 1 year (aged). Again, increase of 5 and decrease of 2 were able to describe the ripening of this rennet coagulated cheese. Therefore, both chemical parameters are potent markers to characterize the degree of maturation, independent of coagulation.

  1. Formation of conjugated delta8,delta10-double bonds by delta12-oleic-acid desaturase-related enzymes: biosynthetic origin of calendic acid.

    Science.gov (United States)

    Cahoon, E B; Ripp, K G; Hall, S E; Kinney, A J

    2001-01-26

    Divergent forms of the plant Delta(12)-oleic-acid desaturase (FAD2) have previously been shown to catalyze the formation of acetylenic bonds, epoxy groups, and conjugated Delta(11),Delta(13)-double bonds by modification of an existing Delta(12)-double bond in C(18) fatty acids. Here, we report a class of FAD2-related enzymes that modifies a Delta(9)-double bond to produce the conjugated trans-Delta(8),trans-Delta(10)-double bonds found in calendic acid (18:3Delta(8trans,10trans,12cis)), the major component of the seed oil of Calendula officinalis. Using an expressed sequence tag approach, cDNAs for two closely related FAD2-like enzymes, designated CoFADX-1 and CoFADX-2, were identified from a C. officinalis developing seed cDNA library. The deduced amino acid sequences of these polypeptides share 40-50% identity with those of other FAD2 and FAD2-related enzymes. Expression of either CoFADX-1 or CoFADX-2 in somatic soybean embryos resulted in the production of calendic acid. In embryos expressing CoFADX-2, calendic acid accumulated to as high as 22% (w/w) of the total fatty acids. In addition, expression of CoFADX-1 and CoFADX-2 in Saccharomyces cerevisiae was accompanied by calendic acid accumulation when induced cells were supplied exogenous linoleic acid (18:2Delta(9cis,12cis)). These results are thus consistent with a route of calendic acid synthesis involving modification of the Delta(9)-double bond of linoleic acid. Regiospecificity for Delta(9)-double bonds is unprecedented among FAD2-related enzymes and further expands the functional diversity found in this family of enzymes.

  2. Synthesis and characterization of cobalt-nichel oxides for the oxygen formation reaction

    International Nuclear Information System (INIS)

    Morales G, P.

    2001-01-01

    In this work the compounds of cobalt and nickel oxides and the mixtures of cobalt-nickel were prepared which were characterized and evaluated as electrocatalysts in the oxygen release reaction in alkaline media. The compounds were synthesised by the sol-gel method: heated at 400 and 500 Centigrade. The compounds characterization was realized by thermogravimetry, X-ray diffraction and Scanning electron microscopy. As the Co 3 O 4 and the Ni O as the mixtures Ni O/Co 3 O 4 were obtained as a porous material with a small particle size, characteristics which are presented by cause of the low temperature of synthesis. The electrocatalytic evaluation for the synthesised compounds for the oxygen release reaction was realized by cyclic volt amperometry in a 0.5M KOH solution. The oxides mixtures presented a well electrocatalytic activity to be used in the electrochemical release of oxygen. The current density and the electrochemically active area, in all the cases of mixtures is very higher to the Co 3 O 4 and Ni O ones. Observing with greater clearness the synergic effects, in the obtained mixture at 400 C. The oxides mixtures heated at 400 C were stables for the oxygen formation reaction. Therefore it is be able to say that the Ni O/Co 3 O 4 mixture counts on a great reactive area: electrocatalytic characteristic desirable to be a material used as anode in the electrolysis of water, which increases the oxygen release in the anode and so the hydrogen release in the cathode. (Author)

  3. Effect of interlayer configurations on joint formation in TLP bonding of Ti-6AI-4V to Mg-AZ31

    International Nuclear Information System (INIS)

    Atieh, A. M.; Khan, T. I.

    2013-01-01

    In this research work, the transient liquid phase (TLP) bonding process was utilized to fabricate joints using thin (20 micro m) nickel and copper foils placed between two bonding surfaces to help facilitate joint formation. Two joint configurations were investigated, first, Ti-6Al-4V/CuNi/Mg-AZ31 and second, Ti-6Al-4V/NiCu/Mg-AZ3L The effect of bonding time on microstructural developments across the joint and the changes in mechanical properties were studied as a function of bonding temperature and pressure. The bonded specimens were examined by metallographic analysis, scanning electron microscopy (SEM), and X-ray diffraction (XRD). In both cases, intermetallic phase of CuMg/sub 2/ and Mg/sub 3/AlNi/sub 2/ was observed inside the joint region. The results show that joint shear strengths for the Ti-6Al-4V/CuNi/Mg-AZ31 setup produce joints with shear strength of 57 MPa compared to 27MPa for joints made using the Ti-6Al-4V/NiCu/Mg-AZ31 layer arrangement. (author)

  4. Effect of interlayer configurations on joint formation in TLP bonding of Ti-6Al-4V to Mg-AZ31

    International Nuclear Information System (INIS)

    Atieh, A M; Khan, T I

    2014-01-01

    In this research work, the transient liquid phase (TLP) bonding process was utilized to fabricate joints using thin (20μm) nickel and copper foils placed between two bonding surfaces to help facilitate joint formation. Two joint configurations were investigated, first, Ti-6Al-4V/CuNi/Mg-AZ31 and second, Ti-6Al-4V/NiCu/Mg-AZ3L The effect of bonding time on microstructural developments across the joint and the changes in mechanical properties were studied as a function of bonding temperature and pressure. The bonded specimens were examined by metallographic analysis, scanning electron microscopy (SEM), and X-ray diffraction (XRD). In both cases, intermetallic phase of CuMg 2 and Mg 3 AlNi 2 was observed inside the joint region. The results show that joint shear strengths for the Ti-6Al-4V/CuNi/Mg-AZ31 setup produce joints with shear strength of 57 MPa compared to 27MPa for joints made using the Ti-6Al-4V/NiCu/Mg-AZ31 layer arrangement

  5. Covalent bonds and their crucial effects on pseudogap formation in α-Al(Mn,Re)Si icosahedral quasicrystalline approximant

    International Nuclear Information System (INIS)

    Kirihara, K.; Nagata, T.; Kimura, K.; Kato, K.; Takata, M.; Nishibori, E.; Sakata, M.

    2003-01-01

    X-ray charge densities of Al-based icosahedral quasicrystalline approximant crystals α-AlReSi, α-AlMnSi, and Al 12 Re were observed by a combination of the maximum entropy method with the Rietveld method. We successfully obtained the clear images of interatomic covalent bonds between Al and transition metals (Mn, Re) and those in the Al (or Si) icosahedron in Mackay icosahedral clusters of both α-AlReSi and α-AlMnSi approximant crystals. The bonding nature of the three kinds of glue atom sites connecting Mackay icosahedral clusters was also clarified. This covalent bonding nature should strongly relate with the enhancement of the electron density-of-states pseudogap near the Fermi level. In addition, the interatomic covalent bonds of α-AlReSi are stronger than those of α-AlMnSi. This fact leads to the low effective carrier density of α-AlReSi in comparison with that of α-AlMnSi. Unlike the covalent bonding nature of an icosahedron in α-AlReSi and α-AlMnSi crystals, the Al icosahedron with an Re center atom exhibits no Al-Al interatomic covalent bonds in the Al 12 Re crystal. The tendency for metallic-covalent bonding conversion in the Al icosahedron, which is related to the atom site occupancy of the icosahedral cluster center, is also strongly supported

  6. Bond breaking and bond formation: how electron correlation is captured in many-body perturbation theory and density-functional theory.

    Science.gov (United States)

    Caruso, Fabio; Rohr, Daniel R; Hellgren, Maria; Ren, Xinguo; Rinke, Patrick; Rubio, Angel; Scheffler, Matthias

    2013-04-05

    For the paradigmatic case of H(2) dissociation, we compare state-of-the-art many-body perturbation theory in the GW approximation and density-functional theory in the exact-exchange plus random-phase approximation (RPA) for the correlation energy. For an unbiased comparison and to prevent spurious starting point effects, both approaches are iterated to full self-consistency (i.e., sc-RPA and sc-GW). The exchange-correlation diagrams in both approaches are topologically identical, but in sc-RPA they are evaluated with noninteracting and in sc-GW with interacting Green functions. This has a profound consequence for the dissociation region, where sc-RPA is superior to sc-GW. We argue that for a given diagrammatic expansion, sc-RPA outperforms sc-GW when it comes to bond breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

  7. Humic-like Products Formation via the Reaction of Phenol with Nitrite in Ice Phase

    Science.gov (United States)

    Min, D. W.; Choi, W.

    2017-12-01

    Understanding the chemical nature of humic substances is very important but the origin of humic substances in nature is not well known. Therefore, elucidating the mechanisms leading to the generation of humic substances in nature is of great interests. It is believed that humic substances are produced from the transformation of natural organic matters, like lignin, by biological pathways. Recently, it has been reported that monomer molecules like quinones and sugars could be polymerized with amino compounds to form humic-like substances. This humification process is considered as a possible mechanism of humic substances production in the environment. In this work, we report the first observation on the formation of humic-like substances from the reaction between phenol and nitrite under a frozen state. In aqueous solution, nitrite slowly reacts with phenol, producing phenolic compounds like nitrophenol. Under frozen state, however, phenol reacted rapidly with nitrite and produced diverse organic compounds, like hydroquinone, dimerized phenolic substances, and much bigger molecules such as humic-like substances. The humic-like substances produced in ice are likely caused by the formation of phenolic radical and nitrosonium ion. This work may provide some insights into unknown pathways for the origin of humic substances especially in frozen environments.

  8. Formation of furan and methylfuran by maillard-type reactions in model systems and food.

    Science.gov (United States)

    Limacher, Anita; Kerler, Josef; Davidek, Tomas; Schmalzried, Frank; Blank, Imre

    2008-05-28

    The formation of furan and 2-methylfuran was studied in model systems based on sugars and selected amino acids. Both compounds were preferably formed under roasting conditions in closed systems yielding up to 330 micromol of furan and 260 micromol of 2-methylfuran per mol of precursor. The amounts obtained under pressure cooking conditions were much lower, usually below 20 micromol/mol, except for 2-furaldehyde, which yielded 70-100 micromol/mol of furan. Labeling studies indicated two major formation pathways for both furans: (i) from the intact sugar skeleton and (ii) by recombination of reactive C(2) and/or C(3) fragments. Under roasting conditions in the absence of amino acids, furan was mainly formed from the intact sugar skeleton. Formic and acetic acid were identified as byproducts of sugar degradation, indicating the split off of C(1) and/or C(2) units from hexoses. The presence of alanine, threonine, or serine promoted furan formation by the recombination of C(2) fragments, such as acetaldehyde and glycolaldehyde, which may originate from both sugars and amino acids. In aqueous solution, about half of furan was generated by the recombination of sugar fragments. 2-Methylfuran was preferably formed in the presence of amino acids by aldol-type reactions of C(2) and C(3) fragments with lactaldehyde as a key intermediate, the Strecker aldehyde of threonine. The total furan levels in cooked vegetables were increased by spiking with hexoses. However, in pumpkin puree, only about 20% of furan was formed from sugars, preferably from the intact carbon skeleton.

  9. Bonds broken and formed during the mixed-linkage glucan : xyloglucan endotransglucosylase reaction catalysed by Equisetum hetero-trans-β-glucanase.

    Science.gov (United States)

    Simmons, Thomas J; Fry, Stephen C

    2017-03-08

    Mixed-linkage glucan∶xyloglucan endotransglucosylase (MXE) is one of the three activities of the recently characterised hetero-trans-β-glucanase (HTG), which among land plants is known only from Equisetum species. The biochemical details of the MXE reaction were incompletely understood - details that would promote understanding of MXE's role in vivo and enable its full technological exploitation. We investigated HTG's site of attack on one of its donor substrates, mixed-linkage (1→3),(1→4)-β-d-glucan (MLG), with radioactive oligosaccharides of xyloglucan as the acceptor substrate. Comparing three different MLG preparations, we showed that the enzyme favours those with a high content of cellotetraose blocks. The reaction products were analysed by enzymic digestion, thin-layer chromatography (TLC), high-pressure liquid chromatography (HPLC) and gel-permeation chromatography (GPC). Equisetum HTG consistently cleaved the MLG at the third consecutive β-(1→4)-bond following (towards the reducing terminus) a β-(1→3)-bond. It then formed a β-(1→4)-bond between the MLG and the non-reducing terminal glucose residue of the xyloglucan oligosaccharide, consistent with its xyloglucan endotransglucosylase/hydrolase subfamily membership. Using size-homogeneous barley MLG as the donor substrate, we showed that HTG does not favour any particular region of the MLG chain relative to the polysaccharide's reducing and non-reducing termini; rather, it selects its target cellotetraosyl unit stochastically along the MLG molecule. This work improves our understanding of how enzymes can exhibit promiscuous substrate specificities and provides the foundations to explore strategies for engineering novel substrate specificities into transglycanases. © 2017 The Author(s).

  10. Bond energies of ThO+ and ThC+: A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O2 and CO

    Science.gov (United States)

    Cox, Richard M.; Citir, Murat; Armentrout, P. B.; Battey, Samuel R.; Peterson, Kirk A.

    2016-05-01

    Kinetic energy dependent reactions of Th+ with O2 and CO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO+ in the reaction of Th+ with O2 is observed to be exothermic and barrierless with a reaction efficiency at low energies of k/kLGS = 1.21 ± 0.24 similar to the efficiency observed in ion cyclotron resonance experiments. Formation of ThO+ and ThC+ in the reaction of Th+ with CO is endothermic in both cases. The kinetic energy dependent cross sections for formation of these product ions were evaluated to determine 0 K bond dissociation energies (BDEs) of D0(Th+-O) = 8.57 ± 0.14 eV and D0(Th+-C) = 4.82 ± 0.29 eV. The present value of D0 (Th+-O) is within experimental uncertainty of previously reported experimental values, whereas this is the first report of D0 (Th+-C). Both BDEs are observed to be larger than those of their transition metal congeners, TiL+, ZrL+, and HfL+ (L = O and C), believed to be a result of lanthanide contraction. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to coupled-cluster singles and doubles with iterative triples and quadruples (CCSDTQ) for ThC, ThC+, ThO, and ThO+, as well as more approximate CCSD with perturbative (triples) [CCSD(T)] calculations where a semi-empirical model was used to estimate spin-orbit energy contributions. Finally, the ThO+ BDE is compared to other actinide (An) oxide cation BDEs and a simple model utilizing An+ promotion energies to the reactive state is used to estimate AnO+ and AnC+ BDEs. For AnO+, this model yields predictions that are typically within experimental uncertainty and performs better than density functional theory calculations presented previously.

  11. Bond energies of ThO{sup +} and ThC{sup +}: A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O{sub 2} and CO

    Energy Technology Data Exchange (ETDEWEB)

    Cox, Richard M; Citir, Murat; Armentrout, P. B., E-mail: armentrout@chem.utah.edu [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850 (United States); Battey, Samuel R.; Peterson, Kirk A. [Department of Chemistry, Washington State University, Pullman, Washington 99164-4630 (United States)

    2016-05-14

    Kinetic energy dependent reactions of Th{sup +} with O{sub 2} and CO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO{sup +} in the reaction of Th{sup +} with O{sub 2} is observed to be exothermic and barrierless with a reaction efficiency at low energies of k/k{sub LGS} = 1.21 ± 0.24 similar to the efficiency observed in ion cyclotron resonance experiments. Formation of ThO{sup +} and ThC{sup +} in the reaction of Th{sup +} with CO is endothermic in both cases. The kinetic energy dependent cross sections for formation of these product ions were evaluated to determine 0 K bond dissociation energies (BDEs) of D{sub 0}(Th{sup +}–O) = 8.57 ± 0.14 eV and D{sub 0}(Th{sup +}–C) = 4.82 ± 0.29 eV. The present value of D{sub 0} (Th{sup +}–O) is within experimental uncertainty of previously reported experimental values, whereas this is the first report of D{sub 0} (Th{sup +}–C). Both BDEs are observed to be larger than those of their transition metal congeners, TiL{sup +}, ZrL{sup +}, and HfL{sup +} (L = O and C), believed to be a result of lanthanide contraction. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to coupled-cluster singles and doubles with iterative triples and quadruples (CCSDTQ) for ThC, ThC{sup +}, ThO, and ThO{sup +}, as well as more approximate CCSD with perturbative (triples) [CCSD(T)] calculations where a semi-empirical model was used to estimate spin-orbit energy contributions. Finally, the ThO{sup +} BDE is compared to other actinide (An) oxide cation BDEs and a simple model utilizing An{sup +} promotion energies to the reactive state is used to estimate AnO{sup +} and AnC{sup +} BDEs. For AnO{sup +}, this model yields predictions that are typically within experimental uncertainty and performs better than density functional theory calculations presented previously.

  12. Nickel-Catalyzed C-S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters

    KAUST Repository

    Lee, Shao-Chi

    2018-01-15

    A nickel catalyzed cross-coupling protocol for the straightforward C-S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed. The utility of this protocol has been demonstrated in the synthesis of benzothiophene on the bench top.

  13. Nickel-Catalyzed C-S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters

    KAUST Repository

    Lee, Shao-Chi; Liao, Hsuan-Hung; Chatupheeraphat, Adisak; Rueping, Magnus

    2018-01-01

    A nickel catalyzed cross-coupling protocol for the straightforward C-S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed. The utility of this protocol has been demonstrated in the synthesis of benzothiophene on the bench top.

  14. Computational Investigation of the Competition between the Concerted Diels-Alder Reaction and Formation of Diradicals in Reactions of Acrylonitrile with Non-Polar Dienes

    Science.gov (United States)

    James, Natalie C.; Um, Joann M.; Padias, Anne B.; Hall, H. K.; Houk, K. N.

    2013-01-01

    The energetics of the Diels-Alder cycloaddition reactions of several 1,3-dienes with acrylonitrile, and the energetics of formation of diradicals, were investigated with density functional theory (B3LYP and M06-2X) and compared to experimental data. For the reaction of 2,3-dimethyl-1,3-butadiene with acrylonitrile, the concerted reaction is favored over the diradical pathway by 2.5 kcal/mol using B3LYP/6-31G(d); experimentally this reaction gives both cycloadduct and copolymer. The concerted cycloaddition of cyclopentadiene with acrylonitrile is preferred computationally over the stepwise pathway by 5.9 kcal/mol; experimentally, only the Diels-Alder adduct is formed. For the reactions of (E)-1,3-pentadiene and acrylonitrile, both cycloaddition and copolymerization were observed experimentally; these trends were mimicked by the computational results, which showed only a 1.2 kcal/mol preference for the concerted pathway. For the reactions of (Z)-1,3-pentadiene and acrylonitrile, the stepwise pathway is preferred by 3.9 kcal/mol, in agreement with previous experimental findings that only polymerization occurs. M06-2X is known to give more accurate activation and reaction energetics but the energies of diradicals are too high. PMID:23758325

  15. C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

    OpenAIRE

    Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

    2012-01-01

    We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

  16. Mechanistic insights into the hydrocyanation reaction

    NARCIS (Netherlands)

    Bini, L.

    2009-01-01

    The hydrocyanation of an alkene is a catalytic carbon-carbon bond formation reaction and the obtained nitriles can be converted into a variety of valuable products. The investigation of this reaction has mainly focused on the DuPont adiponitrile (AdN) process. This process is so far the only example

  17. Kinetic study on bonding reaction of gelatin with CdS nanopaticles by UV-visible spectroscopy.

    Science.gov (United States)

    Tang, Shihua; Wang, Baiyang; Li, Youqun

    2015-04-15

    The chemical kinetics on gelatin-CdS direct conjugates has been systematically investigated as a function of different temperature and reactant concentration (i.e. Cd(2+), S(2-) and gelatin) by UV-visible spectroscopy, for the first time. The nonlinear fitting and the differential method were used to calculate the initial rate based on the absorbance-time data. A double logarithmic linear equation for calculating the rate constant (k) and the reaction order (n) was introduced. The reaction kinetic parameters (n, k, Ea, and Z) and activation thermodynamic parameters (ΔG(≠), ΔH(≠), and ΔS(≠)) were obtained from variable temperature kinetic studies. The overall rate equation allowing evaluation of conditions that provide required reaction rate could be expressed as: r = 1.11 × 10(8) exp(-4971/T)[Cd(2+)][gelatin](0.6)[S(2-)](0.6) (M/S) The calculated values of the reaction rate are well coincide with the experimental results. A suitable kinetic model is also proposed. This work will provide guidance for the rational design of gelatin-directed syntheses of metal sulfide materials, and help to understand the biological effects of nanoparticles at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Optimised formation of blue Maillard reaction products of xylose and glycine model systems and associated antioxidant activity.

    Science.gov (United States)

    Yin, Zi; Sun, Qian; Zhang, Xi; Jing, Hao

    2014-05-01

    A blue colour can be formed in the xylose (Xyl) and glycine (Gly) Maillard reaction (MR) model system. However, there are fewer studies on the reaction conditions for the blue Maillard reaction products (MRPs). The objective of this study is to investigate characteristic colour formation and antioxidant activities in four different MR model systems and to determine the optimum reaction conditions for the blue colour formation in a Xyl-Gly MR model system, using the random centroid optimisation program. The blue colour with an absorbance peak at 630 nm appeared before browning in the Xyl-Gly MR model system, while no blue colour formation but only browning was observed in the xylose-alanine, xylose-aspartic acid and glucose-glycine MR model systems. The Xyl-Gly MR model system also showed higher antioxidant activity than the other three model systems. The optimum conditions for blue colour formation were as follows: xylose and glycine ratio 1:0.16 (M:M), 0.20 mol L⁻¹ NaHCO₃, 406.1 mL L⁻¹ ethanol, initial pH 8.63, 33.7°C for 22.06 h, which gave a much brighter blue colour and a higher peak at 630 nm. A characteristic blue colour could be formed in the Xyl-Gly MR model system and the optimum conditions for the blue colour formation were proposed and confirmed. © 2013 Society of Chemical Industry.

  19. Competition between reaction-induced expansion and creep compaction during gypsum formation: Experimental and numerical investigation

    Science.gov (United States)

    Skarbek, R. M.; Savage, H. M.; Spiegelman, M. W.; Kelemen, P. B.; Yancopoulos, D.

    2017-12-01

    Deformation and cracking caused by reaction-driven volume increase is an important process in many geological settings, however the conditions controlling these processes are poorly understood. The interaction of rocks with reactive fluids can change permeability and reactive surface area, leading to a large variety of feedbacks. Gypsum is an ideal material to study these processes. It forms rapidly at room temperature via bassanite hydration, and is commonly used as an analogue for rocks in high-temperature, high-pressure conditions. We conducted uniaxial strain experiments to study the effects of applied axial load on deformation and fluid flow during the formation of gypsum from bassanite. While hydration of bassanite to gypsum involves a solid volume increase, gypsum exhibits significant creep compaction when in contact with water. These two volume changing processes occur simultaneously during fluid flow through bassanite. We cold-pressed bassanite powder to form cylinders 2.5 cm in height and 1.2 cm in diameter. Samples were compressed with a static axial load of 0.01 to 4 MPa. Water infiltrated initially unsaturated samples through the bottom face and the height of the samples was recorded as a measure of the total volume change. We also performed experiments on pure gypsum samples to constrain the amount of creep observed in tests on bassanite hydration. At axial loads 1 MPa, creep in the gypsum dominates and samples exhibit monotonic compaction. At intermediate loads, samples exhibit alternating phases of compaction and expansion due to the interplay of the two volume changing processes. We observed a change from net compaction to net expansion at an axial load of 0.250 MPa. We explain this behavior with a simple model that predicts the strain evolution, but does not take fluid flow into account. We also implement a 1D poro-visco-elastic model of the imbibition process that includes the reaction and gypsum creep. We use the results of these models, with

  20. The samarium Grignard reaction. In situ formation and reactions of primary and secondary alkylsamarium(III) reagents

    Energy Technology Data Exchange (ETDEWEB)

    Curran, D.P.; Totleben, M.J. [Univ. of Pittsburgh, PA (United States)

    1992-07-15

    This work shows that primary and secondary radicals are rapidly reduced in THF/HMPA to form primary- and secondary-alkylsamarium reagents. The primary- and secondary-radicals can be formed either by direct SmI{sup 2} reductions of primary- and secondary-halides or by a previous rapid radical cyclization. The samarium reagents have moderate stability in solution, and they react with a variety of typical electrophiles, including aldehydes and ketones. The work further shows that organosamarium intermediates can be involved in the traditional samarium Barbier reaction of aldehydes and ketones conducted in THF/HMPA. A new procedure called the {open_quotes}samarium Grignard{close_quotes} method is introduced, and it is suggested that this new procedure will have considerably more scope and generality than the samarium Barbier reaction. 37 refs., 4 tabs.

  1. Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

    DEFF Research Database (Denmark)

    Jensen, Frank Bo

    2008-01-01

    The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

  2. Calculations of radiation defect formation cross sections in reactor materials in (n,p) and (n,α) reactions

    International Nuclear Information System (INIS)

    Kupchishin, A.A.; Kupchishin, A.I.; Omarbekova, Zh.

    2001-01-01

    In the work an experimental data analysis by integral σ(E 1 ) and differential [dσ(E 1 ,E 2 )]/dE 2 neutron interaction cross sections with reactor materials with the secondary protons and alpha particles generation as well as with the primarily knock-on atoms production in such reactions are carried out. It is shown, that in the (n,p) and (n',α) reactions the recoil nuclei receive essential energy portion and they are the patriarchs for atom-atom cascades in the substance. Nuclear reactions with formation of the secondary α-particles and and recoil nuclei are considered. It is shown, that these reactions are effectively proceeding within neutrons energy range 0.3-15 MeV. The nuclear reactions kinematics of above mentioned processes is studied. Energy conservation law for these reaction is applied. Deferential cross section conservation and transformation law for radiation defect formation in the (n,α) reaction are considered as well

  3. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  4. Evaporation Rate Study and NDMA Formation from UDMH/NO2 Reaction Products

    Science.gov (United States)

    Buchanan, Vanessa D.; Dee, Louis A.; Baker, David L.

    2003-01-01

    Laboratory samples of uns-dimethylhydrazine (UDMH) fuel/oxidizer (nitrogen dioxide) non-combustion reaction products (UFORP) were prepared using a unique permeation tube technology. Also, a synthetic UFORP was prepared from UDMH, N-nitrosodimethylamine (NDMA), dimethylammonium nitrate, sodium nitrite and purified water. The evaporation rate of UFORP and synthetic UFORP was determined under space vacuum (approx 10(exp -3) Torr) at -40 ?C and 0 ?C. The material remaining was analyzed and showed that the UFORP weight and NDMA concentration decreased over time; however, NDMA had not completely evaporated. Over 85% of the weight was removed by subjecting the UFORP to 10(-3) Torr for 7 hours at -40 ?C and 4 hours at 0 ?C. A mixture of dimethylammonium nitrate and sodium nitrite formed NDMA at a rapid rate in a moist air environment. A sample of UFORP residue was analyzed for formation of NDMA under various conditions. It was found that NDMA was not formed unless nitrite was added.

  5. Chemistry of tetravalent plutonium and zirconium. Hydrolysis, solubility, colloid formation and redox reactions

    International Nuclear Information System (INIS)

    Cho, Hye-Ryun

    2006-01-01

    in acidic condition, the concentration of each oxidation state of Pu must be determined prior to each experiment. The solubility data are determined directly after preparation and then the redox reactions between four different plutonium oxidation states are observed at different pH and Pu concentrations as a function of time. The results indicate that the redox behavior of Pu cannot be described by disproportionation of Pu alone. Under the experimental conditions, the redox reactions of Pu seem to be divided into two groups, Pu(IV) aq <-> Pu(III) aq and Pu(IV) coll <-> Pu(V) aq <-> Pu(VI) aq . In the Pu solution containing initially only Pu(IV), the reduction of Pu(IV) to Pu(III) aq dominates rather than the oxidation to Pu(V) aq and Pu(VI) aq . The observed two groups of reactions show the dependency of pH due to the related hydrolysis and colloid formation of Pu(IV). With increasing pH, the [Pu 4+ ] decreases either through its hydrolysis and colloid formation (increase of Pu(IV) coll ) or through its reduction (increase of Pu(III) aq ). The polymer species or colloids may dissolve to Pu(V)aq through the second reaction group (increase Pu(V) aq + Pu(VI) aq ). Consequently, it is observed that with increase of pH, [Pu(IV) aq ] decreases, [Pu(III) aq ] increases, and [Pu(IV) coll ]+[Pu(V) aq ]+[Pu(VI) aq ] increases. This study is also performed under inert gas conditions in order to investigate the influence of dissolved oxygen on the oxidation of Pu(IV) (Pu(IV) coll <-> Pu(V) aq ). From the relative abundance of the Pu oxidation states, namely the couples PuO 2 2+ /PuO 2 + and PuO 2 + /Pu(IV) coll , the redox potential Eh(V) can be obtained. The respective values agree well with the measured Eh values. In order to use the redox couple Pu 4+ /Pu 3+ , one has to take into account the strong hydrolysis of Pu(IV) which sets in below pH 1. When the abundance of Pu 4+ is calculated from the amount of [Pu(IV) aq. ]=[Pu 4+ ]+ sum y=1 4 [Pu(OH) y 4-y ] by use of hydrolysis

  6. Biofilm formation on stainless steel and gold wires for bonded retainers in vitro and in vivo and their susceptibility to oral antimicrobials.

    Science.gov (United States)

    Jongsma, Marije A; Pelser, Floris D H; van der Mei, Henny C; Atema-Smit, Jelly; van de Belt-Gritter, Betsy; Busscher, Henk J; Ren, Yijin

    2013-05-01

    Bonded retainers are used in orthodontics to maintain treatment result. Retention wires are prone to biofilm formation and cause gingival recession, bleeding on probing and increased pocket depths near bonded retainers. In this study, we compare in vitro and in vivo biofilm formation on different wires used for bonded retainers and the susceptibility of in vitro biofilms to oral antimicrobials. Orthodontic wires were exposed to saliva, and in vitro biofilm formation was evaluated using plate counting and live/dead staining, together with effects of exposure to toothpaste slurry alone or followed by antimicrobial mouthrinse application. Wires were also placed intra-orally for 72 h in human volunteers and undisturbed biofilm formation was compared by plate counting and live/dead staining, as well as by denaturing gradient gel electrophoresis for compositional differences in biofilms. Single-strand wires attracted only slightly less biofilm in vitro than multi-strand wires. Biofilms on stainless steel single-strand wires however, were much more susceptible to antimicrobials from toothpaste slurries and mouthrinses than on single-strand gold wires and biofilms on multi-strand wires. Also, in vivo significantly less biofilm was found on single-strand than on multi-strand wires. Microbial composition of biofilms was more dependent on the volunteer involved than on wire type. Biofilms on single-strand stainless steel wires attract less biofilm in vitro and are more susceptible to antimicrobials than on multi-strand wires. Also in vivo, single-strand wires attract less biofilm than multi-strand ones. Use of single-strand wires is preferred over multi-strand wires, not because they attract less biofilm, but because biofilms on single-strand wires are not protected against antimicrobials as in crevices and niches as on multi-strand wires.

  7. The unusually strong hydrogen bond between the carbonyl of Q(A) and His M219 in the Rhodobacter sphaeroides reaction center is not essential for efficient electron transfer from Q(A)(-) to Q(B).

    Science.gov (United States)

    Breton, Jacques; Lavergne, Jérôme; Wakeham, Marion C; Nabedryk, Eliane; Jones, Michael R

    2007-06-05

    In native reaction centers (RCs) from photosynthetic purple bacteria the primary quinone (QA) and the secondary quinone (QB) are interconnected via a specific His-Fe-His bridge. In Rhodobacter sphaeroides RCs the C4=O carbonyl of QA forms a very strong hydrogen bond with the protonated Npi of His M219, and the Ntau of this residue is in turn coordinated to the non-heme iron atom. The second carbonyl of QA is engaged in a much weaker hydrogen bond with the backbone N-H of Ala M260. In previous work, a Trp side chain was introduced by site-directed mutagenesis at the M260 position in the RC of Rb. sphaeroides, resulting in a complex that is completely devoid of QA and therefore nonfunctional. A photochemically competent derivative of the AM260W mutant was isolated that contains a Cys side chain at the M260 position (denoted AM260(W-->C)). In the present work, the interactions between the carbonyl groups of QA and the protein in the AM260(W-->C) suppressor mutant have been characterized by light-induced FTIR difference spectroscopy of the photoreduction of QA. The QA-/QA difference spectrum demonstrates that the strong interaction between the C4=O carbonyl of QA and His M219 is lost in the mutant, and the coupled CO and CC modes of the QA- semiquinone are also strongly perturbed. In parallel, a band assigned to the perturbation of the C5-Ntau mode of His M219 upon QA- formation in the native RC is lacking in the spectrum of the mutant. Furthermore, a positive band between 2900 and 2400 cm-1 that is related to protons fluctuating within a network of highly polarizable hydrogen bonds in the native RC is reduced in amplitude in the mutant. On the other hand, the QB-/QB FTIR difference spectrum is essentially the same as for the native RC. The kinetics of electron transfer from QA- to QB were measured by the flash-induced absorption changes at 780 nm. Compared to native RCs the absorption transients are slowed by a factor of about 2 for both the slow phase (in the

  8. Thermal effects on the mechanical properties of SiC fiber reinforced reaction bonded silicon nitride matrix (SiC/RBSN) composites

    Science.gov (United States)

    Bhatt, R. T.; Phillips, R. E.

    1988-01-01

    The elevated temperature four-point flexural strength and the room temperature tensile and flexural strength properties after thermal shock were measured for ceramic composites consisting of 30 vol pct uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The elevated temperature strengths were measured after 15 min of exposure in air at temperatures to 1400 C. Thermal shock treatment was accomplished by heating the composite in air for 15 min at temperatures to 1200 C and then quenching in water at 25 C. The results indicate no significant loss in strength properties either at temperature or after thermal shock when compared with the strength data for composites in the as-fabricated condition.

  9. Ultrafine and fine particle formation in a naturally ventilated office as a result of reactions between ozone and scented products

    DEFF Research Database (Denmark)

    Toftum, Jørn; Dijken, F. v.

    2003-01-01

    Ultrafine and fine particle formation as a result of chemical reactions between ozone and four different air fresheners and a typical lemon-scented domestic cleaner was studied in a fully furnished, naturally ventilated office. The study showed that under conditions representative of those...

  10. Bond formation in hafnium atom implantation into SiC induced by high-energy electron irradiation

    International Nuclear Information System (INIS)

    Yasuda, H.; Mori, H.; Sakata, T.; Naka, M.; Fujita, H.

    1992-01-01

    Bilayer films of Hf (target atoms)/α-SiC (substrate) were irradiated with 2 MeV electrons in an ultra-high voltage electron microscope (UHVEM), with the electron beam incident on the hafnium layer. As a result of the irradiation, hafnium atoms were implanted into the SiC substrate. Changes in the microstructure and valence electronic states associated with the implantation were studied by a combination of UHVEM and Auger valence electron spectroscopy. The implantation process is summarized as follows. (1) Irradiation with 2 MeV electrons first induces a crystalline-to-amorphous transition in α-SiC. (2) Hafnium atoms which have been knocked-off from the hafnium layer by collision with the 2 MeV electrons are implanted into the resultant amorphous SiC. (3) The implanted hafnium atoms make preferential bonding to carbon atoms. (4) With continued irradiation, the hafnium atoms repeat the displacement along the beam direction and the subsequent bonding with the dangling hybrids of carbon and silicon. The repetition of the displacement and subsequent bonding lead to the deep implantation of hafnium atoms into the SiC substrate. It is concluded that implantation successfully occurs when the bond strength between a constituent atom of a substrate and an injected atom is stronger than that between constituent atoms of a substrate. (Author)

  11. Formation of a Six-Coordinate fac-[Re(Co)3]+ Complex by the N-C bond cleavage of a potentially tetradentate ligand

    International Nuclear Information System (INIS)

    Booysen, I.; Gerber, T. I. A.; Hosten, E.; Mayer, P.

    2008-01-01

    The rhenium(I) compound fac-[Re(CO) 3 (daa)]. Hpab.H 2 O (Hpab N,N'-(l,2-phenylene)bis(2'-aminobenzamide); Hdaa 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO) 5 ,Br] with two equivalent of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. The compound was characterized by IR spectroscopy and X-ray crystallography, and daa is coordinated as a diamino amide via three nitrogen-donor atoms

  12. Primary retention following nuclear recoil in β-decay: Proposed synthesis of a metastable rare gas oxide ((38)ArO4) from ((38)ClO4(-)) and the evolution of chemical bonding over the nuclear transmutation reaction path.

    Science.gov (United States)

    Timm, Matthew J; Matta, Chérif F

    2014-12-01

    Argon tetroxide (ArO4) is the last member of the N=50 e(-) isoelectronic and isosteric series of ions: SiO4(4-), PO4(3-), SO4(2-), and ClO4(-). A high level computational study demonstrated that while ArO4 is kinetically stable it has a considerable positive enthalpy of formation (of ~298kcal/mol) (Lindh et al., 1999. J. Phys. Chem. A 103, pp. 8295-8302) confirming earlier predictions by Pyykkö (1990. Phys. Scr. 33, pp. 52-53). ArO4 can be expected to be difficult to synthesize by traditional chemistry due to its metastability and has not yet been synthesized at the time of writing. A computational investigation of the changes in the chemical bonding of chlorate (ClO4(-)) when the central chlorine atom undergoes a nuclear transmutation from the unstable artificial chlorine isotope (38)Cl to the stable rare argon isotope (38)Ar through β-decay, hence potentially leading to the formation of ArO4, is reported. A mathematical model is presented that allows for the prediction of yields following the recoil of a nucleus upon ejecting a β-electron. It is demonstrated that below a critical angle between the ejected β-electron and that of the accompanying antineutrino their respective linear momentums can cancel to such an extent as imparting a recoil to the daughter atom insufficient for breaking the Ar-O bond. As a result, a primary retention yield of ~1% of ArO4 is predicted following the nuclear disintegration. The study is conducted at the quadratic configuration interaction with single and double excitations [QCISD/6-311+G(3df)] level of theory followed by an analysis of the electron density by the quantum theory of atoms in molecules (QTAIM). Crossed potential energy surfaces (PES) were used to construct a PES from the metastable ArO4 ground singlet state to the Ar-O bond dissociation product ArO3+O((3)P) from which the predicted barrier to dissociation is ca. 22kcal/mol and the exothermic reaction energy is ca. 28kcal/mol [(U)MP2/6-311+G(d)]. Copyright © 2014

  13. Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)

    2016-06-07

    Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

  14. Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

    International Nuclear Information System (INIS)

    Xu, Wen-Sheng; Freed, Karl F.

    2016-01-01

    Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

  15. Aldimine Formation Reaction, the First Step of the Maillard Early-phase Reaction, Might be Enhanced in Variant Hemoglobin, Hb Himeji.

    Science.gov (United States)

    Koga, Masafumi; Inada, Shinya; Shimizu, Sayoko; Hatazaki, Masahiro; Umayahara, Yutaka; Nishihara, Eijun

    2015-01-01

    Hb Himeji (β140Ala→Asp) is known as a variant hemoglobin in which glycation is enhanced and HbA1c measured by immunoassay shows a high value. The phenomenon of enhanced glycation in Hb Himeji is based on the fact that the glycation product of variant hemoglobin (HbX1c) shows a higher value than HbA1c. In this study, we investigated whether aldimine formation reaction, the first step of the Maillard early-phase reaction, is enhanced in Hb Himeji in vitro. Three non-diabetic subjects with Hb Himeji and four non-diabetic subjects without variant hemoglobin were enrolled. In order to examine aldimine formation reaction, whole blood cells were incubated with 500 mg/dl of glucose at 37°C for 1 hour and were analyzed by high-performance liquid chromatography. Both HbA1c and HbX1c were not increased in this condition. After incubation with glucose, labile HbA1c (LA1c) fraction increased in the controls (1.1±0.3%). In subjects with Hb Himeji increases in the labile HbX1c (LX1c) fraction as well as the LA1c fraction were observed, and the degree of increase in the LX1c fraction was significantly higher than that of the LA1c fraction (1.8±0.1% vs. 0.5±0.2%, Preaction might be enhanced in Hb Himeji in vitro. The 140th amino acid in β chain of hemoglobin is suggested to be involved in aldimine formation reaction. © 2015 by the Association of Clinical Scientists, Inc.

  16. Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

    2010-01-04

    The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

  17. Quantum chemical and thermodynamic calculations of fulvic and humic copper complexes in reactions of malachite and azurite formation

    International Nuclear Information System (INIS)

    Fomin, Vitaliy N.; Gogol, Daniil B.; Rozhkovoy, Ivan E.; Ponomarev, Dmitriy L.

    2017-01-01

    This article provides a thermodynamic evaluation of the reactions of humic and fulvic acids in the process of malachite and azurite mineralogenesis. Semi-empirical methods AM/1, MNDO, PM3, PM5, PM6 and PM7 were used to compute the heat of formation, enthalpy and entropy for thermodynamic calculations of the reactions performed on the basis of Hess's law. It is shown that methods PM6 and PM7 in the MOPAC software package provide good compliance with experimental and calculated heats of formation for copper complexes and alkaline earth metal complexes with organic acids. It is found that the malachite and azurite formation processes involving humus complexing substances are thermodynamically possible. - Highlights: • Copper and alkali-earth metal complexes with humic and fulvic acids are considered. • Quantum chemical calculation of thermodynamics for the structures was performed. • Semi-empirical methods PM6 and PM7 provide best correlation for the properties. • Parameters of basic copper carbonate formation reactions were obtained by Hess's law. • Processes of malachite and azurite formation from humus complexes are possible.

  18. Reactions of N+ ions with ethylene: a theoretical study on the addition mechanism into the olefin double bond

    International Nuclear Information System (INIS)

    Di Stefano, Marco; Rosi, Marzio; Sgamellotti, Antonio

    2004-01-01

    The potential energy surface of the reaction between ethylene molecules and N + ions is investigated by using the DFT hybrid functional B3LYP with the 6-31G* basis set. The addition channel leading to the intermediate C 2 NH 4 + is considered. We study eighteen structures of the triplet C 2 NH 4 + cations and the transition states for their isomerizations. Then, we consider the release of a H atom to form the doublet C 2 NH 3 + cations. To obtain more accurate values of reaction energetics and barrier heights, coupled cluster CCSD(T) calculations with the 6-311G** basis set are performed on the B3LYP/6-31G* optimized geometries. The addition of N + into C 2 H 4 is computed as a barrierless process leading to the triplet 1-aziridynil cation which, by ring opening, can easily evolve into the 2-azaallyl isomer. This species can then release a hydrogen atom to form the 2-azaallene cation, process that is computed to be the most likely channel

  19. Asymmetric C-C Bond-Formation Reaction with Pd: How to Favor Heterogeneous or Homogeneous Catalysis?

    DEFF Research Database (Denmark)

    Reimann, S.; Grunwaldt, Jan-Dierk; Mallat, T.

    2010-01-01

    The enantioselective allylic alkylation of (E)-1,3-diphenylallyl acetate was studied to clarify the heterogeneous or homogeneous character of the Pd/Al2O3-(R)-BINAP catalyst system. A combined approach was applied: the catalytic tests were completed with in situ XANES measurements to follow...

  20. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    International Nuclear Information System (INIS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH 3 + , NH 4 + , NH 3 OH + , and NH 2 OH + ) and neutral molecules having one carbonyl group (H 2 CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  1. Some Insights into Formamide Formation through Gas-phase Reactions in the Interstellar Medium

    Science.gov (United States)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH_{3}^{+}, NH_{4}^{+}, NH3OH+, and NH2OH+) and neutral molecules having one carbonyl group (H2CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  2. Preparation of catalytically active, covalent α-polylysine-enzyme conjugates via UV/vis-quantifiable bis-aryl hydrazone bond formation.

    Science.gov (United States)

    Grotzky, Andrea; Manaka, Yuichi; Kojima, Taisuke; Walde, Peter

    2011-01-10

    Covalent UV/vis-quantifiable bis-aryl hydrazone bond formation was investigated for the preparation of conjugates between α-poly-d-lysine (PDL) and either α-chymotrypsin (α-CT) or horseradish peroxidase (HRP). PDL and the enzymes were first modified via free amino groups with the linking reagents succinimidyl 6-hydrazinonicotinate acetone hydrazone (S-HyNic, at pH 7.6) and succinimidyl 4-formylbenzoate (S-4FB, at pH 7.2), respectively. The modified PDL and enzymes were then conjugated at pH 4.7, whereby polymer chains carrying several enzymes were obtained. Kinetics of the bis-aryl hydrazone bond formation was investigated spectrophotometrically at 354 nm. Retention of the enzymatic activity after conjugate formation was confirmed by using the substrates N-succinimidyl-l-Ala-l-Ala-l-Pro-l-Phe-p-nitroanilide (for α-CT) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS, for HRP). Thus, not only a mild and efficient preparation and convenient quantification of a conjugate between the polycationic α-polylysine and enzymes could be shown, but also the complete preservation of the enzymatic activity.

  3. Formation of iodo-trihalomethanes, iodo-acetic acids, and iodo-acetamides during chloramination of iodide-containing waters: Factors influencing formation and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shaogang [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China); Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530006, Guangxi (China); Li, Zhenlin [Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530006, Guangxi (China); Dong, Huiyu [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China); Goodman, Bernard A. [College of Physical Science and Engineering, State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources, Guangxi University, Nanning, 520004, Guangxi (China); Qiang, Zhimin, E-mail: qiangz@rcees.ac.cn [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China)

    2017-01-05

    This study investigated systematically the factors influencing the formation of iodinated disinfection by-products (I-DBPs) during chloramination of I{sup −}-containing waters, including reaction time, NH{sub 2}Cl dose, I{sup −} concentration, pH, natural organic matter (NOM) concentration, Br{sup −}/I{sup −} molar ratio, and water matrix. Among the I-DBPs detected, iodoform (CHI{sub 3}), iodoacetic acid (IAA), diiodoacetic acid (DIAA), triiodoacetic acid (TIAA), and diiodoacetamide (DIAcAm) were the major species produced from reactions between reactive iodine species (HOI/I{sub 2}) and NOM. A kinetic model involving the reactions of NH{sub 2}Cl auto-decomposition, iodine species transformation and NOM consumption was developed, which could well describe NH{sub 2}Cl decay and HOI/I{sub 2} evolution. Higher concentrations of CHI{sub 3}, IAA, DIAA, TIAA, and DIAcAm were observed in chloramination than in chlorination, whereas IO{sub 3}{sup −} was only formed significantly in chlorination. Maximum formation of I-DBPs occurred at pH 8.0, but acidic conditions favored the formation of iodinated haloacetic acids and DIAcAm. Increasing Br{sup −}/I{sup −} molar ratio from 1 to 10 did not increase the total amount of I-DBPs, but produced more bromine-substituting species. In addition, chloramination of 18 model compounds indicated that low-SUVA{sub 254} (specific ultraviolet absorbance at 254 nm) NOM generally favored the formation of I-DBPs compared to high-SUVA{sub 254} NOM. Finally, potential pathways for I-DBPs formation from chloramination of NOM were proposed.

  4. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    International Nuclear Information System (INIS)

    Brymora, Katarzyna; Fouineau, Jonathan; Eddarir, Asma; Chau, François; Yaacoub, Nader; Grenèche, Jean-Marc; Pinson, Jean; Ammar, Souad; Calvayrac, Florent

    2015-01-01

    Combining ab initio modeling and 57 Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal–oxygen–carbon bonding and not a metal–carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces

  5. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    Science.gov (United States)

    Brymora, Katarzyna; Fouineau, Jonathan; Eddarir, Asma; Chau, François; Yaacoub, Nader; Grenèche, Jean-Marc; Pinson, Jean; Ammar, Souad; Calvayrac, Florent

    2015-11-01

    Combining ab initio modeling and 57Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal-oxygen-carbon bonding and not a metal-carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  6. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Brymora, Katarzyna [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Fouineau, Jonathan; Eddarir, Asma; Chau, François [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Yaacoub, Nader; Grenèche, Jean-Marc [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France); Pinson, Jean; Ammar, Souad [Université Paris Diderot, Sorbonne Paris Cité, ITODYS CNRS UMR 7086 (France); Calvayrac, Florent, E-mail: florent.calvayrac@univ-lemans.fr [LUNAM Université du Maine, IMMM UMR CNRS 6283 (France)

    2015-11-15

    Combining ab initio modeling and {sup 57}Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal–oxygen–carbon bonding and not a metal–carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  7. Effects of Interface Coating and Nitride Enhancing Additive on Properties of Hi-Nicalon SiC Fiber Reinforced Reaction-Bonded Silicon Nitride Composites

    Science.gov (United States)

    Bhatt, Ramakrishana T.; Hull, David R.; Eldridge, Jeffrey I.; Babuder, Raymond

    2000-01-01

    Strong and tough Hi-Nicalon SiC fiber reinforced reaction-bonded silicon nitride matrix composites (SiC/ RBSN) have been fabricated by the fiber lay-up approach. Commercially available uncoated and PBN, PBN/Si-rich PBN, and BN/SiC coated SiC Hi-Nicalon fiber tows were used as reinforcement. The composites contained approximately 24 vol % of aligned 14 micron diameter SiC fibers in a porous RBSN matrix. Both one- and two-dimensional composites were characterized. The effects of interface coating composition, and the nitridation enhancing additive, NiO, on the room temperature physical, tensile, and interfacial shear strength properties of SiC/RBSN matrix composites were evaluated. Results indicate that for all three coated fibers, the thickness of the coatings decreased from the outer periphery to the interior of the tows, and that from 10 to 30 percent of the fibers were not covered with the interface coating. In the uncoated regions, chemical reaction between the NiO additive and the SiC fiber occurs causing degradation of tensile properties of the composites. Among the three interface coating combinations investigated, the BN/SiC coated Hi-Nicalon SiC fiber reinforced RBSN matrix composite showed the least amount of uncoated regions and reasonably uniform interface coating thickness. The matrix cracking stress in SiC/RBSN composites was predicted using a fracture mechanics based crack bridging model.

  8. A novel stibacarbaborane cluster with adjacent antimony atoms exhibiting unique pnictogen bond formation that dominates its crystal packing.

    Science.gov (United States)

    Holub, Josef; Melichar, Petr; Růžičková, Zdeňka; Vrána, Jan; Wann, Derek A; Fanfrlík, Jindřich; Hnyk, Drahomír; Růžička, Aleš

    2017-10-17

    We have prepared nido-7,8,9,11-Sb 2 C 2 B 7 H 9 , the first cluster with simultaneous Sb-B, Sb-C and Sb-Sb atom pairs with interatomic separations with magnitudes that approach the respective sums of covalent radii. However, the length of the Sb-Sb separation in this cluster is slightly less than the sum of the covalent radii. Quantum chemical analysis has revealed that the crystal packing of nido-7,8,9,11-Sb 2 C 2 B 7 H 9 is predominantly dictated by pnictogen (Pn) bonding, an unconventional σ-hole interaction. Indeed, the interaction energy of a very strong Sb 2 H-B Pn-bond in the nido-7,8,9,11-Sb 2 C 2 B 7 H 9 dimer exceeds -6.0 kcal mol -1 . This is a very large value and is comparable to the strengths of known Pn-bonds in Cl 3 Pnπ complexes (Pn = As, Sb).

  9. A study of fundamental reaction pathways for transition metal alkyl complexes. I. The reaction of a nickel methyl complex with alkynes. Ii. The mechanism of aldehyde formation in the reaction of a molybdenum hydride with molybdenum alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Huggins, John Mitchell [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1980-06-12

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl-acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO)3H (1a) with CpMo(CO)3R (2, R= CH3, C2H5) at 50°C in THF gives the aldehyde RCHO and the dimers [CpMo(CO)3]2 (3a) and [CpMo(CO)2]2 (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand

  10. Zinc and cadmium complexes of a plant metallothionein under radical stress: desulfurisation reactions associated with the formation of trans-lipids in model membranes.

    Science.gov (United States)

    Torreggiani, Armida; Domènech, Jordi; Orihuela, Ruben; Ferreri, Carla; Atrian, Sílvia; Capdevila, Mercè; Chatgilialoglu, Chryssostomos

    2009-06-08

    Metallothioneins (MTs) are sulfur-rich proteins capable of binding metal ions to give metal clusters. The metal-MT aggregates used in this work were Zn- and Cd-QsMT, where QsMT is an MT from the plant Quercus suber. Reactions of reductive reactive species (H(*) atoms and e(aq)(-)), produced by gamma irradiation of water, with Zn- and Cd-QsMT were carried out in both aqueous solutions and vesicle suspensions, and were characterized by different approaches. By using a biomimetic model based on unsaturated lipid vesicle suspensions, the occurrence of tandem protein/lipid damage was shown. The reactions of reductive reactive species with methionine residues and/or sulfur-containing ligands afford diffusible sulfur-centred radicals, which migrate from the aqueous phase to the lipid bilayer and transform the cis double bond of the oleate moiety into the trans isomer. Tailored experiments allowed the reaction mechanism to be elucidated in some detail. The formation of sulfur-centred radicals is accompanied by the modification of the metal-QsMT complexes, which were monitored by various spectroscopic and spectrometric techniques (Raman, CD, and ESI-MS). Attack of the H(*) atom and e(aq)(-) on the metal-QsMT aggregates can induce significant structural changes such as partial deconstruction and/or rearrangement of the metal clusters and breaking of the protein backbone. Substantial differences were observed in the behaviour of the Zn- and Cd-QsMT aggregates towards the reactive species, depending on the different folding of the polypeptide in these two cases.

  11. Roles of different initial Maillard intermediates and pathways in meat flavor formation for cysteine-xylose-glycine model reaction systems.

    Science.gov (United States)

    Hou, Li; Xie, Jianchun; Zhao, Jian; Zhao, Mengyao; Fan, Mengdie; Xiao, Qunfei; Liang, Jingjing; Chen, Feng

    2017-10-01

    To explore initial Maillard reaction pathways and mechanisms for maximal formation of meaty flavors in heated cysteine-xylose-glycine systems, model reactions with synthesized initial Maillard intermediates, Gly-Amadori, TTCA (2-threityl-thiazolidine-4-carboxylic acids) and Cys-Amadori, were investigated. Relative relativities were characterized by spectrophotometrically monitoring the development of colorless degradation intermediates and browning reaction products. Aroma compounds formed were determined by solid-phase microextraction combined with GC-MS and GC-olfactometry. Gly-Amadori showed the fastest reaction followed by Cys-Amadori then TTCA. Free glycine accelerated reaction of TTCA, whereas cysteine inhibited that of Gly-Amadori due to association forming relatively stable thiazolidines. Cys-Amadori/Gly had the highest reactivity in development of both meaty flavors and brown products. TTCA/Gly favored yielding meaty flavors, whereas Gly-Amadori/Cys favored generation of brown products. Conclusively, initial formation of TTCA and pathway involving TTCA with glycine were more applicable to efficiently produce processed-meat flavorings in a cysteine-xylose-glycine system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. The Mechanism of Redox Reaction between Palladium(II Complex Ions and Potassium Formate in Acidic Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Wojnicki M.

    2017-06-01

    Full Text Available The kinetics studies of redox reaction between palladium(II chloride complex ions and potassium formate in acidic aqueous solutions was investigated. It was shown, that the reduction reaction of Pd(II is selective in respect to Pd(II complex structure. The kinetic of the process was monitored spectrophotometrically. The influence of chloride ions concentration, Pd(II initial concentration, reductant concentration, ionic strength as well as the temperature were investigated in respect to the process dynamics. Arrhenius equation parameters were determined and are equal to 65.8 kJ/mol, and A = 1.12×1011 s−1.

  13. Study on reaction mechanism by analysis of kinetic energy spectra of light particles and formation of final products

    Science.gov (United States)

    Giardina, G.; Mandaglio, G.; Nasirov, A. K.; Anastasi, A.; Curciarello, F.; Fazio, G.

    2018-05-01

    The sensitivity of reaction mechanism in the formation of compound nucleus (CN) by the analysis of kinetic energy spectra of light particles and of reaction products are shown. The dependence of the P CN fusion probability of reactants and W sur survival probability of CN against fission at its deexcitation on the mass and charge symmetries in the entrance channel of heavy-ion collisions, as well as on the neutron numbers is discussed. The possibility of conducting a complex program of investigations of the complete fusion by reliable ways depends on the detailed and refined methods of experimental and theoretical analyses.

  14. Molecular treatment of the ion-pair formation reaction in H(1s) + H(1s) collisions

    Energy Technology Data Exchange (ETDEWEB)

    Borondo, F.; Martin, F.; Yaez, M.

    1987-01-01

    All the available theoretical calculations of the cross section for the ion-pair formation reaction H(1s)+H(1s)..-->..H/sup +/H/sup -/(1s/sup 2/) have been performed using methods that are only valid at high collision energies. They get good agreement with the experiments for impact energies greater than 25 keV, but fail completely at smaller energies. In this work we report the cross section for this reaction at impact energies less than 10 keV, calculated in the framework of the impact-parameter approximation and using the molecular method with a common translation factor.

  15. Nonequilibrium transition and pattern formation in a linear reaction-diffusion system with self-regulated kinetics

    Science.gov (United States)

    Paul, Shibashis; Ghosh, Shyamolina; Ray, Deb Shankar

    2018-02-01

    We consider a reaction-diffusion system with linear, stochastic activator-inhibitor kinetics where the time evolution of concentration of a species at any spatial location depends on the relative average concentration of its neighbors. This self-regulating nature of kinetics brings in spatial correlation between the activator and the inhibitor. An interplay of this correlation in kinetics and disparity of diffusivities of the two species leads to symmetry breaking non-equilibrium transition resulting in stationary pattern formation. The role of initial noise strength and the linear reaction terms has been analyzed for pattern selection.

  16. Molecular treatment of the ion-pair formation reaction in H(1s) + H(1s) collisions

    International Nuclear Information System (INIS)

    Borondo, F.; Martin, F.; Yaez, M.

    1987-01-01

    All the available theoretical calculations of the cross section for the ion-pair formation reaction H(1s)+H(1s)→H + H - (1s 2 ) have been performed using methods that are only valid at high collision energies. They get good agreement with the experiments for impact energies greater than 25 keV, but fail completely at smaller energies. In this work we report the cross section for this reaction at impact energies less than 10 keV, calculated in the framework of the impact-parameter approximation and using the molecular method with a common translation factor

  17. The functional properties of chitosan-glucose-asparagine Maillard reaction products and mitigation of acrylamide formation by chitosans.

    Science.gov (United States)

    Sung, Wen-Chieh; Chang, Yu-Wei; Chou, Yu-Hao; Hsiao, Hsin-I

    2018-03-15

    This research aims to clarify the interactions that occur in a food model system consisting of glucose, asparagine and chitosans. Low molecular weight chitosan exerted a potent inhibitory effect (46.8%) on acrylamide and Maillard reaction products (MRPs) (>52.6%), respectively. Compared to a previous study conducted using the fructose system, the novel findings of this research demonstrate that the formation of acrylamide and Maillard reaction products was lower with glucose than with fructose when they were used as reducing sugars in food model systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    Science.gov (United States)

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

  19. Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

    Science.gov (United States)

    Yi, Chae S.; Lee, Do W.

    2010-01-01

    Summary The cationic ruthenium-hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of arylketones with cycloalkenes. The preliminary mechanistic analysis revealed that electrophilic ruthenium-vinyl complex is the key species for mediating both vinyl C–H bond activation and the dehydrative olefination steps of the coupling reaction. PMID:20567607

  20. Fluorine-enhanced low-temperature wafer bonding of native-oxide covered Si wafers

    Science.gov (United States)

    Tong, Q.-Y.; Gan, Q.; Fountain, G.; Enquist, P.; Scholz, R.; Gösele, U.

    2004-10-01

    The bonding energy of bonded native-oxide-covered silicon wafers treated in the HNO3/H2O/HF or the HNO3/HF solution prior to room-temperature contact is significantly higher than bonded standard RCA1 cleaned wafer pairs after low-temperature annealing. The bonding energy reaches over 2000mJ/m2 after annealing at 100 °C. The very slight etching and fluorine in the chemically grown oxide are believed to be the main contributors to the enhanced bonding energy. Transmission-electron-microscopic images have shown that the chemically formed native oxide at bonding interface is embedded with many flake-like cavities. The cavities can absorb the by-products of the interfacial reactions that result in covalent bond formation at low temperatures allowing the strong bond to be retained.

  1. The Possibility of Ce3+ and Mn2+ Complex Ions Formation With Iodine Species in a Dushman Reaction

    Directory of Open Access Journals (Sweden)

    Iurie Ungureanu

    2018-06-01

    Full Text Available This contribution presents investigations into possible effects of Ce3+ and Mn2+ on the reduction of UV-spectral signal for I3- observed e.g. in the Dushman reaction. The potential of the metal ions to form complexes with iodine-containing species was analysed. It was shown that no complex ions are formed between Ce3+ and Mn2+ metals ions with IO3-, I-, I2 species. Only the formation of a very weak CeI32+ complex ion was found to occur. An effect of a complex formation on the studied systems could be excluded.

  2. Formation of base triplets by non-Watson-Crick bonds mediates homologous recognition in RecA recombination filaments.

    OpenAIRE

    Rao, B J; Radding, C M

    1994-01-01

    Whereas complementary strands of DNA recognize one another by forming Watson-Crick base pairs, the way in which RecA protein enables a single strand to recognize homology in duplex DNA has remained unknown. Recent experiments, however, have shown that a single plus strand in the RecA filament can recognize an identical plus strand via bonds that, by definition, are non-Watson-Crick. In experiments reported here, base substitutions had the same qualitative and quantitative effects on the pairi...

  3. Real-time nonlinear feedback control of pattern formation in (bio)chemical reaction-diffusion processes: a model study.

    Science.gov (United States)

    Brandt-Pollmann, U; Lebiedz, D; Diehl, M; Sager, S; Schlöder, J

    2005-09-01

    Theoretical and experimental studies related to manipulation of pattern formation in self-organizing reaction-diffusion processes by appropriate control stimuli become increasingly important both in chemical engineering and cellular biochemistry. In a model study, we demonstrate here exemplarily the application of an efficient nonlinear model predictive control (NMPC) algorithm to real-time optimal feedback control of pattern formation in a bacterial chemotaxis system modeled by nonlinear partial differential equations. The corresponding drift-diffusion model type is representative for many (bio)chemical systems involving nonlinear reaction dynamics and nonlinear diffusion. We show how the computed optimal feedback control strategy exploits the system inherent physical property of wave propagation to achieve desired control aims. We discuss various applications of our approach to optimal control of spatiotemporal dynamics.

  4. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2014-01-10

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH{sub 3}{sup +}, NH{sub 4}{sup +}, NH{sub 3}OH{sup +}, and NH{sub 2}OH{sup +}) and neutral molecules having one carbonyl group (H{sub 2}CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  5. Water Mediated Wittig Reactions of Aldehydes in the Teaching Laboratory: Using Sodium Bicarbonate for the in Situ Formation of Stabilized Ylides

    Science.gov (United States)

    Kelly, Michael J. B.; Fallot, Lucas B.; Gustafson, Jeffrey L.; Bergdahl, B. Mikael

    2016-01-01

    The synthesis of alkenes using the Wittig reaction is a traditional part of many undergraduate organic chemistry teaching laboratory curricula. The aqueous medium version of the Wittig reaction presented is a reliable adaptation of this alkene formation reaction as a very safe alternative in the introductory organic chemistry laboratory. The…

  6. Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

    Science.gov (United States)

    Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

    2012-02-07

    Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

  7. An investigation of molybdenum and molybdenum oxide catalyzed hydrocarbon formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tysoe, W.T.

    1995-09-01

    The document is divided into: experiments on model catalysts at high pressure, reaction studies on metallic Mo, surface chemistry experiments (metallic surfaces in ultrahigh vacuum; Mo(CO){sub 6} adsorption on alumina), and theoretical calculations.

  8. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  9. A conserved residue of l-alanine dehydrogenase from Bacillus pseudofirmus, Lys-73, participates in the catalytic reaction through hydrogen bonding.

    Science.gov (United States)

    He, Guangzheng; Xu, Shujing; Wang, Shanshan; Zhang, Qing; Liu, Dong; Chen, Yuling; Ju, Jiansong; Zhao, Baohua

    2018-03-01

    A multiple protein sequence alignment of l-alanine dehydrogenases from different bacterial species revealed that five highly conserved amino acid residues Arg-15, Lys-73, Lys-75, His-96 and Asp-269 are potential catalytic residues of l-alanine dehydrogenase from Bacillus pseudofirmus OF4. In this study, recombinant OF4Ald and its mutants of five conserved residues were constructed, expressed in Escherichia coli, purified by His 6 -tag affinity column and gel filtration chromatography, structure homology modeling, and characterized. The purified protein OF4Ald displayed high specificity to l-alanine (15Umg -1 ) with an optimal temperature and pH of 40°C and 10.5, respectively. Enzymatic assay and activity staining in native gels showed that mutations at four conserved residue Arg-15, Lys-75, His-96 and Asp-269 (except residue Lys-73) resulted in a complete loss in enzymatic activity, which signified that these predicted active sites are indispensable for OF4Ald activity. In contrast, the mutant K73A resulted in 6-fold improvement in k cat /K m towards l-alanine as compared to the wild type protein. Further research of the residue Lys-73 substituted by various amino acids and structural modeling revealed that residue Lys-73 might be involved in the catalytic reaction of the enzyme by influencing the enzyme-substrate binding through the hydrogen-bonding interaction with conserved residue Lys-75. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Reaction Decoder Tool (RDT): extracting features from chemical reactions.

    Science.gov (United States)

    Rahman, Syed Asad; Torrance, Gilliean; Baldacci, Lorenzo; Martínez Cuesta, Sergio; Fenninger, Franz; Gopal, Nimish; Choudhary, Saket; May, John W; Holliday, Gemma L; Steinbeck, Christoph; Thornton, Janet M

    2016-07-01

    Extracting chemical features like Atom-Atom Mapping (AAM), Bond Changes (BCs) and Reaction Centres from biochemical reactions helps us understand the chemical composition of enzymatic reactions. Reaction Decoder is a robust command line tool, which performs this task with high accuracy. It supports standard chemical input/output exchange formats i.e. RXN/SMILES, computes AAM, highlights BCs and creates images of the mapped reaction. This aids in the analysis of metabolic pathways and the ability to perform comparative studies of chemical reactions based on these features. This software is implemented in Java, supported on Windows, Linux and Mac OSX, and freely available at https://github.com/asad/ReactionDecoder : asad@ebi.ac.uk or s9asad@gmail.com. © The Author 2016. Published by Oxford University Press.

  11. Formation of Bonded Exciplex in the Excited States of Dicyanoanthracene-Pyridine System : Time Dependent Density Functional Theory Study

    NARCIS (Netherlands)

    Setiawan, D.; Sethio, D.; Martoprawiro, M.A.; Filatov, M.; Gaol, FL; Nguyen, QV

    2012-01-01

    Strong quenching of fluorescence was recently observed in pyridine solutions of 9,10-dicyanoanthracene chromophore. It was hypothesized that quenching may be attributed to the formation of bound charge transfer complexes in the excited states of the molecules. In this work, using time-dependent

  12. Kinetics of rapid covalent bond formation of aniline with humic acid: ESR investigations with nitroxide spin labels

    Science.gov (United States)

    Glinka, Kevin; Matthies, Michael; Theiling, Marius; Hideg, Kalman; Steinhoff, Heinz-Jürgen

    2016-04-01

    Sulfonamide antibiotics used in livestock farming are distributed to farmland by application of slurry as fertilizer. Previous work suggests rapid covalent binding of the aniline moiety to humic acids found in soil. In the current work, kinetics of this binding were measured in X-band EPR spectroscopy by incubating Leonardite humic acid (LHA) with a paramagnetic aniline spin label (anilino-NO (2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-oxyl)). Binding was detected by a pronounced broadening of the spectral lines after incubation of LHA with anilino-NO. The time evolution of the amplitude of this feature was used for determining the reaction kinetics. Single- and double-exponential models were fitted to the data obtained for modelling one or two first-order reactions. Reaction rates of 0.16 min-1 and 0.012 min-1, were found respectively. Addition of laccase peroxidase did not change the kinetics but significantly enhanced the reacting fraction of anilino-NO. This EPR-based method provides a technically simple and effective method for following rapid binding processes of a xenobiotic substance to humic acids.

  13. Model of deep centers formation and reactions in electron irradiated InP

    International Nuclear Information System (INIS)

    Sibille, A.; Suski, J.; Gilleron, M.

    1986-01-01

    We present a model of the production of deep centers and their reactions following electron irradiations in InP. We propose that the dominant hole traps in p-InP and electron traps in p + n InP junctions are complexes between shallow acceptors and a common intrinsic entity, the phosphorus interstitial or vacancy. The reactions observed below and above room temperature are then due to a local mobility of this entity, which can be obtained as well by thermal as by electronic stimulation of the reactions. This model implies the long-range migration (at least down to 16 K) of this entity, and explains the strongly different behavior of n-InP compared to p-InP samples

  14. The formation of light absorbing insoluble organic compounds from the reaction of biomass burning precursors and Fe(III)

    Science.gov (United States)

    Lavi, Avi; Lin, Peng; Bhaduri, Bhaskar; Laskin, Alexander; Rudich, Yinon

    2017-04-01

    Dust particles and volatile organic compounds from fuel or biomass burning are two major components that affect air quality in urban polluted areas. We characterized the products from the reaction of soluble Fe(III), a reactive transition metal originating from dust particles dissolution processes, with phenolic compounds , namely, guaiacol, syringol, catechol, o- and p- cresol that are known products of incomplete fuel and biomass combustion but also from other natural sources such as humic compounds degradation. We found that under acidic conditions comparable to those expected on a dust particle surface, phenolic compounds readily react with dissolved Fe(III), leading to the formation of insoluble polymeric compounds. We characterized the insoluble products by x-ray photoelectron microscopy, UV-Vis spectroscopy, mass spectrometry, elemental analysis and thermo-gravimetric analysis. We found that the major chromophores formed are oligomers (from dimers to pentamers) of the reaction precursors that efficiently absorb light between 300nm and 500nm. High variability of the mass absorption coefficient of the reaction products was observed with catechol and guaiacol showing high absorption at the 300-500nm range that is comparable to that of brown carbon (BrC) from biomass burning studies. The studied reaction is a potential source for the in-situ production of secondary BrC material under dark conditions. Our results suggest a reaction path for the formation of bio-available iron in coastal polluted areas where dust particles mix with biomass burning pollution plumes. Such mixing can occur, for instance in the coast of West Africa or North Africa during dust and biomass burning seasons

  15. Study of the competitive reaction ability of harmine and harmaline during complex formation with transition metals

    International Nuclear Information System (INIS)

    Chepulsky, S.A.; Kadirova, Z.Ch.; Parpiev, N.A.

    2006-01-01

    New coordination compounds of d-metals (Zn(II), Co(II), Mn(II), Mo(VI), Cr(VI)) β-carboline alkaloids were synthesized. The structure of obtained substances was established by IR, PMR spectroscopy. The quantum-chemical assessment of the harmine and harmaline reactivity in complexation reactions with d-metals was carried out. (author)

  16. Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.

    Science.gov (United States)

    Thompson, Matthew G K; Parnis, J Mark

    2005-10-27

    The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.

  17. Fast fission phenomenon, deep inelastic reactions and compound nucleus formation described within a dynamical macroscopic model

    International Nuclear Information System (INIS)

    Gregoire, C.; Ngo, C.; Remaud, B.

    1982-01-01

    We present a dynamical model to describe dissipative heavy ion reactions. It treats explicitly the relative motion of the two ions, the mass asymmetry of the system and the projection of the isospin of each ion. The deformations, which are induced during the collision, are simulated with a time-dependent interaction potential. This is done by a time-dependent transition between a sudden interaction potential in the entrance channel and an adiabatic potential in the exit channel. The model allows us to compute the compound-nucleus cross section and multidifferential cross-sections for deep inelastic reactions. In addition, for some systems, and under certain conditions which are discussed in detail, a new dissipative heavy ion collision appears: fast-fission phenomenon which has intermediate properties between deep inelastic and compound nucleus reactions. The calculated properties concerning fast fission are compared with experimental results and reproduce some of those which could not be understood as belonging to deep inelastic or compound-nucleus reactions. (orig.)

  18. Kinetic modeling of acrylamide formation in aqueous reaction systems and potato crisps : Text & Figures

    NARCIS (Netherlands)

    Knol, J.J.

    2008-01-01

    Acrylamide can be formed in foods that have undergone a high temperature treatment (>120 °C) such as French fries, crisps, coffee and bread, due to the Maillard reaction. The evidence of acrylamide in foods posing a risk for different types of cancer has been strengthened. Mitigation of

  19. Effect of gradual ordering of Ge/Sb atoms on chemical bonding: A proposed mechanism for the formation of crystalline Ge2Sb2Te5

    Science.gov (United States)

    Singh, Janpreet; Singh, Gurinder; Kaura, Aman; Tripathi, S. K.

    2018-04-01

    Using first principle calculations, we study the atomic arrangement and bonding mechanism in the crystalline phase of Ge2Sb2Te5 (GST). It is found that the stability of GST depends on the gradual ordering of Ge/Sb atoms. The configurations with different concentration of Ge/Sb in layers have been analyzed by the partial density of state, electron localization function and Bader charge distribution. The s and p-states of Ge atom alter with different stacking configurations but there is no change in Sb and Te atom states. Our findings show that the bonding between Ge-Te is not only responsible for the stability of GST alloy but can also predict which composition can show generic features of phase change material. As the number of Ge atoms near to vacancy layer decreases, Ge donates more charge. A growth model has been proposed for the formation of crystalline phase which justifies the structure models proposed in the literature.

  20. Identification of coevolving residues and coevolution potentials emphasizing structure, bond formation and catalytic coordination in protein evolution.

    Directory of Open Access Journals (Sweden)

    Daniel Y Little

    Full Text Available The structure and function of a protein is dependent on coordinated interactions between its residues. The selective pressures associated with a mutation at one site should therefore depend on the amino acid identity of interacting sites. Mutual information has previously been applied to multiple sequence alignments as a means of detecting coevolutionary interactions. Here, we introduce a refinement of the mutual information method that: 1 removes a significant, non-coevolutionary bias and 2 accounts for heteroscedasticity. Using a large, non-overlapping database of protein alignments, we demonstrate that predicted coevolving residue-pairs tend to lie in close physical proximity. We introduce coevolution potentials as a novel measure of the propensity for the 20 amino acids to pair amongst predicted coevolutionary interactions. Ionic, hydrogen, and disulfide bond-forming pairs exhibited the highest potentials. Finally, we demonstrate that pairs of catalytic residues have a significantly increased likelihood to be identified as coevolving. These correlations to distinct protein features verify the accuracy of our algorithm and are consistent with a model of coevolution in which selective pressures towards preserving residue interactions act to shape the mutational landscape of a protein by restricting the set of admissible neutral mutations.

  1. Tetrapeptide-coumarin conjugate 3D networks based on hydrogen-bonded charge transfer complexes: gel formation and dye release.

    Science.gov (United States)

    Guo, Zongxia; Gong, Ruiying; Jiang, Yi; Wan, Xiaobo

    2015-08-14

    Oligopeptide-based derivatives are important synthons for bio-based functional materials. In this article, a Gly-(L-Val)-Gly-(L-Val)-coumarin (GVGV-Cou) conjugate was synthesized, which forms 3D networks in ethanol. The gel nanostructures were characterized by UV-vis spectroscopy, FT-IR spectroscopy, X-ray diffraction (XRD), SEM and TEM. It is suggested that the formation of charge transfer (CT) complexes between the coumarin moieties is the main driving force for the gel formation. The capability of the gel to encapsulate and release dyes was explored. Both Congo Red (CR) and Methylene Blue (MB) can be trapped in the CT gel matrix and released over time. The present gel might be used as a functional soft material for guest encapsulation and release.

  2. Eutectic and solid-state wafer bonding of silicon with gold

    International Nuclear Information System (INIS)

    Abouie, Maryam; Liu, Qi; Ivey, Douglas G.

    2012-01-01

    Highlights: ► Eutectic and solid-state Au-Si bonding are compared for both a-Si and c-Si samples. ► Exchange of a-Si and Au layer was observed in both types of bonded samples. ► Use of c-Si for bonding resulted in formation of craters at the Au/c-Si interface. ► Solid-state Au-Si bonding produces better bonds in terms of microstructure. - Abstract: The simple Au-Si eutectic, which melts at 363 °C, can be used to bond Si wafers. However, faceted craters can form at the Au/Si interface as a result of anisotropic and non-uniform reaction between Au and crystalline silicon (c-Si). These craters may adversely affect active devices on the wafers. Two possible solutions to this problem were investigated in this study. One solution was to use an amorphous silicon layer (a-Si) that was deposited on the c-Si substrate to bond with the Au. The other solution was to use solid-state bonding instead of eutectic bonding, and the wafers were bonded at a temperature (350 °C) below the Au-Si eutectic temperature. The results showed that the a-Si layer prevented the formation of craters and solid-state bonding not only required a lower bonding temperature than eutectic bonding, but also prevented spill out of the solder resulting in strong bonds with high shear strength in comparison with eutectic bonding. Using amorphous silicon, the maximum shear strength for the solid-state Au-Si bond reached 15.2 MPa, whereas for the eutectic Au-Si bond it was 13.2 MPa.

  3. Studies on the selectivity of the reaction of (CO){sub 5}W=C(aryl)H with enynes: transfer of the carbene ligand to the C=C Bond versus insertion of the C triple bond C into the W=C Bond

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, H.; Volkland, H.P.; Stumpf, R.

    1996-10-01

    The strongly electrophilic monophenylcarbene complex [(CO){sub 5}W=C(Ph)H] (2a) reacts with the enynes H-C triple bond C-R(R=-C(Me)=CH{sub 2})(3), -C{sub 6}H{sub 4}-CH=CH{sub 2}-p (5) and subsequently with PMe{sub 3} to form the C{sub a}lpha-PMe{sub 3} adducts of the vinylidene complexes [(CO){sub 5}W-{l_brace}C(PMe{sub 3})=CH-C{sub 3}H{sub 3}(Me)Ph{r_brace}] (4) and [(CO){sub 5}W {l_brace}C(PMe{sub 3})=CH-C{sub 6}H{sub 4}-C{sub 3}H{sub 4}Ph{r_brace}] (6). The reaction very likely proceeds by transfer of the carbene ligand to the C=C bond of the enyne to form a cyclopropyl-substituted alkyne complex which is in equilibrium with its vinylidene isomer.

  4. Reactions of hypoiodous acid with model compounds and the formation of iodoform in absence/presence of permanganate.

    Science.gov (United States)

    Zhao, Xiaodan; Ma, Jun; von Gunten, Urs

    2017-08-01

    The kinetics for the reactions of hypoiodous acid (HOI) with various phenols (phenol, 4-nitrophenol, 4-hydroxybenzoic acid), 3-oxopentanedioic acid (3-OPA) and flavone were investigated in the pH range of 6.0-11.0. The apparent second order rate constants for the reactions of HOI with phenolic compounds, 3-OPA, flavone and citric acid at pH 8.0 are 10-10 7  M -1 s -1 , (4.0 ± 0.3) × 10 3  M -1 s -1 , (2.5 ± 0.2) × 10 3  M -1 s -1 and permanganate/HOI/3-OPA and permanganate/iodide/3-OPA system at pH permanganate. For pH > 8.0, in presence of permanganate, iodoform formation is significantly inhibited and iodate formation enhanced, which is due to a faster permanganate-mediated HOI disproportionation to iodate compared to the iodination process. The production of reactive iodine in real waters containing iodide in contact with permanganate may lead to the formation of iodinated organic compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Formation of methemoglobin and metmyoglobin using 8-aminoquinoline derivatives or sodium nitrite and subsequent reaction with cyanide.

    Science.gov (United States)

    Steinhaus, R K; Baskin, S I; Clark, J H; Kirby, S D

    1990-10-01

    The kinetics of the oxidation of hemoglobin (Hb) and myoglobin (Mb) by sodium nitrite, 8-[(4-amino-1-methylbutyl)amino]-6-methoxy-quinoline diphosphate (primaquine), 6-methoxy-8-(6-diethylaminohexylamino)-4-methyl-quinoline dihydrochloride (WR6026) and 8-[(4-amino-1-methylbutyl)amino]-2,6-dimethoxy-4-methyl- 5-[(3-trifluoromethyl)phenoxy]quinoline succinate (WR238,605) were studied at pH values ranging from 7.4 to 7.6 and at 37 +/- 1 degrees C. The reaction between Hb and primaquine, WR6026 and WR238,605 resulted in precipitation, as did the reaction between Mb and WR238,605. The reaction between nitrite ion (NO2-) and Hb showed a lag period followed by an autocatalytic phase. The data in this study are consistent with and substantiate the proposed mechanism for the Hb-NO2- oxidation reaction. The reaction between Mb and NO2- at higher NO2- concentrations also showed a lag period followed by an autocatalytic period, while at lower NO2- concentrations no lag period was seen. The data suggest a shift in rate constant at these lower NO2- concentrations. The reaction between Mb and both WR6026 and primaquine followed a two-term rate law with oxidant-dependent and -independent terms. Concentration-effect curve data, along with these results, suggest the presence of a catalytic pathway. The rates of formation of cyanomethemoglobin and cyanometmyoglobin complexes from cyanide ion and methemoglobin (MHb) and metmyoglobin (MMb), respectively, were followed in the presence of the heme oxidants. The rate constants were all within a narrow range and suggest that complexation of cyanide by MHb and MMb is not affected by the presence of oxidants.

  6. Quadrupole corrections to matrix elements of transitions in resonant reactions of muonic molecule formation

    International Nuclear Information System (INIS)

    Faifman, M.P.; Strizh, T.A.; Armour, E.A.G.; Harston, M.R.

    1996-01-01

    The calculated resonant formation rates of the muonic molecules DDμ and DTμ are presented. The approach developed earlier for calculating the transition matrix elements in the dipole approximation has been extended to include the quadrupole terms in the multipole expansion of the interaction operator. The calculated dependence of the DTμ formation rates on the energies of the incident Tμ muonic atoms shows that the effect of including the quadrupole correction is to reduce the magnitude of the peak rates by about 20-30% at the different temperatures, compared to those calculated in the dipole approximation. The dependence on temperature for the DDμ formation rates is obtained with the differences between the presented and previous calculations being less than 5%. (orig.)

  7. Reaction kinetics of the formation of intermetallic Fe – Zn during hot - dip galvanizing of steel

    Directory of Open Access Journals (Sweden)

    P. Pokorny

    2016-01-01

    Full Text Available This review article mainly describes the composition of intermetallic Fe - Zn, i.e. zeta (ζ, delta (δ1k + δ1p, gamma1 (Γ1 and gamma (Γ on galvanized steel during low temperature galvanization (t ~ 450 °C. It gives detailed the formation, growth of individual phases during galvanization and their interaction. In terms of the kinetics, the formation of the coating is defined by a parabolic kinetic equation of the growth of different intermetallic phases under ideal conditions. From the available literature the rate constants of the formation of individual intermetallic phases and also for the total coating are cited. The composition of the intermetallic phases, iron content, crystal structure, and group symmetry in which the surface of galvanized steel forms.

  8. Kinetics and mechanism of solid-phase reactions of formation of yttrium ferrite with garnet structure

    Energy Technology Data Exchange (ETDEWEB)

    Pashchenko, V P; Yakushevskaya, F T; Chalyi, V P

    1977-04-01

    The perovskite phase is formed in the process of ferrogarnet formation both from the mixture of Y and Fe oxides and from mutually precipitated carbonates. The amount of the perovskite phase decreases with increasing duration of annealing. The process of the ferritoformation in the investigated systems can be presented as isovalent cationic substitution on the basis of the crystalline structure of Y/sub 2/O/sub 3/ with the formation of the perovskite structure. When the Fe concentration in orthoferrite increases, the phase with a garnet structure is formed.

  9. Effect of curing modes of dual-curing core systems on microtensile bond strength to dentin and formation of an acid-base resistant zone.

    Science.gov (United States)

    Li, Na; Takagaki, Tomohiro; Sadr, Alireza; Waidyasekera, Kanchana; Ikeda, Masaomi; Chen, Jihua; Nikaido, Toru; Tagami, Junji

    2011-12-01

    To evaluate the microtensile bond strength (μTBS) and acid-base resistant zone (ABRZ) of two dualcuring core systems to dentin using four curing modes. Sixty-four caries-free human molars were randomly divided into two groups according to two dual-curing resin core systems: (1) Clearfil DC Core Automix; (2) Estelite Core Quick. For each core system, four different curing modes were applied to the adhesive and core resin: (1) dual-cured and dual-cured (DD); (2) chemically cured and dual-cured (CD); (3) dual-cured and chemically cured (DC); (4) chemically cured and chemically cured (CC). The specimens were sectioned into sticks (n = 20 for each group) for the microtensile bond test. μTBS data were analyzed using two-way ANOVA and the Dunnett T3 test. Failure patterns were examined with scanning electron microscopy (SEM) to determine the proportion of each mode. Dentin sandwiches were produced and subjected to an acid-base challenge. After argon-ion etching, the ultrastructure of ABRZ was observed using SEM. For Clearfil DC Core Automix, the μTBS values in MPa were as follows: DD: 29.1 ± 5.4, CD: 21.6 ± 5.6, DC: 17.9 ± 2.8, CC: 11.5 ± 3.2. For Estelite Core Quick, they were: DD: 48.9 ±5.7, CD: 20.5 ± 4.7, DC: 41.4 ± 8.3, CC: 19.1 ± 6.0. The bond strength was affected by both material and curing mode, and the interaction of the two factors was significant (p < 0.001). Within both systems, there were significant differences among groups, and the DD group showed the highest μTBS (p < 0.05). ABRZ morphology was not affected by curing mode, but it was highly adhesive-material dependent. The curing mode of dual-curing core systems affects bond strength to dentin, but has no significant effect on the formation of ABRZ.

  10. Reaction of iminopropadienones with amines--formation of zwitterionic intermediates, ketenes, and ketenimines.

    Science.gov (United States)

    Veedu, Rakesh Naduvile; Kokas, Okanya J; Couturier-Tamburelli, Isabelle; Koch, Rainer; Aycard, Jean-Pierre; Borget, Fabien; Wentrup, Curt

    2008-10-09

    Five aryliminopropadienones 4a- d have been synthesized by flash vacuum thermolysis (FVT) by using two different precursors in each case. These compounds were deposited at 50 K at a pressure of ca. 10(-6) mbar together with three different nucleophiles, namely, trimethylamine (TMA), dimethylamine (DMA), and diethylamine (DEA), in order to study their reactions as neat solids during warm-up by FTIR spectroscopy. The reaction with TMA showed that a zwitterionic species (5 and/or 6) was formed in all the cases. With DMA and DEA, an alpha-oxoketenimine and/or an imidoylketene (7 and 8 or 9 and 10) was formed as the final product. In addition, several bands were observed, which can be assigned to zwitterionic intermediates (11 or 12). Optimized structures and vibrational spectra for all products were calculated at the B3LYP/6-31G(d) level of theory by using the polarizable continuum model (epsilon = 5).

  11. The factor that determines photo-induced crystalline-state reaction

    International Nuclear Information System (INIS)

    Takenaka, Y.

    1995-01-01

    The photo-induced crystalline-state reaction of cobaloxime complexes were investigated by X-ray diffraction method. The reactivity or the reaction rate is dependent only on the volume of the reaction cavity. The hydrogen bond formation of the reactive group and the difference of the base ligand have no effect. (author)

  12. Synthesis of isoprenoid bisphosphonate ethers through C–P bond formations: Potential inhibitors of geranylgeranyl diphosphate synthase

    Directory of Open Access Journals (Sweden)

    Xiang Zhou

    2014-07-01

    Full Text Available A set of bisphosphonate ethers has been prepared through sequential phosphonylation and alkylation of monophosphonate ethers. After formation of the corresponding phosphonic acid salts, these compounds were tested for their ability to inhibit the enzyme geranylgeranyl diphosphate synthase (GGDPS. Five of the new compounds show IC50 values of less than 1 μM against GGDPS with little to no activity against the related enzyme farnesyl diphosphate synthase (FDPS. The most active compound displayed an IC50 value of 82 nM when assayed with GGDPS, and no activity against FDPS even at a 10 μM concentration.

  13. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Yuefei [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); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

    2016-08-05

    Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

  14. Direct formation of LiAlH4 by a mechanochemical reaction

    International Nuclear Information System (INIS)

    Kojima, Yoshitsugu; Kawai, Yasuaki; Haga, Tetsuya; Matsumoto, Mitsuru; Koiwai, Akihiko

    2007-01-01

    A small amount of lithium tetrahydridoaluminate (LiAlH 4 ) was directly synthesized by ball-milling of lithium hydride LiH and aluminum Al in a H 2 atmosphere (1 MPa) at room temperature. Concomitant formation of lithium hexahydridoaluminate Li 3 AlH 6 was confirmed

  15. A DFT study on the enthalpies of thermite reactions and enthalpies of formation of metal composite oxide

    Science.gov (United States)

    Zhang, Yu-ying; Wang, Meng-jie; Chang, Chun-ran; Xu, Kang-zhen; Ma, Hai-xia; Zhao, Feng-qi

    2018-05-01

    The standard thermite reaction enthalpies (ΔrHmθ) for seven metal oxides were theoretically analyzed using density functional theory (DFT) under five different functional levels, and the results were compared with experimental values. Through the comparison of the linear fitting constants, mean error and root mean square error, the Perdew-Wang functional within the framework of local density approximation (LDA-PWC) and Perdew-Burke-Ernzerhof exchange-correlation functional within the framework of generalized gradient approximation (GGA-PBE) were selected to further calculate the thermite reaction enthalpies for metal composite oxides (MCOs). According to the Kirchhoff formula, the standard molar reaction enthalpies for these MCOs were obtained and their standard molar enthalpies of formation (ΔfHmθ) were finally calculated. The results indicated that GGA-PBE is the most suitable one out of the total five methods to calculate these oxides. Tungstate crystals present the maximum deviation of the enthalpies of thermite reactions for MCOs and these of their physical metal oxide mixtures, but ferrite crystals are the minimum. The correlation coefficients are all above 0.95, meaning linear fitting results are very precise. And the molar enthalpies of formation for NiMoO4, CuMoO4, PbZrO3 (Pm/3m), PbZrO3 (PBA2), PbZrO3 (PBam), MgZrO3, CdZrO3, MnZrO3, CuWO4 and Fe2WO6 were first obtained as -1078.75, -1058.45, -1343.87, -1266.54, -1342.29, -1333.03, -1210.43, -1388.05, -1131.07 and - 1860.11 kJ·mol-1, respectively.

  16. Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

    Science.gov (United States)

    Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

    2016-04-01

    It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

  17. Excitation functions for the formation of some short-lived products in proton-induced reactions on silver

    OpenAIRE

    Uddin, M. S.; Baba, M.; Hagiwara, M.; Latif, S. K. A.; Qaim, S. M.

    2008-01-01

    Excitation functions of the Ag-nat(p, xn)Cd-104,Cd-105 and Ag-nat(p, pxn) Ag-103,Ag-104m.g,Ag- 1049 reactions were measured for the first time over the proton energy range of 32 to about 60 MeV. The data were compared with the results of precompound-hybrid model calculations, whereby only partial agreement was obtained. The contribution of the Ag-103 precursor decay to the total formation of the therapeutic radionuclide Pd-103 in proton activation of silver was estimated: it amounted to about...

  18. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    Science.gov (United States)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  19. Synthesis of the proteinase inhibitor LEKTI domain 6 by the fragment condensation method and regioselective disulfide bond formation.

    Science.gov (United States)

    Vasileiou, Zoe; Barlos, Kostas K; Gatos, Dimitrios; Adermann, Knut; Deraison, Celine; Barlos, Kleomenis

    2010-01-01

    Proteinase inhibitors are of high pharmaceutical interest and are drug candidates for a variety of indications. Specific kallikrein inhibitors are important for their antitumor activity and their potential application to the treatment of skin diseases. In this study we describe the synthesis of domain 6 of the kallikrein inhibitor Lympho-Epithilial Kazal-Type Inhibitor (LEKTI) by the fragment condensation method and site-directed cystine bridge formation. To obtain the linear LEKTI precursor, the condensation was best performed in solution, coupling the protected fragment 1-22 to 23-68. This method yielded LEKTI domain 6 of high purity and equipotent to the recombinantly produced peptide. (c) 2010 Wiley Periodicals, Inc.

  20. Antioxidants Inhibit Formation of 3-Monochloropropane-1,2-diol Esters in Model Reactions.

    Science.gov (United States)

    Li, Chang; Jia, Hanbing; Shen, Mingyue; Wang, Yuting; Nie, Shaoping; Chen, Yi; Zhou, Yongqiang; Wang, Yuanxing; Xie, Mingyong

    2015-11-11

    The capacities of six antioxidants to inhibit the formation of 3-monochloropropane-1,2 diol (3-MCPD) esters were examined in this study. Inhibitory capacities of the antioxidants were investigated both in chemical models containing the precursors (tripalmitoyl glycerol, 1,2-dipalmitoyl-sn-glycerol, monopalmitoyl glycerol, and sodium chloride) of 3-MCPD esters and in oil models (rapeseed oil and sodium chloride). Six antioxidants, butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), tert-butyl hydroquinone (TBHQ), propyl gallate (PG), L-ascorbyl palmitate (AP), and α-tocopherol (VE), were found to exhibit inhibiting capacities on 3-MCPD ester formation both in chemical models and in oil models. TBHQ provided the highest inhibitory capacity both in chemical models and in oil models; 44% of 3-MCPD ester formation was inhibited in the presence of TBHQ (66 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min, followed by PG and AP. BHT, BHA, and VE appeared to have weaker inhibitory abilities in both models. VE exhibited the lowest inhibition rate; 22% of 3-MCPD esters were inhibited in the presence of VE (172 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min. In addition, the inhibition rates of PG and VE decreased dramatically with an increase in temperature or heating time. The results suggested that some antioxidants, such as TBHQ, PG, and AP, could be the potential inhibitors of 3-MCPD esters in practice.

  1. Reaction of aromatic diazonium salts with carrier-free radioiodine and astatine, evidence for complex formation

    International Nuclear Information System (INIS)

    Meyer, G.J.; Roessler, K.; Stoecklin, G.

    1979-01-01

    Systematic studies of the astatodiazoniation reaction and a comparison with iododediazoniation under comparable conditions are reported. The yields for all astatohalobenzenes and -toluenes were nearly constant and unaffected by the nature of the diazonium compound, its isomeric form, and the number of isomers used at the same time. Only astatofluorobenzenes were obtained at higher yields. An electron-transfer mechanism is proposed for dediazoniation at these low halide concentration levels. At sufficient thermal excitation levels the electron transfer leads to the dissociation of nitrogen, while the phenyl and halogen radicals recombine. The isomer distribution found for some of the derivatives from dediazoniation may also be due to steric effects

  2. Suppression of Boride Formation in Transient Liquid Phase Bonding of Pairings of Parent Superalloy Materials with Different Compositions and Grain Structures and Resulting Mechanical Properties

    Science.gov (United States)

    Steuer, Susanne; Singer, Robert F.

    2014-07-01

    Two Ni-based superalloys, columnar grained Alloy 247 and single-crystal PWA1483, are joined by transient liquid phase bonding using an amorphous brazing foil containing boron as a melting point depressant. At lower brazing temperatures, two different morphologies of borides develop in both base materials: plate-like and globular ones. Their ratio to each other is temperature dependent. With very high brazing temperatures, the deleterious boride formation in Alloy 247 can be totally avoided, probably because the three-phase-field moves to higher alloying element contents. For the superalloy PWA1483, the formation of borides cannot be completely avoided at high brazing temperatures as incipient melting occurs. During subsequent solidification of these areas, Chinese-script-like borides precipitate. The mechanical properties (tensile tests at room and elevated temperatures and short-term creep rupture tests at elevated temperatures) for brazed samples without boride precipitation are very promising. Tensile strengths and creep times to 1 pct strain are comparable, respectively, higher than the ones of the weaker parent material for all tested temperatures and creep conditions (from 90 to 100 pct rsp. 175 to 250 pct).

  3. Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

    Science.gov (United States)

    Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

    2018-05-23

    Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

  4. Development of a reduced model of formation reactions in Zr-Al nanolaminates

    KAUST Repository

    Vohra, Manav

    2014-12-15

    A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

  5. DNA damage and radical reactions: Mechanistic aspects, formation in cells and repair studies

    International Nuclear Information System (INIS)

    Cadet, J.; Ravanat, J.L.; Carell, T.; Cellai, L.; Chatgilialoglu, Ch.; Gimisis, Th.; Miranda, M.; O'Neill, P.; Robert, M.

    2008-01-01

    Several examples of oxidative and reductive reactions of DNA components that lead to single and tandem modifications are discussed in this review. These include nucleophilic addition reactions of the one-electron oxidation-mediated guanine radical cation and the one-electron reduced intermediate of 8-bromo-purine 2'-de-oxy-ribo-nucleosides that give rise to either an oxidizing guanine radical or related 5',8-cyclo-purine nucleosides. In addition, mechanistic insights into the reductive pathways involved in the photolyase induced reversal of cyclo-buta-cli-pyrimidine and pyrimidine (6-4) pyrimidone photoproducts are provided. Evidence for the occurrence and validation in cellular DNA of (OH) · radical degradation pathways of guanine that have been established in model systems has been gained from the accurate measurement of degradation products. Relevant information on biochemical aspects of the repair of single and clustered oxidatively generated damage to DNA has been gained from detailed investigations that rely on the synthesis of suitable modified probes. Thus the preparation of stable carbocyclic derivatives of purine nucleoside containing defined sequence oligonucleotides has allowed detailed crystallographic studies of the recognition step of the base damage by enzymes implicated in the base excision repair (BER) pathway. Detailed insights are provided on the BER processing of non-double strand break bi-stranded clustered damage that may consist of base lesions, a single strand break or abasic sites and represent one of the main deleterious classes of radiation-induced DNA damage. (authors)

  6. Development of a reduced model of formation reactions in Zr-Al nanolaminates

    KAUST Repository

    Vohra, Manav; Winokur, Justin; Overdeep, Kyle R.; Marcello, Paul; Weihs, Timothy P.; Knio, Omar

    2014-01-01

    A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

  7. The gas phase reaction of ozone with 1,3-butadiene: formation yields of some toxic products

    Science.gov (United States)

    Kramp, Franz; Paulson, Suzanne E.

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separate experiments, small quantities of 1,3,5-trimethyl benzene were added as a tracer for OH. Formation yields of acrolein of (52±7)%, 1,2-epoxy-3-butene of (3.1±0.5)% and OH radicals of (13±3)% were observed. In addition, the rate coefficient of the gas-phase reaction of ozone with 1,2-epoxy-3-butene was measured both directly and relative to propene, finding an average of (1.6±0.4)×10 -18 cm 3 molecule -1 s -1, respectively, at 296±2 K. The results are briefly discussed in terms of the effect of atmospheric processing on the toxicity of 1,3-butadiene.

  8. Search for the formation of new particles in anti pp reactions near 3 GeV

    International Nuclear Information System (INIS)

    Yam, Z.B.; Bensinger, J.R.; Button-Shafer, J.

    1975-01-01

    Using the new Multiparticle Spectrometer facility at BNL, upper limits were set on the formation of a meson state in the mass range 2.99 to 3.14 GeV from proton-antiproton annihilations. The upper limits are, in terms of the cross section integrated over the width, 18 MeV-μb for the final state ΛantiΛ, 18 MeV-μb for K 0 anti K 0 (890) + C.C., and 2 MeV-μb for K/sub S/K/sub L/

  9. Formation and reactions of free radicals in the radiolysis of organic materials by ion beams

    International Nuclear Information System (INIS)

    Koizumi, H.

    2000-01-01

    High-energy heavy ions deposit energy along ion tracks with high density. Chemical effects of the heavy ions may hence differ from that of γ-rays and fast electrons. We can utilize these effects for material modification and fabrication of microstructure. It is necessary to know the dependence of the effects on ion beams and the variation of the effects on materials for developing new application of ion beams. We then studied radical formation in organic solids of alanine and of adipic acid by ion beams irradiation. (author)

  10. Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

    Science.gov (United States)

    Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

    2015-05-21

    Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

  11. Verification of Radicals Formation in Ethanol-Water Mixture Based Solution Plasma and Their Relation to the Rate of Reaction.

    Science.gov (United States)

    Sudare, Tomohito; Ueno, Tomonaga; Watthanaphanit, Anyarat; Saito, Nagahiro

    2015-12-03

    Our previous research demonstrated that using ethanol-water mixture as a liquid medium for the synthesis of gold nanoparticles by the solution plasma process (SPP) could lead to an increment of the reaction rate of ∼35.2 times faster than that in pure water. This drastic change was observed when a small amount of ethanol, that is, at an ethanol mole fraction (χethanol) of 0.089, was added in the system. After this composition, the reaction rate decreased continuously. To better understand what happens in the ethanol-water mixture-based SPP, in this study, effect of the ethanol content on the radical formation in the system was verified. We focused on detecting the magnetic resonance of electronic spins using electron spin resonance spectroscopy to determine the type and quantity of the generated radicals at each χethanol. Results indicated that ethanol radicals were generated in the ethanol-water mixtures and exhibited maximum quantity at the xethanol of 0.089. Relationship between the ethanol radical yield and the rate of reaction, along with possible mechanism responsible for the observed phenomenon, is discussed in this paper.

  12. Formation of Reactive Intermediates, Color, and Antioxidant Activity in the Maillard Reaction of Maltose in Comparison to d-Glucose.

    Science.gov (United States)

    Kanzler, Clemens; Schestkowa, Helena; Haase, Paul T; Kroh, Lothar W

    2017-10-11

    In this study, the Maillard reaction of maltose and d-glucose in the presence of l-alanine was investigated in aqueous solution at 130 °C and pH 5. The reactivity of both carbohydrates was compared in regards of their degradation, browning, and antioxidant activity. In order to identify relevant differences in the reaction pathways, the concentrations of selected intermediates such as 1,2-dicarbonyl compounds, furans, furanones, and pyranones were determined. It was found, that the degradation of maltose predominantly yields 1,2-dicarbonyls that still carry a glucosyl moiety and thus subsequent reactions to HMF, furfural, and 2-acetylfuran are favored due to the elimination of d-glucose, which is an excellent leaving group in aqueous solution. Consequently, higher amounts of these heterocycles are formed from maltose. 3-deoxyglucosone and 3-deoxygalactosone represent the only relevant C 6 -1,2-dicarbonyls in maltose incubations and are produced in nearly equimolar amounts during the first 60 min of heating as byproducts of the HMF formation.

  13. Dependence of compound nucleus formation probability on K equilibration time in heavy-ion reactions

    International Nuclear Information System (INIS)

    Yadav, C.; Thomas, R.G.; Mohanty, A.K.; Kapoor, S.S.

    2014-01-01

    In the present work, we have carried out the analysis of fragment anisotropy data of various systems selected for cases Z 1 Z 2 < 1600 and Z CN < 96 so that both QF and FF are absent and the anomalous anisotropies are only due to PEF. It may also be noted that in such cases J cr (the J above which the fusion pocket vanishes) is less than J Bf = 0 (the J at which the liquid drop fission barrier vanishes) so that all J's will be contributing to PEF as well. According to PEF model, the observed angular anisotropy of fission fragments in heavy-ion induced reactions can be written as an admixture of two components: the anisotropy from compound nucleus fission (CN) and anisotropy due to non-compound nucleus fission (NCN)

  14. A new building block for DNA network formation by self-assembly and polymerase chain reaction.

    Science.gov (United States)

    Bußkamp, Holger; Keller, Sascha; Robotta, Marta; Drescher, Malte; Marx, Andreas

    2014-01-01

    The predictability of DNA self-assembly is exploited in many nanotechnological approaches. Inspired by naturally existing self-assembled DNA architectures, branched DNA has been developed that allows self-assembly to predesigned architectures with dimensions on the nanometer scale. DNA is an attractive material for generation of nanostructures due to a plethora of enzymes which modify DNA with high accuracy, providing a toolbox for many different manipulations to construct nanometer scaled objects. We present a straightforward synthesis of a rigid DNA branching building block successfully used for the generation of DNA networks by self-assembly and network formation by enzymatic DNA synthesis. The Y-shaped 3-armed DNA construct, bearing 3 primer strands is accepted by Taq DNA polymerase. The enzyme uses each arm as primer strand and incorporates the branched construct into large assemblies during PCR. The networks were investigated by agarose gel electrophoresis, atomic force microscopy, dynamic light scattering, and electron paramagnetic resonance spectroscopy. The findings indicate that rather rigid DNA networks were formed. This presents a new bottom-up approach for DNA material formation and might find applications like in the generation of functional hydrogels.

  15. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  16. Potential of metal nanoparticles in organic reactions

    International Nuclear Information System (INIS)

    Ranu, B C; Chattopadhyay, K; Saha, A; Adak, L; Jana, R; Bhadra, S; Dey, R; Saha, D

    2008-01-01

    Palladium(0) nanoparticle has been used as efficient catalyst for (a) the stereoselective synthesis of (E)- and (Z)-2-alkene-4-ynoates and -nitriles by a simple reaction of vic-diiodo-(E)-alkenes with acrylic esters and nitriles and (b) for the allylation of active methylene compounds by allylacetate and its derivatives. Copper(0) nanoparticle catalyzes aryl-sulfur bond formation very efficiently. All these reactions are ligand-free

  17. Evidence of two-channel distortion effects in positronium formation reactions

    International Nuclear Information System (INIS)

    Macri, P A; Miraglia, J E; Hanssen, J; Fojon, O A; Rivarola, R D

    2004-01-01

    The formation of ground-state positronium in collisions of positrons on hydrogen-like atoms is considered. In previous theoretical works, two-centre distorted wavefunctions were employed to approximate either the initial or the final channel. Here we report results obtained by means of the eikonal final state continuum distorted wave approximation for which asymptotically correct distorted wavefunctions are used for both the initial and final states of the scattering system. Comparison of the present theoretical total cross sections with experimental data reveals that distortion effects become important in both channels as the impact energy decreases. This work also shows that distorted-wave theories may be extended from their usual domain of high impact energies to lower ones. (letter to the editor)

  18. Physicochemical investigation of reactions of some basic cadmium salts formation in aqueous solutions

    International Nuclear Information System (INIS)

    Gyunner, Eh.A.; Mel'nichenko, L.M.; Yakhkind, N.D.; Vel'mozhnyj, I.S.; Pevzner, N.S.

    1980-01-01

    By the methods of physicochemical analysis (the method of residual concentrations, refractometry), the composition of slightly soluble products of interaction in the five systems of the Cd(CHsub(3)COO)sub(2)-Msub(z)X-NaOH-Hsub(2)O type (Msub(z)X - NaF, KClO 3 , KBrO 3 , NaHCOO, Na 2 S 2 O 3 ) has been detemined. It has been established that in systems with NaF, NaHCOO and Na 2 S 2 O 3 , cadmium hydroxide formation is preceded by deposition of the basic salts Cd(OH)F, Cd(OH)HCOO, and Cd 4 (OH) 6 S 2 O 3 . In systems with KClO 3 and KBrO 3 the only interaction slightly soluble product is Cd(OH) 2

  19. Evidence of two-channel distortion effects in positronium formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Macri, P A [Instituto de AstronomIa y FIsica del Espacio, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad de Buenos Aires, Casilla de Correo 67, Suc. 28, 1428 Buenos Aires (Argentina); Miraglia, J E [Instituto de AstronomIa y FIsica del Espacio, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad de Buenos Aires, Casilla de Correo 67, Suc. 28, 1428 Buenos Aires (Argentina); Hanssen, J [Laboratoire de Physique Moleculaire et des Collisions, Institute de Physique Rue Arago, Tecnopole 2000, Metz (France); Fojon, O A [Instituto de FIsica de Rosario, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad Nacional de Rosario, Av. Pellegrini 250, 2000 Rosario (Argentina); Rivarola, R D [Instituto de FIsica de Rosario, Consejo Nacional de Investigaciones CientIficas y Tecnicas-Universidad Nacional de Rosario, Av. Pellegrini 250, 2000 Rosario (Argentina)

    2004-03-28

    The formation of ground-state positronium in collisions of positrons on hydrogen-like atoms is considered. In previous theoretical works, two-centre distorted wavefunctions were employed to approximate either the initial or the final channel. Here we report results obtained by means of the eikonal final state continuum distorted wave approximation for which asymptotically correct distorted wavefunctions are used for both the initial and final states of the scattering system. Comparison of the present theoretical total cross sections with experimental data reveals that distortion effects become important in both channels as the impact energy decreases. This work also shows that distorted-wave theories may be extended from their usual domain of high impact energies to lower ones. (letter to the editor)

  20. Synergistic effect of displacement damage, helium and hydrogen on microstructural change of SiC/SiC composites fabricated by reaction bonding process

    Energy Technology Data Exchange (ETDEWEB)

    Taguchi, T.; Igawa, N.; Wakai, E.; Jitsukawa, S. [Japan Atomic Energy Agency, Naga-gun, Ibaraki-ken (Japan); Hasegawa, A. [Tohoku Univ., Dept. of Quantum Science and Energy Engr., Sendai (Japan)

    2007-07-01

    Full text of publication follows: Continuous silicon carbide (SiC) fiber reinforced SiC matrix (SiC/SiC) composites are known to be attractive candidate materials for first wall and blanket components in fusion reactors. In the fusion environment, helium and hydrogen are produced and helium bubbles can be formed in the SiC by irradiation of 14-MeV neutrons. Authors reported the synergistic effect of helium and hydrogen as transmutation products on swelling behavior and microstructural change of the SiC/SiC composites fabricated by chemical vapor infiltration (CVI) process. Authors also reported about the fabrication of high thermal conductive SiC/SiC composites by reaction bonding (RB) process. The matrix fabricated by RB process has different microstructures such as bigger grain size of SiC and including Si phase as second phase from that by CVI process. It is, therefore, investigated the synergistic effect of displacement damage, helium and hydrogen as transmutation products on the microstructure of SiC/SiC composite by RB process in this study. The SiC/SiC composites by RB process were irradiated by the simultaneous triple ion irradiation (Si{sup 2+}, He{sup +} and H{sup +}) at 800 and 1000 deg. C. The displacement damage was induced by 6.0 MeV Si{sup 2+} ion irradiation up to 10 dpa. The microstructures of irradiated SiC/SiC composites by RB process were observed by TEM. The double layer of carbon and SiC as interphase between fiber and matrix by a chemical vapor deposition (CVD) was coated on SiC fibers in the SiC/SiC composites by RB process. The TEM observation revealed that He bubbles were formed both in the matrix by RB and SiC interphase by CVD process. Almost all He bubbles were formed at the grain boundary in SiC interphase by CVD process. On the other hand, He bubbles were formed both at the grain boundary and in Si grain of the matrix by RB process. The average size of He bubbles in the matrix by RB was smaller than that in SiC interphase by CVD

  1. Cu(II) salen complex with propylene linkage: An efficient catalyst in the formation of Csbnd X bonds (X = N, O, S) and biological investigations

    Science.gov (United States)

    Azam, Mohammad; Dwivedi, Sourabh; Al-Resayes, Saud I.; Adil, S. F.; Islam, Mohammad Shahidul; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Lee, Dong-Ung

    2017-02-01

    The catalytic property of a mononuclear Cu(II) salen complex in Chan-Lam coupling reaction with phenyl boronic acid at room temperature is reported. The studied complex is found to be potential catalyst in the preparation of carbon-heteroatom bonds with excellent yields. The studied Cu(II) salen complex is monoclinic with cell parameters, a = 9.6807(5) (α 90°), (b = 17.2504(8) (β 112.429 (2), c = 11.1403 (6) (γ = 90°), and has distorted square planar environment around Cu(II) ion. Furthermore, there is no π⋯π interactions in the reported complex due to large distance between the centroid of aromatic rings. In addition, DNA binding study of Cu(II) salen complex by fluorescence and absorption spectroscopy is also reported. Moreover, the reported Cu(II) salen complex exhibits significant anticancer activity against MCF-7 cancer cell lines, and displays potential antimicrobial biofilm activity against P. aeruginosa, suggesting antimicrobial biofilm an important tool for suppression of resistant infections caused by P. aeruginosa.

  2. Formation of poorly crystalline iron monosulfides: Surface redox reactions on high purity iron, spectroelectrochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Hansson, E.B. [Geological Institute, University of Copenhagen, Oster Voldgade 10, Copenhagen K, DK-1350 (Denmark); Odziemkowski, M.S. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)]. E-mail: marek@sciborg.uwaterloo.ca; Gillham, R.W. [Department of Earth Sciences, University of Waterloo, Waterloo, Ont., N2L 3G1 (Canada)

    2006-11-15

    In the use of iron for reductive dehalogenation of chlorinated solvents in ground water, due to presence of sulfate-reducing bacteria the formation of hydrogen sulfide is expected. To simulate those processes the interface between 99.99% pure iron and 0.1 M NaHCO{sub 3} deoxygenated solution with 3.1 x 10{sup -5}-7.8 x 10{sup -3} M Na{sub 2}S . 9H{sub 2}O added was studied. The surface processes were characterised by the in situ normal Raman spectroscopy (NRS) and ex situ techniques; X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX). The open circuit potential (OCP) was monitored during in situ NRS measurements, and potentiodynamic anodic polarization measurements were carried out to reveal electrochemical behaviour of iron electrode. Open circuit potential-time transients indicated that the native oxide is unstable in deaerated bicarbonate solution and undergoes reductive dissolution (i.e. autoreduction) leaving the metallic Fe covered by Fe(OH){sub 2}, adsorbed OH{sup -}, and patches of 'magnetite-like' oxide. Immediately upon injection of the Na{sub 2}S-solution the iron interface undergoes complex redox surface processes and a poorly crystalline FeS film forms. Potentiodynamic anodic polarization measurements indicated a mechanical breakdown of the FeS film. The origin and initiation of this breakdown process is not clear but is probably a result of internal stress developed during film growth. Based on surface studies supported by electrochemical measurements, a conceptual model for the complex redox processes occurring at the iron interface is proposed. This model describes the structural development of a poorly crystalline FeS, which breaks down, allowing further dissolution of the Fe and formation of FeOOH at the interface. Simultaneously and despite the existence of thick layer of FeS the entrance of hydrogen was evident as the typical hydrogen cracks in bulk of the

  3. Quantum-chemical analysis of formation reactions of Со2+ complexes

    Directory of Open Access Journals (Sweden)

    Viktor F. Vargalyuk

    2017-11-01

    Full Text Available Based on the analysis of quantum chemical calculations results (GAMESS, density functional theory, B3LYP method as to coordination compounds of Co2+ions with H2O, NH3, OH–, F–, Cl–, Br–, I–, CN–, Ac–, Ak– generally given by [Co(H2O6–nLn]2+nx, it has been demonstrated that within the selected series of ligands, there is no correlation between the amount of energy of monosubstituted cobalt aqua complexes formation(∆Е and pK1,just like between the effective nuclear charge of the central atom (z*Со and pK1. According to the behavior of ∆Е and z*Со,we identified two groups of ligands. The first group (OH–, F–, Ac–, Ak–, CN–, NH3 demonstrates logical ∆Е decrease caused by the growth of z*Со. On the contrary, the second group (Cl–, Br–, I– demonstrates ∆Е increase caused by the growth of z*Со. This phenomenon is explained by the change in electronegativity and polarizability of donor atoms in groups and periods of the periodic table. It is established that linear correlations given by lgK = A + B·z*Со can be actualized only for complexes having ligands with similar donor atoms. Referring to the literature on stepwise complex formation of hydroxide, amine and chloride cobalt complexes in combination with z*Со calculations results, we determined A and B constants of lgK, z*Со-correlations for the atoms of oxygen (30.2, –17.7; nitrogen (125.4, –69.9 and chlorine (–6.3, 5.8. The existence of the detected correlation series enables us to lean on lgK,z*М–dependence parameters for the fixed donor atom and to determine Kn values for various complexes with complex-based ligands using calculations and z*М data. This applies to complexes having central atoms of the same nature as well as simple monodentate ligands. The mentioned approach was used to calculate the stability constants for acrylate cobalt complexes (lgK1 = 1.2 и lgК2 = 4.3, which are not covered in literature.

  4. Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

    Science.gov (United States)

    Shukla, P. K.; Mishra, P. C.; Suhai, S.

    Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the

  5. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  6. Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol α-linkages in lignin: a density functional theory study.

    Science.gov (United States)

    Watts, Heath D; Mohamed, Mohamed Naseer Ali; Kubicki, James D

    2011-12-21

    Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

  7. Cerimetric determination of simvastatin in pharmaceuticals based on redox and complex formation reactions

    International Nuclear Information System (INIS)

    Basavaiah, K.; Devi, O.Z

    2008-01-01

    Two sensitive spectrophotometric methods are described for the determination of simvastatin (SMT) in bulk drug and in tablets. The methods are based on the oxidation of SMT by a measured excess of cerium (IV) in acid medium followed by determination of unreacted oxidant by two different reaction schemes. In one procedure (method A), the residual cerium (IV) is reacted with a fixed concentration of ferroin and the increase in absorbance is measured at 510 nm. The second approach (method B) involves the reduction of the unreacted cerium (IV) with a fixed quantity of iron (II), and the resulting iron (III) is complexed with thiocyanate and the absorbance measured at 470 nm. In both methods, the amount of cerium (IV) reacted corresponds to SMT concentration. The experimental conditions for both methods were optimized. In method A, the absorbance is found to increase linearly with SMT concentration (r = 0.9995) whereas in method B, the same decreased (r = -0.9943). The systems obey Beer's law for 0.6-7.5 and 0.5-5.0 μg mL -1 for method A and method B, respectively. The calculated molar absorptivity values are 2.7 X 104 and 1.06 X 105 Lmol -1 cm -1 , respectively; and the corresponding sandel sensitivity values are 0.0153 and 0.0039 μg cm -2 , respectively. The limit of detection (LOD) and quantification (LOQ) are reported for both methods. Intra-day and inter-day precision, and accuracy of the methods were established as per the current ICH guidelines. The methods were successfully applied to the determination of SMT in tablets and the results were statistically compared with those of the reference method by applying the Student's t-test and F-test. No interference was observed from the common excipients added to tablets. The accuracy and validity of the methods were further ascertained by performing recovery experiments via standard addition procedure. (author)

  8. Interlaboratory Reproducibility of Droplet Digital Polymerase Chain Reaction Using a New DNA Reference Material Format.

    Science.gov (United States)

    Pinheiro, Leonardo B; O'Brien, Helen; Druce, Julian; Do, Hongdo; Kay, Pippa; Daniels, Marissa; You, Jingjing; Burke, Daniel; Griffiths, Kate; Emslie, Kerry R

    2017-11-07

    Use of droplet digital PCR technology (ddPCR) is expanding rapidly in the diversity of applications and number of users around the world. Access to relatively simple and affordable commercial ddPCR technology has attracted wide interest in use of this technology as a molecular diagnostic tool. For ddPCR to effectively transition to a molecular diagnostic setting requires processes for method validation and verification and demonstration of reproducible instrument performance. In this study, we describe the development and characterization of a DNA reference material (NMI NA008 High GC reference material) comprising a challenging methylated GC-rich DNA template under a novel 96-well microplate format. A scalable process using high precision acoustic dispensing technology was validated to produce the DNA reference material with a certified reference value expressed in amount of DNA molecules per well. An interlaboratory study, conducted using blinded NA008 High GC reference material to assess reproducibility among seven independent laboratories demonstrated less than 4.5% reproducibility relative standard deviation. With the exclusion of one laboratory, laboratories had appropriate technical competency, fully functional instrumentation, and suitable reagents to perform accurate ddPCR based DNA quantification measurements at the time of the study. The study results confirmed that NA008 High GC reference material is fit for the purpose of being used for quality control of ddPCR systems, consumables, instrumentation, and workflow.

  9. Physicochemical investigation of reactions of some basic cadmium salts formation in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gyunner, E A; Mel' nichenko, L M; Yakhkind, N D; Vel' mozhnyi, I S; Pevzner, N S [Simferopol' skij Gosudarstvennyj Univ. (Ukrainian SSR)

    1980-04-01

    By the methods of physicochemical analysis (the method of residual concentrations, refractometry), the composition of slightly soluble products of interaction in the five systems of the Cd(CHsub(3)COO)sub(2)-Msub(z)X-NaOH-Hsub(2)O type (Msub(z)X - NaF, KClO/sub 3/, KBrO/sub 3/, NaHCOO, Na/sub 2/S/sub 2/O/sub 3/) has been detemined. It has been established that in systems with NaF, NaHCOO and Na/sub 2/S/sub 2/O/sub 3/, cadmium hydroxide formation is preceded by deposition of the basic salts Cd(OH)F, Cd(OH)HCOO, and Cd/sub 4/(OH)/sub 6/S/sub 2/O/sub 3/. In systems with KClO/sub 3/ and KBrO/sub 3/ the only interaction slightly soluble product is Cd(OH)/sub 2/.

  10. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  11. Reaction pathways of proton transfer in hydrogen-bonded phenol-carboxylate complexes explored by combined UV-vis and NMR spectroscopy.

    Science.gov (United States)

    Koeppe, Benjamin; Tolstoy, Peter M; Limbach, Hans-Heinrich

    2011-05-25

    Combined low-temperature NMR/UV-vis spectroscopy (UVNMR), where optical and NMR spectra are measured in the NMR spectrometer under the same conditions, has been set up and applied to the study of H-bonded anions A··H··X(-) (AH = 1-(13)C-2-chloro-4-nitrophenol, X(-) = 15 carboxylic acid anions, 5 phenolates, Cl(-), Br(-), I(-), and BF(4)(-)). In this series, H is shifted from A to X, modeling the proton-transfer pathway. The (1)H and (13)C chemical shifts and the H/D isotope effects on the latter provide information about averaged H-bond geometries. At the same time, red shifts of the π-π* UV-vis absorption bands are observed which correlate with the averaged H-bond geometries. However, on the UV-vis time scale, different tautomeric states and solvent configurations are in slow exchange. The combined data sets indicate that the proton transfer starts with a H-bond compression and a displacement of the proton toward the H-bond center, involving single-well configurations A-H···X(-). In the strong H-bond regime, coexisting tautomers A··H···X(-) and A(-)···H··X are observed by UV. Their geometries and statistical weights change continuously when the basicity of X(-) is increased. Finally, again a series of single-well structures of the type A(-)···H-X is observed. Interestingly, the UV-vis absorption bands are broadened inhomogeneously because of a distribution of H-bond geometries arising from different solvent configurations.

  12. A coumarin-specific prenyltransferase catalyzes the crucial biosynthetic reaction for furanocoumarin formation in parsley.

    Science.gov (United States)

    Karamat, Fazeelat; Olry, Alexandre; Munakata, Ryosuke; Koeduka, Takao; Sugiyama, Akifumi; Paris, Cedric; Hehn, Alain; Bourgaud, Frédéric; Yazaki, Kazufumi

    2014-02-01

    Furanocoumarins constitute a sub-family of coumarin compounds with important defense properties against pathogens and insects, as well as allelopathic functions in plants. Furanocoumarins are divided into two sub-groups according to the alignment of the furan ring with the lactone structure: linear psoralen and angular angelicin derivatives. Determination of furanocoumarin type is based on the prenylation position of the common precursor of all furanocoumarins, umbelliferone, at C6 or C8, which gives rise to the psoralen or angelicin derivatives, respectively. Here, we identified a membrane-bound prenyltransferase PcPT from parsley (Petroselinum crispum), and characterized the properties of the gene product. PcPT expression in various parsley tissues is increased by UV irradiation, with a concomitant increase in furanocoumarin production. This enzyme has strict substrate specificity towards umbelliferone and dimethylallyl diphosphate, and a strong preference for the C6 position of the prenylated product (demethylsuberosin), leading to linear furanocoumarins. The C8-prenylated derivative (osthenol) is also formed, but to a much lesser extent. The PcPT protein is targeted to the plastids in planta. Introduction of this PcPT into the coumarin-producing plant Ruta graveolens showed increased consumption of endogenous umbelliferone. Expression of PcPT and a 4-coumaroyl CoA 2'-hydroxylase gene in Nicotiana benthamiana, which does not produce furanocoumarins, resulted in formation of demethylsuberosin, indicating that furanocoumarin production may be reconstructed by a metabolic engineering approach. The results demonstrate that a single prenyltransferase, such as PcPT, opens the pathway to linear furanocoumarins in parsley, but may also catalyze the synthesis of osthenol, the first intermediate committed to the angular furanocoumarin pathway, in other plants. © 2013 The Authors The Plant Journal © 2013 John Wiley & Sons Ltd.

  13. Sidewall Covalent Functionalization of Single Wall Carbon Nanotubes through C-N Bond Forming Reactions of Fluoronanotubes with Urea, Guanidine and Thiourea (Preprint)

    National Research Council Canada - National Science Library

    Pulikkathara, Merlyn X; Khabashesku, Valery N

    2007-01-01

    ...) as starting materials in the reactions with either urea, thiourea, or guanidine. Through these reactions, the derivatives with terminal amide and heteroamide groups on the nanotube sidewalls have been prepared...

  14. Excitation functions for the formation of some short-lived products in proton-induced reactions on silver

    International Nuclear Information System (INIS)

    Uddin, M.S.; Latif, S.K.A.; Baba, M.; Hagiwara, M.; Qaim, S.M.

    2008-01-01

    Excitation functions of the nat Ag(p, xn) 104, 105 Cd and nat Ag(p, pxn) 103, 104m,g, 104g Ag reactions were measured for the first time over the proton energy range of 32 to about 60 MeV. The data were compared with the results of precompound-hybrid model calculations, whereby only partial agreement was obtained. The contribution of the 103 Ag precursor decay to the total formation of the therapeutic radionuclide 103 Pd in proton activation of silver was estimated: it amounted to about 70%. The various possible routes for the production of 103 Pd were also considered: the nat Ag(p, x) 103 Pd and 103 Rh(p, n) 103 Pd processes were found to be most interesting. Despite its somewhat lower yield, the latter process is preferred because it can be applied at a low-energy cyclotron. (orig.)

  15. Thermodynamic Characteristics of Reactions of the Formation of Complexes between Triglycine and Ni2+ Ions in Aqueous Solution

    Science.gov (United States)

    Gorboletova, G. G.; Metlin, A. A.; Bychkova, S. A.

    2018-05-01

    Thermal effects of reactions of the formation of complexes between Ni(II) and triglycine are determined via direct calorimetry in aqueous solutions at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). Standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°) of complexing processes in the investigated systems are calculated. The structures of triglycinate complexes NiL+, NiH-1L, NiL2, NiH-2L2- 2, NiL- 3, and NiH-3L4- 3 are introduced to compare the obtained values and data on the thermodynamics of triglycinate complexes of Ni(II).

  16. Nickel-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents in the presence of 1,3-butadiene: mechanistic studies of four-component coupling and competing cross-coupling reactions† †Electronic supplementary information (ESI) available: Detailed experimental and computational results, procedures, characterization data, copies of NMR charts, and crystallographic data. CCDC 1572238. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04675h

    Science.gov (United States)

    Fukuoka, Asuka; Yokoyama, Wataru; Min, Xin; Hisaki, Ichiro; Kuniyasu, Hitoshi

    2018-01-01

    We describe the mechanism, substituent effects, and origins of the selectivity of the nickel-catalyzed four-component coupling reactions of alkyl fluorides, aryl Grignard reagents, and two molecules of 1,3-butadiene that affords a 1,6-octadiene carbon framework bearing alkyl and aryl groups at the 3- and 8-positions, respectively, and the competing cross-coupling reaction. Both the four-component coupling reaction and the cross-coupling reaction are triggered by the formation of anionic nickel complexes, which are generated by the oxidative dimerization of two molecules of 1,3-butadiene on Ni(0) and the subsequent complexation with the aryl Grignard reagents. The C–C bond formation of the alkyl fluorides with the γ-carbon of the anionic nickel complexes leads to the four-component coupling product, whereas the cross-coupling product is yielded via nucleophilic attack of the Ni center toward the alkyl fluorides. These steps are found to be the rate-determining and selectivity-determining steps of the whole catalytic cycle, in which the C–F bond of the alkyl fluorides is activated by the Mg cation rather than a Li or Zn cation. ortho-Substituents of the aryl Grignard reagents suppressed the cross-coupling reaction leading to the selective formation of the four-component products. Such steric effects of the ortho-substituents were clearly demonstrated by crystal structure characterizations of ate complexes and DFT calculations. The electronic effects of the para-substituent of the aryl Grignard reagents on both the selectivity and reaction rates are thoroughly discussed. The present mechanistic study offers new insight into anionic complexes, which are proposed as the key intermediates in catalytic transformations even though detailed mechanisms are not established in many cases, and demonstrates their synthetic utility as promising intermediates for C–C bond forming reactions, providing useful information for developing efficient and straightforward

  17. Inhibition of peptide bond formation by pleuromutilins: the structure of the 50S ribosomal subunit from Deinococcus radiodurans in complex with tiamulin.

    Science.gov (United States)

    Schlünzen, Frank; Pyetan, Erez; Fucini, Paola; Yonath, Ada; Harms, Jörg M

    2004-12-01

    Tiamulin, a prominent member of the pleuromutilin class of antibiotics, is a potent inhibitor of protein synthesis in bacteria. Up to now the effect of pleuromutilins on the ribosome has not been determined on a molecular level. The 3.5 A structure of the 50S ribosomal subunit from Deinococcus radiodurans in complex with tiamulin provides for the first time a detailed picture of its interactions with the 23S rRNA, thus explaining the molecular mechanism of the antimicrobial activity of the pleuromutilin class of antibiotics. Our results show that tiamulin is located within the peptidyl transferase center (PTC) of the 50S ribosomal subunit with its tricyclic mutilin core positioned in a tight pocket at the A-tRNA binding site. Also, the extension, which protrudes from its mutilin core, partially overlaps with the P-tRNA binding site. Thereby, tiamulin directly inhibits peptide bond formation. Comparison of the tiamulin binding site with other PTC targeting drugs, like chloramphenicol, clindamycin and streptogramins, may facilitate the design of modified or hybridized drugs that extend the applicability of this class of antibiotics.

  18. Phylogeny of the Vitamin K 2,3-Epoxide Reductase (VKOR) Family and Evolutionary Relationship to the Disulfide Bond Formation Protein B (DsbB) Family.

    Science.gov (United States)

    Bevans, Carville G; Krettler, Christoph; Reinhart, Christoph; Watzka, Matthias; Oldenburg, Johannes

    2015-07-29

    In humans and other vertebrate animals, vitamin K 2,3-epoxide reductase (VKOR) family enzymes are the gatekeepers between nutritionally acquired K vitamins and the vitamin K cycle responsible for posttranslational modifications that confer biological activity upon vitamin K-dependent proteins with crucial roles in hemostasis, bone development and homeostasis, hormonal carbohydrate regulation and fertility. We report a phylogenetic analysis of the VKOR family that identifies five major clades. Combined phylogenetic and site-specific conservation analyses point to clade-specific similarities and differences in structure and function. We discovered a single-site determinant uniquely identifying VKOR homologs belonging to human pathogenic, obligate intracellular prokaryotes and protists. Building on previous work by Sevier et al. (Protein Science 14:1630), we analyzed structural data from both VKOR and prokaryotic disulfide bond formation protein B (DsbB) families and hypothesize an ancient evolutionary relationship between the two families where one family arose from the other through a gene duplication/deletion event. This has resulted in circular permutation of primary sequence threading through the four-helical bundle protein folds of both families. This is the first report of circular permutation relating distant a-helical membrane protein sequences and folds. In conclusion, we suggest a chronology for the evolution of the five extant VKOR clades.

  19. Collapsed tetragonal phase as a strongly covalent and fully nonmagnetic state: Persistent magnetism with interlayer As-As bond formation in Rh-doped Ca0 .8Sr0 .2Fe2As2

    Science.gov (United States)

    Zhao, K.; Glasbrenner, J. K.; Gretarsson, H.; Schmitz, D.; Bednarcik, J.; Etter, M.; Sun, J. P.; Manna, R. S.; Al-Zein, A.; Lafuerza, S.; Scherer, W.; Cheng, J. G.; Gegenwart, P.

    2018-02-01

    A well-known feature of the CaFe2As2 -based superconductors is the pressure-induced collapsed tetragonal phase that is commonly ascribed to the formation of an interlayer As-As bond. Using detailed x-ray scattering and spectroscopy, we find that Rh-doped Ca0.8Sr0.2Fe2As2 does not undergo a first-order phase transition and that local Fe moments persist despite the formation of interlayer As-As bonds. Our density functional theory calculations reveal that the Fe-As bond geometry is critical for stabilizing magnetism and the pressure-induced drop in the c lattice parameter observed in pure CaFe2As2 is mostly due to a constriction within the FeAs planes. The collapsed tetragonal phase emerges when covalent bonding of strongly hybridized Fe 3 d and As 4 p states completely wins out over their exchange splitting. Thus the collapsed tetragonal phase is properly understood as a strong covalent phase that is fully nonmagnetic with the As-As bond forming as a by-product.

  20. Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

    Science.gov (United States)

    Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

    2009-12-31

    Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.