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Sample records for activated double bond

  1. Mechanochemical C-H bond activation: rapid and regioselective double cyclopalladation monitored by in situ Raman spectroscopy.

    PubMed

    Juribašić, Marina; Užarević, Krunoslav; Gracin, Davor; Ćurić, Manda

    2014-09-14

    The first direct mechanochemical transition-metal-mediated activation of strong phenyl C-H bonds is reported. The mechanochemical procedure, resulting in cyclopalladated complexes, is quantitative and significantly faster than solution synthesis and allows highly regioselective activation of two C-H bonds by palladium(II) acetate in asymmetrically substituted azobenzene. Milling is monitored by in situ solid-state Raman spectroscopy which in combination with quantum-chemical calculations enabled characterization of involved reaction species, direct insight into the dynamics and reaction pathways, as well as the optimization of a milling process.

  2. The Reductive Activation of CO2 Across a Ti=Ti Double Bond: Synthetic, Structural, and Mechanistic Studies

    PubMed Central

    2015-01-01

    The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti2Pn†2 (1) (Pn† = 1,4-{SiiPr3}2C8H4) with CO2 is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO2 reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO2 molecule bound symmetrically to the two Ti centers in a μ:η2,η2 binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO2 is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η8 fashion to each of the formally TiIII centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti2Pn2 (Pn = C8H6) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO2 reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-TiIII species to yield di-TiII and di-TiIV products. 1 forms a structurally characterized, thermally stable CS2 adduct 8 that shows symmetrical binding to the Ti2 unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph3PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti

  3. A History of the Double-Bond Rule

    NASA Astrophysics Data System (ADS)

    Hoogenboom, Bernard E.

    1998-05-01

    The tautomeric polar systems recognized by Laar in 1886 contain an active atom that appeared to migrate from its original position. The tautomeric systems are of a general structural form and can be represented as X=Y-Z-A. Later workers recognized the same bond weakening effect in a variety of organic structures in which atom A is halogen, hydrogen, carbon, or nitrogen. Hermann Staudinger recognized the weakness of that bond, an allyl bond, in hydrocarbons and exploited the behavior for the preparation of isoprene from terpene hydrocarbons. In 1922 he formulated a generality, a rule, regarding the allyl bond reactivity He noted that natural rubber also decomposed to form isoprene and therefore concluded that natural rubber is an unsaturated hydrocarbon, that isoprene units in natural rubber represent weakly held allyl substituents, and that natural rubber is a macromolecular combination of isoprene units. From his different experience as an industrial chemist, Otto Schmidt recognized the same bond weakening effect in hydrocarbons and in 1932 postulated the "Double-Bond Rule," stating that the presence of a double bond in a hydrocarbon has an alternating strengthening and weakening effect on single bonds throughout the molecule, diminishing with distance from the double bond. Schmidt not only understood the practical benefit of this rule, but he also offered an explanation for the Rule on theoretical grounds. Novel in its time, his theoretical explanation did not find popular acceptance, despite his considerable efforts to promote it in the literature. His concept of the Rule was supplanted by the new theory of resonance devised by Pauling and Wheland and by the implied notion of the stabilization of products by delocalization effects.

  4. Interaction geometries and energies of hydrogen bonds to C[double bond]O and C[double bond]S acceptors: a comparative study.

    PubMed

    Wood, Peter A; Pidcock, Elna; Allen, Frank H

    2008-08-01

    The occurrence, geometries and energies of hydrogen bonds from N-H and O-H donors to the S acceptors of thiourea derivatives, thioamides and thiones are compared with data for their O analogues - ureas, amides and ketones. Geometrical data derived from the Cambridge Structural Database indicate that hydrogen bonds to the C[double bond]S acceptors are much weaker than those to their C[double bond]O counterparts: van der Waals normalized hydrogen bonds to O are shorter than those to S by approximately 0.25 A. Further, the directionality of the approach of the hydrogen bond with respect to S, defined by the C[double bond]S...H angle, is in the range 102-109 degrees , much lower than the analogous C[double bond]O...H angle which lies in the range 127-140 degrees . Ab initio calculations using intermolecular perturbation theory show good agreement with the experimental results: the differences in hydrogen-bond directionality are closely reproduced, and the interaction energies of hydrogen bonds to S are consistently weaker than those to O, by approximately 12 kJ mol(-1), for each of the three compound classes. There are no CSD examples of hydrogen bonds to aliphatic thiones, (Csp(3))(2)C=S, consistent with the near-equality of the electronegativities of C and S. Thioureas and thioamides have electron-rich N substituents replacing the Csp(3) atoms. Electron delocalization involving C[double bond]S and the N lone pairs then induces a significant >C(delta+)[double bond]S(delta-) dipole, which enables the formation of the medium-strength C[double bond]S...H bonds observed in thioureas and thioamides.

  5. Understanding Rotation about a C=C Double Bond

    ERIC Educational Resources Information Center

    Barrows, Susan E.; Eberlein, Thomas H.

    2005-01-01

    The study focuses on the process and energetic cost of twisting around a C=C double bond and provides instructors with a simple vehicle for rectifying the common misrepresentation of C=C double bonds as rigid and inflexible. Discussions of cis and trans isomers of cycloalkenes are a good entry point for introducing students to the idea of a…

  6. Investigation of double bond conversion, mechanical properties, and antibacterial activity of dental resins with different alkyl chain length quaternary ammonium methacrylate monomers (QAM).

    PubMed

    He, Jingwei; Söderling, Eva; Vallittu, Pekka K; Lassila, Lippo V J

    2013-01-01

    In order to endow dental resin with antibacterial activity, a series of antibacterial quaternary ammonium methacrylate monomers (QAM) with different substituted alkyl chain length (from 10 to 18) were incorporated into commonly used 2,2-bis[4-(2'-hydroxy-3'-methacryloyloxy-propoxy)-phenyl]propane (Bis-GMA)/triethyleneglycol dimethacrylate (TEGDMA) (50 wt/50 wt) dental resin as immobilized antibacterial agents. Double bond conversion (DC), flexural strength (FS) and modulus (FM), and young and mature biofilms inhibition effectiveness of prepared dental resins were studied and Bis-GMA/TEGDMA without QAM was used as reference. Results showed that there was no significant difference on DC, FS, and FM between copolymer with and without 5 wt% QAM. Substituted alkyl chain length of QAM had no influence on DC, FS, and FM of copolymer, but had influence on antibacterial activity of copolymer. Antibacterial activity of copolymer increased with increasing of substituted alkyl chain length of QAM, and the sequence followed as 5%C10 < 5%C11 ≈ 5%C12 < 5%C16 ≈ 5%C18. Copolymers containing C18 and C16 had the best inhibition effectiveness on both young biofilm and mature biofilm, copolymers containing C12 and C11 only had inhibition effectiveness on young biofilm and copolymer containing C10 had none inhibition effectiveness on neither young biofilm nor mature biofilm.

  7. Double C-H bond activation of hydrocarbons by a gas phase neutral oxide cluster: the importance of spin state.

    PubMed

    Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R

    2013-03-21

    The neutral cluster V2O5 is generated and detected in the gas phase. Its reactivity toward butane is studied both experimentally and theoretically. Experimental results show clearly that neutral V2O5 can react with n-butane (C4H10) to generate V2O5H2, indicating double hydrogen atom transfer from C4H10 to V2O5 to produce C4H8. Further experimental evidence indicates that V2O5 is only partially reacted even at very high concentrations of C4H10. Density functional theory (DFT) studies show that the lowest energy triplet state of V2O5 is reactive toward C4H10, whereas the ground state singlet V2O5 is inert. Calculated results are in agreement with experimental findings, and a detailed reaction mechanism is provided. Reactions of V2O5H2 with several oxidants are also studied theoretically to find a path to regenerate V2O5. Neutral (3)V2O5 can also react with C2H6 to form V2O5H2 and C2H4, but only as a minor reaction channel; the major product is the adsorption product V2O5(C2H6). PMID:23441829

  8. Low-valent niobium-mediated double activation of C-F/C-H bonds: fluorene synthesis from o-arylated alpha,alpha,alpha-trifluorotoluene derivatives.

    PubMed

    Fuchibe, Kohei; Akiyama, Takahiko

    2006-02-01

    By the treatment of 0.3 molar amount of NbCl5 and LiAlH4, o-arylated alpha,alpha,alpha-trifluorotoluenes afforded fluorene derivatives in good yields. C-F bonds of the CF3 group and the neighboring ortho C-H bond were doubly activated to give the coupling products. PMID:16448098

  9. cis-trans isomerization of carbon double bonds in monounsaturated triacylglycerols via generation of free radicals.

    PubMed

    Tsuzuki, Wakako

    2010-09-01

    We investigated the heat-induced cis/trans isomerization of double bonds in monounsaturated lipids. When triolein (9-cis, 18:1) was heated around 180 degrees C, small amounts of isomerization products were obtained depending on the heating period. The heat-induced isomerization of triolein was considerably suppressed by the addition of different antioxidants or under nitrogen stream, and these additives simultaneously inhibited the thermal oxidation of double bonds in triolein. Therefore, an intermediate of the thermal oxidation reaction might be responsible for the heat-induced isomerization of the double bonds in triolein. The thermodynamics of the heat-induced isomerization of triolein (9-cis, 18:1) and trielaidin (9-trans, 18:1) were investigated using Arrhenius plot. The Arrhenius activation energies of cis double bonds in triolein and trans double bonds in trielaidin were 106 kJ/mol and 137 kJ/mol, respectively. The calculated internal rotational barrier heights of these double bonds were similar to those of the double bond of 2-butene radical and significantly lower than those of non-radicalized double bonds in 2-butene. These results suggest that heat-induced cis/trans isomerization of triolein and trielaidin occurs mainly through the formation of radical species, which are the intermediates produced during thermal oxidation. The activation energy difference between the two forms suggests that trans trielaidin radicals are more stable than cis triolein radicals. The high thermodynamic stability of the trans double bonds in lipid radicals would influence the population of cis and trans isomers in edible oils and contribute to slight accumulation of trans-18:1 isomers during heating or industrial processing.

  10. Determination of double bond location in fatty acids by manganese adduction and electron induced dissociation.

    PubMed

    Yoo, Hyun Ju; Håkansson, Kristina

    2010-08-15

    Double bond locations in fatty acids can be determined from characteristic charge-remote fragmentation patterns of alkali metal-adducted fatty acids following high energy collision activated dissociation (CAD). With low energy CAD, several chemical derivatization methods, including ozonization, epoxidation, and hydroxylation, have been used to generate characteristic fragments. However, high energy CAD is not universally available and involves a high degree of scattering, causing product ion loss. Further, derivatization reactions involve side reactions and sample loss. Here, we analyzed metal-adducted fatty acids to investigate the utility of electron induced dissociation (EID) for determining double bond location. EID has been proposed to involve both electronic excitation, similar to high energy CAD, and vibrational excitation. Various metals (Li, Zn, Co, Ni, Mg, Ca, Fe, and Mn) were investigated to fix one charge at the carboxylate end of fatty acids to promote charge-remote fragmentation. EID of Mn(II)-adducted fatty acids allowed determination of all double bond locations of arachidonic acid, linolenic acid, oleic acid, and stearic acid. For Mn(II)-adducted fatty acids, reduced characteristic charge-remote product ion abundances at the double bond positions are indicative of double bond locations. However, other metal adducts did not generally provide characteristic product ion abundances at all double bond locations.

  11. α-Halogenoacetanilides as hydrogen-bonding organocatalysts that activate carbonyl bonds: fluorine versus chlorine and bromine.

    PubMed

    Koeller, Sylvain; Thomas, Coralie; Peruch, Fréderic; Deffieux, Alain; Massip, Stéphane; Léger, Jean-Michel; Desvergne, Jean-Pierre; Milet, Anne; Bibal, Brigitte

    2014-03-01

    α-Halogenoacetanilides (X=F, Cl, Br) were examined as H-bonding organocatalysts designed for the double activation of CO bonds through NH and CH donor groups. Depending on the halide substituents, the double H-bond involved a nonconventional CH⋅⋅⋅O interaction with either a HCXn (n=1-2, X=Cl, Br) or a HCAr bond (X=F), as shown in the solid-state crystal structures and by molecular modeling. In addition, the catalytic properties of α-halogenoacetanilides were evaluated in the ring-opening polymerization of lactide, in the presence of a tertiary amine as cocatalyst. The α-dichloro- and α-dibromoacetanilides containing electron-deficient aromatic groups afforded the most attractive double H-bonding properties towards CO bonds, with a NH⋅⋅⋅O⋅⋅⋅HCX2 interaction.

  12. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    ERIC Educational Resources Information Center

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  13. Radiation Crosslinking of Polyurethane Enhanced by Introducing Terminal Double-Bonds

    NASA Astrophysics Data System (ADS)

    Zhou, Cheng-Fei; Liu, Yang; Jiu, Yong-Bin; Cao, Wei; Zhai, Tong; Wang, Lian-Cai

    2016-05-01

    In this article, the enhanced radiation crosslinking of polyurethane via double-bond capping method were discussed in detail. Meanwhile, the Enhanced radiation crosslinking of polyurethane based on polyimide as hard segment were emphasized. In addition, the preparation of radiation crosslinking foam by introducing terminal double-bond were introduced.

  14. The sEDA(=) and pEDA(=) descriptors of the double bonded substituent effect.

    PubMed

    Mazurek, Andrzej; Dobrowolski, Jan Cz

    2013-05-14

    New descriptors of the double bonded substituent effect, sEDA(=) and pEDA(=), were constructed based on quantum chemical calculations and NBO methodology. They show to what extent the σ and π electrons are donated to or withdrawn from the substituted system by a double bonded substituent. The new descriptors differ from descriptors of the classical substituent effect for which the pz orbital of the ipso carbon atom is engaged in the π-electron system of the two neighboring atoms in the ring. For double bonded substituents, the pz orbital participates in double bond formation with only one external atom. Moreover, the external double bond forces localization of the double bond system of the ring, significantly changing the core molecule. We demonstrated good agreement between our descriptors and the Weinhold and Landis' "natural σ and π-electronegativities": so far only descriptors allowing for evaluation of the substitution effect by a double bonded atom. The equivalency between descriptors constructed for 5- and 6-membered model structures as well as linear dependence/independence of the constructed parameters was discussed. Some interrelations between sEDA(=) and pEDA(=) and the other descriptors of (hetero)cyclic systems such as aromaticity and electron density in the ring and bond critical points were also examined.

  15. Double pancake bonds: pushing the limits of strong π-π stacking interactions.

    PubMed

    Cui, Zhong-hua; Lischka, Hans; Beneberu, Habtamu Z; Kertesz, Miklos

    2014-09-17

    The concept of a double-bonded pancake bonding mechanism is introduced to explain the extremely short π-π stacking contacts in dimers of dithiatriazines. While ordinary single pancake bonds occur between radicals and already display significantly shorter interatomic distances in comparison to van der Waals (vdW) contacts, the double-bonded pancake dimer is based on diradicaloid or antiaromatic molecules and exhibits even shorter and stronger intermolecular bonds that breach into the range of extremely stretched single bonds in terms of bond distances and binding energies. These properties give rise to promising possibilities in the design of new materials with high electrical conductivity and for the field of spintronics. The analysis of the double pancake bond is based on cutting edge electron correlation theory combining multireference (nondynamical) effects and dispersion (dynamical) contributions in a balanced way providing accurate interaction energies and distributions of unpaired spins. It is also shown that the present examples do not stand isolated but that similar mechanisms operate in several analogous nonradical molecular systems to form double-bonded π-stacking pancake dimers. We report on the amazing properties of a new type of stacking interaction mechanism between π conjugated molecules in the form of a "double pancake bond" which breaks the record for short intermolecular distances and provides formidable strength for some π-π stacking interactions. PMID:25203200

  16. Theoretical study of the OH addition to the endocyclic and exocyclic double bonds of the d-limonene

    NASA Astrophysics Data System (ADS)

    Ramírez-Ramírez, Víctor M.; Nebot-Gil, Ignacio

    2005-06-01

    The initial step of the d-limonene + OH gas-phase reaction mechanism was investigated by means of ab initio calculations. We have considered eight different possibilities for the OH addition, corresponding to the two C-C double bonds, the two C atoms of each double bond, and the syn or anti orientation, with respect to the isopropenyl group (endocyclic attack) or the ring cycle (exocyclic attack). Activation energies calculated at the QCISD(T)/6-31G(d)//UMP2/6-31G(d) level, show that there are preferred orientations for the OH addition under atmospheric conditions of temperature and pressure.

  17. Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

    DOEpatents

    Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

    2002-01-01

    The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  18. Double hydrogen bond mediating self-assembly structure of cyanides on metal surface

    NASA Astrophysics Data System (ADS)

    Wang, Zhongping; Xiang, Feifei; Lu, Yan; Wei, Sheng; Li, Chao; Liu, Xiaoqing; Liu, Lacheng; Wang, Li

    2016-10-01

    Cyanides with different numbers of -C≡N, 1,2,4,5-Tetracyanobenzene (TCNB) and 2,3-Dicyanonaphthalene (2,3-DCN) deposited on Ag(111) and Ag(110) surfaces, have been investigated by room temperature scanning tunneling microscopy (RTSTM), respectively. High resolution STM images show double hydrogen bond is the main driving force to form variety of self-assembly structures, indicating the double hydrogen bond affects the electron distribution of cyanides and leads to a more stable structure with lower energy. In addition, the difference between Ag(111) and Ag(110) surfaces in their lattice structure induces a bigger assembly structural change of 2,3-DCN than that of 1,2,4,5-TCNB, which confirms the fact that the opposite double hydrogen bond formation formed by 1,2,4,5-TCNB is more stable than the neighboring double hydrogen bond formation formed by molecule 2,3-DCN.

  19. Silylene extrusion from organosilanes via double geminal Si-H bond activation by a Cp*Ru(kappa2-P,N)+ complex: observation of a key stoichiometric step in the glaser-tilley alkene hydrosilylation mechanism.

    PubMed

    Rankin, Matthew A; MacLean, Darren F; Schatte, Gabriele; McDonald, Robert; Stradiotto, Mark

    2007-12-26

    Treatment of Cp*RuCl(kappa2-P,N-2b) (2b = 2-NMe2-3-PiPr2-indene) with TlSO3CF3 produced the cyclometalated complex [4]+SO3CF3- in 94% isolated yield. Exposure of [4]+X- (X = B(C6F5)4 or SO3CF3) to Ph2SiH2 (10 equiv) or PhSiH3 afforded the corresponding [Cp*(mu-P,N-2b)(H)2Ru=SiRPh]+X- complexes, [5]+X- (R = Ph; X = B(C6F5)4, 82%; X = SO3CF3, 39%) and [6]+X- (R = H; X = B(C6F5)4, 94%; X = SO3CF3, 95%). Notably, these transformations represent the first documented examples of Ru-mediated silylene extrusion via double geminal Si-H bond activation of an organosilane-a key step in the recently proposed Glaser-Tilley (G-T) alkene hydrosilylation mechanism. Treatment of [5]+B(C6F5)4- with KN(SiMe3)2 or [6]+SO3CF3- with NaN(SiMe3)2 afforded the corresponding zwitterionic Cp*(mu-2-NMe2-3-PiPr2-indenide)(H)2Ru=SiRPh complex in 69% (R = Ph, 7) or 86% (R = H, 8) isolated yield. Both [6]+X- and 8 proved unreactive toward 1-hexene and styrene and provided negligible catalytic turnover in the attempted metal-mediated hydrosilylation of these substrates with PhSiH3, thereby providing further empirical evidence for the required intermediacy of base-free Ru=Si species in the G-T mechanism. Isomerization of the P,N-indene ligand backbone in [6]+X-, giving rise to [Cp*(mu-1-PiPr2-2-NMe2-indene)(H)2Ru=SiHPh]+X- ([9]+X-), was observed. In the case of [9]+SO3CF3-, net intramolecular addition of the Ru=Si-H group across the styrene-like C=C unit within the ligand backbone to give 10 (96% isolated yield) was observed. Crystallographic characterization data are provided for [4]+X-, [5]+X-, [6]+X-, 8, and 10.

  20. THz quantum cascade lasers with wafer bonded active regions.

    PubMed

    Brandstetter, M; Deutsch, C; Benz, A; Cole, G D; Detz, H; Andrews, A M; Schrenk, W; Strasser, G; Unterrainer, K

    2012-10-01

    We demonstrate terahertz quantum-cascade lasers with a 30 μm thick double-metal waveguide, which are fabricated by stacking two 15 μm thick active regions using a wafer bonding process. By increasing the active region thickness more optical power is generated inside the cavity, the waveguide losses are decreased and the far-field is improved due to a larger facet aperture. In this way the output power is increased by significantly more than a factor of 2 without reducing the maximum operating temperature and without increasing the threshold current.

  1. The Double-Bond Configuration of Corynanthean Alkaloids and Its Impact on Monoterpenoid Indole Alkaloid Biosynthesis.

    PubMed

    Eckermann, Ruben; Gaich, Tanja

    2016-04-11

    Experimental evidence is provided for the coherence of the double-bond geometry and the occurrence of "secondary cyclizations" in the biosynthesis of monoterpenoid indole alkaloids. Biosynthetically, akuammiline, C-mavacurine, and Strychnos alkaloids are proposed to be derived from the corynanthean alkaloid geissoschizine, a key intermediate in the biosynthetic pathway of these monoterpenoid indole alkaloids. This process occurs by so-called "secondary cyclizations" from geissoschizine or its derivatives. Although corynanthean alkaloids like geissoschizine incorporate E or Z double bonds located at C19-C20, the alkaloids downstream in the biosynthesis exclusively exhibit the E double bond. This study shows that secondary cyclizations preferentially occur with the E isomer of geissoschizine or its derivatives. This is attributed to the flexibility of the quinolizidine system of the corynanthean alkaloids, which can adopt a cis or trans conformation. For the secondary cyclization to take place, the cis-quinolizidine conformation is required. Experimental evidence supports the hypothesis that the E double bond of geissoschizine induces the cis conformation, whereas the Z double bond induces the trans conformation, which prohibits secondary cyclization of the Z compounds.

  2. 76 FR 12364 - Agency Information Collection Activities: Bonded Warehouse Regulations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-07

    ... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse... Bonded Warehouse Regulations. This request for comment is being made pursuant to the Paperwork Reduction... concerning the following information collection: Title: Bonded Warehouse Regulations. OMB Number:...

  3. Rhodium-catalyzed annulative coupling of 3-phenylthiophenes with alkynes involving double C-H bond cleavages.

    PubMed

    Iitsuka, Tomonori; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2014-01-01

    Double CH bond activation took place efficiently upon treatment of 3-phenylthiophenes with alkynes in the presence of a rhodium catalyst and a copper salt oxidant to form the corresponding naphthothiophene derivatives. Dehydrogenative coupling with alkenes was also found to occur on the phenyl moiety rather than the thiophene ring. These reactions provide straightforward synthetic methods for π-conjugated molecules involving a thiophene unit from readily available, simple building blocks. PMID:24288235

  4. Reactions of (Cp(CO) sub 2 Fe double bond CHAr) sup + (Ar = p-C sub 6 H sub 4 OMe) with O double bond N-Ar prime (Ar prime = C sub 6 H sub 5 , p-C sub 6 H sub 4 NMe sub 2 ) and PhN double bond NPh

    SciTech Connect

    Peng, Wei-Jun; Gamble, A.S.; Templeton, J.L.; Brookhart, M. )

    1990-02-07

    Organometallic products formed from the reaction of an electrophilic iron carbene complex with nitrosoarenes or azobenzene reflect net insertion of the ArN{double bond}X moiety into the Fe{double bond}CHAr bond. Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} and Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}CHAr{sup +} (Ar = p-C{sub 6}H{sub 4}OMe, Ar{prime} = p-C{sub 6}H{sub 4}NMe{sub 2}) have been isolated and spectroscopically characterized; the crystal structure of Cp(CO){sub 2}Fe-O-N(Ph){double bond}CHAr{sup +} is reported. Exposure of acetone solutions of Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} or Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}char{sup +} to light yields imine products Ar{prime}N{double bond}CHAr or PhN{double bond}CHAr, respectively. There is no evidence to support the formation of the simple stoichiometric iron-containing products of these reactions, the oxo and nitrene complexes Cp(CO){sub 2}Fe{double bond}O{sup +} and Cp(CO){sub 2}Fe{double bond}NPh{sup +}. Hydrolysis of the nitrone complexes Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} in aqueous acetone yields aldehyde products Ar{prime}CHO. 30 refs., 1 fig., 4 tabs.

  5. THP-1 macrophage lipid accumulation unaffected by fatty acid double bond geometric or positional configuration

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dietary fatty acid type alters atherosclerotic lesion progression and macrophage lipid accumulation. Incompletely elucidated are the mechanisms by which fatty acids differing in double-bond geometric or positional configuration alter arterial lipid accumulation. The objective of this study was to ev...

  6. Single and double substrate insertion into the Ti=N(alpha) bonds of terminal titanium hydrazides.

    PubMed

    Tiong, Pei-Jen; Schofield, A Daniel; Selby, Jonathan D; Nova, Ainara; Clot, Eric; Mountford, Philip

    2010-01-01

    Nitriles, CO(2) and isocyanates undergo net single or double insertion reactions into the Ti=N(alpha) multiple bonds of terminal titanium hydrazides. These are the first such examples of this type of reactivity for any transition metal hydrazide complex.

  7. Directionality of Double-Bond Photoisomerization Dynamics Induced by a Single Stereogenic Center.

    PubMed

    Marchand, Gabriel; Eng, Julien; Schapiro, Igor; Valentini, Alessio; Frutos, Luis Manuel; Pieri, Elisa; Olivucci, Massimo; Léonard, Jérémie; Gindensperger, Etienne

    2015-02-19

    In light-driven single-molecule rotary motors, the photoisomerization of a double bond converts light energy into the rotation of a moiety (the rotor) with respect to another (the stator). However, at the level of a molecular population, an effective rotary motion can only be achieved if a large majority of the rotors rotate in the same, specific direction. Here we present a quantitative investigation of the directionality (clockwise vs counterclockwise) induced by a single stereogenic center placed in allylic position with respect to the reactive double bond of a model of the biomimetic indanylidene-pyrrolinium framework. By computing ensembles of nonadiabatic trajectories at 300 K, we predict that the photoisomerization is >70% unidirectional for the Z → E and E → Z conversions. Most importantly, we show that such directionality, resulting from the asymmetry of the excited state force field, can still be observed in the presence of a small (ca. 2°) pretwist or helicity of the reactive double bond. This questions the validity of the conjecture that a significant double-bond pretwist (e.g., >10°) in the ground state equilibrium structure of synthetic or natural rotary motors would be required for unidirectional motion. PMID:26262473

  8. Flow in out-of-plane double S-bonds

    NASA Technical Reports Server (NTRS)

    Schmidt, M. C.; Whitelaw, J. H.; Yianneskis, M.

    1986-01-01

    Developing flows in two out-of-plane double S-bend configurations have been measured by laser-Doppler anemometry. The first duct had a rectangular cross-section 40mmx40mm at the inlet and consisted of a uniform area 22.5 deg. - 22.5 deg. S-duct upstream with a 22.5 deg.- 22.5 deg. S- diffuser downstream. The second duct had a circular cross-section and consisted of a 45 deg. - 45 deg. uniform area S-duct upstream with a 22.5 deg. -22.5 deg. S-diffuser downstream. In both configurations the ratio of the mean radius of curvature to the inlet hydraulic diameter was 7.0, the exit-to-inlet area ratio of the diffusers was 1.5 and the ducts were connected so that the centerline of the S-duct lay in a plane normal to that of the S-diffuser. Streamwise and cross-stream velocity components were measured in laminar flow for the rectangular duct and in turbulent flow for both configurations; measurements of the turbulence levels, cross-correlations and wall static pressures were also made in the turbulent flow cases. Secondary flows of the first kind are present in the first S-duct and they are complemented or counteracted by the secondary flows generated by the area expansion and by the curvature of the S-diffusers downstream. Cross-stream velocities with magnitudes up to 0.19 and 0.11 of the bulk velocity were measured in the laminar and turbulent flows respectively in the rectangular duct and six cross-flow vortices were evident at the exit of the duct in both flow cases. The turbulent flow in the circular duct was qualitatively similar to that in the rectangular configuration, but the cross-stream velocities measured at the exit plane were smaller in the circular geometry. The results are presented in sufficient detail and accuracy for the assessment of numerical calculation methods and are listed in tabular form for this purpose.

  9. Catalytic Diamination of Olefins via N–N Bond Activation

    PubMed Central

    2015-01-01

    Conspectus Vicinal diamines are important structural motifs present in various biologically and chemically significant molecules. Direct diamination of olefins provides an effective approach to this class of compounds. Unlike well-established oxidation processes such as epoxidation, dihydroxylation, and aminohydroxylation, direct diamination of olefins had remained a long-standing challenge and had been less well developed. In this Account, we summarize our recent studies on Pd(0)- and Cu(I)-catalyzed diaminations of olefins using di-tert-butyldiaziridinone and its related analogues as nitrogen sources via N–N bond activation. A wide variety of imidazolidinones, cyclic sulfamides, indolines, imidazolinones, and cyclic guanidines can be obtained from conjugated dienes and terminal olefins. For conjugated dienes, the diamination proceeds regioselectively at the internal double bond with the Pd(0) catalyst. Mechanistic studies show that the diamination likely involves a four-membered Pd(II) species resulting from the insertion of Pd(0) into the N–N bond of di-tert-butyldiaziridinone. Interestingly, the Cu(I)-catalyzed process occurs regioselectively at either the terminal or internal double bond depending on the reaction conditions via two mechanistically distinct pathways. The Cu(I) catalyst cleaves the N–N bond of di-tert-butyldiaziridinone to form a Cu(II) nitrogen radical and a four-membered Cu(III) species, which are likely in rapid equilibrium. The Cu(II) nitrogen radical and the four-membered Cu(III) species lead to the terminal and internal diamination, respectively. Terminal olefins are effectively C–H diaminated at the allylic and homoallylic carbons with Pd(0) as catalyst and di-tert-butyldiaziridinone as nitrogen source, likely involving a diene intermediate generated in situ from the terminal olefin via formation of a π-allyl Pd complex and subsequent β-hydride elimination. When di-tert-butylthiadiaziridine 1,1-dioxide is used as nitrogen source

  10. Catalytic diamination of olefins via N-N bond activation.

    PubMed

    Zhu, Yingguang; Cornwall, Richard G; Du, Haifeng; Zhao, Baoguo; Shi, Yian

    2014-12-16

    CONSPECTUS: Vicinal diamines are important structural motifs present in various biologically and chemically significant molecules. Direct diamination of olefins provides an effective approach to this class of compounds. Unlike well-established oxidation processes such as epoxidation, dihydroxylation, and aminohydroxylation, direct diamination of olefins had remained a long-standing challenge and had been less well developed. In this Account, we summarize our recent studies on Pd(0)- and Cu(I)-catalyzed diaminations of olefins using di-tert-butyldiaziridinone and its related analogues as nitrogen sources via N-N bond activation. A wide variety of imidazolidinones, cyclic sulfamides, indolines, imidazolinones, and cyclic guanidines can be obtained from conjugated dienes and terminal olefins. For conjugated dienes, the diamination proceeds regioselectively at the internal double bond with the Pd(0) catalyst. Mechanistic studies show that the diamination likely involves a four-membered Pd(II) species resulting from the insertion of Pd(0) into the N-N bond of di-tert-butyldiaziridinone. Interestingly, the Cu(I)-catalyzed process occurs regioselectively at either the terminal or internal double bond depending on the reaction conditions via two mechanistically distinct pathways. The Cu(I) catalyst cleaves the N-N bond of di-tert-butyldiaziridinone to form a Cu(II) nitrogen radical and a four-membered Cu(III) species, which are likely in rapid equilibrium. The Cu(II) nitrogen radical and the four-membered Cu(III) species lead to the terminal and internal diamination, respectively. Terminal olefins are effectively C-H diaminated at the allylic and homoallylic carbons with Pd(0) as catalyst and di-tert-butyldiaziridinone as nitrogen source, likely involving a diene intermediate generated in situ from the terminal olefin via formation of a π-allyl Pd complex and subsequent β-hydride elimination. When di-tert-butylthiadiaziridine 1,1-dioxide is used as nitrogen source

  11. Novel dehydrogenase catalyzes oxidative hydrolysis of carbon-nitrogen double bonds for hydrazone degradation.

    PubMed

    Itoh, Hideomi; Suzuta, Tetsuya; Hoshino, Takayuki; Takaya, Naoki

    2008-02-29

    Hydrazines and their derivatives are versatile artificial and natural compounds that are metabolized by elusive biological systems. Here we identified microorganisms that assimilate hydrazones and isolated the yeast, Candida palmioleophila MK883. When cultured with adipic acid bis(ethylidene hydrazide) as the sole source of carbon, C. palmioleophila MK883 degraded hydrazones and accumulated adipic acid dihydrazide. Cytosolic NAD+- or NADP+-dependent hydrazone dehydrogenase (Hdh) activity was detectable under these conditions. The production of Hdh was inducible by adipic acid bis(ethylidene hydrazide) and the hydrazone, varelic acid ethylidene hydrazide, under the control of carbon catabolite repression. Purified Hdh oxidized and hydrated the C=N double bond of acetaldehyde hydrazones by reducing NAD+ or NADP+ to produce relevant hydrazides and acetate, the latter of which the yeast assimilated. The deduced amino acid sequence revealed that Hdh belongs to the aldehyde dehydrogenase (Aldh) superfamily. Kinetic and mutagenesis studies showed that Hdh formed a ternary complex with the substrates and that conserved Cys is essential for the activity. The mechanism of Hdh is similar to that of Aldh, except that it catalyzed oxidative hydrolysis of hydrazones that requires adding a water molecule to the reaction catalyzed by conventional Aldh. Surprisingly, both Hdh and Aldh from baker's yeast (Ald4p) catalyzed the Hdh reaction as well as aldehyde oxidation. Our findings are unique in that we discovered a biological mechanism for hydrazone utilization and a novel function of proteins in the Aldh family that act on C=N compounds. PMID:18096698

  12. Chemical Bond Activation Observed with an X-ray Laser.

    PubMed

    Beye, Martin; Öberg, Henrik; Xin, Hongliang; Dakovski, Georgi L; Dell'Angela, Martina; Föhlisch, Alexander; Gladh, Jörgen; Hantschmann, Markus; Hieke, Florian; Kaya, Sarp; Kühn, Danilo; LaRue, Jerry; Mercurio, Giuseppe; Minitti, Michael P; Mitra, Ankush; Moeller, Stefan P; Ng, May Ling; Nilsson, Anders; Nordlund, Dennis; Nørskov, Jens; Öström, Henrik; Ogasawara, Hirohito; Persson, Mats; Schlotter, William F; Sellberg, Jonas A; Wolf, Martin; Abild-Pedersen, Frank; Pettersson, Lars G M; Wurth, Wilfried

    2016-09-15

    The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding-antibonding splitting following bond-activation using an ultrashort optical laser pulse. PMID:27584914

  13. Spontaneous and specific activation of chemical bonds in macromolecular fluids.

    PubMed

    Park, Insun; Shirvanyants, David; Nese, Alper; Matyjaszewski, Krzysztof; Rubinstein, Michael; Sheiko, Sergei S

    2010-09-01

    Mechanical activation of chemical bonds typically involves the application of external forces, which implies a broad distribution of bond tensions. We demonstrate that controlling the flow profile of a macromolecular fluid generates and delineates mechanical force concentration, enabling a hierarchical activation of chemical bonds on different length scales from the macroscopic to the molecular. Bond tension is spontaneously generated within brushlike macromolecules as they spread on a solid substrate. The molecular architecture creates an uneven distribution of tension in the covalent bonds, leading to spatially controlled bond scission. By controlling the flow rate and the gradient of the film pressure, one can sever the flowing macromolecules with high precision. Specific chemical bonds are activated within distinct macromolecules located in a defined area of a thin film. Furthermore, the flow-controlled loading rate enables quantitative analysis of the bond activation parameters.

  14. A diabatic state model for double proton transfer in hydrogen bonded complexes

    SciTech Connect

    McKenzie, Ross H.

    2014-09-14

    Four diabatic states are used to construct a simple model for double proton transfer in hydrogen bonded complexes. Key parameters in the model are the proton donor-acceptor separation R and the ratio, D{sub 1}/D{sub 2}, between the proton affinity of a donor with one and two protons. Depending on the values of these two parameters the model describes four qualitatively different ground state potential energy surfaces, having zero, one, two, or four saddle points. Only for the latter are there four stable tautomers. In the limit D{sub 2} = D{sub 1} the model reduces to two decoupled hydrogen bonds. As R decreases a transition can occur from a synchronous concerted to an asynchronous concerted to a sequential mechanism for double proton transfer.

  15. Characterization of Heronamide Biosynthesis Reveals a Tailoring Hydroxylase and Indicates Migrated Double Bonds.

    PubMed

    Zhu, Yiguang; Zhang, Wenjun; Chen, Yaolong; Yuan, Chengshan; Zhang, Haibo; Zhang, Guangtao; Ma, Liang; Zhang, Qingbo; Tian, Xinpeng; Zhang, Si; Zhang, Changsheng

    2015-09-21

    Heronamides belong to a growing family of β-amino acid polyketide macrolactams (βPMs) with an unsaturated side chain. The biosynthetic gene cluster for heronamide F was identified from the deep-sea-derived Streptomyces sp. SCSIO 03032. The involvement of the gene cluster in heronamide biosynthesis was confirmed by the functional characterization of the P450 enzyme HerO as an 8-hydroxylase for tailoring heronamide biosynthesis. The presence of migrated double bonds in the conjugated diene-containing side chain of heronamides was confirmed by feeding experiments with labeled small carboxylic acid molecules. This study is the first demonstration of migrated double bonds in βPMs with an unsaturated side chain.

  16. Antibacterial activity of four dentin bonding systems.

    PubMed

    Herrera, M; Carrión, P; Bravo, M; Castillo, A

    2000-08-01

    The antibacterial action of bonding systems Gluma 2000, Syntac, Prisma Universal Bond 3, Scotchbond Multipurpose and Prime-Bond was tested against 32 strains of the caries-producing bacteria Streptococcus spp., Lactobacillus spp., Actinomyces spp., Porphyromonas spp. and Clostridium spp. An agar plate diffusion method was used with chlorhexidine as the positive control. Assays were performed in triplicate for each component (primer and adhesive) of the bonding systems. All the adhesives were found to inhibit bacterial growth but with differences in their spectra of action. The sum action of the Scotchbond Multipurpose components were most inhibitory and Prime-Bond was found to be the least effective system.

  17. A Bonded Double-Doped Graphene Nanoribbon Framework for Advanced Electrocatalysis.

    PubMed

    Chen, Liang; Xiao, Jingjing; Liu, Baohong; Yi, Tao

    2016-07-01

    The preparation of a low-cost, high-efficient, and stable electrocatalyst as an alternative to platinum for the oxygen reduction reaction (ORR) is especially important to various energy storage components, such as fuel cells and metal-air batteries. Here, we report a new type of bonded double-doped graphene nanoribbon-based nonprecious metal catalysts in which Fe3C nanoparticles embedded in Fe-N-doped graphene nanoribbon (GNRs) frameworks through a simple pyrolysis. The as-obtained catalyst possesses several desirable merits for the ORR, such as diverse high-efficiency catalytic sites, a high specific surface area, an ideal hierarchical cellular structure, and a highly conductive N-doped GNR network. Accordingly, the prepared catalyst shows a superior ORR activity (an onset potential of 0.02 V and a half-wave potential of -0.148 V versus an Ag/AgCl electrode) in alkaline media, close to the commercial Pt/C catalyst. Moreover, it also displays good ORR behavior in an acidic solution. PMID:27300690

  18. Aryl isomerization during aliphatic CH bond activation

    SciTech Connect

    Chamberlain, L.R.; Rothwell, I.P.

    1983-03-23

    The transition-metal-stablized benzyne or o-phenylene (n/sup 2/-C/sub 6/H/sub 4/) ligand has been shown to be both an interesting and reactive group. The ligand is normally generated in mononuclear systems by ..beta..- (ortho-) hydrogen abstraction from an aryl group, and this synthetic approach has allowed a stable example to be isolated and structurally characterized. Here the conclusive identification of a benzyne intermediate during the isomerization of a tantalum-aryl compound is reported. The reaction is interesting in that the ortho hydrogen is transferred to the carbon atom of a cyclometalated chelate, the reverse (isomerization) step thus involving the activation of an aliphatic CH bond by the intermediate benzyne.

  19. Using ambient ozone for assignment of double bond position in unsaturated lipids.

    PubMed

    Ellis, Shane R; Hughes, Jessica R; Mitchell, Todd W; in het Panhuis, Marc; Blanksby, Stephen J

    2012-03-01

    Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions.

  20. Adhesive-bonded double-lap joints. [analytical solutions for static load carrying capacity

    NASA Technical Reports Server (NTRS)

    Hart-Smith, L. J.

    1973-01-01

    Explicit analytical solutions are derived for the static load carrying capacity of double-lap adhesive-bonded joints. The analyses extend the elastic solution Volkersen and cover adhesive plasticity, adherend stiffness imbalance and thermal mismatch between the adherends. Both elastic-plastic and bi-elastic adhesive representations lead to the explicit result that the influence of the adhesive on the maximum potential bond strength is defined uniquely by the strain energy in shear per unit area of bond. Failures induced by peel stresses at the ends of the joint are examined. This failure mode is particularly important for composite adherends. The explicit solutions are sufficiently simple to be used for design purposes

  1. On the activation of σ-bonds by electric fields: A Valence Bond perspective

    NASA Astrophysics Data System (ADS)

    Rincón, Luis; Mora, Jose R.; Torres, F. Javier; Almeida, Rafael

    2016-09-01

    The activation of non-polar σ -bonds induced by an electric field is studied from the perspective of the Valence Bond theory. As representative examples we study the dissociation of the H-H and C-H bonds of molecular hydrogen and methane, respectively, under the experience of an homogeneous as well as an heterogeneous field oriented along the bond axis. For all cases, the increase in the electric field have similar effects: (i) the stabilization of the potential energy, (ii) an increment of the equilibrium bond length and (iii) the transition from an homolytic dissociation mechanism to an heterolytic one when the bond is subjected under a strong enough field. These general observations are thoroughly explained using a simple Valence Bond model that involve the increment of the resonance energy between the covalent and the ionic structures, and the curve crossing between the two structures after some field strength.

  2. Ozonolysis of the double bond of the unsaturated uronate residue in low-molecular-weight heparin and K5 heparosan.

    PubMed

    Masuko, Sayaka; Higashi, Kyohei; Wang, Zhenyu; Bhaskar, Ujjwal; Hickey, Anne Marie; Zhang, Fuming; Toida, Toshihiko; Dordick, Jonathan S; Linhardt, Robert J

    2011-09-27

    Ozone is known to add across and cleave carbon-carbon double bonds. Ozonolysis is widely used for the preparation of pharmaceuticals, for bleaching substances and for killing microorganisms in air and water sources. Some polysaccharides and oligosaccharides, such as those prepared using chemical or enzymatic β-elimination, contain a site of unsaturation. We examined ozonolysis of low-molecular-weight heparins (LMWHs), enoxaparin and logiparin, and heparosan oligo- and polysaccharides for the removal of the nonreducing terminal unsaturated uronate residue. 1D (1)H NMR showed that these ozone-treated polysaccharides retained the same structure as the starting polysaccharide, except that the C4-C5 double bond in the nonreducing end unsaturated uronate had been removed. The anticoagulant activity of the resulting product from enoxaparin and logiparin was comparable to that of the starting material. These results demonstrate that ozonolysis is an important tool for the removal of unsaturated uronate residues from LMWHs and heparosan without modification of the core polysaccharide structure or diminution of anticoagulant activity. This reaction also has potential applications in the chemoenzymatic synthesis of bioengineered heparin from Escherichia coli-derived K5 heparosan.

  3. Double-decker bis(tetradiazepinoporphyrazinato) rare earth complexes: crucial role of intramolecular hydrogen bonding.

    PubMed

    Tarakanova, Ekaterina N; Trashin, Stanislav A; Simakov, Anton O; Furuyama, Taniyuki; Dzuban, Alexander V; Inasaridze, Liana N; Tarakanov, Pavel A; Troshin, Pavel A; Pushkarev, Victor E; Kobayashi, Nagao; Tomilova, Larisa G

    2016-07-26

    A series of homoleptic bis{tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazinato}lanthanide sandwich complexes [(tBuPh)DzPz]2Ln (Ln = Lu, Er, Dy, Eu, Nd, Ce, La) were prepared and their physicochemical properties were studied to gain insight into the nature of specific interactions in diazepinoporphyrazines. The effect of annulated diazepine moieties and the Ln ionic radius on the properties of the complexes was investigated in comparison with double-decker phthalocyanines. A combination of experimental and theoretical studies revealed the presence of two types of hydrogen bonding interactions in the metal-free porphyrazine and the corresponding sandwich complexes, namely, interligand C-H(ax)N(meso) hydrogen bonding and O-HN(Dz) ligand-water interaction. The interligand hydrogen bonding imparts high stability of the ligand dimer and the double-decker compounds in a reduced state. This work is the first comprehensive investigation into the fundamental understanding of the unusual properties of diazepine-containing macroheterocycles. PMID:27396712

  4. Theoretical Analysis of the Effect of C═C Double Bonds on the Low-Temperature Reactivity of Alkenylperoxy Radicals.

    PubMed

    You, Xiaoqing; Chi, Yawei; He, Tanjin

    2016-08-01

    Biodiesel contains a large proportion of unsaturated fatty acid methyl esters. Its combustion characteristics, especially its ignition behavior at low temperatures, have been greatly affected by these C═C double bonds. In this work, we performed a theoretical analysis of the effect of C═C double bonds on the low-temperature reactivity of alkenylperoxy radicals, the key intermediates from the low-temperature combustion of biodiesel. To understand how double bonds affect the fate of peroxy radicals, we selected three representative peroxy radicals from heptane, heptene, and heptadiene having zero, one, and two double C═C bonds, respectively, for study. The potential energy surfaces were explored at the CBS-QB3 level, and the reaction rate constants were computed using canonical/variational transition state theories. We have found that the double bond is responsible for the very different bond dissociation energies of the various types of C-H bonds, which in turn affect significantly the reaction kinetics of alkenylperoxy radicals.

  5. Theoretical Analysis of the Effect of C═C Double Bonds on the Low-Temperature Reactivity of Alkenylperoxy Radicals.

    PubMed

    You, Xiaoqing; Chi, Yawei; He, Tanjin

    2016-08-01

    Biodiesel contains a large proportion of unsaturated fatty acid methyl esters. Its combustion characteristics, especially its ignition behavior at low temperatures, have been greatly affected by these C═C double bonds. In this work, we performed a theoretical analysis of the effect of C═C double bonds on the low-temperature reactivity of alkenylperoxy radicals, the key intermediates from the low-temperature combustion of biodiesel. To understand how double bonds affect the fate of peroxy radicals, we selected three representative peroxy radicals from heptane, heptene, and heptadiene having zero, one, and two double C═C bonds, respectively, for study. The potential energy surfaces were explored at the CBS-QB3 level, and the reaction rate constants were computed using canonical/variational transition state theories. We have found that the double bond is responsible for the very different bond dissociation energies of the various types of C-H bonds, which in turn affect significantly the reaction kinetics of alkenylperoxy radicals. PMID:27404895

  6. Predicting Promoter-Induced Bond Activation on Solid Catalysts Using Elementary Bond Orders.

    PubMed

    Tsai, Charlie; Latimer, Allegra A; Yoo, Jong Suk; Studt, Felix; Abild-Pedersen, Frank

    2015-09-17

    In this Letter, we examine bond activation induced by nonmetal surface promoters in the context of dehydrogenation reactions. We use C-H bond activation in methane dehydrogenation on transition metals as an example to understand the origin of the promoting or poisoning effect of nonmetals. The electronic structure of the surface and the bond order of the promoter are found to establish all trends in bond activation. On the basis of these results, we develop a predictive model that successfully describes the energetics of C-H, O-H, and N-H bond activation across a range of reactions. For a given reaction step, a single data point determines whether a nonmetal will promote bond activation or poison the surface and by how much. We show how our model leads to general insights that can be directly used to predict bond activation energetics on transition metal sulfides and oxides, which can be perceived as promoted surfaces. These results can then be directly used in studies on full catalytic pathways. PMID:26722740

  7. Functionalized alkynyl-chlorogermanes: hydrometallation, Ge-Cl bond activation, Ge-H bond formation and chlorine-tert-butyl exchange via a transient germyl cation.

    PubMed

    Honacker, Christian; Qu, Zheng-Wang; Tannert, Jens; Layh, Marcus; Hepp, Alexander; Grimme, Stefan; Uhl, Werner

    2016-04-14

    Treatment of alkynyl-arylchlorogermanes ArylnGe(Cl)(C[triple bond, length as m-dash]C-(t)Bu)3-n (n = 1, 2) with HM(t)Bu2 (M = Al, Ga) yielded mixed Al or Ga alkenyl-alkynylchlorogermanes via hydrometallation reactions. Intramolecular interactions between the Lewis-basic Cl atoms and the Lewis-acidic Al or Ga atoms afforded MCGeCl heterocycles. The endocyclic M-Cl distances were significantly lengthened compared to the starting compounds and indicated Ge-Cl bond activation. Dual hydrometallation succeeded only with HGa(t)Bu2. One Ga atom of the product was involved in a Ga-Cl bond, while the second one had an interaction to a C-H bond of a phenyl group. In two cases treatment of chlorogermanes with two equivalents of HAl(t)Bu2 resulted in hydroalumination of one alkynyl group and formation of unprecedented Ge-H functionalized germanes, Aryl-Ge(H)(C[triple bond, length as m-dash]C-(t)Bu)[C(Al(t)Bu2)[double bond, length as m-dash]C(H)-(t)Bu] (Aryl = mesityl, triisopropylphenyl). The Al atoms of these compounds interacted with the α-C atoms of the alkynyl groups. Ph(Cl)Ge(C[triple bond, length as m-dash]C-(t)Bu)[C(Al(t)Bu2}[double bond, length as m-dash]C(H)-(t)Bu] reacted in an unusual Cl/(t)Bu exchange to yield the tert-butylgermane Ph((t)Bu)Ge(C[triple bond, length as m-dash]C-(t)Bu)[C{Al((t)Bu)(Cl)}[double bond, length as m-dash]C(H)-(t)Bu]. Quantum chemical calculations suggested the formation of a germyl cation as a transient intermediate.

  8. Substituent effects in double-helical hydrogen-bonded AAA-DDD complexes.

    PubMed

    Wang, Hong-Bo; Mudraboyina, Bhanu P; Wisner, James A

    2012-01-27

    Two series of DDD and AAA hydrogen-bond arrays were synthesized that form triply-hydrogen-bonded double-helical complexes when combined in CDCl(3) solution. Derivatization of the DDD arrays with electron-withdrawing groups increases the complex association constants by up to a factor of 30 in those arrays examined. Derivatization of the AAA arrays with electron donating substituents reveals a similar magnitude effect on the complex stabilities. The effect of substitution on both types of arrays are modeled quite satisfactorily (R(2) > 0.96 in all cases) as free energy relationships with respect to the sums of their Hammett substituent constants. In all, the complex stabilities can be manipulated over more than three orders of magnitude (>20 kJ mol(-1)) using this type of modification.

  9. Quantum dynamics study of fulvene double bond photoisomerization: The role of intramolecular vibrational energy redistribution and excitation energy

    SciTech Connect

    Blancafort, Lluis; Gatti, Fabien; Meyer, Hans-Dieter

    2011-10-07

    The double bond photoisomerization of fulvene has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method. Fulvene is a test case to develop optical control strategies based on the knowledge of the excited state decay mechanism. The decay takes place on a time scale of several hundred femtoseconds, and the potential energy surface is centered around a conical intersection seam between the ground and excited state. The competition between unreactive decay and photoisomerization depends on the region of the seam accessed during the decay. The dynamics are carried out on a four-dimensional model surface, parametrized from complete active space self-consistent field calculations, that captures the main features of the seam (energy and locus of the seam and associated branching space vectors). Wave packet propagations initiated by single laser pulses of 5-25 fs duration and 1.85-4 eV excitation energy show the principal characteristics of the first 150 fs of the photodynamics. Initially, the excitation energy is transferred to a bond stretching mode that leads the wave packet to the seam, inducing the regeneration of the reactant. The photoisomerization starts after the vibrational energy has flowed from the bond stretching to the torsional mode. In our propagations, intramolecular energy redistribution (IVR) is accelerated for higher excess energies along the bond stretch mode. Thus, the competition between unreactive decay and isomerization depends on the rate of IVR between the bond stretch and torsion coordinates, which in turn depends on the excitation energy. These results set the ground for the development of future optical control strategies.

  10. Pancake π-π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls.

    PubMed

    Tian, Yong-Hui; Sumpter, Bobby G; Du, Shiyu; Huang, Jingsong

    2015-06-18

    Chemical bonding interactions are the main driving force for the formation of molecules and materials from atoms. The two-electron/multicenter pancake π-π bonding found in phenalenyl (PLY, 1) radical π-dimers is intriguing due to its unconventional nature of covalent bonding for molecular aggregations and its propensity to induce unique optical, electronic, and magnetic properties. By using high-level quantum chemistry calculations, we show that the B- or N-doped PLYs (2 and 4), usually considered closed-shell and therefore trifling, can be rendered open-shell singlet by proper edge substitutions (3 and 5). The resulting two unpaired valence electrons on each molecular unit contribute to the formation of a genuine pancake-shaped 4e/all-sites double π-π bonding upon intermolecular π-dimerization, in contrast to the 2e/half-sites single π-π bonding in the parent PLY π-dimers. The unusual double π-π bonding motif discovered in these PLY analogues may broaden the landscape of, and find new applications for, intermolecular covalent bonding interactions.

  11. 76 FR 28801 - Agency Information Collection Activities: Bonded Warehouse Regulations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-18

    ... Federal Register (76 FR 11254) on March 1, 2011, allowing for a 60-day comment period. This notice allows... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse... approval in accordance with the Paperwork Reduction Act: Bonded Warehouse Regulations. This is a...

  12. 26 CFR 1.141-2 - Private activity bond tests.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... (CONTINUED) INCOME TAXES (CONTINUED) Tax Exemption Requirements for State and Local Bonds § 1.141-2 Private... and deliberate actions—(1) In general. An issue is an issue of private activity bonds if the issuer reasonably expects, as of the issue date, that the issue will meet either the private business tests or...

  13. 26 CFR 1.141-2 - Private activity bond tests.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... (CONTINUED) INCOME TAXES (CONTINUED) Tax Exemption Requirements for State and Local Bonds § 1.141-2 Private... and deliberate actions—(1) In general. An issue is an issue of private activity bonds if the issuer reasonably expects, as of the issue date, that the issue will meet either the private business tests or...

  14. On the bonding nature of electron states for the Fe-Mo double perovskite

    SciTech Connect

    Carvajal, E.; Cruz-Irisson, M.; Oviedo-Roa, R.; Navarro, O.

    2014-05-15

    The electronic transport as well as the effect of an external magnetic field has been investigated on manganese-based materials, spinels and perovskites. Potential applications of double perovskites go from magnetic sensors to electrodes in solid-oxide fuel cells; besides the practical interests, it is known that small changes in composition modify radically the physical properties of double perovskites. We have studied the Sr{sub 2}FeMoO{sub 6} double perovskite compound (SFMO) using first-principles density functional theory. The calculations were done within the generalized gradient approximation (GGA) scheme with the Perdew-Burke-Ernzerhof (PBE) functional. We have made a detailed analysis of each electronic state and the charge density maps around the Fermi level. For the electronic properties of SFMO it was used a primitive cell, for which we found the characteristic half-metallic behavior density of states composed by e{sub g} and t{sub 2g} electrons from Fe and Mo atoms. Those peaks were tagged as bonding or antibonding around the Fermi level at both, valence and conduction bands.

  15. Hydrogen bonds and antiviral activity of benzaldehyde derivatives

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Belkov, M. V.; Shadyro, O. I.; Brinkevich, S. D.; Samovich, S. N.

    2012-09-01

    We have obtained the Fourier transform IR spectra of solutions of benzaldehyde derivatives having different antiviral activities against a herpes virus. We observe a correlation between the presence of hydrogen bonds in the benzaldehyde molecules and the appearance of antiviral properties in the compounds. For compounds having antiviral activity, we have obtained spectral data suggesting the existence of hydrogen bonds of the type C=OṡṡṡH-O and O-HṡṡṡO in the molecules. When the hydrogen atom in the hydroxyl groups are replaced by a methyl group, no intramolecular hydrogen bonds are formed and the compounds lose their antiviral activity.

  16. A search for thermal isomerization of olefins to carbenes: Thermal generations of the silicon-nitrogen double bond

    SciTech Connect

    Zhang, Xianping.

    1990-09-21

    The first part of this thesis will search for the thermal isomerization of olefins to carbenes which is predicted to be a high energy process by calculations and has only been observed in a few strained olefins. The possibility of thermal isomerization of simple olefins to carbenes will be explored. Substitution of a silyl group on the double bond of an olefin allows a potential intermediate which has a {beta}-radical to the silyl group during the cis-trans isomerization. The effects of a trimethylsilyl group on this isomerization are the subject of this study. The second part of this thesis will include the generation and chemistry of intermediates containing a silicon-nitrogen double bond. The isomerization of parent silanimine to the aminosilylene was calculated to be a high energy process. New approaches to the silicon-nitrogen double bond will also be presented. 92 refs., 12 figs., 11 tabs.

  17. Diffusion ordered spectroscopy for resolution of double bonded cis, trans-isomers

    NASA Astrophysics Data System (ADS)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-06-01

    NMR spectroscopic separation of double bonded cis- and trans-isomers, that have different molecular shapes but identical mass have been carried out using Diffusion Ordered Spectroscopy (DOSY). The mixtures of fumaric acid and maleic acid, that have similar hydrodynamic radii, have resolved been 'on the basis of their diffusion coefficients arising due to their different tendencies to associate with micelles or reverse micelles. Sodium dodecyl sulfate (SDS) and Dioctyl sulfosuccinate sodium salt (AOT) have been used as the media to mimic the chromatographic conditions, modify the average mobility and to achieve differential diffusion rates. The best separation of the components has been achieved by Dioctyl sulfosuccinate sodium salt (AOT) in D2O solution.

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

    PubMed

    Bidange, Johan; Fischmeister, Cédric; Bruneau, Christian

    2016-08-22

    Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross-metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon-carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications. PMID:27359344

  19. Can HN[double bond, length as m-dash]NH, FN[double bond, length as m-dash]NH, or HN[double bond, length as m-dash]CHOH bridge the σ-hole and the lone pair at P in binary complexes with H2XP, for X = F, Cl, NC, OH, CN, CCH, CH3, and H?

    PubMed

    Del Bene, Janet E; Alkorta, Ibon; Elguero, José

    2015-11-11

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the properties of complexes formed between H2XP, for X = F, Cl, NC, OH, CN, CCH, CH3, and H, and the possible bridging molecules HN[double bond, length as m-dash]NH, FN[double bond, length as m-dash]NH, and HN[double bond, length as m-dash]CHOH. H2XP:HNNH and H2XP:FNNH complexes are stabilized by PN pnicogen bonds, except for H2(CH3)P:FNNH and H3P:FNNH which are stabilized by N-HP hydrogen bonds. H2XP:HNCHOH complexes are stabilized by PN pnicogen bonds and nonlinear O-HP hydrogen bonds. For a fixed H2XP molecule, binding energies decrease in the order HNCHOH > HNNH > FNNH, except for the binding energies of H2(CH3)P and H3P with HNNH and FNNH. Binding energies of complexes with HNCHOH and HNNH increase as the P-N1 distance decreases, but binding energies of complexes with FNNH show little dependence on this distance. The large binding energies of H2XP:HNCHOH complexes arise from a cooperative effect involving electron-pair acceptance by P to form a pnicogen bond, and electron-pair donation by P to form a hydrogen bond. The dominant charge-transfer interaction in these complexes involves electron-pair donation by N across the pnicogen bond, except for complexes in which X is one of the more electropositive substituents, CCH, CH3, and H. For these, lone-pair donation by P across the hydrogen bond dominates. AIM and NBO data for these complexes are consistent with their bonding characteristics, showing molecular graphs with bond critical points and charge-transfer interactions associated with hydrogen and pnicogen bonds. EOM-CCSD spin-spin coupling constants (1p)J(P-N) across the pnicogen bond for each series of complexes correlate with the P-N distance. In contrast, (2h)J(O-P) values for complexes H2XP:HNCHOH do not correlate with the O-P distance, a consequence of the nonlinearity of these hydrogen bonds.

  20. Influence of chain length and double bond on the aqueous behavior of choline carboxylate soaps.

    PubMed

    Rengstl, Doris; Diat, Olivier; Klein, Regina; Kunz, Werner

    2013-02-26

    In preceding studies, we demonstrated that choline carboxylates ChC(m) with alkyl chain lengths of m = 12 - 18 are highly water-soluble (for m = 12, soluble up to 93 wt % soap and 0 °C). In addition, choline soaps are featured by an extraordinary lyotropic phase behavior. With decreasing water concentration, the following phases were found: micellar phase (L(1)), discontinuous cubic phase (I(1)' and I(1)"), hexagonal phase (H(1)), bicontinuous cubic phase (V(1)), and lamellar phase (L(α)). The present work is also focused on the lyotropic phase behavior of choline soaps but with shorter alkyl chains or different alkyl chain properties. We have investigated the aqueous phase behavior of choline soaps with C(8) and C(10) chain-lengths (choline octanoate and choline decanoate) and with a C(18) chain-length with a cis-double bond (choline oleate). We found that choline decanoate follows the lyotropic phase behavior of the longer-chain homologues mentioned above. Choline octanoate in water shows no discontinuous cubic phases, but an extended, isotropic micellar solution phase. In addition, choline octanoate is at the limit between a surfactant and a hydrotrope. The double bond in choline oleate leads also to a better solubility in water and a decrease of the solubilization temperature. It also influences the Gaussian curvature of the aggregates which results in a loss of discontinuous cubic phases in the binary phase diagram. The different lyotropic mesophases were identified by the penetration scan technique with polarizing light microscope and visual observations. To clarify the structural behavior small (SAXS) and wide (WAXS) angle X-ray scattering were performed. To further characterize the extended, isotropic micellar solution phase in the binary phase diagram of choline octanoate viscosity and conductivity measurements were also carried out.

  1. Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

    DOE PAGES

    Tian, Yong-Hui; Sumpter, Bobby G.; Du, Shiyu; Huang, Jingsong

    2015-06-03

    Phenalenyl is an important neutral pi-radical due to its capability to form unconventional pancake pi-pi bonding interactions, whereas its analogues with graphitic boron (B) or nitrogen (N)-doping have been regarded as closed-shell systems and therefore received much less attention. By using high-level quantum chemistry calculations, we also show that the B- and N-doped closed-shell phenalenyls unexpectedly form open-shell singlet pi-dimers with diradicaloid character featuring 2e/all-sites double pi-pi bonding. Moreover, by proper substitutions, the doped phenalenyl derivatives can be made open-shell species that form closed shell singlet pi-dimers bound by stronger 4e/all-sites double pi-pi bonding. Moreover, covalent pi-pi bonding overlap ismore » distributed on all of the atomic sites giving robust and genuine pancake-shaped pi-dimers which, depending on the number of electrons available in the bonding interactions, are equally or more stable than the pi-dimers of the pristine phenalenyl.« less

  2. Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

    SciTech Connect

    Tian, Yong-Hui; Sumpter, Bobby G.; Du, Shiyu; Huang, Jingsong

    2015-06-03

    Phenalenyl is an important neutral pi-radical due to its capability to form unconventional pancake pi-pi bonding interactions, whereas its analogues with graphitic boron (B) or nitrogen (N)-doping have been regarded as closed-shell systems and therefore received much less attention. By using high-level quantum chemistry calculations, we also show that the B- and N-doped closed-shell phenalenyls unexpectedly form open-shell singlet pi-dimers with diradicaloid character featuring 2e/all-sites double pi-pi bonding. Moreover, by proper substitutions, the doped phenalenyl derivatives can be made open-shell species that form closed shell singlet pi-dimers bound by stronger 4e/all-sites double pi-pi bonding. Moreover, covalent pi-pi bonding overlap is distributed on all of the atomic sites giving robust and genuine pancake-shaped pi-dimers which, depending on the number of electrons available in the bonding interactions, are equally or more stable than the pi-dimers of the pristine phenalenyl.

  3. The Mechanism of N-N Double Bond Cleavage by an Iron(II) Hydride Complex.

    PubMed

    Bellows, Sarina M; Arnet, Nicholas A; Gurubasavaraj, Prabhuodeyara M; Brennessel, William W; Bill, Eckhard; Cundari, Thomas R; Holland, Patrick L

    2016-09-21

    The use of hydride species for substrate reductions avoids strong reductants, and may enable nitrogenase to reduce multiple bonds without unreasonably low redox potentials. In this work, we explore the N═N bond cleaving ability of a high-spin iron(II) hydride dimer with concomitant release of H2. Specifically, this diiron(II) complex reacts with azobenzene (PhN═NPh) to perform a four-electron reduction, where two electrons come from H2 reductive elimination and the other two come from iron oxidation. The rate law of the H2 releasing reaction indicates that diazene binding occurs prior to H2 elimination, and the negative entropy of activation and inverse kinetic isotope effect indicate that H-H bond formation is the rate-limiting step. Thus, substrate binding causes reductive elimination of H2 that formally reduces the metals, and the metals use the additional two electrons to cleave the N-N multiple bond. PMID:27598037

  4. Effect of UVA-activated riboflavin on dentin bonding.

    PubMed

    Cova, A; Breschi, L; Nato, F; Ruggeri, A; Carrilho, M; Tjäderhane, L; Prati, C; Di Lenarda, R; Tay, F R; Pashley, D H; Mazzoni, A

    2011-12-01

    Recent studies have reported collagen cross-linking after exposure to riboflavin followed by ultraviolet-A (UVA) exposure. This study is the first to investigate the effect of a riboflavin-containing primer on adhesive interface stability and dentinal matrix metalloproteinase activity. Human dentin was etched with 35% phosphoric acid, treated with 0.1% riboflavin, exposed to UVA for 2 min, and bonded with a two-step etch-and-rinse adhesive. Adhesive was applied to control specimens without riboflavin/UVA. Specimens were subjected to microtensile bond strength tests and pulled to failure after storage for 24 hrs, 6 mos, or 1 yr. Interfacial nanoleakage was evaluated by light and transmission electron microscopy. To investigate dentinal matrix metalloproteinase activity, we performed correlative zymographic assays on protein extracts obtained from phosphoric-acid-etched dentin powder with or without riboflavin/UVA treatment and XP Bond. Ultraviolet-activated riboflavin treatment increased the immediate bond strength to dentin at all aging intervals (p < 0.05 vs. control) and decreased interfacial nanoleakage in aged specimens (1 yr; p < 0.05). Zymograms revealed that riboflavin/UVA pre-treatment inhibited dentinal matrix metalloproteinase activity (especially MMP-9). In conclusion, dentinal collagen cross-linking induced by riboflavin/UVA increased immediate bond strength, stabilized the adhesive interface, and inhibited dentin matrix metalloproteinases, thereby increasing the durability of resin-dentin bonds. PMID:21940521

  5. Changes in active site histidine hydrogen bonding trigger cryptochrome activation.

    PubMed

    Ganguly, Abir; Manahan, Craig C; Top, Deniz; Yee, Estella F; Lin, Changfan; Young, Michael W; Thiel, Walter; Crane, Brian R

    2016-09-01

    Cryptochrome (CRY) is the principal light sensor of the insect circadian clock. Photoreduction of the Drosophila CRY (dCRY) flavin cofactor to the anionic semiquinone (ASQ) restructures a C-terminal tail helix (CTT) that otherwise inhibits interactions with targets that include the clock protein Timeless (TIM). All-atom molecular dynamics (MD) simulations indicate that flavin reduction destabilizes the CTT, which undergoes large-scale conformational changes (the CTT release) on short (25 ns) timescales. The CTT release correlates with the conformation and protonation state of conserved His378, which resides between the CTT and the flavin cofactor. Poisson-Boltzmann calculations indicate that flavin reduction substantially increases the His378 pKa Consistent with coupling between ASQ formation and His378 protonation, dCRY displays reduced photoreduction rates with increasing pH; however, His378Asn/Arg variants show no such pH dependence. Replica-exchange MD simulations also support CTT release mediated by changes in His378 hydrogen bonding and verify other responsive regions of the protein previously identified by proteolytic sensitivity assays. His378 dCRY variants show varying abilities to light-activate TIM and undergo self-degradation in cellular assays. Surprisingly, His378Arg/Lys variants do not degrade in light despite maintaining reactivity toward TIM, thereby implicating different conformational responses in these two functions. Thus, the dCRY photosensory mechanism involves flavin photoreduction coupled to protonation of His378, whose perturbed hydrogen-bonding pattern alters the CTT and surrounding regions. PMID:27551082

  6. Three-Component Azidation of Styrene-Type Double Bonds: Light-Switchable Behavior of a Copper Photoredox Catalyst.

    PubMed

    Fumagalli, Gabriele; Rabet, Pauline T G; Boyd, Scott; Greaney, Michael F

    2015-09-21

    [Cu(dap)2]Cl effectively catalyzes azide addition from the Zhdankin reagent to styrene-type double bonds, and subsequent addition of a third component to the benzylic position. In the presence of light, a photoredox cycle is implicated with polar components such as methanol or bromide adding to a benzylic cation. In the absence of light, by contrast, double azidation takes place to give diazides. Therefore, regioselective double functionalization can be achieved in good to excellent yields, with a switch between light and dark controlling the degree of azidation.

  7. Three-Component Azidation of Styrene-Type Double Bonds: Light-Switchable Behavior of a Copper Photoredox Catalyst**

    PubMed Central

    Fumagalli, Gabriele; Rabet, Pauline T G; Boyd, Scott; Greaney, Michael F

    2015-01-01

    [Cu(dap)2]Cl effectively catalyzes azide addition from the Zhdankin reagent to styrene-type double bonds, and subsequent addition of a third component to the benzylic position. In the presence of light, a photoredox cycle is implicated with polar components such as methanol or bromide adding to a benzylic cation. In the absence of light, by contrast, double azidation takes place to give diazides. Therefore, regioselective double functionalization can be achieved in good to excellent yields, with a switch between light and dark controlling the degree of azidation. PMID:26119004

  8. Methandiide as a non-innocent ligand in carbene complexes: from the electronic structure to bond activation reactions and cooperative catalysis.

    PubMed

    Becker, Julia; Modl, Tanja; Gessner, Viktoria H

    2014-09-01

    The synthesis of a ruthenium carbene complex based on a sulfonyl-substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal-carbon interaction can be tuned between a Ru-C single bond with additional electrostatic interactions and a Ru=C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non-polar bonds (O-H, H-H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non-innocent ligand supporting the bond activation as nucleophilic center in the 1,2-addition across the metal-carbon double bond. This metal-ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis. PMID:25047390

  9. Methandiide as a non-innocent ligand in carbene complexes: from the electronic structure to bond activation reactions and cooperative catalysis.

    PubMed

    Becker, Julia; Modl, Tanja; Gessner, Viktoria H

    2014-09-01

    The synthesis of a ruthenium carbene complex based on a sulfonyl-substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal-carbon interaction can be tuned between a Ru-C single bond with additional electrostatic interactions and a Ru=C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non-polar bonds (O-H, H-H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non-innocent ligand supporting the bond activation as nucleophilic center in the 1,2-addition across the metal-carbon double bond. This metal-ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis.

  10. Bent Bonds and Multiple Bonds.

    ERIC Educational Resources Information Center

    Robinson, Edward A.; Gillespie, Ronald J.

    1980-01-01

    Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

  11. The unexpected mechanism of carbonyl hydrosilylation catalyzed by (Cp)(ArN[double bond, length as m-dash])Mo(H)(PMe(3)).

    PubMed

    Shirobokov, Oleg G; Gorelsky, Serge I; Simionescu, Razvan; Kuzmina, Lyudmila G; Nikonov, Georgii I

    2010-11-01

    Complex (Cp)(ArN[double bond, length as m-dash])Mo(H)(PMe(3)) (2, Ar = 2,6-diisopropylphenyl) catalyzes the hydrosilylation of carbonyls by an unexpected associative mechanism. Complex 2 also reacts with PhSiH(3) by a σ-bond metathesis mechanism to give the silyl derivative (Cp)(ArN[double bond, length as m-dash])Mo(SiH(2)Ph)(PMe(3)).

  12. Bonding techniques for hybrid active pixel sensors (HAPS)

    NASA Astrophysics Data System (ADS)

    Bigas, M.; Cabruja, E.; Lozano, M.

    2007-05-01

    A hybrid active pixel sensor (HAPS) consists of an array of sensing elements which is connected to an electronic read-out unit. The most used way to connect these two different devices is bump bonding. This interconnection technique is very suitable for these systems because it allows a very fine pitch and a high number of I/Os. However, there are other interconnection techniques available such as direct bonding. This paper, as a continuation of a review [M. Lozano, E. Cabruja, A. Collado, J. Santander, M. Ullan, Nucl. Instr. and Meth. A 473 (1-2) (2001) 95-101] published in 2001, presents an update of the different advanced bonding techniques available for manufacturing a hybrid active pixel detector.

  13. Localization of double bonds in wax esters by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry utilizing the fragmentation of acetonitrile-related adducts.

    PubMed

    Vrkoslav, Vladimír; Háková, Martina; Pecková, Karolina; Urbanová, Klára; Cvačka, Josef

    2011-04-15

    Unsaturated wax esters (WEs) provided molecular adducts with C(3)H(5)N ([M + 55](+•)) in APCI sources in the presence of acetonitrile. CID MS/MS of [M + 55](+•) yielded fragments allowing the localization of double bond(s) in the hydrocarbon chains of the WEs. These fragments were formed by a cleavage on each side of the double bond. In methylene-interrupted polyunsaturated WEs, diagnostic fragments related to each double bond were detected; the most abundant were those corresponding to the cleavage of the C-C bond next to the first and the last double bond. To differentiate between those fragments differing in their structure or origin, a simple nomenclature based on α and ω ions has been introduced. Fragmentation of the α-type ions (fragments containing an ester bond) provided information on the occurrence of a double bond in the acid or alcohol part of the WEs. While no significant differences between the spectra of the WEs differing by cis/trans isomerism were found, the isomers were separated chromatographically. A data-dependent HPLC/APCI-MS(2) method for the comprehensive characterization of WEs in their complex mixtures has been developed and applied to natural mixtures of WEs isolated from jojoba oil and beeswax. More than 50 WE molecular species were completely identified, including the information on the acid and alcohol chain length and the position of the double bonds.

  14. THE PROTOTYPE ALUMINUM - CARBON SINGLE, DOUBLE, AND TRIPLE BONDS: Al - CH3, Al = CH2, AND Al. = CH

    SciTech Connect

    Fox, Douglas J.; Ray, Douglas; Rubesin, Philip C.; Schaefer III, Henry F.

    1980-06-01

    Nonempirical quantum mechanical methods have been used to investigate the A{ell}CH{sub 3}, A{ell}CH{sub 2}, and A{ell}CH molecules, which may be considered to represent the simplest aluminum-carbon single, double, and triple bonds. Equilibrium geometries and vibrational frequencies were determined at the self-consistent-field level of theory using double zeta basis set: A{ell}(11s7p/6s4p), C(9s5p/4s2p), H(4s/2s). The {sup 1}A{sub 1} ground state of A{ell}CH{sub 3} has a reasonably conventional A{ell}-C single bond of length 2.013 {angstrom}, compared to 1.96 {angstrom} in the known molecule A{ell}(CH{sub 3}){sub 3}. The CH equilibrium distance is 1.093 {angstrom} and the A{ell}-C-H angle 111.9{sup o}. The structures of three electron states each of A{ell}CH{sub 2} and A{ell}CH were similarly predicted, The interesting result is that the ground state of A{ell}CH{sub 2} does not contain an A{ell}-C double bond, and the ground state of A{ell}CH is not characterized by an A{ell}{triple_bond}C bond. The multiply-bonded electronic states do exist but they lie 21 kcal (A{ell}CH{sub 2}) and 86 kcal (A{ell}CH) above the respective ground states. The dissociation energies of the three ground electronic states are predicted to be 68 kcal (A{ell}CH{sub 3}), 77 kcal (A{ell}CH{sub 2}), and 88 kcal (A{ell}CH), Vibrational frequencies are also predicted for the three molecules, and their electronic structures are discussed with reference to Mulliken populations and dipole moments.

  15. Fabrication of extremely thermal-stable GaN template on Mo substrate using double bonding and step annealing process

    NASA Astrophysics Data System (ADS)

    Qing, Wang; Yang, Liu; Yongjian, Sun; Yuzhen, Tong; Guoyi, Zhang

    2016-08-01

    A new layer transfer technique which comprised double bonding and a step annealing process was utilized to transfer the GaN epilayer from a sapphire substrate to a Mo substrate. Combined with the application of the thermal-stable bonding medium, the resulting two-inch-diameter GaN template showed extremely good stability under high temperature and low stress state. Moreover, no cracks and winkles were observed. The transferred GaN template was suitable for homogeneous epitaxial, thus could be used for the direct fabrication of vertical LED chips as well as power electron devices. It has been confirmed that the double bonding and step annealing technique together with the thermal-stable bonding layer could significantly improve the bonding strength and stress relief, finally enhancing the thermal stability of the transferred GaN template. Project supported by the Guangdong Innovative Research Team Program (No. 2009010044), the China Postdoctoral Science Foundation (No. 2014M562233), the National Natural Science Foundation of Guangdong, China (No. 2015A030312011), and the Opened Fund of the State Key Laboratory on Integrated Optoelectronics (No. IOSKL2014KF17).

  16. Double Pancake Versus Long Chalcogen-Chalcogen Bonds in Six-Membered C,N,S-Heterocycles.

    PubMed

    Haberhauer, Gebhard; Gleiter, Rolf

    2016-06-13

    The double "pancake" bonding in the dimers of the six-membered heterocycles 1,3-dithia-2,4,6-triazine (4) and 1,3-dithia-2,4-diazine (16) were investigated by means of high-level quantum chemical calculations (B3LYP and CCSD(T)). It was found that the S-S dimers, 20 a and 27, are not the most stable isomers, but the dimers showing short S-N (21 a) and S-C (25, 28) bonds. An investigation of the 5-phenyl-1,3-dithia-2,4,6-triazine (4 b) yields that the syn dimer with two S-S bonds (2.57 Å) is the most stable one. In this dimer, the phenyl groups are placed on top of each other. The additional dispersion energy of the phenyl rings causes a stabilization of the syn-S-S (C2v -like) isomer. As a result, two weak albeit relevant single S-S bonds (2.57 Å) are predicted. These findings contradict the recently published concept of double "pancake" bonding in the dimer 4 b2 .

  17. Selenium bond decreases ON resistance of light-activated switch

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Vitrified amorphous selenium bond decreases the ON resistance of a gallium arsenide-silicon light-activated, low-level switch. The switch is used under a pulse condition to prolong switch life and minimize errors due to heating, devitrification, and overdrawing.

  18. Double CO2 activation by 14-electron η(8)-permethylpentalene titanium dialkyl complexes.

    PubMed

    Cooper, Robert T; Chadwick, F Mark; Ashley, Andrew E; O'Hare, Dermot

    2015-07-28

    The novel 14 electron species η(8)-Pn*TiR2 (Pn* = C8Me6; R = Me, CH2Ph) have been synthesised and spectroscopically and structurally characterised. Subsequent reaction with CO2 leads to the activation and double insertion of CO2 into both Ti-alkyl bonds to form the electronically saturated η(8)-Pn*Ti(κ(2)-O2CR)2 (R = Me, CH2Ph) complexes.

  19. C-H bond activation by f-block complexes.

    PubMed

    Arnold, Polly L; McMullon, Max W; Rieb, Julia; Kühn, Fritz E

    2015-01-01

    Most homogeneous catalysis relies on the design of metal complexes to trap and convert substrates or small molecules to value-added products. Organometallic lanthanide compounds first gave a tantalizing glimpse of their potential for catalytic C-H bond transformations with the selective cleavage of one C-H bond in methane by bis(permethylcyclopentadienyl)lanthanide methyl [(η(5) -C5 Me5 )2 Ln(CH3 )] complexes some 25 years ago. Since then, numerous metal complexes from across the periodic table have been shown to selectively activate hydrocarbon C-H bonds, but the challenges of closing catalytic cycles still remain; many f-block complexes show great potential in this important area of chemistry.

  20. C-H bond activation by f-block complexes.

    PubMed

    Arnold, Polly L; McMullon, Max W; Rieb, Julia; Kühn, Fritz E

    2015-01-01

    Most homogeneous catalysis relies on the design of metal complexes to trap and convert substrates or small molecules to value-added products. Organometallic lanthanide compounds first gave a tantalizing glimpse of their potential for catalytic C-H bond transformations with the selective cleavage of one C-H bond in methane by bis(permethylcyclopentadienyl)lanthanide methyl [(η(5) -C5 Me5 )2 Ln(CH3 )] complexes some 25 years ago. Since then, numerous metal complexes from across the periodic table have been shown to selectively activate hydrocarbon C-H bonds, but the challenges of closing catalytic cycles still remain; many f-block complexes show great potential in this important area of chemistry. PMID:25384554

  1. Infrared Spectra and Hydrogen Bonds of Biologically Active Benzaldehydes

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Belkov, M. V.; Shimko, A. N.; Shadyro, O. I.; Brinkevich, S. D.; Samovich, S. N.

    2013-09-01

    IR-Fourier spectra of solutions and crystals of biologically active benzaldehyde derivatives were studied. Specific features of the formation of intra- and intermolecular hydrogen bonds were analyzed. Spectral signatures that characterized participation of the hydroxyl OH group and also the OCH3 and C=O groups in the formation of intramolecular hydrogen bonds of the three different types O-H···O-H, O-H···O-CH3, and O-H···O=C were revealed. Intramolecular hydrogen bonds of the types O-H···O-H and O-H···O-CH3 were absent for benzaldehyde derivatives in the crystal phase. Only hydroxyl and carbonyl groups participated in intermolecular interactions. This resulted in the formation of linear intermolecular dimers. Seven various configurations of the linear dimers were identified in solutions and crystals.

  2. Transition Metals Catalyzed Element-Cyano Bonds Activations

    PubMed Central

    Wang, Rui; Falck, John R.

    2014-01-01

    Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation. PMID:25558119

  3. Competitive Low Pressure Oxygen Plasma Interactions with Different= Carbon-Carbon Double Bonds

    NASA Astrophysics Data System (ADS)

    Patiño, P.; Sifontes, A.; Gambús, G.

    1999-10-01

    Recently we have shown advances from reactions of O(^3P) with both, l ong-chain hydrocarbons and refinery residuum. The oxidation products of t he process, a mixture of alcohols, epoxides and carbonyl compounds, might have potential properties as additives in formulating fuels. This work s hows the results of the interactions of an oxygen plasma with double bond s, both olefin and aromatic, in the same compound. The reactions have bee n carried out by making the plasma, created by a high voltage glow discha rge, reach the low vapor pressure surface of liquid 4-phenyl-1-butene. Th is (3 mL) was cooled down to -45 ^oC in a glass reactor, applied power was 24 W, at an oxygen pressure of 20 Pa. Products were analyzed by IR, N MR and mass spectroscopies. Conversions were studied as a function of the reaction time, this ranging from 5 to 120 minutes. At short times the O( ^3P) atoms produced in the discharge only reacted with the alkene fra ction of the hydrocarbon, 4-phenyl-1,2-epoxibutane (52%) and 4-phenyl-bu tanal (48%) being the products. Reactions on the benzene ring were obser ved from about 30 minutes on, the corresponding phenols having being prod uced at ratios ortho:para:meta :: 4:1:0.7. At 120 minutes, the ol efin have been completely oxidized and a low fraction of the non-equivale nt two methylene groups have reacted to produce alcohols and ketones.

  4. Bis(pentalene)di-titanium: a bent double-sandwich complex with a very short Ti-Ti bond.

    PubMed

    Kilpatrick, Alexander F R; Green, Jennifer C; Cloke, F Geoffrey N; Tsoureas, Nikolaos

    2013-10-21

    The novel bimetallic bis(pentalene) complex Ti2(μ:η(5),η(5)-Pn(†))2 (Pn(†) = C8H4{Si(i)Pr3-1,4}2) has been synthesised and structurally characterised. Structural data show a Ti-Ti distance of 2.399(2) Å, consistent with a strong metal-metal interaction, which DFT calculations best describe as a double bond with σ and π components.

  5. Dynamic covalent bond based on reversible photo [4 + 4] cycloaddition of anthracene for construction of double-dynamic polymers.

    PubMed

    Xu, Jiang-Fei; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

    2013-12-20

    Dynamic covalent bonds supplied by reversible anthracene dimerization were combined with pillar[5]arene/imidazole host-guest interactions to construct double-dynamic polymers. Heating such polymers (in solution or as a gel) led to depolymerization by dissociation of either the host-guest complexes alone or the complexes and the anthracene dimers, depending on the extent of heating. The polymers reformed readily upon cooling or irradiation.

  6. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

    PubMed Central

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-01-01

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen. PMID:25902034

  7. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds.

    PubMed

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-04-22

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

  8. Functionalization of the benzobicyclo[3.2.1] octadiene skeleton possessing one isolated double bond via photocatalytic oxygenation

    NASA Astrophysics Data System (ADS)

    Vuk, Dragana; Horváth, Ottó; Marinić, Željko; Škorić, Irena

    2016-03-01

    Photocatalytic oxygenation of three phenyl derivatives of a bicyclic skeleton with a free double bond 1a, 1b and 1c were carried out by utilizing a cationic and an anionic manganese(III) porphyrin irradiated in the visible range. While photocatalysis of 1a and 1b led to the formation of the corresponding hydroperoxy derivatives 2 and 3, respectively, (besides unidentified high-molecular-weight products) in the presence of the anionic Mn(III) porphyrin, the cationic photocatalyst proved to be less efficient and less selective with 1a. In the case of 1b, also with the cationic porphyrin, the corresponding hydroperoxy derivative (3) was the main product at a shorter reaction time (2 h), whereas a longer irradiation (4 h) led to the significant formation of a keto derivative (5) with a hydroperoxy substituent and a free double bond at positions deviating from those in the previous products (2 and 3). A dramatic change in the reactivity was observed for the methoxy derivative (1c). It gave only traces of identifiable products by using the anionic photocatalyst, while application of the cationic Mn(III) porphyrin resulted in a relatively efficient formation of an epoxy derivative (6) due to the reaction of the isolated double bond.

  9. Fracture Analysis of Double-Side Adhesively Bonded Composite Repairs to Cracked Aluminium Plate Using Line Spring Model

    NASA Astrophysics Data System (ADS)

    Niu, Yong; Su, Weiguo

    2016-06-01

    A line spring model is developed for analyzing the fracture problem of cracked metallic plate repaired with the double-sided adhesively bonded composite patch. The restraining action of the bonded patch is modeled as continuous distributed linear springs bridging the crack faces provided that the cracked plate is subjected to extensional load. The effective spring constant is determined from 1-D bonded joint theory. The hyper-singular integral equation (HSIE), which can be solved using the second kind Chebyshev polynomial expansion method, is applied to determine the crack opening displacements (COD) and the crack tip stress intensity factors (SIF) of the repaired cracked plate. The numerical result of SIF for the crack-tip correlates very well with the finite element (FE) computations based on the virtual crack closure technique (VCCT). The present analysis approaches and mathematical techniques are critical to the successful design, analysis and implementation of crack patching.

  10. Latex Clearing Protein—an Oxygenase Cleaving Poly(cis-1,4-Isoprene) Rubber at the cis Double Bonds

    PubMed Central

    Hiessl, Sebastian; Böse, Dietrich; Oetermann, Sylvia; Eggers, Jessica; Pietruszka, Jörg

    2014-01-01

    Gordonia polyisoprenivorans strain VH2, a potent rubber-degrading actinomycete, harbors two latex clearing proteins (Lcps), which are known to be essential for the microbial degradation of rubber. However, biochemical information on the exact role of this protein in the degradation of polyisoprene was lacking. In this study, the gene encoding Lcp1VH2 was heterologously expressed in strains of Escherichia coli, the corresponding protein was purified, and its role in rubber degradation was examined by measurement of oxygen consumption as well as by chromatographic and spectroscopic methods. It turned out that active Lcp1VH2 is a monomer and is responsible for the oxidative cleavage of poly(cis-1,4-isoprene) in synthetic as well as in natural rubber by the addition of oxygen (O2) to the cis double bonds. The resulting oligomers possess repetitive isoprene units with aldehyde (CHO-CH2—) and ketone (—CH2-CO-CH3) functional groups at the termini. Two fractions with average isoprene contents of 18 and 10, respectively, were isolated, thus indicating an endocleavage mechanism. The activity of Lcp1VH2 was determined by applying a polarographic assay. Alkenes, acyclic terpenes, or other rubber-like polymers, such as poly(cis-1,4-butadiene) or poly(trans-1,4-isoprene), are not oxidatively cleaved by Lcp1VH2. The pH and temperature optima of the enzyme are at pH 7 and 30°C, respectively. Furthermore, it was demonstrated that active Lcp1VH2 is a Cu(II)-containing oxygenase that exhibits a conserved domain of unknown function which cannot be detected in any other hitherto-characterized enzyme. The results presented here indicate that this domain might represent a new protein family of oxygenases. PMID:24928880

  11. Latex clearing protein-an oxygenase cleaving poly(cis-1,4-isoprene) rubber at the cis double bonds.

    PubMed

    Hiessl, Sebastian; Böse, Dietrich; Oetermann, Sylvia; Eggers, Jessica; Pietruszka, Jörg; Steinbüchel, Alexander

    2014-09-01

    Gordonia polyisoprenivorans strain VH2, a potent rubber-degrading actinomycete, harbors two latex clearing proteins (Lcps), which are known to be essential for the microbial degradation of rubber. However, biochemical information on the exact role of this protein in the degradation of polyisoprene was lacking. In this study, the gene encoding Lcp1VH2 was heterologously expressed in strains of Escherichia coli, the corresponding protein was purified, and its role in rubber degradation was examined by measurement of oxygen consumption as well as by chromatographic and spectroscopic methods. It turned out that active Lcp1VH2 is a monomer and is responsible for the oxidative cleavage of poly(cis-1,4-isoprene) in synthetic as well as in natural rubber by the addition of oxygen (O2) to the cis double bonds. The resulting oligomers possess repetitive isoprene units with aldehyde (CHO-CH2-) and ketone (-CH2-CO-CH3) functional groups at the termini. Two fractions with average isoprene contents of 18 and 10, respectively, were isolated, thus indicating an endocleavage mechanism. The activity of Lcp1VH2 was determined by applying a polarographic assay. Alkenes, acyclic terpenes, or other rubber-like polymers, such as poly(cis-1,4-butadiene) or poly(trans-1,4-isoprene), are not oxidatively cleaved by Lcp1VH2. The pH and temperature optima of the enzyme are at pH 7 and 30°C, respectively. Furthermore, it was demonstrated that active Lcp1VH2 is a Cu(II)-containing oxygenase that exhibits a conserved domain of unknown function which cannot be detected in any other hitherto-characterized enzyme. The results presented here indicate that this domain might represent a new protein family of oxygenases.

  12. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cvačka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa.

  13. Carbon-nitrogen bond construction and carbon-oxygen double bond cleavage on a molecular titanium oxonitride: a combined experimental and computational study.

    PubMed

    Carbó, Jorge J; García-López, Diego; González-Del Moral, Octavio; Martín, Avelino; Mena, Miguel; Santamaría, Cristina

    2015-10-01

    New carbon-nitrogen bonds were formed on addition of isocyanide and ketone reagents to the oxonitride species [{Ti(η(5)-C5Me5)(μ-O)}3(μ3-N)] (1). Reaction of 1 with XylNC (Xyl = 2,6-Me2C6H3) in a 1:3 molar ratio at room temperature leads to compound [{Ti(η(5)-C5Me5)(μ-O)}3(μ-XylNCCNXyl)(NCNXyl)] (2), after the addition of the nitrido group to one coordinated isocyanide and the carbon-carbon coupling of the other two isocyanide molecules have taken place. Thermolysis of 2 gives [{Ti(η(5)-C5Me5)(μ-O)}3(XylNCNXyl)(CN)] (3) where the heterocumulene [XylNCCNXyl] moiety and the carbodiimido [NCNXyl] fragment in 2 have undergone net transformations. Similarly, tert-butyl isocyanide (tBuNC) reacts with the starting material 1 under mild conditions to give the paramagnetic derivative [{Ti3(η(5)-C5Me5)3(μ-O)3(NCNtBu)}2(μ-CN)2] (4). However, compound 1 provides the oxo ketimide derivatives [{Ti3(η(5)-C5Me5)3(μ-O)4}(NCRPh)] [R = Ph (5), p-Me(C6H4) (6), o-Me(C6H4) (7)] upon reaction with benzophenone, p-methylbenzophenone, and o-methylbenzophenone, respectively. In these reactions, the carbon-oxygen double bond is completely ruptured, leading to the formation of a carbon-nitrogen and two metal-oxygen bonds. The molecular structures of complexes 2-4, 6, and 7 were determined by single-crystal X-ray diffraction analyses. Density functional theory calculations were performed on the incorporation of isocyanides and ketones to the model complex [{Ti(η(5)-C5H5)(μ-O)}3(μ3-N)] (1H). The mechanism involves the coordination of the substrates to one of the titanium metal centers, followed by an isomerization to place those substrates cis with respect to the apical nitrogen of 1H, where carbon-nitrogen bond formation occurs with a low-energy barrier. In the case of aryl isocyanides, the resulting complex incorporates additional isocyanide molecules leading to a carbon-carbon coupling. With ketones, the high oxophilicity of titanium promotes the unusual total cleavage of the

  14. Carbon-nitrogen bond construction and carbon-oxygen double bond cleavage on a molecular titanium oxonitride: a combined experimental and computational study.

    PubMed

    Carbó, Jorge J; García-López, Diego; González-Del Moral, Octavio; Martín, Avelino; Mena, Miguel; Santamaría, Cristina

    2015-10-01

    New carbon-nitrogen bonds were formed on addition of isocyanide and ketone reagents to the oxonitride species [{Ti(η(5)-C5Me5)(μ-O)}3(μ3-N)] (1). Reaction of 1 with XylNC (Xyl = 2,6-Me2C6H3) in a 1:3 molar ratio at room temperature leads to compound [{Ti(η(5)-C5Me5)(μ-O)}3(μ-XylNCCNXyl)(NCNXyl)] (2), after the addition of the nitrido group to one coordinated isocyanide and the carbon-carbon coupling of the other two isocyanide molecules have taken place. Thermolysis of 2 gives [{Ti(η(5)-C5Me5)(μ-O)}3(XylNCNXyl)(CN)] (3) where the heterocumulene [XylNCCNXyl] moiety and the carbodiimido [NCNXyl] fragment in 2 have undergone net transformations. Similarly, tert-butyl isocyanide (tBuNC) reacts with the starting material 1 under mild conditions to give the paramagnetic derivative [{Ti3(η(5)-C5Me5)3(μ-O)3(NCNtBu)}2(μ-CN)2] (4). However, compound 1 provides the oxo ketimide derivatives [{Ti3(η(5)-C5Me5)3(μ-O)4}(NCRPh)] [R = Ph (5), p-Me(C6H4) (6), o-Me(C6H4) (7)] upon reaction with benzophenone, p-methylbenzophenone, and o-methylbenzophenone, respectively. In these reactions, the carbon-oxygen double bond is completely ruptured, leading to the formation of a carbon-nitrogen and two metal-oxygen bonds. The molecular structures of complexes 2-4, 6, and 7 were determined by single-crystal X-ray diffraction analyses. Density functional theory calculations were performed on the incorporation of isocyanides and ketones to the model complex [{Ti(η(5)-C5H5)(μ-O)}3(μ3-N)] (1H). The mechanism involves the coordination of the substrates to one of the titanium metal centers, followed by an isomerization to place those substrates cis with respect to the apical nitrogen of 1H, where carbon-nitrogen bond formation occurs with a low-energy barrier. In the case of aryl isocyanides, the resulting complex incorporates additional isocyanide molecules leading to a carbon-carbon coupling. With ketones, the high oxophilicity of titanium promotes the unusual total cleavage of the

  15. Effect of temperature and duration of post-cure on in vitro wear and quantity of remaining double bonds of resins containing carboxylic anhydride.

    PubMed

    Peutzfeldt, A

    1995-08-01

    The present study determined the effect of post-cure temperature and duration on in vitro wear resistance and quantity of remaining double bonds of anhydride-containing resins. Temperatures were varied between 37 degrees C and 225 degrees C, and durations were varied between 0 and 24 h. The quantity of remaining double bonds could not be established for post-cure temperatures of 200 degrees C or more due to melting of the polymer. A temperature of approximately 120 degrees C had optimal effect on wear resistance. Quantity of remaining double bonds and wear were found to decrease with increasing duration of post-cure. Low quantities of remaining double bonds were generally associated with low in vitro wear.

  16. Antibacterial activity and ion release of bonding agent containing amorphous calcium phosphate nanoparticles

    PubMed Central

    Chen, Chen; Weir, Michael D.; Cheng, Lei; Lin, Nancy; Lin-Gibson, Sheng; Chow, Laurence C.; Zhou, Xuedong; Xu, Hockin H. K.

    2015-01-01

    Objectives Recurrent caries at the margins is a primary reason for restoration failure. The objectives of this study were to develop bonding agent with the double benefits of antibacterial and remineralizing capabilities, to investigate the effects of NACP filler level and solution pH on Ca and P ion release from adhesive, and to examine the antibacterial and dentin bond properties. Methods Nanoparticles of amorphous calcium phosphate (NACP) and a quaternary ammonium monomer (dimethylaminododecyl methacrylate, DMADDM) were synthesized. Scotchbond Multi-Purpose (SBMP) primer and adhesive served as control. DMADDM was incorporated into primer and adhesive at 5% by mass. NACP was incorporated into adhesive at filler mass fractions of 10%, 20%, 30% and 40%. A dental plaque microcosm biofilm model was used to test the antibacterial bonding agents. Calcium (Ca) and phosphate (P) ion releases from the cured adhesive samples were measured vs. filler level and solution pH of 7, 5.5 and 4. Results Adding 5% DMADDM and 10–40% NACP into bonding agent, and water-aging for 28 days, did not affect dentin bond strength, compared to SBMP control at 1 day (p > 0.1). Adding DMADDM into bonding agent substantially decreased the biofilm metabolic activity and lactic acid production. Total microorganisms, total streptococci, and mutans streptococci were greatly reduced for bonding agents containing DMADDM. Increasing NACP filler level from 10% to 40% in adhesive increased the Ca and P ion release by an order of magnitude. Decreasing solution pH from 7 to 4 increased the ion release from adhesive by 6–10 folds. Significance Bonding agents containing antibacterial DMADDM and remineralizer NACP were formulated to have Ca and P ion release, which increased with NACP filler level from 10% to 40% in adhesive. NACP adhesive was “smart” and dramatically increased the ion release at cariogenic pH 4, when these ions would be most-needed to inhibit caries. Therefore, bonding agent

  17. Activation of C-H and B-H bonds through agostic bonding: an ELF/QTAIM insight.

    PubMed

    Zins, Emilie-Laure; Silvi, Bernard; Alikhani, M Esmaïl

    2015-04-14

    Agostic bonding is of paramount importance in C-H bond activation processes. The reactivity of the σ C-H bond thus activated will depend on the nature of the metallic center, the nature of the ligand involved in the interaction and co-ligands, as well as on geometric parameters. Because of their importance in organometallic chemistry, a qualitative classification of agostic bonding could be very much helpful. Herein we propose descriptors of the agostic character of bonding based on the electron localization function (ELF) and Quantum Theory of Atoms in Molecules (QTAIM) topological analysis. A set of 31 metallic complexes taken, or derived, from the literature was chosen to illustrate our methodology. First, some criteria should prove that an interaction between a metallic center and a σ X-H bond can indeed be described as "agostic" bonding. Then, the contribution of the metallic center in the protonated agostic basin, in the ELF topological description, may be used to evaluate the agostic character of bonding. A σ X-H bond is in agostic interaction with a metal center when the protonated X-H basin is a trisynaptic basin with a metal contribution strictly larger than the numerical uncertainty, i.e. 0.01 e. In addition, it was shown that the weakening of the electron density at the X-Hagostic bond critical point with respect to that of X-Hfree well correlates with the lengthening of the agostic X-H bond distance as well as with the shift of the vibrational frequency associated with the νX-H stretching mode. Furthermore, the use of a normalized parameter that takes into account the total population of the protonated basin, allows the comparison of the agostic character of bonding involved in different complexes. PMID:25760795

  18. Tissue factor activation: is disulfide bond switching a regulatory mechanism?

    PubMed Central

    Ghosh, Samit; Mandal, Samir K.

    2007-01-01

    A majority of tissue factor (TF) on cell surfaces exists in a cryptic form (ie, coagulation function inactive) but retains its functionality in cell signaling. Recent studies have suggested that cryptic TF contains unpaired cysteine thiols and that activation involves the formation of the disulfide bond Cys186-Cys 209 and that protein disulfide isomerase (PDI) regulates TF coagulant and signaling activities by targeting this disulfide bond. This study was carried out to investigate the validity of this novel concept. Although treatment of MDA 231 tumor cells, fibroblasts, and stimulated endothelial cells with the oxidizing agent HgCl2 markedly increased the cell-surface TF coagulant activity, the increase is associated with increased anionic phospholipids at the cell surface. Annexin V, which binds to anionic phospholipids, attenuated the increased TF coagulant activity. It is noteworthy that treatment of cells with reducing agents also increased the cell surface TF activity. No evidence was found for either detectable expression of PDI at the cell surface or association of TF with PDI. Furthermore, reduction of PDI with the gene silencing had no effect on either TF coagulant or cell signaling functions. Overall, the present data undermine the recently proposed hypothesis that PDI-mediated disulfide exchange plays a role in regulating TF procoagulant and cell signaling functions. PMID:17726162

  19. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... the term “student loan bond.” There are five exceptions to the general definition of the term “private... apply to obligations issued to refund a prior issue of student loan bonds? A-14: In the case of...

  20. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... the term “student loan bond.” There are five exceptions to the general definition of the term “private... apply to obligations issued to refund a prior issue of student loan bonds? A-14: In the case of...

  1. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... the term “student loan bond.” There are five exceptions to the general definition of the term “private... apply to obligations issued to refund a prior issue of student loan bonds? A-14: In the case of...

  2. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... the term “student loan bond.” There are five exceptions to the general definition of the term “private... apply to obligations issued to refund a prior issue of student loan bonds? A-14: In the case of...

  3. 26 CFR 1.103(n)-2T - Private activity bond defined (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... activity bond” means any industrial development bond or student loan bond the interest on which is exempt... the term “student loan bond.” There are five exceptions to the general definition of the term “private... apply to obligations issued to refund a prior issue of student loan bonds? A-14: In the case of...

  4. Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage.

    PubMed

    Svitova, A L; Ghiassi, K B; Schlesier, C; Junghans, K; Zhang, Y; Olmstead, M M; Balch, A L; Dunsch, L; Popov, A A

    2014-01-01

    In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu2C@I(h)-C80 with an icosahedral Ih(7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a μ3-carbido ligand and Ti-C double bond. The Ti(IV) in TiLu2C@I(h)-C80 can be reversibly reduced to the Ti(III) state. The Ti = C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu2C@Ih-C80 bear a certain resemblance to titanium alkylidenes. TiLu2C@I(h)-C80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster.

  5. Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage.

    PubMed

    Svitova, A L; Ghiassi, K B; Schlesier, C; Junghans, K; Zhang, Y; Olmstead, M M; Balch, A L; Dunsch, L; Popov, A A

    2014-01-01

    In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu2C@I(h)-C80 with an icosahedral Ih(7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a μ3-carbido ligand and Ti-C double bond. The Ti(IV) in TiLu2C@I(h)-C80 can be reversibly reduced to the Ti(III) state. The Ti = C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu2C@Ih-C80 bear a certain resemblance to titanium alkylidenes. TiLu2C@I(h)-C80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster. PMID:24699547

  6. Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions

    PubMed Central

    Chen, Jianzhong; Green, Kari B; Nichols, Kelly K

    2015-01-01

    A series of different types of wax esters (represented by RCOOR′) were systematically studied by using electrospray ionization (ESI) collision-induced dissociation tandem mass spectrometry (MS/MS) along with pseudo MS3 (in-source dissociation combined with MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer. The tandem mass spectra patterns resulting from dissociation of ammonium/proton adducts of these wax esters were influenced by the wax ester type and the collision energy applied. The product ions [RCOOH2]+, [RCO]+ and [RCO – H2O]+ that have been reported previously were detected; however, different primary product ions were demonstrated for the three wax ester types including: 1) [RCOOH2]+ for saturated wax esters, 2) [RCOOH2]+, [RCO]+ and [RCO – H2O]+ for unsaturated wax esters containing only one double bond in the fatty acid moiety or with one additional double bond in the fatty alcohol moiety, and 3) [RCOOH2]+ and [RCO]+ for unsaturated wax esters containing a double bond in the fatty alcohol moiety alone. Other fragments included [R′]+ and several series of product ions for all types of wax esters. Interestingly, unusual product ions were detected, such as neutral molecule (including water, methanol and ammonia) adducts of [RCOOH2]+ ions for all types of wax esters and [R′ – 2H]+ ions for unsaturated fatty acyl-containing wax esters. The patterns of tandem mass spectra for different types of wax esters will inform future identification and quantification approaches of wax esters in biological samples as supported by a preliminary study of quantification of isomeric wax esters in human meibomian gland secretions. PMID:26178197

  7. Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions.

    PubMed

    Chen, Jianzhong; Green, Kari B; Nichols, Kelly K

    2015-08-01

    A series of different types of wax esters (represented by RCOOR') were systematically studied by using electrospray ionization (ESI) collision-induced dissociation tandem mass spectrometry (MS/MS) along with pseudo MS(3) (in-source dissociation combined with MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer. The tandem mass spectra patterns resulting from dissociation of ammonium/proton adducts of these wax esters were influenced by the wax ester type and the collision energy applied. The product ions [RCOOH2](+), [RCO](+) and [RCO-H2O](+) that have been reported previously were detected; however, different primary product ions were demonstrated for the three wax ester types including: (1) [RCOOH2](+) for saturated wax esters, (2) [RCOOH2](+), [RCO](+) and [RCO-H2O](+) for unsaturated wax esters containing only one double bond in the fatty acid moiety or with one additional double bond in the fatty alcohol moiety, and (3) [RCOOH2](+) and [RCO](+) for unsaturated wax esters containing a double bond in the fatty alcohol moiety alone. Other fragments included [R'](+) and several series of product ions for all types of wax esters. Interestingly, unusual product ions were detected, such as neutral molecule (including water, methanol and ammonia) adducts of [RCOOH2](+) ions for all types of wax esters and [R'-2H](+) ions for unsaturated fatty acyl-containing wax esters. The patterns of tandem mass spectra for different types of wax esters will inform future identification and quantification approaches of wax esters in biological samples as supported by a preliminary study of quantification of isomeric wax esters in human meibomian gland secretions.

  8. Platinum-mediated dinitrogen liberation from 2-picolyl azide through a putative Pt═N double bond containing intermediate.

    PubMed

    Pinter, Balazs; Urankar, Damijana; Pevec, Andrej; De Proft, Frank; Košmrlj, Janez

    2013-04-15

    2-Picolyl azide reacts with cis-[PtCl2(DMSO)2] to form the diimino complex [Pt(II)Cl2{NH═C(H)Py}] with subsequent dinitrogen liberation. The formation of the latter complex is scrutinized in a combined experimental and theoretical analysis. We establish in silico that the transformation involves a highly reactive intermediate containing a Pt═N double bond formed after the extrusion of N2 from the azide functionality. The prerequisites for N2 liberation and for the stabilization of the nitrene-related intermediate are analyzed in detail. PMID:23534346

  9. ELECTRON DONOR ACCEPTOR DESCRIPTORS OF THE SINGLE AND DOUBLE BONDED SUBSTITUENT AND HETEROATOM INCORPORATION EFFECTS. A REVIEW.

    PubMed

    Mazurek, Andrzej

    2016-01-01

    The properties of the series of Electron Donor-Acceptor (EDA) descriptors of classical substituent effect (sEDA(I), pEDA(I)), double bonded substituent effect (sEDA(=), pEDA(=)), heteroatom incorporation effect in monocyclic systems (sEDA(II), pEDA(II)), and in ring-junction position (sEDA(III), pEDA(III)), are reviewed. The descriptors show the amount of electrons donated to or withdrawn from the σ-(sEDA) or π(pEDA) valence orbitals by the substituent or incorporant. The new descriptors are expected to enrich the potency of QSAR analyses in drug design and materials chemistry.

  10. Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes.

    PubMed

    Hsu, Shih-Hsien; Chang, Jr-Chiuan; Lai, Chun-Liang; Hu, Ching-Han; Lee, Hon Man; Lee, Gene-Hsiang; Peng, Shie-Ming; Huang, Jui-Hsien

    2004-10-18

    Treatment of (t-)BuN=TiCl(2)Py(3) with 2 equiv lithium ketiminate compound, Li[OCMeCHCMeN(Ar)] (where Ar = 2,6-diisopropylphenyl), in toluene at room temperature gave (t-)BuN=Ti[OCMeCHCMeN(Ar)](2) (1) in high yield. The reaction of 1 with phenyl isocyanate at room-temperature resulted in imido ligand exchange producing PhN=Ti[OCMeCHCMeN(Ar)](2) (2). Compound 1 decomposed at 90 degrees C to form a terminal titanium oxo compound O=Ti[OCMeCHCMeN(Ar)](2) (3) and (t-)BuNHCMeCHCMeNAr (4). Also, the compound 3 could be obtained by reacting 1 with CO(2) under mild condition. Similarly, while 1 reacts with an excess of carbon disulfide, a novel terminal titanium sulfido compound S=Ti[OCMeCHCMeN(Ar)](2) (5) was formed via a C=S bond breaking reaction. A novel titanium isocyanate compound Ti[OCMeCHCMeN(Ar)](2)(NCO)(OEt) (6) was formed on heating 1 with 1 equiv of urethane, H(2)NCOOEt. Compounds 1-6 have been characterized by (1)H and (13)C NMR spectroscopies. The molecular structures of 1, 3, 5, and 6 were determined by single-crystal X-ray diffraction. A theoretical calculation predicted that the cleavage of the C-S double bonds for carbon disulfide with the Ti=N bond of compound 1 was estimated at ca. 21.8 kcal.mol(-1) exothermic.

  11. Chemical bonding and dynamic fluxionality of a B15(+) cluster: a nanoscale double-axle tank tread.

    PubMed

    Wang, Ying-Jin; You, Xue-Rui; Chen, Qiang; Feng, Lin-Yan; Wang, Kang; Ou, Ting; Zhao, Xiao-Yun; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-21

    A planar, elongated B15(+) cationic cluster is shown to be structurally fluxional and functions as a nanoscale tank tread on the basis of electronic structure calculations, bonding analyses, and molecular dynamics simulations. The outer B11 peripheral ring behaves like a flexible chain gliding around an inner B4 rhombus core, almost freely at the temperature of 500 K. The rotational energy barrier is only 1.37 kcal mol(-1) (0.06 eV) at the PBE0/6-311+G* level, further refined to 1.66 kcal mol(-1) (0.07 eV) at the single-point CCSD(T)/6-311G*//CCSD/6-311G* level. Two soft vibrational modes of 166.3 and 258.3 cm(-1) are associated with the rotation, serving as double engines for the system. Bonding analysis suggests that the "island" electron clouds, both σ and π, between the peripheral ring and inner core flow and shift continuously during the intramolecular rotation, facilitating the dynamic fluxionality of the system with a small rotational barrier. The B15(+) cluster, roughly 0.6 nm in dimension, is the first double-axle nanoscale tank tread equipped with two engines, which expands the concepts of molecular wheels, Wankel motors, and molecular tanks.

  12. Chemical bonding and dynamic fluxionality of a B15(+) cluster: a nanoscale double-axle tank tread.

    PubMed

    Wang, Ying-Jin; You, Xue-Rui; Chen, Qiang; Feng, Lin-Yan; Wang, Kang; Ou, Ting; Zhao, Xiao-Yun; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-21

    A planar, elongated B15(+) cationic cluster is shown to be structurally fluxional and functions as a nanoscale tank tread on the basis of electronic structure calculations, bonding analyses, and molecular dynamics simulations. The outer B11 peripheral ring behaves like a flexible chain gliding around an inner B4 rhombus core, almost freely at the temperature of 500 K. The rotational energy barrier is only 1.37 kcal mol(-1) (0.06 eV) at the PBE0/6-311+G* level, further refined to 1.66 kcal mol(-1) (0.07 eV) at the single-point CCSD(T)/6-311G*//CCSD/6-311G* level. Two soft vibrational modes of 166.3 and 258.3 cm(-1) are associated with the rotation, serving as double engines for the system. Bonding analysis suggests that the "island" electron clouds, both σ and π, between the peripheral ring and inner core flow and shift continuously during the intramolecular rotation, facilitating the dynamic fluxionality of the system with a small rotational barrier. The B15(+) cluster, roughly 0.6 nm in dimension, is the first double-axle nanoscale tank tread equipped with two engines, which expands the concepts of molecular wheels, Wankel motors, and molecular tanks. PMID:27229290

  13. Double bond stereochemistry influences the susceptibility of short-chain isoprenoids and polyprenols to decomposition by thermo-oxidation.

    PubMed

    Molińska, Ewa; Klimczak, Urszula; Komaszyło, Joanna; Derewiaka, Dorota; Obiedziński, Mieczysław; Kania, Magdalena; Danikiewicz, Witold; Swiezewska, Ewa

    2015-04-01

    Isoprenoid alcohols are common constituents of living cells. They are usually assigned a role in the adaptation of the cell to environmental stimuli, and this process might give rise to their oxidation by reactive oxygen species. Moreover, cellular isoprenoids may also undergo various chemical modifications resulting from the physico-chemical treatment of the tissues, e.g., heating during food processing. Susceptibility of isoprenoid alcohols to heat treatment has not been studied in detail so far. In this study, isoprenoid alcohols differing in the number of isoprene units and geometry of the double bonds, β-citronellol, geraniol, nerol, farnesol, solanesol and Pren-9, were subjected to thermo-oxidation at 80 °C. Thermo-oxidation resulted in the decomposition of the tested short-chain isoprenoids as well as medium-chain polyprenols with simultaneous formation of oxidized derivatives, such as hydroperoxides, monoepoxides, diepoxides and aldehydes, and possible formation of oligomeric derivatives. Oxidation products were monitored by GC-FID, GC-MS, ESI-MS and spectrophotometric methods. Interestingly, nerol, a short-chain isoprenoid with a double bond in the cis (Z) configuration, was more oxidatively stable than its trans (E) isomer, geraniol. However, the opposite effect was observed for medium-chain polyprenols, since Pren-9 (di-trans-poly-cis-prenol) was more susceptible to thermo-oxidation than its all-trans isomer, solanesol. Taken together, these results experimentally confirm that both short- and long-chain polyisoprenoid alcohols are prone to thermo-oxidation.

  14. Interactions of Molecules with cis and trans Double Bonds: A Theoretical Study of cis- and trans-2-Butene.

    PubMed

    Zarić, Milana M; Bugarski, Branko; Kijevčanin, Mirjana Lj

    2016-01-18

    Noncovalent interactions of cis- and trans-2-butene, as the smallest model systems of molecules with cis and trans double bonds, were studied to find potential differences in interactions of these molecules. The study was performed using quantum chemical methods including very accurate CCSD(T)/CBS method. We studied parallel and displaced parallel interactions in 2-butene dimers, in butane dimers, and between 2-butene and saturated butane. The results show the trend that interactions of 2-butene with butane are the strongest, followed by interactions in butane dimers, whereas the interaction in 2-butene dimers are the weakest. The strongest calculated interaction energy is between trans-2-butene and butane, with a CCSD(T)/CBS energy of -2.80 kcal mol(-1) . Interactions in cis-2-butene dimers are stronger than interactions in trans-2-butene dimers. Interestingly, some of the interactions involving 2-butene are as strong as interactions in a benzene dimer. These insights into interactions of cis- and trans-2-butene can improve understanding of the properties and processes that involve molecules with cis and trans double bonds, such as fatty acids and polymers.

  15. Role of the protein cavity in phytochrome chromoprotein assembly and double-bond isomerization: a comparison with model compounds.

    PubMed

    Rohmer, Thierry; Lang, Christina; Gärtner, Wolfgang; Hughes, Jon; Matysik, Jörg

    2010-01-01

    Difference patterns of (13)C NMR chemicals shifts for the protonation of a free model compound in organic solution, as reported in the literature (M. Stanek, K. Grubmayr [1998] Chem. Eur. J.4, 1653-1659), were compared with changes in the protonation state occurring during holophytochrome assembly from phycocyanobilin (PCB) and the apoprotein. Both processes induce identical changes in the NMR signals, indicating that the assembly process is linked to protonation of the chromophore, yielding a cationic cofactor in a heterogeneous, quasi-liquid protein environment. The identity of both difference patterns implies that the protonation of a model compound in solution causes a partial stretching of the geometry of the macrocycle as found in the protein. In fact, the similarity of the difference pattern within the bilin family for identical chemical transformations represents a basis for future theoretical analysis. On the other hand, the change of the (13)C NMR chemical shift pattern upon the Pr --> Pfr photoisomerization is very different to that of the free model compound upon ZZZ --> ZZE photoisomerization. Hence, the character of the double-bond isomerization in phytochrome is essentially different from that of a classical photoinduced double-bond isomerization, emphasizing the role of the protein environment in the modulation of this light-induced process. PMID:20492561

  16. Theoretical in-Solution Conformational/Tautomeric Analyses for Chain Systems with Conjugated Double Bonds Involving Nitrogen(s)

    PubMed Central

    Nagy, Peter I.

    2015-01-01

    Conformational/tautomeric transformations for X=CH–CH=Y structures (X = CH2, O, NH and Y = NH) have been studied in the gas phase, in dichloromethane and in aqueous solutions. The paper is a continuation of a former study where s-cis/s-trans conformational equilibria were predicted for analogues. The s-trans conformation is preferred for the present molecules in the gas phase on the basis of its lowest internal free energy as calculated at the B97D/aug-cc-pvqz and CCSD(T)CBS (coupled-cluster singles and doubles with non-iterative triples extrapolated to the complete basis set) levels. Transition state barriers are of 29–36 kJ/mol for rotations about the central C–C bonds. In solution, an s-trans form is still favored on the basis of its considerably lower internal free energy compared with the s-cis forms as calculated by IEF-PCM (integral-equation formalism of the polarizable continuum dielectric solvent model) at the theoretical levels indicated. A tetrahydrate model in the supermolecule/continuum approach helped explore the 2solute-solvent hydrogen bond pattern. The calculated transition state barrier for rotation about the C–C bond decreased to 27 kJ/mol for the tetrahydrate. Considering explicit solvent models, relative solvation free energies were calculated by means of the free energy perturbation method through Monte Carlo simulations. These calculated values differ remarkably from those by the PCM approach in aqueous solution, nonetheless the same prevalent conformation was predicted by the two methods. Aqueous solution structure-characteristics were determined by Monte Carlo. Equilibration of conformers/tautomers through water-assisted double proton-relay is discussed. This mechanism is not viable, however, in non-protic solvents where the calculated potential of mean force curve does not predict remarkable solute dimerization and subsequent favorable orientation. PMID:25984602

  17. A theoretical view on CrO2+-mediated C-H bond activation in ethane

    NASA Astrophysics Data System (ADS)

    Tong, YongChun; Zhang, XiaoYong; Wang, QingYun; Xu, XinJian; Wang, YongCheng

    2015-06-01

    The gas-phase reaction of C-H bond activation in ethane by CrO2+ has been investigated using density functional theory (DFT) at the UB3LYP/6-311G(2d,p) level. Our results reveal that the activation process is actually a spin-forbidden reaction. The involved crossing point between the doublet and quartet potential energy surfaces (PES) has been discussed by two well-known methods, i.e., intrinsic reaction coordinate (IRC) approach for crossing point (CP) and Harvey's algorithm for minimum energy crossing point (MECP). The obtained single ( P1ISC = 2.48 × 10-3) and double ( P1ISC = 4.95 × 10-3) passes estimated at MECP show that the intersystem crossing (ISC) occurs with a little probability. The C-H bond activation processes should proceed to be endothermic by 73.16 kJ/mol on the doublet surface without any spin change.

  18. Chemically Non-Innocent Cyclic (Alkyl)(Amino)Carbenes: Ligand Rearrangement, C-H and C-F Bond Activation.

    PubMed

    Turner, Zoë R

    2016-08-01

    A cyclic (alkyl)(amino)carbene (CAAC) was found to undergo unprecedented rearrangements and transformations of its core structure in the presence of Group 1 and 2 metals. Although the carbene was also found to be prone to intramolecular C-H activation, it was competent for intermolecular activation of a variety of sp-, sp(2) -, and sp(3) -hybridized C-H bonds. Double C-F activation of hexafluorobenzene was also observed in this work. These processes all hold relevance to the role of these carbenes in catalysis, as well as to their use in the synthesis of new and unusual main group or transition metal complexes. PMID:27363588

  19. Formation of disulfide bonds in insect prophenoloxidase enhances immunity through improving enzyme activity and stability.

    PubMed

    Lu, Anrui; Peng, Qin; Ling, Erjun

    2014-06-01

    Type 3 copper proteins, including insect prophenoloxidase (PPO), contain two copper atoms in the active site pocket and can oxidize phenols. Insect PPO plays an important role in immunity. Insects and other invertebrates show limited recovery from pathogen invasion and wounds if phenoloxidase (PO) activity is low. In most insect PPOs, two disulfide bonds are present near the C-terminus. However, in Pimpla hypochondriaca (a parasitoid wasp), each PPO contains one disulfide bond. We thus questioned whether the formation of two sulfide bonds in insect PPOs improved protein stability and/or increased insect innate immunity over time. Using Drosophila melanogaster PPO1 as a model, one or two disulfide bonds were deleted to evaluate the importance of disulfide bonds in insect immunity. rPPO1 and mutants lacking disulfide bonds could be expressed and showed PO activity. However, the PO activities of mutants lacking one or two disulfide bonds significantly decreased. Deletion of disulfide bonds also reduced PPO thermostability. Furthermore, antibacterial activities against Escherichia coli and Bacillus subtilis significantly decreased when disulfide bonds were deleted. Therefore, the formation of two disulfide bond(s) in insect PPO enhances antibacterial activity by increasing PO activity and stability.

  20. Construction of hybrid material with double chemical bond from functional bridge ligand: Molecular modification, lotus root-like micromorphology and strong luminescence

    NASA Astrophysics Data System (ADS)

    Yan, Bing; Sui, Yu-Long

    2006-07-01

    Modifying benzoic acid with a cross-linking molecule (3-aminopropyl)triethoxysilane (abbreviated as APES), a fictional molecular bridge with double reactivity was achieved by the amidation reaction between them. Then the modified functional molecule, which behaving as a bridge, both coordinate with terbium ion through amide's oxygen atom and form the Si-O chemical bond in an in situ sol-gel process with matrix precursor (tetraethoxysilane, TEOS). As a result, a novel molecular hybrid material (Tb-BA-APES) with double chemical bond (Tb-O coordination bond and Si-O covalent bond) was constructed. The strong luminescence of Tb 3+ substantiates optimum energy couple and effective intramolecular energy transfer between the triplet state energy of modified ligand bridge and emissive energy level of Tb 3+. Especially SEM of the molecular hybrid material exhibits unexpected microlotus root-like pore morphology.

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

    PubMed

    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.

  2. Halogen bonding-enhanced electrochemical halide anion sensing by redox-active ferrocene receptors.

    PubMed

    Lim, Jason Y C; Cunningham, Matthew J; Davis, Jason J; Beer, Paul D

    2015-10-01

    The first examples of halogen bonding redox-active ferrocene receptors and their anion electrochemical sensing properties are reported. Halogen bonding was found to significantly amplify the magnitude of the receptor's metallocene redox-couple's voltammetric responses for halide sensing compared to their hydrogen bonding analogues in both acetonitrile and aqueous-acetonitrile solvent media.

  3. Halogen bonding-enhanced electrochemical halide anion sensing by redox-active ferrocene receptors.

    PubMed

    Lim, Jason Y C; Cunningham, Matthew J; Davis, Jason J; Beer, Paul D

    2015-10-01

    The first examples of halogen bonding redox-active ferrocene receptors and their anion electrochemical sensing properties are reported. Halogen bonding was found to significantly amplify the magnitude of the receptor's metallocene redox-couple's voltammetric responses for halide sensing compared to their hydrogen bonding analogues in both acetonitrile and aqueous-acetonitrile solvent media. PMID:26289779

  4. Active sound attenuation across a double wall structure

    NASA Technical Reports Server (NTRS)

    Grosveld, Ferdinand W.; Shepherd, Kevin P.

    1991-01-01

    The possibility of achieving significant local and global sound attenuation across a flat double wall is demonstrated. It is also shown that sound can be prevented from entering the interior of a cabinlike environment. The approach used is unlike established active noise control techniques.

  5. Contrast enhancement and polymer identification in the electron microscope by the formation and staining of unsaturated double bonds

    SciTech Connect

    Parker, M.A.; Vesely, D. )

    1993-03-01

    A new technique for the identification of phases contained within a polymer blend is described in this paper. The technique utilizes the beam damage which occurs when polymers are irradiated in an electron microscope. It has been found that during the irradiation process isolated double bonds are formed which can be revealed by staining with osmium tetroxide. The density of staining and its relationship to electron exposure is shown to be a characteristic feature of a particular chemical structure. It allows for polymer phase identification with a high spatial resolution and also for contrast enhancement and preservation. This technique offers a unique way of studying a fine dispersion of phases in polymer blends, even where only low atomic number elements such as C, H, and O are present.

  6. A monotopic aluminum telluride with an Al=Te double bond stabilized by N-heterocyclic carbenes

    PubMed Central

    Franz, Daniel; Szilvási, Tibor; Irran, Elisabeth; Inoue, Shigeyoshi

    2015-01-01

    Aluminum chalcogenides are mostly encountered in the form of bulk aluminum oxides that are structurally diverse but typically consist of networks with high lattice energy in which the chalcogen atoms bridge the metal centres. This makes their molecular congeners difficult to synthesize because of a pronounced tendency for oligomerization. Here we describe the isolation of the monotopic aluminum chalcogenide (LDipN)AlTe(LEt)2 (LDip=1,3-(2,6-diisopropylphenyl)-imidazolin-2-imine, LEt=1,3-diethyl-4,5-dimethyl-imidazolin-2-ylidene). Unique features of (LDipN)AlTe(LEt)2 are the terminal position of the tellurium atom, the shortest aluminum–tellurium distance hitherto reported for a molecular complex and the highest bond order reported for an interaction between these elements, to the best of our knowledge. At elevated temperature (LDipN)AlTe(LEt)2 equilibrates with dimeric {(LDipN)AlTe(LEt)}2 in which the chalcogen atoms assume their common role as bridges between the metal centres. These findings demonstrate that (LDipN)AlTe(LEt)2 comprises the elusive Al=Te double bond in the form of an N-heterocyclic carbene-stabilized species. PMID:26612781

  7. Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Tsukanov, A. A.; Psakhie, S. G.

    2016-01-01

    The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered.

  8. Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

    PubMed Central

    Tsukanov, A.A.; Psakhie, S.G.

    2016-01-01

    The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered. PMID:26817816

  9. Chelation-Assisted Nickel-Catalyzed Oxidative Annulation via Double C-H Activation/Alkyne Insertion Reaction.

    PubMed

    Misal Castro, Luis C; Obata, Atsushi; Aihara, Yoshinori; Chatani, Naoto

    2016-01-22

    A nickel/NHC system for regioselective oxidative annulation by double C-H bond activation and concomitant alkyne insertion is described. The catalytic reaction requires a bidentate directing group, such as an 8-aminoquinoline, embedded in the substrate. Various 5,6,7,8-tetrasubstituted-N-(quinolin-8-yl)-1-naphthamides can be prepared as well as phenanthrene and benzo[h]quinoline amide derivatives. Diarylalkynes, dialkylalkynes, and arylalkylalkynes can be used in the system. A Ni(0)/Ni(II) catalytic cycle is proposed as the main catalytic cycle. The alkyne plays a double role as a two-component coupling partner and as a hydrogen acceptor. PMID:26689750

  10. 78 FR 75576 - Agency Information Collection Activities: Importation Bond Structure

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-12

    ... Structure AGENCY: U.S. Customs and Border Protection (CBP), Department of Homeland Security. ACTION: 60-day... Importation Bond Structure. This request for comment is being made pursuant to the Paperwork Reduction Act of... Structure. OMB Number: 1651-0050. Form Number: CBP Forms 301 and 5297. Abstract: Bonds are used to...

  11. 75 FR 50772 - Agency Information Collection Activities: Importation Bond Structure

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-17

    ... Structure AGENCY: U.S. Customs and Border Protection, Department of Homeland Security. ] ACTION: 60-Day... concerning the: Importation Bond Structure. This request for comment is being made pursuant to the Paperwork...: Title: Importation Bond Structure. OMB Number: 1651-0050. Form Numbers: 301 and 5297. Abstract:...

  12. Carbon–carbon bond activation of cyclobutenones enabled by the addition of chiral organocatalyst to ketone

    PubMed Central

    Li, Bao-Sheng; Wang, Yuhuang; Jin, Zhichao; Zheng, Pengcheng; Ganguly, Rakesh; Chi, Yonggui Robin

    2015-01-01

    The activation of carbon–carbon (C–C) bonds is an effective strategy in building functional molecules. The C–C bond activation is typically accomplished via metal catalysis, with which high levels of enantioselectivity are difficult to achieve due to high reactivity of metal catalysts and the metal-bound intermediates. It remains largely unexplored to use organocatalysis for C–C bond activation. Here we describe an organocatalytic activation of C–C bonds through the addition of an NHC to a ketone moiety that initiates a C–C single bond cleavage as a key step to generate an NHC-bound intermediate for chemo- and stereo-selective reactions. This reaction constitutes an asymmetric functionalization of cyclobutenones using organocatalysts via a C–C bond activation process. Structurally diverse and multicyclic compounds could be obtained with high optical purities via an atom and redox economic process. PMID:25652912

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

    SciTech Connect

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has

  14. Synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks via the direct condensation of acetals and amines.

    PubMed

    Li, Zhi-Jun; Ding, San-Yuan; Xue, Hua-Dong; Cao, Wei; Wang, Wei

    2016-06-01

    We demonstrate herein a facile approach for constructing -C[double bond, length as m-dash]N- linked COFs from acetals. Three new COFs (imine-linked LZU-20, hydrazone-linked LZU-21, and azine-linked LZU-22) were synthesized by the direct condensation of dimethyl acetals and amines. All the synthesized COFs are highly crystalline and exhibit good thermal stability.

  15. Cholesterol induces surface localization of polyphenols in model membranes thus enhancing vesicle stability against lysozyme, but reduces protection of distant double bonds from reactive-oxygen species.

    PubMed

    de Athayde Moncorvo Collado, Alejandro; Dupuy, Fernando G; Morero, Roberto D; Minahk, Carlos

    2016-07-01

    The main scope of the present study was to analyze the membrane interaction of members of different classes of polyphenols, i.e. resveratrol, naringenin, epigallocatechin gallate and enterodiol, in model systems of different compositions and phase states. In addition, the possible association between membrane affinity and membrane protection against both lipid oxidation and bilayer-disruptive compounds was studied. Gibbs monolayer experiments indicated that even though polyphenols showed poor surface activity, it readily interacted with lipid films. Actually, a preferential interaction with expanded monolayers was observed, while condensed and cholesterol-containing monolayers decreased the affinity of these phenolic compounds. On the other hand, fluorescence anisotropy studies showed that polyphenols were able to modulate membrane order degree, but again this effect was dependent on the cholesterol concentration and membrane phase state. In fact, cholesterol induced a surface rather than deep into the hydrophobic core localization of phenolic compounds in the membranes. In general, the polyphenolic molecules tested had a better antioxidant activity when they were allowed to get inserted into the bilayers, i.e. in cholesterol-free membranes. On the other hand, a membrane-protective effect against bilayer permeabilizing activity of lysozyme, particularly in the presence of cholesterol, could be assessed. It can be hypothesized that phenolic compounds may protect membrane integrity by loosely covering the surface of lipid vesicles, once cholesterol push them off from the membrane hydrophobic core. However, this cholesterol-driven distribution may lead to a reduced antioxidant activity of linoleic acid double bonds.

  16. The Stereoselective Formation of Bicyclic Enamines with Bridgehead Unsaturation via Tandem C-H Bond Activation/Alkenylation/Electrocyclization

    SciTech Connect

    Ellman, Jonathan A.; Yotphan, Sirilata; Bergman, Robert

    2007-12-10

    Rhodium-catalyzed intermolecular C-H activation of {alpha}, {beta}-unsaturated imines in the presence of alkynes leads to a tandem process in which coupling to the alkyne occurs at the {beta}-C-H bond of the imine, followed by electrocyclization of the resulting azatriene intermediates to give dihydropyridines (eq 1). Consideration of the intramolecular version of this overall transformation (Scheme 1) raises interesting regiochemical issues. For example in a compound such as 1, where the nitrogen and alkyne are connected by a 4-carbon tether, the presumed first-formed hydrido(vinyl)rhodium function can add to the triple bond in a 1,2-fashion, producing complex 2 with a new endocyclic double bond. Alternatively, addition might occur in a 2,1-fashion, leading to product 4 with an exocyclic double bond. We now wish to report that this intramolecular cyclization occurs smoothly at 100 C, and the exocyclic double bond route is exclusively followed. Remarkably, products such as 4 do not resist further cyclization. Even though both the transition state for this process and the resulting product are presumably strained, the overall transformation leads to good yields of unusual bridgehead doubly-bonded enamines such as 5. The unique chemistry of conjugated enamine 5 is consistent with the increased strain of this molecule as well as with inhibited conjugation between the nitrogen lone pair and the adjacent double bond (vida infra). We began our investigation into the C-H activation/cyclization of alkyne-tethered imine 1 by extensive screening of transition metal catalysts for this process. Rhodium-based catalysts were found to be the most efficient (Table 1), leading exclusively to the bridgehead dienamine; none of the catalysts that were employed in the screening led to quinolizidine 3 or to the product of intramolecular Diels-Alder reaction. The optimized reaction conditions employ the electron-rich monophosphine ligand (p-NMe{sub 2})PhPEt{sub 2} in 1:1 ratio relative

  17. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 26 Internal Revenue 2 2011-04-01 2011-04-01 false Private activity bond limit (temporary). 1.103(n)-3T Section 1.103(n)-3T Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE TREASURY....103(n)-3T Private activity bond limit (temporary). Q-1: What is the “State ceiling”? A-1: In...

  18. 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.

    PubMed

    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).

  19. Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds

    NASA Technical Reports Server (NTRS)

    Brown, R. L.; Laufer, A. H.

    1981-01-01

    Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

  20. Human Defensin 5 Disulfide Array Mutants: Disulfide Bond Deletion Attenuates Antibacterial Activity Against Staphylococcus aureus

    PubMed Central

    Wanniarachchi, Yoshitha A.; Kaczmarek, Piotr; Wan, Andrea; Nolan, Elizabeth M.

    2011-01-01

    Human α-defensin 5 (HD5, HD5ox to specify the oxidized and disulfide linked form) is a 32-residue cysteine-rich host-defense peptide, expressed and released by small intestinal Paneth cells, that exhibits antibacterial activity against a number of Gram-negative and –positive bacterial strains. To ascertain the contributions of its disulfide array to structure, antimicrobial activity, and proteolytic stability, a series of HD5 double mutant peptides where pairs of cysteine residues corresponding to native disulfide linkages (Cys3—Cys31, Cys5—Cys20, Cys10—Cys30) were mutated to Ser or Ala residues were overexpressed in E. coli, purified and characterized. A hexa mutant peptide, HD5[Serhexa], where all six native Cys residues are replaced by Ser residues was also evaluated. Removal of a single native S—S linkage influences oxidative folding and regioisomerization, antibacterial activity, Gram-negative bacterial membrane permeabilization, and proteolytic stability. Whereas the majority of the HD5 mutant peptides show low-micromolar activity against Gram-negative E. coli ATCC 25922 in colony counting assays, the wild-type disulfide array is essential for low-micromolar activity against Gram-positive S. aureus ATCC 25923. Removal of a single disulfide bond attenuates the activity observed for HD5ox against this Gram-positive bacterial strain. This observation supports the notion that the HD5ox mechanism of antibacterial action differs for Gram-negative and Gram-positive species (Wei, G.; de Leeuw, E., Pazgier, M., Yuan, W., Zou, G., Wang, J., Ericksen, B., Lu, W.-Y.; Lehrer, R. I.; Lu, W. (2009) J. Biol. Chem. 284, 29180-29192), and that the native disulfide array is a requirement for its activity against S. aureus. PMID:21861459

  1. Study and characterization of the smectic X* phase in binary mixtures of thermotropic double hydrogen bonded ferroelectric liquid crystals

    NASA Astrophysics Data System (ADS)

    Sangameswari, G.; Pongali Sathya Prabu, N.; Madhu Mohan, M. L. N.

    2015-09-01

    Thermotropic double hydrogen bonded ferroelectric liquid crystals (DHBFLCs) composed of N-carbamyl-L-glutamic acid (CGA) and p-n-alkyloxy benzoic acids (BAO) have been investigated. Variation in the molar proportion of X and Y (where X = CGA + 5BAO and Y = CGA + 6BAO, CGA + 7BAO, and CGA + 8BAO) composed of three series yielded 27 binary mixtures. Optical and thermal properties of these mixtures are meticulously studied in the present article. A novel smectic ordering, namely smectic X*, is observed in all the three series. The aim of the investigation is to obtain an abundance occurrence of smectic X* and hence the proportions of the binary mixtures are so chosen that the preamble task is accomplished. Phase diagrams of three series are constructed from the data obtained from polarizing optical microscope (POM) and differential scanning calorimetry (DSC) studies. Odd-even effect, order of the phase transition, thermal stability factor, thermal equilibrium, and optical tilt angle are also premeditated.

  2. Influence of preheating the bonding agent of a conventional three-step adhesive system and the light activated resin cement on dentin bond strength

    PubMed Central

    Holanda, Daniel Brandão Vilela; França, Fabiana Mantovani Gomes; do Amaral, Flávia Lucisano Botelho; Flório, Flávia Martão; Basting, Roberta Tarkany

    2013-01-01

    Aims: to evaluate the influence of preheating the bonding agent (Scotchbond Multipurpose Adhesive/3M ESPE) and the light-activated resin cement (RelyX Venner/3M ESPE) on dentin microtensile bond strength. Materials and Methods: The exposed flat dentin surface of 40 human third molars were randomly distributed into four groups for cementation (SR Adoro/Ivoclar Vivadent) (n = 10): G1-bond and resin cement, both at room temperature (22°C), G2-bond preheated to 58°C and cement at room temperature (22°C), G3-bond at room temperature (22°C) and the cement preheated to 58°C, G4-bond preheated to 58°C and cement preheated to 58°C. Sticks of dentin/block set measuring approximately 1 mm2 were obtained and used for the microtensile bond strength test. All sticks had their failure mode classified. Statistical analysis used: Factorial analysis of variance was applied, 2 × 2 (bond × cement) (P < 0.05). Results: Preheating the bonding agent (P = 0.8411) or the cement (P = 0.7155), yielded no significant difference. The interaction bond × cement was not significant (P = 0.9389). Conclusions: Preheating the bond and/or the light-activated resin cement did not influence dentin bond strength or fracture failure mode. PMID:24347889

  3. Car-Parrinello Molecular Dynamics Simulations of Infrared Spectra of Crystalline Vitamin C with Analysis of Double Minimum Proton Potentials for Medium-Strong Hydrogen Bonds.

    PubMed

    Brela, Mateusz Z; Wójcik, Marek J; Boczar, Marek; Witek, Łukasz; Yasuda, Mitsuru; Ozaki, Yukihiro

    2015-06-25

    We studied proton dynamics of a hydrogen bonds of the crystalline l-ascorbic acid. Our approach was based on the Car-Parrinello molecular dynamics. The focal point of our study was simulation of the infrared spectra of l-ascorbic acid associated with the O-H stretching modes that are very sensitive to the strength of hydrogen bonding. In the l-ascorbic acid there are four kinds of hydrogen bonds. We calculated their spectra by using anharmonic approximation and the time course of the dipole moment function as obtained from the Car-Parrinello simulation. The quantization of the nuclear motion of the protons was made to perform detailed analysis of strength and properties of hydrogen bonds. We presented double minimum proton potentials with small value of barriers for medium-strong hydrogen bonds. We have also shown the difference character of medium-strong hydrogen bonds compared to weaker hydrogen bonds in the l-ascorbic acid. PMID:26028251

  4. Tomato carotenoid cleavage dioxygenases 1A and 1B: Relaxed double bond specificity leads to a plenitude of dialdehydes, mono-apocarotenoids and isoprenoid volatiles

    PubMed Central

    Ilg, Andrea; Bruno, Mark; Beyer, Peter; Al-Babili, Salim

    2014-01-01

    The biosynthetic processes leading to many of the isoprenoid volatiles released by tomato fruits are still unknown, though previous reports suggested a clear correlation with the carotenoids contained within the fruit. In this study, we investigated the activity of the tomato (Solanum lycopersicum) carotenoid cleavage dioxygenase (SlCCD1B), which is highly expressed in fruits, and of its homolog SlCCD1A. Using in vitro assays performed with purified recombinant enzymes and by analyzing products formed by the two enzymes in carotene-accumulating Escherichia coli strains, we demonstrate that SlCCD1A and, to a larger extent, SlCCD1B, have a very relaxed specificity for both substrate and cleavage site, mediating the oxidative cleavage of cis- and all-trans-carotenoids as well as of different apocarotenoids at many more double bonds than previously reported. This activity gives rise to a plenitude of volatiles, mono-apocarotenoids and dialdehyde products, including cis-pseudoionone, neral, geranial, and farnesylacetone. Our results provide a direct evidence for a carotenoid origin of these compounds and point to CCD1s as the enzymes catalyzing the formation of the vast majority of tomato isoprenoid volatiles, many of which are aroma constituents. PMID:25057464

  5. 75 FR 68809 - Agency Information Collection Activities: Importation Bond Structure

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-09

    ... information collection was previously published in the Federal Register (75 FR 50772) on August 17, 2010... Structure AGENCY: U.S. Customs and Border Protection, Department of Homeland Security. ACTION: 30-day notice... review and approval in accordance with the Paperwork Reduction Act: Importation Bond Structure. This is...

  6. Repeatable mechanochemical activation of dynamic covalent bonds in thermoplastic elastomers.

    PubMed

    Imato, Keiichi; Kanehara, Takeshi; Nojima, Shiki; Ohishi, Tomoyuki; Higaki, Yuji; Takahara, Atsushi; Otsuka, Hideyuki

    2016-08-18

    Repeated mechanical scission and recombination of dynamic covalent bonds incorporated in segmented polyurethane elastomers are demonstrated by utilizing a diarylbibenzofuranone-based mechanophore and by the design of the segmented polymer structures. The repeated mechanochemical reactions can accompany clear colouration and simultaneous fading.

  7. Repeatable mechanochemical activation of dynamic covalent bonds in thermoplastic elastomers.

    PubMed

    Imato, Keiichi; Kanehara, Takeshi; Nojima, Shiki; Ohishi, Tomoyuki; Higaki, Yuji; Takahara, Atsushi; Otsuka, Hideyuki

    2016-08-18

    Repeated mechanical scission and recombination of dynamic covalent bonds incorporated in segmented polyurethane elastomers are demonstrated by utilizing a diarylbibenzofuranone-based mechanophore and by the design of the segmented polymer structures. The repeated mechanochemical reactions can accompany clear colouration and simultaneous fading. PMID:27424868

  8. Rhodium mediated bond activation: from synthesis to catalysis

    SciTech Connect

    Ho, Hung-An

    2012-01-01

    Recently, our lab has developed monoanionic tridentate ligand, ToR, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the ToR-supported rhodium compounds. Tl[ToR] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[ToM] with [Rh(μ-Cl)(CO)]2 and [Rh(μ- Cl)(COE)]2 gives ToMRh(CO)2 (2.2) and ToMRhH(β3-C8H13) (3.1) respectively while Tl[ToM] with [Rh(μ-Cl)(CO)]2 affords ToPRh(CO)2 (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex ToMRh(H)2CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary

  9. Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation.

    PubMed

    Yedage, Subhash L; Bhanage, Bhalchandra M

    2016-05-20

    This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level. PMID:27088815

  10. Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation.

    PubMed

    Yedage, Subhash L; Bhanage, Bhalchandra M

    2016-05-20

    This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level.

  11. Merging photoredox catalysis with Lewis acid catalysis: activation of carbon-carbon triple bonds.

    PubMed

    Jin, Ruiwen; Chen, Yiyong; Liu, Wangsheng; Xu, Dawen; Li, Yawei; Ding, Aishun; Guo, Hao

    2016-08-01

    Here, we demonstrate that merging photoredox catalysis with Lewis acid catalysis provides a fundamentally new activation mode of C-C triple bonds, to achieve the bond-forming reaction of alkynes with weak nucleophiles. Using a synergistic merger of Eosin Y and Cu(OTf)2, a highly efficient cyclization reaction of arene-ynes was developed. PMID:27432542

  12. 77 FR 26024 - Agency Information Collection Activities: Bonded Warehouse Proprietor's Submission

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-02

    ... previously published in the Federal Register (77 FR 6814) on February 9, 2012, allowing for a 60-day comment... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse... approval in accordance with the Paperwork Reduction Act: Bonded Warehouse Proprietor's Submission (CBP...

  13. Phosphate-intercalated Ca-Fe-layered double hydroxides: Crystal structure, bonding character, and release kinetics of phosphate

    SciTech Connect

    Woo, Myong A.; Woo Kim, Tae; Paek, Mi-Jeong; Ha, Hyung-Wook; Choy, Jin-Ho; Hwang, Seong-Ju

    2011-01-15

    The nitrate-form of Ca-Fe-layered double hydroxide (Ca-Fe-LDH) was synthesized via co-precipitation method, and its phosphate-intercalates were prepared by ion-exchange reaction. According to X-ray diffraction analysis, the Ca-Fe-LDH-NO{sub 3}{sup -} compound and its H{sub 2}PO{sub 4}{sup -}-intercalate showed hexagonal layered structures, whereas the ion-exchange reaction with HPO{sub 4}{sup 2-} caused a frustration of the layer ordering of LDH. Fe K-edge X-ray absorption spectroscopy clearly demonstrated that the Ca-Fe-LDH lattice with trivalent iron ions was well-maintained after the ion-exchange with HPO{sub 4}{sup 2-} and H{sub 2}PO{sub 4}{sup -}. Under acidic conditions, phosphate ions were slowly released from the Ca-Fe-LDH lattice and the simultaneous release of hydroxide caused the neutralization of acidic media. Fitting analysis based on kinetic models indicated a heterogeneous diffusion process of phosphates and a distinct dependence of release rate on the charge of phosphates. This study strongly suggested that Ca-Fe-LDH is applicable as bifunctional vector for slow release of phosphate fertilizer and for the neutralization of acid soil. -- Graphical abstract: We synthesized phosphate-intercalated Ca-Fe-LDH materials that can act as bifunctional inorganic vectors for the slow release of phosphate fertilizer and also the neutralization of acid soil. Fitting analysis based on kinetic models indicated a heterogeneous diffusion process of phosphates and a distinct dependence of release rate on the charge of phosphates. Display Omitted Research Highlights: {yields} The phosphate forms of Ca-Fe-layered double hydroxide (Ca-Fe-LDH) were synthesized via co-precipitation method. The crystal structure, bonding character, and release kinetics of phosphate of the phosphate-intercalates were investigated. These Ca-Fe-LDH materials are applicable as bifunctional vector for slow release of phosphate fertilizer and for the neutralization of acid soil.

  14. Thermally-Activated Metal-to-Glass Bonding

    NASA Technical Reports Server (NTRS)

    Gallagher, B. D.

    1986-01-01

    Hermetic seals formed easily by use of metallo-organic film. Metallo-organic film thermally bonded to glass and soldered or welded to form hermetic seal. Film applied as ink consisting of silver neodecanoate in xylene. Relative amounts of ingredients selected to obtain desired viscosity. Material applied by printing or even by scribing with pen. Sealing technique useful in making solar-cell modules, microelectronic packages, and other hermetic silicon devices.

  15. Double hybrid functionals and the Π-system bond length alternation challenge: rivaling accuracy of post-HF methods.

    PubMed

    Wykes, Michael; Su, Neil Qiang; Xu, Xin; Adamo, Carlo; Sancho-García, Juan-Carlos

    2015-02-10

    Predicting accurate bond length alternations (BLAs) in long conjugated oligomers has been a significant challenge for electronic-structure methods for many decades, made particularly important by the close relationships between BLA and the rich optoelectronic properties of π-delocalized systems. Here, we test the accuracy of recently developed, and increasingly popular, double hybrid (DH) functionals, positioned at the top of Jacobs Ladder of DFT methods of increasing sophistication, computational cost, and accuracy, due to incorporation of MP2 correlation energy. Our test systems comprise oligomeric series of polyacetylene, polymethineimine, and polysilaacetylene up to six units long. MP2 calculations reveal a pronounced shift in BLAs between the 6-31G(d) basis set used in many studies of BLA to date and the larger cc-pVTZ basis set, but only modest shifts between cc-pVTZ and aug-cc-pVQZ results. We hence perform new reference CCSD(T)/cc-pVTZ calculations for all three series of oligomers against which we assess the performance of several families of DH functionals based on BLYP, PBE, and TPSS, along with lower-rung relatives including global- and range-separated hybrids. Our results show that DH functionals systematically improve the accuracy of BLAs relative to single hybrid functionals. xDH-PBE0 (N(4) scaling using SOS-MP2) emerges as a DH functional rivaling the BLA accuracy of SCS-MP2 (N(5) scaling), which was found to offer the best compromise between computational cost and accuracy the last time the BLA accuracy of DFT- and wave function-based methods was systematically investigated. Interestingly, xDH-PBE0 (XYG3), which differs to other DHs in that its MP2 term uses PBE0 (B3LYP) orbitals that are not self-consistent with the DH functional, is an outlier of trends of decreasing average BLA errors with increasing fractions of MP2 correlation and HF exchange. PMID:26579607

  16. Adsorption of water on reconstructed rutile TiO2(011)-(2 x 1): Ti=O double bonds and surface reactivity.

    PubMed

    Di Valentin, Cristiana; Tilocca, Antonio; Selloni, Annabella; Beck, T J; Klust, Andreas; Batzill, Matthias; Losovyj, Yaroslav; Diebold, Ulrike

    2005-07-13

    Recent combined experimental and theoretical studies (Beck et al., Phys. Rev. Lett. 2004, 93, 036104) have provided evidence for Ti=O double-bonded titanyl groups on the reconstructed rutile TiO(2)(011)-(2 x 1) surface. The adsorption of water on the same surface is now investigated to further probe the properties of these groups, as well as to confirm their existence. Ultraviolet photoemission experiments show that water is adsorbed in molecular form at a sample temperature of 110 K. At the same time, the presence of a 3sigma state in the photoemission spectra and work function measurements indicate a significant amount of hydroxyls within the first monolayer of water. At room temperature, scanning tunneling microscopy (STM) suggests that dissociated water is present, and about 30% of the surface active sites are hydroxylated. These findings are well explained by total energy density functional theory calculations and Car-Parrinello molecular dynamics simulations for water adsorption on the titanyl model of TiO(2)(011)-(2 x 1). The theoretical results show that a mixed molecular/dissociative layer is the most stable configuration in the monolayer regime at low temperatures, while complete dissociation takes place at 250 K. The arrangement of the protonated mono-coordinated oxygens in the mixed molecular/dissociated layer is consistent with the observed short-range order of the hydroxyls in the STM images.

  17. Origin of the 900 cm{sup −1} broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids

    SciTech Connect

    Van Hoozen, Brian L.; Petersen, Poul B.

    2015-03-14

    Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm{sup −1} broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusual feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole—acetic acid and pyridine—acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes.

  18. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  19. 26 CFR 1.103(n)-1T - Limitation on aggregrate amount of private activity bonds (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... activity bonds (temporary). 1.103(n)-1T Section 1.103(n)-1T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-1T Limitation on aggregrate amount of private activity bonds (temporary). Q-1: What does section 103(n) provide? A-1: Interest on an issue of private activity bonds...

  20. Metal-activated histidine carbon donor hydrogen bonds contribute to metalloprotein folding and function.

    PubMed

    Schmiedekamp, Ann; Nanda, Vikas

    2009-07-01

    Carbon donor hydrogen bonds are typically weak interactions that contribute less than 2 kcal/mol, and provide only modest stabilization in proteins. One exception is the class of hydrogen bonds donated by heterocyclic side chain carbons. Histidine is capable of particularly strong interactions through the Cepsilon(1) and Cdelta(2) carbons when the imidazole is protonated or bound to metal. Given the frequent occurrence of metal-bound histidines in metalloproteins, we characterized the energies of these interactions through DFT calculations on model compounds. Imidazole-water hydrogen bonding could vary from -11.0 to -17.0 kcal/mol, depending on the metal identity and oxidation state. A geometric search of metalloprotein structures in the PDB identified a number of candidate His C-H...O hydrogen bonds which may be important for folding or function. DFT calculations on model complexes of superoxide reductase show a carbon donor hydrogen bond positioning a water molecule above the active site.

  1. Carbon-Hydrogen Bond Activation in Hydridotris(pyrazolyl)borate Platinum(IV) Complexes:  Comparison of Density Functionals, Basis Sets, and Bonding Patterns.

    PubMed

    Vastine, Benjamin Alan; Webster, Charles Edwin; Hall, Michael B

    2007-11-01

    The reaction mechanism for the cycle beginning with the reductive elimination (RE) of methane from κ(3)-TpPt(IV)(CH3)2H (1) (Tp = hydridotris(pyrazolyl)borate) and subsequent oxidative addition (OA) of benzene to form finally κ(3)-TpPt(IV)(Ph)2H (19) was investigated by density functional theory (DFT). Two mechanistic steps are of particular interest, namely the barrier to C-H coupling (barrier 1 - Ba1) and the barrier to methane release (barrier 2 - Ba2). For 31 density functionals, the calculated values for Ba1 and Ba2 were benchmarked against the experimentally reported values of 26 (Ba1) and 35 (Ba2) kcal·mol(-1), respectively. Specifically, the values for Ba1 and Ba2, calculated at the B3LYP/double-ζ plus polarization level of theory, are 24.6 and 34.3 kcal·mol(-1), respectively. Overall, the best performing functional was BPW91 where the mae associated with the calculated values of the two barriers is 0.68 kcal·mol(-1). The calculated B3LYP values of Ba1 ranged between 20 and 26 kcal·mol(-1) for 12 effective core potential basis sets for platinum and 29 all-electron basis sets for the first row elements. Polarization functions for the first row elements were important for accurate values, but the addition of diffuse functions to non-hydrogen (+) and hydrogen atoms (++) had little effect on the calculated values. Basis set saturation was achieved with APNO basis sets utilized for first-row atoms. Bader's "Atoms in Molecules" was used to analyze the electron density of several complexes, and the electron density at the Pt-Nax bond critical point (trans to the active site for C-H coupling) varied over a wider range than any of the other Pt-N bonds.

  2. Novel biohybrids of layered double hydroxide and lactate dehydrogenase enzyme: Synthesis, characterization and catalytic activity studies

    NASA Astrophysics Data System (ADS)

    Djebbi, Mohamed Amine; Braiek, Mohamed; Hidouri, Slah; Namour, Philippe; Jaffrezic-Renault, Nicole; Ben Haj Amara, Abdesslem

    2016-02-01

    The present work introduces new biohybrid materials involving layered double hydroxides (LDH) and biomolecule such as enzyme to produce bioinorganic system. Lactate dehydrogenase (Lac Deh) has been chosen as a model enzyme, being immobilized onto MgAl and ZnAl LDH materials via direct ion-exchange (adsorption) and co-precipitation methods. The immobilization efficiency was largely dependent upon the immobilization methods. A comparative study shows that the co-precipitation method favors the immobilization of great and tunable amount of enzyme. The structural behavior, chemical bonding composition and morphology of the resulting biohybrids were determined by X-ray diffraction (XRD) study, Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM), respectively. The free and immobilized enzyme activity and kinetic parameters were also reported using UV-Visible spectroscopy. However, the modified LDH materials showed a decrease in crystallinity as compared to the unmodified LDH. The change in activity of the immobilized lactate dehydrogenase was considered to be due, to the reduced accessibility of substrate molecules to the active sites of the enzyme and the partial conformational change of the Lac Deh molecules as a result of the immobilization way. Finally, it was proven that there is a correlation between structure/microstructure and enzyme activity dependent on the immobilization process.

  3. A DFT and ab initio benchmarking study of metal-alkane interactions and the activation of carbon-hydrogen bonds.

    PubMed

    Flener-Lovitt, Charity; Woon, David E; Dunning, Thom H; Girolami, Gregory S

    2010-02-01

    Density functional theory and ab initio methods have been used to calculate the structures and energies of minima and transition states for the reactions of methane coordinated to a transition metal. The reactions studied are reversible C-H bond activation of the coordinated methane ligand to form a transition metal methyl hydride complex and dissociation of the coordinated methane ligand. The reaction sequence can be summarized as L(x)M(CH(3))H <==> L(x)M(CH(4)) <==> L(x)M + CH(4), where L(x)M is the osmium-containing fragment (C(5)H(5))Os(R(2)PCH(2)PR(2))(+) and R is H or CH(3). Three-center metal-carbon-hydrogen interactions play an important role in this system. Both basis sets and functionals have been benchmarked in this work, including new correlation consistent basis sets for a third transition series element, osmium. Double zeta quality correlation consistent basis sets yield energies close to those from calculations with quadruple-zeta basis sets, with variations that are smaller than the differences between functionals. The energies of important species on the potential energy surface, calculated by using 10 DFT functionals, are compared both to experimental values and to CCSD(T) single point calculations. Kohn-Sham natural bond orbital descriptions are used to understand the differences between functionals. Older functionals favor electrostatic interactions over weak donor-acceptor interactions and, therefore, are not particularly well suited for describing systems--such as sigma-complexes--in which the latter are dominant. Newer kinetic and dispersion-corrected functionals such as MPW1K and M05-2X provide significantly better descriptions of the bonding interactions, as judged by their ability to predict energies closer to CCSD(T) values. Kohn-Sham and natural bond orbitals are used to differentiate between bonding descriptions. Our evaluations of these basis sets and DFT functionals lead us to recommend the use of dispersion corrected functionals in

  4. (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B–H Activation at a Single Metal Center

    PubMed Central

    2016-01-01

    The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B–H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B–Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne–carboranyl transformations reported herein represent a new mode of cooperative metal–ligand reactivity of boron-based complexes. PMID:27526855

  5. (BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center.

    PubMed

    Eleazer, Bennett J; Smith, Mark D; Popov, Alexey A; Peryshkov, Dmitry V

    2016-08-24

    The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B-Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne-carboranyl transformations reported herein represent a new mode of cooperative metal-ligand reactivity of boron-based complexes. PMID:27526855

  6. Low-cost bump bonding activities at CERN

    NASA Astrophysics Data System (ADS)

    Vähänen, S.; Tick, T.; Campbell, M.

    2010-11-01

    Conventional bumping processes used in the fabrication of hybrid pixel detectors for High Energy Physics (HEP) experiments use electroplating for Under Bump Metallization (UBM) and solder bump deposition. This process is laborious, involves time consuming photolithography and can only be performed using whole wafers. Electroplating has been found to be expensive when used for the low volumes which are typical of HEP experiments. In the low-cost bump bonding development work, electroless deposition technology of UBM is studied as an alternative to the electroplating process in the bump size / pitch window beginning from 20 μm / 50 μm. Electroless UBM deposition used in combination with solder transfer techniques has the potential to significantly lower the cost of wafer bumping without requiring increased wafer volumes. A test vehicle design of sensor and readout chip, having daisy chains and Kelvin bump structures, was created to characterize the flip chip process with electroless UBM. Two batches of test vehicle wafers were manufactured with different bump pad metallization. Batch #1 had AlSi(1%) metallization, which is similar to the one used on sensor wafers, and Batch #2 had AlSi(2%)Cu(1%) metallization, which is very similar to the one used on readout wafers. Electroless UBMs were deposited on both wafer batches. In addition, electroplated Ni UBM and SnPb solder bumps were grown on the test sensor wafers. Test assemblies were made by flip chip bonding the solder-bumped test sensors against the test readout chips with electroless UBMs. Electrical yields and individual joint resistances were measured from assemblies, and the results were compared to a well known reference technique based on electroplated solder bumps structures on both chips. The electroless UBMs deposited on AlSi(2%)Cu(1%) metallization showed excellent electrical yields and small tolerances in individual joint resistance. The results from the UBMs deposited on AlSi(1%) metallization were non

  7. Production of the Ramoplanin Activity Analogue by Double Gene Inactivation

    PubMed Central

    Han, Jungang; Chen, Junsheng; Shao, Lei; Zhang, Junliang; Dong, Xiaojing; Liu, Pengyu; Chen, Daijie

    2016-01-01

    Glycopeptides such as vancomycin and telavancin are essential for treating infections caused by Gram-positive bacteria. But the dwindling availability of new antibiotics and the emergence of resistant bacteria are making effective antibiotic treatment increasingly difficult. Ramoplanin, an inhibitor of bacterial cell wall biosynthesis, is a highly effective antibiotic against a wide range of Gram-positive bacteria, including methicillin-resistant Staphylococcus aureus, vancomycin-intermediate resistant Clostridium difficile and vancomycin-resistant Enterococcus sp. Here, two tailoring enzyme genes in the biosynthesis of ramoplanin were deleted by double in-frame gene knockouts to produce new ramoplanin derivatives. The deschlororamoplanin A2 aglycone was purified and its structure was identified with LC-MS/MS. Deschlororamoplanin A2 aglycone and ramoplanin aglycone showed similar activity to ramoplanin A2. The results showed that α-1,2-dimannosyl disaccharide at Hpg11 and chlorination at Chp17 in the ramoplanin structure are not essential for its antimicrobial activity. This work provides new precursor compounds for the semisynthetic modification of ramoplanin. PMID:27149627

  8. Effect of water-ageing on dentine bond strength and anti-biofilm activity of bonding agent containing new monomer dimethylaminododecyl methacrylate

    PubMed Central

    Zhang, Ke; Cheng, Lei; Wu, Eric J.; Weir, Michael D.; Bai, Yuxing; Xu, Hockin H. K.

    2013-01-01

    Objectives The objectives of this study were to develop bonding agent containing a new antibacterial monomer dimethylaminododecyl methacrylate (DMADDM) as well as nanoparticles of silver (NAg) and nanoparticles of amorphous calcium phosphate (NACP), and to investigate the effects of water-ageing for 6 months on dentine bond strength and anti-biofilm properties for the first time. Methods Four bonding agents were tested: Scotchbond Multi-Purpose (SBMP) Primer and Adhesive control; SBMP + 5% DMADDM; SBMP + 5% DMADDM + 0.1% NAg; and SBMP + 5% DMADDM + 0.1% NAg with 20% NACP in adhesive. Specimens were water-aged for 1 d and 6 months at 37 °C. Then the dentine shear bond strengths were measured. A dental plaque microcosm biofilm model was used to inoculate bacteria on water-aged specimens and to measure metabolic activity, colony-forming units (CFUs), and lactic acid production. Results Dentine bond strength showed a 35% loss in 6 months of water-ageing for SBMP control (mean ± sd; n = 10); in contrast, the new antibacterial bonding agents showed no strength loss. The DMADDM–NAg–NACP containing bonding agent imparted a strong antibacterial effect by greatly reducing biofilm viability, metabolic activity and acid production. The biofilm CFU was reduced by more than two orders of magnitude, compared to SBMP control. Furthermore, the DMADDM–NAg–NACP bonding agent exhibited a long-term antibacterial performance, with no significant difference between 1 d and 6 months (p > 0.1). Conclusions Incorporating DMADDM–NAg–NACP in bonding agent yielded potent and long-lasting antibacterial properties, and much stronger bond strength after 6 months of water-ageing than a commercial control. The new antibacterial bonding agent is promising to inhibit biofilms and caries at the margins. The method of DMADDM–NAg–NACP incorporation may have a wide applicability to other adhesives, cements and composites. PMID:23583528

  9. Antibacterial activity and bonding ability of an adhesive incorporating an antibacterial monomer DMAE-CB.

    PubMed

    Xiao, Yu-Hong; Ma, Sai; Chen, Ji-Hua; Chai, Zhi-Guo; Li, Fang; Wang, Ying-Jie

    2009-08-01

    This study evaluated the antibacterial effect and microtensile bond strength of a resin-based adhesive containing an antibacterial monomer DMAE-CB (methacryloxylethyl cetyl dimethyl ammonium chloride). Cured specimens of 1, 2, and 3% DMAE-CB-containing Single Bond 2 (crosslinking monomer: Bis-GMA, dimethacrylates; functional monomer: HEMA) were prepared, and their antibacterial effects on Streptococcus mutans ATCC 25175 were investigated. Antibacterial property after 0, 30, 90, and 180 days of aging was also tested. Bonding ability of the experimental adhesive incorporating 3% DMAE-CB was evaluated by microtensile bond strength test. The cured experimental adhesive exhibited an inhibitory effect on S. mutans growth, and the adhesive containing 3% DMAE-CB showed higher antibacterial efficiency compared with those incorporating 1 or 2% anibacterial monomer. Antibacterial activities of the specimens lasted for at least 180 days. Microtensile bond strength test revealed that the bonding ability of the experimental adhesive was not significantly adversely affected by the incorporation of DMAE-CB. Therefore, dental adhesives with strong and long-lasting bacteriostatic property could be achieved by incorporating DMAE-CB without negatively influencing bonding ability.

  10. O-H...O versus O-H...S hydrogen bonding. 3. IR-UV double resonance study of hydrogen bonded complexes of p-cresol with diethyl ether and its sulfur analog.

    PubMed

    Biswal, Himansu S; Wategaonkar, Sanjay

    2010-05-20

    In this work the hydrogen bonded complexes of diethyl ether (DEE) and diethyl sulfide (DES) with p-cresol (p-CR) were investigated. Only one conformer of the p-CR.DEE complex and three conformers of the p-CR.DES complex were found to be present under the supersonic jet expansion conditions. The conformational assignments were done with the help of IR-UV double resonance studies and ab initio calculations. The red shifts in the OH stretching frequency for the O-H...O and O-H...S hydrogen bonded complexes were quite close to each other. In fact, one of the p-CR.DES conformers showed a slightly larger red shift in the OH stretch than that in the p-CR.DEE conformer, which suggests that in this case sulfur is not a weak hydrogen bond acceptor as noted previously in case of the p-CR.H(2)O and p-CR.H(2)S complexes (Biswal et al. J. Phys. Chem. A 2009, 113, 5633). The natural bond orbital analysis also shows that the extent of overlap between sulfur lone pair orbitals (LP) and OH antibonding orbital (sigma*(OH)) was comparable to the oxygen (LP) and sigma*(OH) overlap, consistent with the similar magnitudes of the red shifts of OH stretch in the DES and DEE complexes. The computed binding energy of the p-CR.DES complex, however, was about 80% of the p-CR.DEE complex. The electron densities at the bond critical points indicated that the O-H...S interaction was weaker than the O-H...O interaction in this particular system also. The important finding of this study was that the IR red shifts in the H-bond donor X-H stretching frequency were not quite consistent with the computed binding energies and the atoms-in-molecules analysis contrary to the general understanding. Energy decomposition analysis suggests that O-H...S hydrogen bonding interaction is dispersive in nature and the dispersion contribution decreases with the increase in the length of the alkyl chain of the "S" hydrogen bond acceptor.

  11. Collision-induced dissociation of fatty acid [M - 2H + Na]- ions: charge-directed fragmentation and assignment of double bond position.

    PubMed

    Thomas, Michael C; Altvater, Jens; Gallagher, Thomas J; Nette, Geoffrey W

    2014-11-01

    The collision-induced dissociation (CID) of cationic fatty acid-metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid-sodium ion complexes, referred to as [M - 2H + Na] (-) ions. In the current manuscript, the CID behavior of these [M - 2H + Na] (-) ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the α-carbon in the formation of fatty acid [M - H + NaF](-) ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M - 2H + Na](-) ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon-carbon double bonds. In addition, CID of [M - 2H + Na](-) ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ∆(9,12,15)18:3, ∆(6,9,12)18:3, and ∆(5,8,11)18:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the α-carbon.

  12. Collision-Induced Dissociation of Fatty Acid [M - 2H + Na]- Ions: Charge-Directed Fragmentation and Assignment of Double Bond Position

    NASA Astrophysics Data System (ADS)

    Thomas, Michael C.; Altvater, Jens; Gallagher, Thomas J.; Nette, Geoffrey W.

    2014-08-01

    The collision-induced dissociation (CID) of cationic fatty acid-metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid-sodium ion complexes, referred to as [M - 2H + Na] - ions. In the current manuscript, the CID behavior of these [M - 2H + Na] - ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the α-carbon in the formation of fatty acid [M - H + NaF]- ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M - 2H + Na]- ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon-carbon double bonds. In addition, CID of [M - 2H + Na]- ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ∆9,12,1518:3, ∆6,9,1218:3, and ∆5,8,1118:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the α-carbon.

  13. Localization of fatty acyl and double bond positions in phosphatidylcholines using a dual stage CID fragmentation coupled with ion mobility mass spectrometry.

    PubMed

    Castro-Perez, Jose; Roddy, Thomas P; Nibbering, Nico M M; Shah, Vinit; McLaren, David G; Previs, Stephen; Attygalle, Athula B; Herath, Kithsiri; Chen, Zhu; Wang, Sheng-Ping; Mitnaul, Lyndon; Hubbard, Brian K; Vreeken, Rob J; Johns, Douglas G; Hankemeier, Thomas

    2011-09-01

    A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M + Li](+) was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C(15)H(31)CO(+), m/z 239) or 18:1 (9Z) (C(17)H(33)CO(+), m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H(2)C-HC = CH-CH = CH(2)). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of (13)C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.

  14. Synthesis and Applications of Rhodacyclopentanones Derived From C-C Bond Activation

    PubMed Central

    Shaw, Megan H.; Bower, John F.

    2016-01-01

    Rhodacyclopentanones, an “sp3-rich” class of metallacycle, underpin an emerging range of catalytic methodologies for the direct generation of complex scaffolds. This review highlights strategies for accessing rhodacyclopentanones (and related species) by C-C bond activation of cyclobutanones or cyclopropanes. The scope and mechanism of methodologies that exploit these activation modes is outlined. PMID:27385089

  15. Hormonal changes and couple bonding in consensual sadomasochistic activity.

    PubMed

    Sagarin, Brad J; Cutler, Bert; Cutler, Nadine; Lawler-Sagarin, Kimberly A; Matuszewich, Leslie

    2009-04-01

    In two studies, 58 sadomasochistic (SM) practitioners provided physiological measures of salivary cortisol and testosterone (hormones associated with stress and dominance, respectively) and psychological measures of relationship closeness before and after participating in SM activities. Observed activities included bondage, sensory deprivation, a variety of painful and pleasurable stimulation, verbal and non-verbal communication, and expressions of caring and affection. During the scenes, cortisol rose significantly for participants who were bound, receiving stimulation, and following orders, but not for participants who were providing stimulation, orders, or structure. Female participants who were bound, receiving stimulation, and following orders also showed increases in testosterone during the scenes. Thereafter, participants who reported that their SM activities went well showed reductions in physiological stress (cortisol) and increases in relationship closeness. Among participants who reported that their SM activities went poorly, some showed decreases in relationship closeness whereas others showed increases. The increases in relationship closeness combined with the displays of caring and affection observed as part of the SM activities offer support for the modern view that SM, when performed consensually, has the potential to increase intimacy between participants. PMID:18563549

  16. Reactions of organoaluminum compounds with acetylene as a method for the synthesis of aliphatic derivatives with a z-disubstituted double bond

    SciTech Connect

    Andreeva, N.I.; Kuchin, A.V.; Tolstikov, G.A.

    1985-11-01

    This paper develops a method for the synthesis of aliphatic compounds with a Z-disubstituted double bond, which are important synthons for the preparation of such natural products as insect pheromones, aromatic principles, etc. In the carbalumination reaction of acetylene Z-alkenyldialkylaluminums are formed selectively. A-Alkenyldialkylaluminums are highly reactive and can readily be converted into Z-allyl alcohols and their ethers, and into Z-iodovinyl derivatives. By the reactions of vinyl organoaluminum compounds with the complex CH/sub 3/COClhaAlCl/sub 3/ E-conjugated ketones were obtained.

  17. Δ(11,12) double bond formation in tirandamycin biosynthesis is atypically catalyzed by TrdE, a glycoside hydrolase family enzyme.

    PubMed

    Mo, Xuhua; Ma, Junying; Huang, Hongbo; Wang, Bo; Song, Yongxiang; Zhang, Si; Zhang, Changsheng; Ju, Jianhua

    2012-02-15

    The tirandamycins (TAMs) are a small group of Streptomyces-derived natural products that target bacterial RNA polymerase. Within the TAM biosynthetic cluster, trdE encodes a glycoside hydrolase whose role in TAM biosynthesis has been undefined until now. We report that in vivo trdE inactivation leads to accumulation of pre-tirandamycin, the earliest intermediate released from its mixed polyketide/nonribosomal peptide biosynthetic assembly line. In vitro and site-directed mutagenesis studies showed that TrdE, a putative glycoside hydrolase, catalyzes in a highly atypical fashion the installation of the Δ(11,12) double bond during TAM biosynthesis.

  18. A Facile Method to Prepare Double-Layer Isoporous Hollow Fiber Membrane by In Situ Hydrogen Bond Formation in the Spinning Line.

    PubMed

    Noor, Nazia; Koll, Joachim; Radjabian, Maryam; Abetz, Clarissa; Abetz, Volker

    2016-03-01

    A double-layer hollow fiber is fabricated where an isoporous surface of polystyrene-block-poly(4-vinylpyridine) is fixed on a support layer by co-extrusion. Due to the sulfonation of the support layer material, delamination of the two layers is suppressed without increasing the number of subsequent processing steps for isoporous composite membrane formation. Electron microscope-energy-dispersive X-ray spectroscopy images unveil the existence of a high sulfur concentration in the interfacial region by which in-process H-bond formation between the layers is evidenced. For the very first time, our study reports a facile method to fabricate a sturdy isoporous double-layer hollow fiber.

  19. Sticker Bonding.

    ERIC Educational Resources Information Center

    Frazier, Laura Corbin

    2000-01-01

    Introduces a science activity on the bonding of chemical compounds. Assigns students the role of either a cation or anion and asks them to write the ions they may bond with. Assesses students' understanding of charge, bonding, and other concepts. (YDS)

  20. Modification of purine and pyrimidine nucleosides by direct C-H bond activation.

    PubMed

    Liang, Yong; Wnuk, Stanislaw F

    2015-03-17

    Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

  1. C-H bond activation by metal-superoxo species: what drives high reactivity?

    PubMed

    Ansari, Azaj; Jayapal, Prabha; Rajaraman, Gopalan

    2015-01-01

    Metal-superoxo species are ubiquitous in metalloenzymes and bioinorganic chemistry and are known for their high reactivity and their ability to activate inert C-H bonds. The comparative oxidative abilities of M-O2(.-) species (M = Cr(III), Mn(III), Fe(III), and Cu(II)) towards C-H bond activation reaction are presented. These superoxo species generated by oxygen activation are found to be aggressive oxidants compared to their high-valent metal-oxo counterparts generated by O⋅⋅⋅O bond cleavage. Our calculations illustrate the superior oxidative abilities of Fe(III)- and Mn(III)-superoxo species compared to the others and suggest that the reactivity may be correlated to the magnetic exchange parameter.

  2. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 29 Labor 9 2013-07-01 2013-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  3. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 29 Labor 9 2012-07-01 2012-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  4. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 29 Labor 9 2011-07-01 2011-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  5. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 9 2014-07-01 2014-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  6. 29 CFR 2580.412-8 - The nature of the duties or activities to which the bonding requirement relates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false The nature of the duties or activities to which the bonding requirement relates. 2580.412-8 Section 2580.412-8 Labor Regulations Relating to Labor (Continued) EMPLOYEE... INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-8 The nature...

  7. Nickel-Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C-N Bond Activation.

    PubMed

    Hu, Jiefeng; Zhao, Yue; Liu, Jingjing; Zhang, Yemin; Shi, Zhuangzhi

    2016-07-18

    A nickel/N-heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B2 nep2 by C-N bond activation. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was first confirmed by X-ray analysis. Furthermore, the decarbonylative process was also observed. These findings confirm the key mechanistic features of the acyl C-N bond activation process. PMID:27258597

  8. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    SciTech Connect

    Lichtenberger, D.L.

    1992-01-01

    Purpose of this research program is to obtain experimental information on the different fundamental ways metals bond and activate organic molecules. Our approach has been to directly probe the electronic interactions between metals and molecules through a wide variety of ionization spectroscopies and other techniques, and to investigate the relationships with bonding modes, structures, and chemical behavior. During this period, we have (1) characterized the electronic features of diphosphines and monophosphines in their coordination to metals, (2) carried out theoretical and experimental investigations of the bonding capabilities of C[sub 60] to transition metals, (3) developed techniques for the imaging of single molecules on gold substrates that emphasizes the electronic backbonding from the metal to the molecule, (4) obtained the high resolution photoelectron spectrum of pure C[sub 70] in the gas phase, (5) compared the bonding of [eta][sup 3]- acetylide ligands to the bonding of other small organic molecules with metals, and (6) reported the photoelectron spectra and bonding of [eta][sup 3]-cyclopropenyl groups to metals.

  9. Effect of bonding on the performance of a piezoactuator-based active control system

    NASA Technical Reports Server (NTRS)

    Baz, A.; Poh, S.

    1987-01-01

    The utilization of piezoelectric actuators in controlling the structural vibrations of flexible beams is studied. A Modified Independent Modal Space Control (MIMSC) method is devised to select the optimal location, control gains and excitation voltage of the piezoelectric actuators in a way that would minimize the amplitudes of vibrations of beams to which these actuators are bonded, as well as the input control energy necessary to suppress these vibrations. The presented method accounts for the effects that the piezoelectric actuators and the bonding layers have on changing the elastic and inertial properties of the flexible beams. Numerical examples are presented to illustrate the application of the MIMSC method and to demonstrate the effect of the physical and geometrical properties of the bonding layer on the dynamic performance of the actively controlled beams. The obtained results emphasize the importance of the devised method in designing more realistic active control systems for flexible beams, in particular, and large flexible structures in general.

  10. Determination of the bond-angle distribution in vitreous B{sub 2}O{sub 3} by {sup 11}B double rotation (DOR) NMR spectroscopy

    SciTech Connect

    Hung, I.; Howes, A.P.; Parkinson, B.G.; Anupold, T.; Samoson, A.; Brown, S.P.; Harrison, P.F.; Holland, D.; Dupree, R.

    2009-09-15

    The B-O-B bond angle distributions for both ring and non-ring boron sites in vitreous B{sub 2}O{sub 3} have been determined by {sup 11}B double rotation (DOR) NMR and multiple-quantum (MQ) DOR NMR. The [B{sub 3}O{sub 6}] boroxol rings are observed to have a mean internal B-O-B angle of 120.0+-0.7 deg. with a small standard deviation, sigma{sub R}=3.2+-0.4 deg., indicating that the rings are near-perfect planar, hexagonal structures. The rings are linked predominantly by non-ring [BO{sub 3}] units, which share oxygens with the boroxol ring, with a mean B{sub ring}-O-B{sub non-ring} angle of 135.1+-0.6 deg. and sigma{sub NR}=6.7+-0.4 deg. In addition, the fraction of boron atoms, f, which reside in the boroxol rings has been measured for this sample as f=0.73+-0.01. - Graphical abstract: Connectivities and B-O-B bond angle distributions of ring and non-ring boron atoms in v-B{sub 2}O{sub 3} have been determined by {sup 11}B double rotation (DOR) NMR, multiple-quantum (MQ) DOR NMR and spin-diffusion DOR. Near-perfect planar, hexagonal [B{sub 3}O{sub 6}] boroxol rings are shown to be present. Display Omitted

  11. Unveiling of novel regio-selective fatty acid double bond hydratases from Lactobacillus acidophilus involved in the selective oxyfunctionalization of mono- and di-hydroxy fatty acids.

    PubMed

    Kim, Kyoung-Rok; Oh, Hye-Jin; Park, Chul-Soon; Hong, Seung-Hye; Park, Ji-Young; Oh, Deok-Kun

    2015-11-01

    The aim of this study is the first time demonstration of cis-12 regio-selective linoleate double-bond hydratase. Hydroxylation of fatty acids, abundant feedstock in nature, is an emerging alternative route for many petroleum replaceable products thorough hydroxy fatty acids, carboxylic acids, and lactones. However, chemical route for selective hydroxylation is still quite challenging owing to low selectivity and many environmental concerns. Hydroxylation of fatty acids by hydroxy fatty acid forming enzymes is an important route for selective biocatalytic oxyfunctionalization of fatty acids. Therefore, novel fatty acid hydroxylation enzymes should be discovered. The two hydratase genes of Lactobacillus acidophilus were identified by genomic analysis, and the expressed two recombinant hydratases were identified as cis-9 and cis-12 double-bond selective linoleate hydratases by in vitro functional validation, including the identification of products and the determination of regio-selectivity, substrate specificity, and kinetic parameters. The two different linoleate hydratases were the involved enzymes in the 10,13-dihydroxyoctadecanoic acid biosynthesis. Linoleate 13-hydratase (LHT-13) selectively converted 10 mM linoleic acid to 13S-hydroxy-9(Z)-octadecenoic acid with high titer (8.1 mM) and yield (81%). Our study will expand knowledge for microbial fatty acid-hydroxylation enzymes and facilitate the designed production of the regio-selective hydroxy fatty acids for useful chemicals from polyunsaturated fatty acid feedstocks.

  12. Diffusion Bonding Beryllium to Reduced Activation Ferritic Martensitic Steel: Development of Processes and Techniques

    NASA Astrophysics Data System (ADS)

    Hunt, Ryan Matthew

    Only a few materials are suitable to act as armor layers against the thermal and particle loads produced by magnetically confined fusion. These candidates include beryllium, tungsten, and carbon fiber composites. The armor layers must be joined to the plasma facing components with high strength bonds that can withstand the thermal stresses resulting from differential thermal expansion. While specific joints have been developed for use in ITER (an experimental reactor in France), including beryllium to CuCrZr as well as tungsten to stainless steel interfaces, joints specific to commercially relevant fusion reactors are not as well established. Commercial first wall components will likely be constructed front Reduced Activation Ferritic Martensitic (RAFM) steel, which will need to be coating with one of the three candidate materials. Of the candidates, beryllium is particularly difficult to bond, because it reacts during bonding with most elements to form brittle intermetallic compounds. This brittleness is unacceptable, as it can lead to interface crack propagation and delamination of the armor layer. I have attempted to overcome the brittle behavior of beryllium bonds by developing a diffusion bonding process of beryllium to RAFM steel that achieves a higher degree of ductility. This process utilized two bonding aids to achieve a robust bond: a. copper interlayer to add ductility to the joint, and a titanium interlayer to prevent beryllium from forming unwanted Be-Cu intermetallics. In addition, I conducted a series of numerical simulations to predict the effect of these bonding aids on the residual stress in the interface. Lastly, I fabricated and characterized beryllium to ferritic steel diffusion bonds using various bonding parameters and bonding aids. Through the above research, I developed a process to diffusion bond beryllium to ferritic steel with a 150 M Pa tensile strength and 168 M Pa shear strength. This strength was achieved using a Hot Isostatic

  13. A computational study on the N-heterocyclic carbene-catalyzed Csp(2)-Csp(3) bond activation/[4+2] cycloaddition cascade reaction of cyclobutenones with imines: a new application of the conservation principle of molecular orbital symmetry.

    PubMed

    Wang, Yang; Wu, Bohua; Zhang, Haoyang; Wei, Donghui; Tang, Mingsheng

    2016-07-20

    A comprehensive density functional theory (DFT) investigation has been performed to interrogate the mechanisms and stereoselectivities of the Csp(2)-Csp(3) single bond activation of cyclobutenones and their [4+2] cycloaddition reaction with imines via N-heterocyclic carbene (NHC) organocatalysis. According to our calculated results, the fundamental reaction pathway contains four steps: nucleophilic addition of NHC to cyclobutenone, C-C bond cleavage for the formation of an enolate intermediate, [4+2] cycloaddition of the enolate intermediate with isatin imine, and the elimination of the NHC catalyst. In addition, the calculated results also reveal that the second reaction step is the rate-determining step, whereas the third step is the regio- and stereo-selectivity determining step. For the regio- and stereo-selectivity determining step, all four possible attack modes were considered. The addition of the C[double bond, length as m-dash]N bond in isatin imine to the dienolate intermediate is more energy favorable than the addition of the C[double bond, length as m-dash]O bond to a dienolate intermediate. Moreover, the Re face addition of the C[double bond, length as m-dash]N bond in isatin imine to the Re face of the dienolate intermediate leading to the SS configuration N-containing product was demonstrated to be most energy favorable, which is mainly due to the stronger second-order perturbation energy value in the corresponding transition state. Furthermore, by tracking the frontier molecular orbital (FMO) changes in the rate-determining C-C bond cleavage step, we found that the reaction obeys the conservation principle of molecular orbital symmetry. We believe that the present work would provide valuable insights into this kind of reaction.

  14. A computational study on the N-heterocyclic carbene-catalyzed Csp(2)-Csp(3) bond activation/[4+2] cycloaddition cascade reaction of cyclobutenones with imines: a new application of the conservation principle of molecular orbital symmetry.

    PubMed

    Wang, Yang; Wu, Bohua; Zhang, Haoyang; Wei, Donghui; Tang, Mingsheng

    2016-07-20

    A comprehensive density functional theory (DFT) investigation has been performed to interrogate the mechanisms and stereoselectivities of the Csp(2)-Csp(3) single bond activation of cyclobutenones and their [4+2] cycloaddition reaction with imines via N-heterocyclic carbene (NHC) organocatalysis. According to our calculated results, the fundamental reaction pathway contains four steps: nucleophilic addition of NHC to cyclobutenone, C-C bond cleavage for the formation of an enolate intermediate, [4+2] cycloaddition of the enolate intermediate with isatin imine, and the elimination of the NHC catalyst. In addition, the calculated results also reveal that the second reaction step is the rate-determining step, whereas the third step is the regio- and stereo-selectivity determining step. For the regio- and stereo-selectivity determining step, all four possible attack modes were considered. The addition of the C[double bond, length as m-dash]N bond in isatin imine to the dienolate intermediate is more energy favorable than the addition of the C[double bond, length as m-dash]O bond to a dienolate intermediate. Moreover, the Re face addition of the C[double bond, length as m-dash]N bond in isatin imine to the Re face of the dienolate intermediate leading to the SS configuration N-containing product was demonstrated to be most energy favorable, which is mainly due to the stronger second-order perturbation energy value in the corresponding transition state. Furthermore, by tracking the frontier molecular orbital (FMO) changes in the rate-determining C-C bond cleavage step, we found that the reaction obeys the conservation principle of molecular orbital symmetry. We believe that the present work would provide valuable insights into this kind of reaction. PMID:27400324

  15. Synthesis of a tricyclic mescaline analogue by catalytic C-H bond activation.

    PubMed

    Ahrendt, Kateri A; Bergman, Robert G; Ellman, Jonathan A

    2003-04-17

    [reaction: see text] A tetrahydrobis(benzofuran) mescaline analogue has been prepared in six steps and 38% overall yield from (4'-O-methyl)methyl gallate. The key step in this synthesis is a tandem cyclization reaction via directed C[bond]H activation followed by olefin insertion.

  16. 77 FR 6814 - Agency Information Collection Activities: Bonded Warehouse Proprietor's Submission

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-09

    ... of other forms of information technology; and (e) the annual cost burden to respondents or record... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Bonded Warehouse.... ACTION: 60-Day Notice and request for comments; Extension of an existing collection of...

  17. 26 CFR 1.103(n)-3T - Private activity bond limit (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Authority M has no private activity bond limit for 1987. Example 2. Under the laws of State U, only the... governmental unit that— (i) Enacts a specific law (e.g., a provision of a State constitution, charter, or... ceiling? A-11: A State, by law enacted at any time, may provide a different formula for allocating...

  18. Double group transfer reactions: role of activation strain and aromaticity in reaction barriers.

    PubMed

    Fernández, Israel; Bickelhaupt, F Matthias; Cossío, Fernando P

    2009-12-01

    Double group transfer (DGT) reactions, such as the bimolecular automerization of ethane plus ethene, are known to have high reaction barriers despite the fact that their cyclic transition states have a pronounced in-plane aromatic character, as indicated by NMR spectroscopic parameters. To arrive at a way of understanding this somewhat paradoxical and incompletely understood phenomenon of high-energy aromatic transition states, we have explored six archetypal DGT reactions using density functional theory (DFT) at the OLYP/TZ2P level. The main trends in reactivity are rationalized using the activation strain model of chemical reactivity. In this model, the shape of the reaction profile DeltaE(zeta) and the height of the overall reaction barrier DeltaE( not equal)=DeltaE(zeta=zeta(TS)) is interpreted in terms of the strain energy DeltaE(strain)(zeta) associated with deforming the reactants along the reaction coordinate zeta plus the interaction energy DeltaE(int)(zeta) between these deformed reactants: DeltaE(zeta)=DeltaE(strain)(zeta)+DeltaE(int)(zeta). We also use an alternative fragmentation and a valence bond model for analyzing the character of the transition states. PMID:19852009

  19. Bond activation with an apparently benign ethynyl dithiocarbamate Ar-C≡C-S-C(S)NR2.

    PubMed

    Ung, Gaël; Frey, Guido D; Schoeller, Wolfgang W; Bertrand, Guy

    2011-10-10

    The hedgehog molecule: A simple ethynyl dithiocarbamate [Ar-C≡C-S-C(S)NR(2)] is able to cleave a broad range of enthalpically strong σ bonds and to activate carbon dioxide and elemental sulfur. Depending on the substrate, the bond activation process involves either the existence of an equilibrium with the nonobservable mesoionic carbene isomer or the cooperation of the nucleophilic carbon-carbon triple bond and the electrophilic CS carbon atom. PMID:23210141

  20. Double-Knudsen-Cell Apparatus Measures Alloy-Component Activities

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Moore, Warren A.

    1995-01-01

    Double-Knudsen-cell apparatus provides molecular beam from selected one of two Knudsen cells. Both cells maintained at same temperature. Molecular beam directed into mass spectrometer for measurement of vapor pressure of selected material component. Designed to minimize undesired thermal gradients, provides appropriate translation to place selected cell in position for sampling, and minimizes mixing of molecular beams from cells.

  1. Bond slip detection of concrete-encased composite structure using shear wave based active sensing approach

    NASA Astrophysics Data System (ADS)

    Zeng, Lei; Parvasi, Seyed Mohammad; Kong, Qingzhao; Huo, Linsheng; Lim, Ing; Li, Mo; Song, Gangbing

    2015-12-01

    Concrete-encased composite structure exhibits improved strength, ductility and fire resistance compared to traditional reinforced concrete, by incorporating the advantages of both steel and concrete materials. A major drawback of this type of structure is the bond slip introduced between steel and concrete, which directly reduces the load capacity of the structure. In this paper, an active sensing approach using shear waves to provide monitoring and early warning of the development of bond slip in the concrete-encased composite structure is proposed. A specimen of concrete-encased composite structure was investigated. In this active sensing approach, shear mode smart aggregates (SAs) embedded in the concrete act as actuators and generate desired shear stress waves. Distributed piezoceramic transducers installed in the cavities of steel plates act as sensors and detect the wave response from shear mode SAs. Bond slip acts as a form of stress relief and attenuates the wave propagation energy. Experimental results from the time domain analysis clearly indicate that the amplitudes of received signal by lead zirconate titanate sensors decreased when bond slip occurred. In addition, a wavelet packet-based analysis was developed to compute the received signal energy values, which can be used to determine the initiation and development of bond slip in concrete-encased composite structure. In order to establish the validity of the proposed method, a 3D finite element analysis of the concrete-steel bond model is further performed with the aid of the commercial finite element package, Abaqus, and the numerical results are compared with the results obtained in experimental study.

  2. [{Fe(tim)}2]: an Fe-Fe dimer containing an unsupported metal-metal bond and redox-active N4 macrocyclic ligands.

    PubMed

    Hess, Corinna R; Weyhermüller, Thomas; Bill, Eckhard; Wieghardt, Karl

    2009-01-01

    Mixed doubles: The dimeric complex [{Fe(tim)}(2)] (see structure, tim = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) represents an unprecedented complex containing an unsupported Fe-Fe bond. The crystal structure confirms the presence of reduced tim units, thus indicating ligand redox activity. Spectroscopic and computational studies establish a triplet ground state for [{Fe(tim)}(2)] and suggest a mixed-valence compound with respect to both the Fe ions and the ligands.

  3. The active site of hen egg-white lysozyme: flexibility and chemical bonding

    SciTech Connect

    Held, Jeanette Smaalen, Sander van

    2014-04-01

    Chemical bonding at the active site of lysozyme is analyzed on the basis of a multipole model employing transferable multipole parameters from a database. Large B factors at low temperatures reflect frozen-in disorder, but therefore prevent a meaningful free refinement of multipole parameters. Chemical bonding at the active site of hen egg-white lysozyme (HEWL) is analyzed on the basis of Bader’s quantum theory of atoms in molecules [QTAIM; Bader (1994 ▶), Atoms in Molecules: A Quantum Theory. Oxford University Press] applied to electron-density maps derived from a multipole model. The observation is made that the atomic displacement parameters (ADPs) of HEWL at a temperature of 100 K are larger than ADPs in crystals of small biological molecules at 298 K. This feature shows that the ADPs in the cold crystals of HEWL reflect frozen-in disorder rather than thermal vibrations of the atoms. Directly generalizing the results of multipole studies on small-molecule crystals, the important consequence for electron-density analysis of protein crystals is that multipole parameters cannot be independently varied in a meaningful way in structure refinements. Instead, a multipole model for HEWL has been developed by refinement of atomic coordinates and ADPs against the X-ray diffraction data of Wang and coworkers [Wang et al. (2007), Acta Cryst. D63, 1254–1268], while multipole parameters were fixed to the values for transferable multipole parameters from the ELMAM2 database [Domagala et al. (2012), Acta Cryst. A68, 337–351] . Static and dynamic electron densities based on this multipole model are presented. Analysis of their topological properties according to the QTAIM shows that the covalent bonds possess similar properties to the covalent bonds of small molecules. Hydrogen bonds of intermediate strength are identified for the Glu35 and Asp52 residues, which are considered to be essential parts of the active site of HEWL. Furthermore, a series of weak C

  4. 26 CFR 1.103(n)-4T - Elective carryforward of unused private activity bond limit (temporary).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... from being issued pursuant to such carryforward election. In addition, where a carryforward election is... unused private activity bond limit in order to provide a sports facility described in section 103(b)(4)(B). In addition, a governmental unit may elect to carry forward its unused private activity bond limit...

  5. Chitosan-Copper (II) complex as antibacterial agent: synthesis, characterization and coordinating bond- activity correlation study

    NASA Astrophysics Data System (ADS)

    Mekahlia, S.; Bouzid, B.

    2009-11-01

    The antimicrobial activity of chitosan is unstable and sensitive to many factors such as molecular weight. Recent investigations showed that low molecular weight chitosan exhibited strong bactericidal activities compared to chitosan with high molecular weight. Since chitosan degradation can be caused by the coordinating bond, we attempt to synthesize and characterize the chitosan-Cu (II) complex, and thereafter study the coordinating bond effect on its antibacterial activity against Salmonella enteritidis. Seven chitosan-copper complexes with different copper contents were prepared and characterized by FT-IR, UV-vis, XRD and atomic absorption spectrophotometry (AAS). Results indicated that for chitosan-Cu (II) complexes with molar ratio close to 1:1, the inhibition rate reached 100%.

  6. Activation of Electron-Deficient Quinones through Hydrogen-Bond-Donor-Coupled Electron Transfer.

    PubMed

    Turek, Amanda K; Hardee, David J; Ullman, Andrew M; Nocera, Daniel G; Jacobsen, Eric N

    2016-01-11

    Quinones are important organic oxidants in a variety of synthetic and biological contexts, and they are susceptible to activation towards electron transfer through hydrogen bonding. Whereas this effect of hydrogen bond donors (HBDs) has been observed for Lewis basic, weakly oxidizing quinones, comparable activation is not readily achieved when more reactive and synthetically useful electron-deficient quinones are used. We have successfully employed HBD-coupled electron transfer as a strategy to activate electron-deficient quinones. A systematic investigation of HBDs has led to the discovery that certain dicationic HBDs have an exceptionally large effect on the rate and thermodynamics of electron transfer. We further demonstrate that these HBDs can be used as catalysts in a quinone-mediated model synthetic transformation.

  7. Chromoselective Photocatalysis: Controlled Bond Activation through Light-Color Regulation of Redox Potentials.

    PubMed

    Ghosh, Indrajit; König, Burkhard

    2016-06-27

    Catalysts that can be regulated in terms of activity and selectivity by external stimuli may allow the efficient multistep synthesis of complex molecules and pharmaceuticals. Herein, we report the light-color regulation of the redox potential of a photocatalyst to control the activation of chemical bonds. Light-color control of the redox power of a photocatalyst introduces a new selectivity parameter to photoredox catalysis: Instead of changing the catalyst or ligand, alteration of the color of the visible-light irradiation adjusts the selectivity in catalytic transformations. By using this principle, the selective activation of aryl-halide bonds for C-H arylation and the sequential conversion of functional groups with different reduction potentials is possible by simply applying different colors of light for excitation of the photocatalyst.

  8. Three critical hydrogen bonds determine the catalytic activity of the Diels–Alderase ribozyme

    PubMed Central

    Kraut, Stefanie; Bebenroth, Dirk; Nierth, Alexander; Kobitski, Andrei Y.; Nienhaus, G. Ulrich; Jäschke, Andres

    2012-01-01

    Compared to protein enzymes, our knowledge about how RNA accelerates chemical reactions is rather limited. The crystal structures of a ribozyme that catalyzes Diels–Alder reactions suggest a rich tertiary architecture responsible for catalysis. In this study, we systematically probe the relevance of crystallographically observed ground-state interactions for catalytic function using atomic mutagenesis in combination with various analytical techniques. The largest energetic contribution apparently arises from the precise shape complementarity between transition state and catalytic pocket: A single point mutant that folds correctly into the tertiary structure but lacks one H-bond that normally stabilizes the pocket is completely inactive. In the rate-limiting chemical step, the dienophile is furthermore activated by two weak H-bonds that contribute ∼7–8 kJ/mol to transition state stabilization, as indicated by the 25-fold slower reaction rates of deletion mutants. These H-bonds are also responsible for the tight binding of the Diels–Alder product by the ribozyme that causes product inhibition. For high catalytic activity, the ribozyme requires a fine-tuned balance between rigidity and flexibility that is determined by the combined action of one inter-strand H-bond and one magnesium ion. A sharp 360° turn reminiscent of the T-loop motif observed in tRNA is found to be important for catalytic function. PMID:21976731

  9. Merging allylic carbon-hydrogen and selective carbon-carbon bond activation

    NASA Astrophysics Data System (ADS)

    Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan

    2014-01-01

    Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.

  10. Highly dispersed buckybowls as model carbocatalysts for C–H bond activation

    SciTech Connect

    Soykal, I. Ilgaz; Wang, Hui; Park, Jewook; Li, An-Ping; Liang, Chengdu; Schwartz, Viviane

    2015-03-19

    Buckybowl fractions dispersed on mesoporous silica constitute an ideal model for studying the catalysis of graphitic forms of carbon since the dispersed carbon nanostructures contain a high ratio of edge defects and curvature induced by non-six-membered rings. Dispersion of the active centers on an easily accessible high surface area material allowed for high density of surface active sites associated with oxygenated structures. This report illustrates a facile method of creating model polycyclic aromatic nano-structures that are not only active for alkane C-H bond activation and oxidative dehydrogenation but also can be practical catalysts to be eventually used in industry.

  11. Activation of carbon dioxide by a terminal uranium-nitrogen bond in the gas-phase: a demonstration of the principle of microscopic reversibility.

    PubMed

    Dau, Phuong D; Armentrout, P B; Michelini, Maria C; Gibson, John K

    2016-03-14

    Activation of CO2 is demonstrated by its spontaneous dissociative reaction with the gas-phase anion complex NUOCl2(-), which can be considered as NUO(+) coordinated by two chloride anion ligands. This reaction was previously predicted by density functional theory to occur exothermically, without barriers above the reactant energy. The present results demonstrate the validity of the prediction of microscopic reversibility, and provide a rare case of spontaneous dissociative addition of CO2 to a gas-phase complex. The activation of CO2 by NUOCl2(-) proceeds by conversion of a U[triple bond, length as m-dash]N bond to a U[double bond, length as m-dash]O bond and creation of an isocyanate ligand to yield the complex UO2(NCO)Cl2(-), in which uranyl, UO2(2+), is coordinated by one isocyanate and two chloride anion ligands. This activation of CO2 by a uranium(vi) nitride complex is distinctive from previous reports of oxidative insertion of CO2 into lower oxidation state U(iii) or U(iv) solid complexes, during which both C-O bonds remain intact. This unusual observation of spontaneous addition and activation of CO2 by NUOCl2(-) is a result of the high oxophilicity of uranium. If the computed Gibbs free energy of the reaction pathway, rather than the energy, is considered, there are barriers above the reactant asymptotes such that the observed reaction should not proceed under thermal conditions. This result provides a demonstration that energy rather than Gibbs free energy determines reactivity under low-pressure bimolecular conditions. PMID:26898535

  12. Pancreatic lipase selectively hydrolyses DPA over EPA and DHA due to location of double bonds in the fatty acid rather than regioselectivity.

    PubMed

    Akanbi, Taiwo O; Sinclair, Andrew J; Barrow, Colin J

    2014-10-01

    The enzymatic hydrolysis of canola, anchovy and seal oils with different types and amounts of polyunsaturated fatty acids was measured using porcine pancreatic lipase (PPL) to establish the fatty acid selectivity of PPL. Substrates were subjected to the same conditions of hydrolysis, with percent hydrolysis monitored using Iatroscan and fatty acid selectivity monitored using gas chromatography (GC). Regardless of their distribution on the glycerol backbone, as monitored by (13)C nuclear magnetic resonance (NMR), α-linolenic acid (ALA) and docosapentaenoic acid (DPA) were rapidly cleaved by PPL while eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and stearidonic acid (STA) were hydrolysed more slowly. Results show that PPL preferentially hydrolyses ALA and DPA over EPA, DHA and STA, and this selectivity is due to fatty acid rather than regioselectivity. The primary structural factor associated with resistance to PPL appears to be the distance of the first double bond from the ester linkage being hydrolysed.

  13. Carbon-Carbon Bond Cleavage in Activation of the Prodrug Nabumetone

    PubMed Central

    Varfaj, Fatbardha; Zulkifli, Siti N. A.; Park, Hyoung-Goo; Challinor, Victoria L.; De Voss, James J.

    2014-01-01

    Carbon-carbon bond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbon bond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbon bond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbon bond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs. PMID:24584631

  14. Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation.

    PubMed

    Sun, Alex D; Leung, Kaylyn; Restivo, Anita D; LaBerge, Nicole A; Takasaki, Harumi; Love, Jennifer A

    2014-03-10

    We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

  15. Palladium-Catalyzed Dearomative Cyclocarbonylation by C-N Bond Activation.

    PubMed

    Yu, Hui; Zhang, Guoying; Huang, Hanmin

    2015-09-01

    A fundamentally novel approach to bioactive quinolizinones is based on the palladium-catalyzed intramolecular cyclocarbonylation of allylamines. [Pd(Xantphos)I2 ], which features a very large bite angle, has been found to facilitate the rapid carbonylation of azaarene-substituted allylamines into bioactive quinolizinones in good to excellent yields. This transformation represents the first dearomative carbonylation and is proposed to proceed by palladium-catalyzed CN bond activation, dearomatization, CO insertion, and a Heck reaction.

  16. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    SciTech Connect

    Watzke, Anja; Wilson, Rebecca; O'Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  17. Ability of zirconia double coated with titanium and hydroxyapatite to bond to bone under load-bearing conditions.

    PubMed

    Suzuki, Takashi; Fujibayashi, Shunsuke; Nakagawa, Yasuaki; Noda, Iwao; Nakamura, Takashi

    2006-03-01

    As a preclinical study, we evaluated the ability of hydroxyapatite and titanium on zirconia (HTOZ) to bond to bone under load-bearing conditions in animal experiments. HTOZ, HA, and Ti on Co-Cr alloy (HTOC) and Ti on Co-Cr alloy (TOC) were implanted into the weight-bearing portion of the femoral condyles of nine beagle dogs. Femurs were extracted 4, 12, and 52 weeks after implantation and examined mechanically by pullout testing, and histologically by toluidine blue staining, SEM, and calculation of the affinity index. The interfacial shear strengths (mean+/-SD) of the HTOZ, HTOC, and TOC groups were 4.42+/-0.453, 3.90+/-0.903, and 4.08+/-0.790 MPa at 4 weeks; 6.82+/-2.64, 6.00+/-1.88, and 6.63+/-1.63 MPa at 12 weeks; and 13.98+/-1.94, 11.95+/-1.51, and 10.78+/-0.83 MPa at 52 weeks. There were no significant differences in the interfacial shear strengths between the three groups at any time. Affinity indices (mean+/-SD) obtained from SEM images of the HTOZ, HTOC, and TOC groups were 49.6+/-6.52%, 43.3+/-10.43%, and 23.7+/-3.95% at 4 weeks; 55.0+/-6.72%, 51.5+/-3.07%, and 28.6+/-4.09% at 12 weeks; and 59.1+/-6.73%, 63.0+/-6.40%, and 34.3+/-6.72% at 52 weeks. HA-coated implants (HTOZ, HTOC) had significantly higher affinity indices than non-HA-coated implants (TOC) at all times. HTOZ has the ability to bond to bone equivalent to HTOC and TOC. HTOZ is an excellent material for components of cementless joint prostheses.

  18. Active and Passive Application of the Phosphoric Acid on the Bond Strength of Lithium Disilicate.

    PubMed

    Giraldo, Tatiana Cardona; Villada, Vanessa Roldan; Castillo, Mauricio Peña; Gomes, Osnara Maria Mongruel; Bittencourt, Bruna Fortes; Dominguez, John Alexis

    2016-01-01

    The objective of this study was to evaluate the effect of passive or active phosphoric acid (PA) application after hydrofluoric acid (HA) treatment on the microshear bond strength of lithium disilicate. Thirty ceramic discs were made with IPS Emax 2 (10 mm thick and 10 mm diameter). The specimens were divided into 3 groups, A: 9.6% HA application; AF: 9.6% HA application + cleaning with 37% PA in passive mode and AFF: 9.6% HA application + cleaning with 37% PA in active mode. For the microshear test, four tygons (0.9 mm diameter and 0.2 mm high) were filled with resin cement (RelyX Ultimate) and placed on the ceramic disks. After testing, the fracture modes were examined under scanning electron microscopy. Data were analyzed by one-way ANOVA and Tukey's post test (α=0.05). The bond strength values were significantly higher in Group AFF (11.0±2.5 MPa) compared with group A (8.1±2.6 MPa) (p<0.002). AF group was not statistically different (9.4±2.5 MPa) from Group A. It was concluded that the active application of 37% PA after 9.6% HA increases the microshear bond strength values between the resin cement and lithium disilicate ceramic.

  19. Silylations of Arenes with Hydrosilanes: From Transition-Metal-Catalyzed C¢X Bond Cleavage to Environmentally Benign Transition-Metal-Free C¢H Bond Activation.

    PubMed

    Xu, Zheng; Xu, Li-Wen

    2015-07-01

    The construction of carbon-silicon bonds is highlighted as an exciting achievement in the field of organosilicon chemistry and green chemistry. Recent developments in this area will enable the sustainable chemical conversion of silicon resources into synthetically useful compounds. Especially, the catalytic silylation through C¢H bond activation without directing groups and hydrogen acceptors is one of the most challenging topics in organic chemistry and green chemistry. These remarkable findings on catalytic silylation can pave the way to a more environmentally benign utilization of earth-abundant silicon-based resources in synthetic chemistry. PMID:26073645

  20. B-H activation and H-H formation: two consecutive heterolytic processes on an osmium-hydrogensulfide bond.

    PubMed

    Esteruelas, Miguel A; López, Ana M; Mora, Malka; Oñate, Enrique

    2013-09-01

    Heterolytic B-H activation and H-H formation on an Os-SH bond give borylthiolate-dihydrogen derivatives. These species exchange borylthiol by borane to afford σ-borane derivatives or release H2 and undergo a hydride-boryl exchange to yield boryl-hydrogensulfide complexes depending on the boryl group bonded to the sulfur atom.

  1. 26 CFR 1.103(n)-4T - Elective carryforward of unused private activity bond limit (temporary).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... bond limit (temporary). 1.103(n)-4T Section 1.103(n)-4T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-4T Elective carryforward of unused private activity bond limit... carryforward for any one or more projects described in A-5 of this § 1.103(n)-4T (carryforward projects)....

  2. 26 CFR 1.103(n)-4T - Elective carryforward of unused private activity bond limit (temporary).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... bond limit (temporary). 1.103(n)-4T Section 1.103(n)-4T Internal Revenue INTERNAL REVENUE SERVICE... Excluded from Gross Income § 1.103(n)-4T Elective carryforward of unused private activity bond limit... carryforward for any one or more projects described in A-5 of this § 1.103(n)-4T (carryforward projects)....

  3. Direct Dehydroxylative Coupling Reaction of Alcohols with Organosilanes through Si-X Bond Activation by Halogen Bonding.

    PubMed

    Saito, Masato; Tsuji, Nobuya; Kobayashi, Yusuke; Takemoto, Yoshiji

    2015-06-19

    The combined use of a halogen bond (XB) donor with trimethylsilyl halide was found to be an efficient cocatalytic system for the direct dehydroxylative coupling reaction of alcohol with various nucleophiles, such as allyltrimethylsilane and trimethylcyanide, to give the corresponding adduct in moderate to excellent yields. Detailed control experiments and mechanistic studies revealed that the XB interaction was crucial for the reaction. The application of this coupling reaction is also described.

  4. An unusual P-P double bond formed via phospha-Wittig transformation of a terminal PO complex.

    PubMed

    Piro, Nicholas A; Cummins, Christopher C

    2009-07-01

    The terminal phosphorus monoxide complex (OP)Mo(N[(t)Bu]Ar)(3), 1 (Ar = 3,5-Me(2)C(6)H(3)), undergoes an O-for-PSiR(3) metathesis reaction with the niobium phosphinidene complex (i)Pr(3)SiPNb(N[CH(2)(t)Bu]Ar)(3), 2, to generate the oxoniobium complex ONb(N[CH(2)(t)Bu]Ar)(3), 3, and the diphosphenido complex (i)Pr(3)SiPPMo(N[(t)Bu]Ar)(3), 4. The structure of 4, as determined by X-ray crystallography, contains a "singly bent" diphosphenido moiety, suggesting that the diphosphenido ligand serves as a 3e(-) donor to a formally d(2) metal center. This bonding characterization was supported by DFT calculations and is unique among known diphosphenido complexes. Diphosphenido 4 was found to react over time to produce products consistent with a bimolecular degradation pathway where the terminal phosphide complex PMo(N[(t)Bu]Ar)(3), 5, serves as a stable leaving group. Mixtures of 4 and PPh(3) were observed to set up an equilibrium (K(eq) = 0.7) between 4, PPh(3), and the products of phosphinidene transfer, 5 and (i)Pr(3)SiP=PPh(3).

  5. In vitro anti-staphylococcal activity of heparinized biomaterials bonded with combinations of rifampicin.

    PubMed

    Fallgren, C; Utt, M; Petersson, A C; Ljungh, A; Wadström, T

    1998-01-01

    Biomaterial implants in various human body tissues are highly susceptible to bacterial colonization. We report here on the coating of heparinized biomaterials with heparin binding extracellular matrix proteins giving special regard to the efficient adsorption and slow release of antibiotics. Heparin was partially degraded and the resulting fragments were covalently end-point attached to 0.5 cm long silicone biomaterial surface. Collagen type I was immobilized on the heparinized biomaterials and then cross-linked with acyl-azide or carbodiimide. Finally, the resulting biosurfaces were exposed to antibiotics, i.e. rifampicin in combination with cefuroxime, fusidic acid, ofloxacin or vancomycin, respectively. The antibiotic bonded biomaterials were evaluated for their anti-staphylococcal activity after elution in NaCl, serum or blood by measuring the zones of inhibition for S. epidermidis strain RP12. Furthermore, we examined the in-vitro colonization resistance to S. epidermidis RP12 for these combinations of rifampicin-bonded biomaterials by an ATP bioluminescence assay. The ATP measurements showed that initially adherent bacteria were eradicated from the polymer surface, for at least 24 or 48 h (fusidic acid > cefuroxime > vancomycin > ofloxacin). The anti-staphylococcal activity of rifampicin-fusidic acid bonded heparinized biomaterials seems of sufficient duration and efficacy to merit testing in an animal model.

  6. In vitro anti-staphylococcal activity of heparinized biomaterials bonded with combinations of rifampicin.

    PubMed

    Fallgren, C; Utt, M; Petersson, A C; Ljungh, A; Wadström, T

    1998-01-01

    Biomaterial implants in various human body tissues are highly susceptible to bacterial colonization. We report here on the coating of heparinized biomaterials with heparin binding extracellular matrix proteins giving special regard to the efficient adsorption and slow release of antibiotics. Heparin was partially degraded and the resulting fragments were covalently end-point attached to 0.5 cm long silicone biomaterial surface. Collagen type I was immobilized on the heparinized biomaterials and then cross-linked with acyl-azide or carbodiimide. Finally, the resulting biosurfaces were exposed to antibiotics, i.e. rifampicin in combination with cefuroxime, fusidic acid, ofloxacin or vancomycin, respectively. The antibiotic bonded biomaterials were evaluated for their anti-staphylococcal activity after elution in NaCl, serum or blood by measuring the zones of inhibition for S. epidermidis strain RP12. Furthermore, we examined the in-vitro colonization resistance to S. epidermidis RP12 for these combinations of rifampicin-bonded biomaterials by an ATP bioluminescence assay. The ATP measurements showed that initially adherent bacteria were eradicated from the polymer surface, for at least 24 or 48 h (fusidic acid > cefuroxime > vancomycin > ofloxacin). The anti-staphylococcal activity of rifampicin-fusidic acid bonded heparinized biomaterials seems of sufficient duration and efficacy to merit testing in an animal model. PMID:9532261

  7. Key amino acids of arabidopsis VKOR in the activity of phylloquinone reduction and disulfide bond formation.

    PubMed

    Yang, Xiao-Jian; Cui, Hao-Ran; Yu, Zhi-Bo; Du, Jia-Jia; Xu, Jia-Ning; Wang, Xiao-Yun

    2015-01-01

    Many proteins in chloroplast are regulated through the disulfide bond/thiol transformation to realize their activities. A homologue of VKOR (Vitamin K epoxide reductase) in Arabidopsis chloroplast is found to catalyze the disulfide bond formation in vivo and to mediate the specific phylloquinone reduction in vitro. It is also called LTO1 (Lumen Thiol Oxidoreductase 1). Investigations about functions and essential amino acid residues of AtVKOR have important theoretical significance to clarify the chloroplast redox regulation mechanism. In this study, several amino acids in the VKOR domain of AtVKOR were identified to be involved in binding of phylloquinone. Site-directed mutagenesis was used to study the function of these positions. The results suggested that residues Ser77, Leu87, Phe137 and Leu141 were quite important in the binding and catalyzing the reduction of phylloquinone. These residues were also involved in the electron transferring and disulfide bond formation of substrate proteins by motility assays in vivo, suggesting that the binding of phylloquinone not only affected the delivery of electrons to phylloquinone but also affected the whole electron transfer process. The conserved cysteines in the AtVKOR domain also played critical roles in phylloquinone reduction. When each of the four conserved cysteines was mutated to alanine, the mutants lost reduction activity entirely, suggesting that the four conserved cysteines played crucial roles in the electron transfer process. PMID:25267254

  8. Mercury Detoxification by Bacteria: Simulations of Transcription Activation and Mercury-Carbon Bond Cleavage

    SciTech Connect

    Guo, Hao-Bo; Parks, Jerry M; Johs, Alexander; Smith, Jeremy C

    2011-01-01

    In this chapter, we summarize recent work from our laboratory and provide new perspective on two important aspects of bacterial mercury resistance: the molecular mechanism of transcriptional regulation by MerR, and the enzymatic cleavage of the Hg-C bond in methylmercury by the organomercurial lyase, MerB. Molecular dynamics (MD) simulations of MerR reveal an opening-and-closing dynamics, which may be involved in initiating transcription of mercury resistance genes upon Hg(II) binding. Density functional theory (DFT) calculations on an active-site model of the enzyme reveal how MerB catalyzes the Hg-C bond cleavage using cysteine coordination and acid-base chemistry. These studies provide insight into the detailed mechanisms of microbial gene regulation and defense against mercury toxicity.

  9. Surface oxidation under ambient air--not only a fast and economical method to identify double bond positions in unsaturated lipids but also a reminder of proper lipid processing.

    PubMed

    Zhou, Ying; Park, Hyejung; Kim, Philseok; Jiang, Yan; Costello, Catherine E

    2014-06-17

    A simple, fast approach elucidated carbon-carbon double bond positions in unsaturated lipids. Lipids were deposited onto various surfaces and the products from their oxidation in ambient air were observed by electrospray ionization (ESI) mass spectrometry (MS). The most common oxidative products, aldehydes, were detected as transformations at the cleaved double bond positions. Ozonides and carboxylic acids were generated in certain lipids. Investigations of the conditions controlling the appearance of these products indicated that the surface oxidation depends on light and ambient air. Since the lipid oxidation was slower in a high concentration of ozone, singlet oxygen appeared to be a parallel oxidant for unsaturated lipids. The 3-hydroxyl group in the sphingoid base of sulfatides offered some protection from oxidation for the Δ4,5-double bond, slowing its oxidation rate relative to that of the isolated double bond in the N-linked fatty acyl chain. Direct sampling by thin-layer chromatography (TLC)-ESI-MS provides a powerful approach to elucidate detailed structural information on biological samples. Co-localization of the starting lipids and their oxidation products after TLC separation allowed assignment of the native unsaturation sites. Phosphatidylserine and N,N-dimethyl phosphatidylethanolamine isomers in a bovine brain total lipid extract were distinguished on the basis of their oxidation products. Meanwhile, the findings reported herein reveal a potential pitfall in the assignment of structures to lipids extracted from TLC plates because of artifactual oxidation after the plate development.

  10. Bile salt-induced intermolecular disulfide bond formation activates Vibrio cholerae virulence.

    PubMed

    Yang, Menghua; Liu, Zhi; Hughes, Chambers; Stern, Andrew M; Wang, Hui; Zhong, Zengtao; Kan, Biao; Fenical, William; Zhu, Jun

    2013-02-01

    To be successful pathogens, bacteria must often restrict the expression of virulence genes to host environments. This requires a physical or chemical marker of the host environment as well as a cognate bacterial system for sensing the presence of a host to appropriately time the activation of virulence. However, there have been remarkably few such signal-sensor pairs identified, and the molecular mechanisms for host-sensing are virtually unknown. By directly applying a reporter strain of Vibrio cholerae, the causative agent of cholera, to a thin layer chromatography (TLC) plate containing mouse intestinal extracts, we found two host signals that activate virulence gene transcription. One of these was revealed to be the bile salt taurocholate. We then show that a set of bile salts cause dimerization of the transmembrane transcription factor TcpP by inducing intermolecular disulfide bonds between cysteine (C)-207 residues in its periplasmic domain. Various genetic and biochemical analyses led us to propose a model in which the other cysteine in the periplasmic domain, C218, forms an inhibitory intramolecular disulfide bond with C207 that must be isomerized to form the active C207-C207 intermolecular bond. We then found bile salt-dependent effects of these cysteine mutations on survival in vivo, correlating to our in vitro model. Our results are a demonstration of a mechanism for direct activation of the V. cholerae virulence cascade by a host signal molecule. They further provide a paradigm for recognition of the host environment in pathogenic bacteria through periplasmic cysteine oxidation.

  11. Ultrafast studies of organometallic photochemistry: The mechanism of carbon-hydrogen bond activation in solution

    SciTech Connect

    Bromberg, S.E.

    1998-05-01

    When certain organometallic compounds are photoexcited in room temperature alkane solution, they are able to break or activate the C-H bonds of the solvent. Understanding this potentially practical reaction requires a detailed knowledge of the entire reaction mechanism. Because of the dynamic nature of chemical reactions, time-resolved spectroscopy is commonly employed to follow the important events that take place as reactants are converted to products. For the organometallic reactions examined here, the electronic/structural characteristics of the chemical systems along with the time scales for the key steps in the reaction make ultrafast UV/Vis and IR spectroscopy along with nanosecond Step-Scan FTIR spectroscopy the ideal techniques to use for this study. An initial study of the photophysics of (non-activating) model metal carbonyls centering on the photodissociation of M(CO){sub 6} (M = Cr, W, Mo) was carried out in alkane solutions using ultrafast IR spectroscopy. Next, picosecond UV/vis studies of the C-H bond activation reaction of Cp{sup *}M(CO){sub 2} (M = Rh, Ir), conducted in room temperature alkane solution, are described in an effort to investigate the origin of the low quantum yield for bond cleavage ({approximately}1%). To monitor the chemistry that takes place in the reaction after CO is lost, a system with higher quantum yield is required. The reaction of Tp{sup *}Rh(CO){sub 2} (Tp{sup *} = HB-Pz{sub 3}{sup *}, Pz{sup *} = 3,5-dimethylpyrazolyl) in alkanes has a quantum yield of {approximately}30%, making time resolved spectroscopic measurements possible. From ultrafast IR experiments, two subsequently formed intermediates were observed. The nature of these intermediates are discussed and the first comprehensive reaction mechanism for a photochemical C-H activating organometallic complex is presented.

  12. Transparent and electrically conductive GaSb/Si direct wafer bonding at low temperatures by argon-beam surface activation

    NASA Astrophysics Data System (ADS)

    Predan, F.; Reinwand, D.; Klinger, V.; Dimroth, F.

    2015-10-01

    Direct wafer bonds of the material system n-GaSb/n-Si have been achieved by means of a low-temperature direct wafer bonding process, enabling an optical transparency of the bonds along with a high electrical conductivity of the boundary layer. In the used technique, the surfaces are activated by sputter-etching with an argon fast-atom-beam (FAB) and bonded in ultra-high vacuum. The bonds were annealed at temperatures between 300 and 400 °C, followed by an optical, mechanical and electrical characterization of the interface. Additionally, the influence of the sputtering on the surface topography of the GaSb was explicitly investigated. Fully bonded wafer pairs with high bonding strengths were found, as no blade could be inserted into the bonds without destroying the samples. The interfacial resistivities of the bonded wafers were significantly reduced by optimizing the process parameters, by which Ohmic interfacial resistivities of less than 5 mΩ cm2 were reached reproducibly. These promising results make the monolithic integration of GaSb on Si attractive for various applications.

  13. Active site remodeling accompanies thioester bond formation in the SUMO E1

    PubMed Central

    Olsen, Shaun K.; Capili, Allan D.; Lu, Xuequan; Tan, Derek S.; Lima, Christopher D.

    2009-01-01

    E1 enzymes activate ubiquitin (Ub) and ubiquitin-like (Ubl) proteins in two steps by carboxy-terminal adenylation and thioester bond formation to a conserved catalytic cysteine in the E1 Cys domain. The structural basis for these intermediates remains unknown. Here we report crystal structures for human SUMO E1 in complex with SUMO adenylate and tetrahedral intermediate analogs at 2.45 Å and 2.6 Å, respectively. These structures show that side chain contacts to ATP·Mg are released after adenylation to facilitate a 130 degree rotation of the Cys domain during thioester bond formation that is accompanied by remodeling of key structural elements including the helix that contains the E1 catalytic cysteine, the cross-over and re-entry loops, and refolding of two helices that are required for adenylation. These changes displace side chains required for adenylation with side chains required for thioester bond formation. Mutational and biochemical analyses suggest these mechanisms are conserved in other E1s. PMID:20164921

  14. Active site remodelling accompanies thioester bond formation in the SUMO E1

    SciTech Connect

    Olsen, Shaun K.; Capili, Allan D.; Lu, Xuequan; Tan, Derek S.; Lima, Christopher D.

    2010-03-30

    E1 enzymes activate ubiquitin (Ub) and ubiquitin-like (Ubl) proteins in two steps by carboxy-terminal adenylation and thioester bond formation to a conserved catalytic cysteine in the E1 Cys domain. The structural basis for these intermediates remains unknown. Here we report crystal structures for human SUMO E1 in complex with SUMO adenylate and tetrahedral intermediate analogues at 2.45 and 2.6 {angstrom}, respectively. These structures show that side chain contacts to ATP-Mg are released after adenylation to facilitate a 130 degree rotation of the Cys domain during thioester bond formation that is accompanied by remodelling of key structural elements including the helix that contains the E1 catalytic cysteine, the crossover and re-entry loops, and refolding of two helices that are required for adenylation. These changes displace side chains required for adenylation with side chains required for thioester bond formation. Mutational and biochemical analyses indicate these mechanisms are conserved in other E1s.

  15. C-H Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3 (-).

    PubMed

    Li, Zi-Yu; Hu, Lianrui; Liu, Qing-Yu; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui; Yao, Jiannian

    2015-12-01

    Although early transition metal (ETM) carbides can activate CH bonds in condensed-phase systems, the electronic-level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3 (-) ) under thermal-collision conditions has been identified by using high-resolution mass spectrometry, photoelectron imaging spectroscopy, and high-level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3 (-) with C2 H6 . The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon-stabilized low-spin ground electronic state than in the high-spin excited state. The reaction efficiency between the MoC3 (-) anion and C2 H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt(+) +C2 H6 ) was made. It turned out that the potential-energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. PMID:26490554

  16. Water-containing hydrogen-bonding network in the active center of channelrhodopsin.

    PubMed

    Ito, Shota; Kato, Hideaki E; Taniguchi, Reiya; Iwata, Tatsuya; Nureki, Osamu; Kandori, Hideki

    2014-03-01

    Channelrhodopsin (ChR) functions as a light-gated ion channel in Chlamydomonas reinhardtii. Passive transport of cations by ChR is fundamentally different from the active transport by light-driven ion pumps such as archaerhodopsin, bacteriorhodopsin, and halorhodopsin. These microbial rhodopsins are important tools for optogenetics, where ChR is used to activate neurons by light, while the ion pumps are used for neural silencing. Ion-transport functions by these rhodopsins strongly depend on the specific hydrogen-bonding networks containing water near the retinal chromophore. In this work, we measured protein-bound water molecules in a chimeric ChR protein of ChR1 (helices A to E) and ChR2 (helices F and G) of Chlamydomonas reinhardtii using low-temperature FTIR spectroscopy at 77 K. We found that the active center of ChR possesses more water molecules (9 water vibrations) than those of other microbial (2-6 water vibrations) and animal (6-8 water vibrations) rhodopsins. We conclude that the protonated retinal Schiff base interacts with the counterion (Glu162) directly, without the intervening water molecule found in proton-pumping microbial rhodopsins. The present FTIR results and the recent X-ray structure of ChR reveal a unique hydrogen-bonding network around the active center of this light-gated ion channel. PMID:24512107

  17. Enantioselective Rh-Catalyzed Carboacylation of C═N Bonds via C-C Activation of Benzocyclobutenones.

    PubMed

    Deng, Lin; Xu, Tao; Li, Hongbo; Dong, Guangbin

    2016-01-13

    Herein we describe the first enantioselective Rh-catalyzed carboacylation of oximes (imines) via C-C activation. In this transformation, the benzocyclobutenone C1-C2 bond is selectively activated by a low valent rhodium catalyst and subsequently the resulting two Rh-C bonds add across a C═N bond, which provides a unique approach to access chiral lactams. A range of polycyclic nitrogen-containing scaffolds were obtained in good yields with excellent enantioselectivity. Further derivatization of the lactam products led to a rapid entry to various novel fused heterocycles.

  18. Enantioselective Rh-Catalyzed Carboacylation of C═N Bonds via C-C Activation of Benzocyclobutenones.

    PubMed

    Deng, Lin; Xu, Tao; Li, Hongbo; Dong, Guangbin

    2016-01-13

    Herein we describe the first enantioselective Rh-catalyzed carboacylation of oximes (imines) via C-C activation. In this transformation, the benzocyclobutenone C1-C2 bond is selectively activated by a low valent rhodium catalyst and subsequently the resulting two Rh-C bonds add across a C═N bond, which provides a unique approach to access chiral lactams. A range of polycyclic nitrogen-containing scaffolds were obtained in good yields with excellent enantioselectivity. Further derivatization of the lactam products led to a rapid entry to various novel fused heterocycles. PMID:26674855

  19. Synthesis of new class of alkyl azarene pyridinium zwitterions via iodine mediated sp3 C-H bond activation.

    PubMed

    Kumar, Atul; Gupta, Garima; Srivastava, Suman

    2011-12-16

    An efficient and conceptually different approach toward C-H bond activation by using iodine mediated sp(3) C-H functionalization for the synthesis of alkyl azaarene pyridinium zwitterions is described. This work has the interesting distinction of being the first synthesis of a new class of alkyl azaarene pyridinium zwitterion via transition-metal-free sp(3) C-H bond activation of an alkyl azaarene.

  20. Highly Active Gold(I)-Silver(I) Oxo Cluster Activating sp³ C-H Bonds of Methyl Ketones under Mild Conditions.

    PubMed

    Pei, Xiao-Li; Yang, Yang; Lei, Zhen; Chang, Shan-Shan; Guan, Zong-Jie; Wan, Xian-Kai; Wen, Ting-Bin; Wang, Quan-Ming

    2015-04-29

    The activation of C(sp(3))-H bonds is challenging, due to their high bond dissociation energy, low proton acidity, and highly nonpolar character. Herein we report a unique gold(I)-silver(I) oxo cluster protected by hemilabile phosphine ligands [OAu3Ag3(PPhpy2)3](BF4)4 (1), which can activate C(sp(3))-H bonds under mild conditions for a broad scope of methyl ketones (RCOCH3, R = methyl, phenyl, 2-methylphenyl, 2-aminophenyl, 2-hydroxylphenyl, 2-pyridyl, 2-thiazolyl, tert-butyl, ethyl, isopropyl). Activation happens via triple deprotonation of the methyl group, leading to formation of heterometallic Au(I)-Ag(I) clusters with formula RCOCAu4Ag4(PPhpy2)4(BF4)5 (PPhpy2 = bis(2-pyridyl)phenylphosphine). Cluster 1 can be generated in situ via the reaction of [OAu3Ag(PPhpy2)3](BF4)2 with 2 equiv of AgBF4. The oxo ion and the metal centers are found to be essential in the cleavage of sp(3) C-H bonds of methyl ketones. Interestingly, cluster 1 selectively activates the C-H bonds in -CH3 rather than the N-H bonds in -NH2 or the O-H bond in -OH which is traditionally thought to be more reactive than C-H bonds. Control experiments with butanone, 3-methylbutanone, and cyclopentanone as substrates show that the auration of the C-H bond of the terminal methyl group is preferred over secondary or tertiary sp(3) C-H bonds; in other words, the C-H bond activation is influenced by steric effect. This work highlights the powerful reactivity of metal clusters toward C-H activation and sheds new light on gold(I)-mediated catalysis.

  1. Annulation of aromatic imines via directed C-H bond activation.

    PubMed

    Thalji, Reema K; Ahrendt, Kateri A; Bergman, Robert G; Ellman, Jonathan A

    2005-08-19

    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh3)3RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

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

    SciTech Connect

    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.

  3. Activities and achievements of the Double Star Committee of the French Astronomical Society

    NASA Astrophysics Data System (ADS)

    Agati, J. L.; Caille, S.; Debackere, A.; Durand, P.; Losse, F.; Mantle, R.; Mauroy, F.; Mauroy A, P.; Morlet, G.; Pinlou, C.; Salaman, M.; Soule, E. J.; Thorel, Y.; Thorel, J. C.

    2007-08-01

    Created in 1981 by Pierre DURAND with the support of Paul MULLER, the Double Star Committee constitutes ever since a forum of exchange of experiences and information in the field of double stars, particularly visual. The Committee relies on the advice of its scientific counsellors (in particular Pierre BACCHUS, Daniel BONNEAU, Paul COUTEAU and Jean DOMMANGET) to guide the work of its members. By fostering missions in observatories, it has stimulated the activities of observation and measurement of double stars. It has also encouraged the publication of measures (A&A and ``Observations et Travaux '') and raised up missions of verification of double star positions. Under its aegis, many series of measures of double stars made in particular with the 50 cm refractor at the Nice Observatory, either with a filar micrometer or with a CCD camera, were published. Uncertain positions of pairs have been checked and corrected. For the treatment of numerical images of double stars, software aiming in particular at the determination of position elements and the magnitude difference between components were tested and others created (e.g. REDUC and SURFACE). The spar plate double image micrometer of Lyot was developed and its fabrication raised up. Preliminary orbits of double stars were calculated, an amateur participates in the maintenance of the database of double star measures SiDoNie and pursues an historical research on the life and work of Robert JONCKHEERE. The Internet site of the Committee, created in 2005, informs the laypersons as well as the experienced amateurs (http:// saf.etoilesdoubles.free.fr).

  4. Simulation of the effect of hydrogen bonds on water activity of glucose and dextran using the Veytsman model.

    PubMed

    De Vito, Francesca; Veytsman, Boris; Painter, Paul; Kokini, Jozef L

    2015-03-01

    Carbohydrates exhibit either van der Waals and ionic interactions or strong hydrogen bonding interactions. The prominence and large number of hydrogen bonds results in major contributions to phase behavior. A thermodynamic framework that accounts for hydrogen bonding interactions is therefore necessary. We have developed an extension of the thermodynamic model based on the Veytsman association theory to predict the contribution of hydrogen bonds to the behavior of glucose-water and dextran-water systems and we have calculated the free energy of mixing and its derivative leading to chemical potential and water activity. We compared our calculations with experimental data of water activity for glucose and dextran and found excellent agreement far superior to the Flory-Huggins theory. The validation of our calculations using experimental data demonstrated the validity of the Veytsman model in properly accounting for the hydrogen bonding interactions and successfully predicting water activity of glucose and dextran. Our calculations of the concentration of hydrogen bonds using the Veytsman model were instrumental in our ability to explain the difference between glucose and dextran and the role that hydrogen bonds play in contributing to these differences. The miscibility predictions showed that the Veytsman model is also able to correctly describe the phase behavior of glucose and dextran.

  5. Temperature-induced melting of double-stranded DNA in the absence and presence of covalently bonded antitumour drugs: insight from molecular dynamics simulations

    PubMed Central

    Bueren-Calabuig, Juan A.; Giraudon, Christophe; Galmarini, Carlos M.; Egly, Jean Marc; Gago, Federico

    2011-01-01

    The difference in melting temperature of a double-stranded (ds) DNA molecule in the absence and presence of bound ligands can provide experimental information about the stabilization brought about by ligand binding. By simulating the dynamic behaviour of a duplex of sequence 5′-d(TAATAACGGATTATT)·5′-d(AATAATCCGTTATTA) in 0.1 M NaCl aqueous solution at 400 K, we have characterized in atomic detail its complete thermal denaturation profile in <200 ns. A striking asymmetry was observed on both sides of the central CGG triplet and the strand separation process was shown to be strongly affected by bonding in the minor groove of the prototypical interstrand crosslinker mitomycin C or the monofunctional tetrahydroisoquinolines trabectedin (Yondelis®), Zalypsis® and PM01183®. Progressive helix unzipping was clearly interspersed with some reannealing events, which were most noticeable in the oligonucleotides containing the monoadducts, which maintained an average of 6 bp in the central region at the end of the simulations. These significant differences attest to the demonstrated ability of these drugs to stabilize dsDNA, stall replication and transcription forks, and recruit DNA repair proteins. This stabilization, quantified here in terms of undisrupted base pairs, supports the view that these monoadducts can functionally mimic a DNA interstrand crosslink. PMID:21727089

  6. Analysis of ground reaction force and electromyographic activity of the gastrocnemius muscle during double support.

    PubMed

    Sousa, Andreia S P; Santos, Rubim; Oliveira, Francisco P M; Carvalho, Paulo; Tavares, João Manuel R S

    2012-05-01

    Mechanisms associated with energy expenditure during gait have been extensively researched and studied. According to the double-inverted pendulum model energy expenditure is higher during double support, as lower limbs need to work to redirect the centre of mass velocity. This study looks into how the ground reaction force of one limb affects the muscle activity required by the medial gastrocnemius of the contralateral limb during step-to-step transition. Thirty-five subjects were monitored as to the medial gastrocnemius electromyographic activity of one limb and the ground reaction force of the contralateral limb during double support. After determination of the Pearson correlation coefficient (r), a moderate correlation was observed between the medial gastrocnemius electromyographic activity of the dominant leg and the vertical (Fz) and anteroposterior (Fy) components of ground reaction force of the non-dominant leg (r = 0.797, p < 0.000 1; r = -0.807, p < 0.000 1). A weak and moderate correlation was observed between the medial gastrocnemius electromyographic activity of the non-dominant leg and the Fz and Fy of the dominant leg, respectively (r = 0.442, p = 0.018; r = -0.684 p < 0.000 1). The results obtained suggest that during double support, ground reaction force is associated with the electromyographic activity of the contralateral medial gastrocnemius and that there is an increased dependence between the ground reaction force of the non-dominant leg and the electromyographic activity of the dominant medial gastrocnemius. PMID:22720393

  7. Numerical Comparison of Active Acoustic and Structural Noise Control in a Stiffened Double Wall Cylinder

    NASA Technical Reports Server (NTRS)

    Grosveld, Ferdinand W.

    1996-01-01

    The active acoustic and structural noise control characteristics of a double wall cylinder with and without ring stiffeners were numerically evaluated. An exterior monopole was assumed to acoustically excite the outside of the double wall cylinder at an acoustic cavity resonance frequency. Structural modal vibration properties of the inner and outer shells were analyzed by post-processing the results from a finite element analysis. A boundary element approach was used to calculate the acoustic cavity response and the coupled structural-acoustic interaction. In the frequency region of interest, below 500 Hz, all structural resonant modes were found to be acoustically slow and the nonresonant modal response to be dominant. Active sound transmission control was achieved by control forces applied to the inner or outer shell, or acoustic control monopoles placed just outside the inner or outer shell. A least mean square technique was used to minimize the interior sound pressures at the nodes of a data recovery mesh. Results showed that single acoustic control monopoles placed just outside the inner or outer shells resulted in better sound transmission control than six distributed point forces applied to either one of the shells. Adding stiffeners to the double wall structure constrained the modal vibrations of the shells, making the double wall stiffer with associated higher modal frequencies. Active noise control obtained for the stiffened double wall configurations was less than for the unstiffened cylinder. In all cases, the acoustic control monopoles controlled the sound transmission into the interior better than the structural control forces.

  8. Structure of a fluid dioleoylphosphatidylcholine bilayer determined by joint refinement of x-ray and neutron diffraction data. I. Scaling of neutron data and the distributions of double bonds and water.

    PubMed Central

    Wiener, M. C.; King, G. I.; White, S. H.

    1991-01-01

    We described in two previous papers a method for the joint refinement of the structure of fluid bilayers using neutron and x-ray diffraction data (Wiener, M. C., and S. H. White 1991a, b. Biophys. J. 59: 162-173 and 174-185). An essential part of the method is the appropriate scaling of the diffraction data. Here we describe the scaling of the neutron data and the determination of the transbilayer distribution of double bonds in liquid-crystalline (L alpha phase) phospholipid bilayers of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The distribution was determined by neutron diffraction of oriented multilayers (66% RH) of DOPC specifically deuterated at the 9- and 10-position of both acyl chains. The double-bond distribution is described accurately by a pair of Gaussian functions each located at a position Zcc = 7.88 +/- 0.09 A from the bilayer center with 1/e-halfwidths of Acc = 4.29 +/- 0.16 A. Previously, we determined the transbilayer distribution of bromine atoms in a specifically halogenated lipid, 1-oleoyl-2-9,10-dibromostearoyl-sn-glycero-3-phosphocholine (OBPC), and showed it to be an isomorphous replacement for DOPC (Wiener, M. C., and S. H. White, 1991c. Biochemistry. In press). A comparison of the double-bond and bromine profiles indicates that the positions of the centers of the deuterated double bond and the brominated methylene Gaussian distributions are equal within experimental error and that each label undergoes similar average thermal motions with respect to the bilayer normal. The observation that the average position of a label on both acyl chains (the deuterated double bonds) is similar to the average position of a label on the 2-chain alone (the brominated methylenes) indicates that the maximum separation along the bilayer normal between the double bonds of the acyl chains is 1 A or less. The fully-resolved transbilayer water distribution, previously determined at lower resolution (Jacobs, R. E., and S. H. White. 1989. Biochemistry. 28

  9. Influence of the cis-9, cis-12 and cis-15 double bond position in octadecenoic acid (18:1) isomers on the rat FADS2-catalyzed Δ6-desaturation.

    PubMed

    Rioux, Vincent; Choque, Benjamin; Ezanno, Hélène; Duby, Cécile; Catheline, Daniel; Legrand, Philippe

    2015-04-01

    Oleic (cis9-18:1), linoleic (cis9,cis12-18:2) and α-linolenic (cis9,cis12,cis15-18:3) acids are well described substrates of the Δ6-desaturase encoded by the mammalian fatty acid desaturase 2 (FADS2) gene. In addition, at least 9 other very structurally different fatty acids have been shown to be Δ6- or even Δ8-desaturated by the FADS2 protein. A better characterization of the substrate specificity of this enzyme is therefore needed. By using commercial cis9-18:1 and chemically synthesized cis12- and cis15-18:1 (sharing the n-6 double bond with 18:2 n-6 and the n-3 double bond with 18:3 n-3, respectively), we tried to decrypt the fatty acid structure driving the FADS2 substrate affinity. We first showed that both recombinant and native rat FADS2 were able to Δ6-desaturate not only the cis9- but also the cis12- and cis15-18:1 isomers. Next, the inhibitory effect of increasing concentrations of each 18:1 isomer was investigated in vitro on the Δ6-desaturation of α-linolenic acid. At equimolar inhibitor/substrate ratio (60 μM), the cis9-18:1 exhibited a significantly higher inhibition (25%) than the cis12- (8%) and cis15-18:1 (5%). This study shows that a single cis double bond in 12- or 15-position in 18:1 is enough to make them low Δ6-desaturable substrates. If a preexisting cis9-double bond is not absolutely required for the Δ6-desaturation of octadecenoic acids, its presence is however crucial to explain the higher enzyme affinity. Compared with oleic acid, the additional presence of a cis12-double bond in linoleic acid increased its inhibitory effect on the Δ6-desaturation of α-linolenic acid at low concentration (30 μM) but not at higher concentrations (60 and 120 μM). In this classification of the decreasing impact of the double bond when it comes closer to the methyl end of octadecenoic acids, the cis11-18:1 (cis-vaccenic acid) should be considered apart since it is itself not Δ6-desaturated but still a good competitive inhibitor of the

  10. Functional characterization of a fatty acid double-bond hydratase from Lactobacillus plantarum and its interaction with biosynthetic membranes.

    PubMed

    Ortega-Anaya, Joana; Hernández-Santoyo, Alejandra

    2015-12-01

    Hydrogenation of linoleic acid and other polyunsaturated fatty acids is a detoxification mechanism that is present in the Lactobacillus genus of lactic bacteria. The first stage in this multi-step process is hydration of the substrate with formation of 10-hydroxy-9-cis-octadecenoic acid due to fatty-acid hydratase activity that has been detected only in the membrane-associated cell fraction; however, its interaction with the cell membrane is unknown. To provide information in this respect we characterized the homotrimeric 64.7 kDa-native protein from Lactobacillus plantarum; afterwards, it was reconstituted in proteoliposomes and analyzed by confocal fluorescence microscopy. The results showed that hydratase is an extrinsic-membrane protein and hence, the enzymatic reaction occurs at the periphery of the cell. This location may be advantageous in the detoxifying process since the toxic linoleic acid molecule can be bound to hydratase and converted to non-toxic 10-hydroxy-9-cis-octadecenoic acid before it reaches cell membrane. Additionally, we propose that the interaction with membrane periphery occurs through electrostatic contacts. Finally, the structural model of L. plantarum hydratase was constructed based on the amino acid sequence and hence, the putative binding sites with linoleic acid were identified: site 1, located in an external hydrophobic pocket at the C-terminus of the protein and site 2, located at the core and in contact with a FAD molecule. Interestingly, it was found that the linoleic acid molecule arranges around a methionine residue in both sites (Met154 and Met81, respectively) that acts as a rigid pole, thus playing a key role in binding unsaturated fatty acids.

  11. Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds.

    PubMed

    Yayla, Hatice G; Wang, Huaiju; Tarantino, Kyle T; Orbe, Hudson S; Knowles, Robert R

    2016-08-31

    We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair. PMID:27515494

  12. Gold/Palladium Alloy for Carbon-Halogen Bond Activation: An Unprecedented Halide Dependence.

    PubMed

    Dhital, Raghu Nath; Bobuatong, Karan; Ehara, Masahiro; Sakurai, Hidehiro

    2015-12-01

    New catalytic activity of gold/palladium alloy nanoclusters (NCs) for carbon-halogen bond activation is demonstrated. In the case of an aryl chloride, the inclusion of gold in a bimetallic catalyst is indispensable to achieve the coupling reactions. Gold has the unique effect of stabilizing palladium, such that Pd(2+) leached from clusters by means of spillover of chloride during oxidative addition. The thus-formed spillover intermediate further reacts heterogeneously in both Ullmann and Suzuki-type coupling reactions through a new type of mechanism. In the case of an aryl bromide, Ullmann coupling occurs through the spillover of bromide, similar to that of aryl chloride. However, a significant fraction of palladium also leached, which diminished the Ullmann coupling activity of the aryl bromide and, as a result, the order of reactivity was ArCl>ArBr. With regard to the activation of the C-Br bond towards a Suzuki-type reaction, the inclusion of a higher gold content in gold/palladium clusters stabilized palladium to prevent the leaching of Pd(2+) from the clusters by means of spillover of bromide. The spillover intermediate reacts heterogeneously with PhB(OH)2, palladium-rich gold/palladium, or pure palladium clusters; the oxidative addition of ArBr favors the extraction of palladium from the clusters, yielding Pd(2+) intermediates. The extracted intermediates react homogenously (Pd(2+/)Pd(0) catalysis) with PhB(OH)2, which results in the higher selectivity of the cross-coupling product. An initial step to observe such unprecedented halide dependency, together with the dynamic behavior of palladium on the surface of gold is the oxidative addition of Ar-X. A detailed insight into the first oxidative addition process was also examined by quantum chemical calculations.

  13. Junk-Bond Colleges.

    ERIC Educational Resources Information Center

    Van Der Werf, Martin

    2003-01-01

    Describes how a long-predicted decline in the fortunes of small private colleges is beginning to show up in the bond market, as the number of colleges now rated in the junk category has nearly doubled. (EV)

  14. Activation of A-H bonds (A = B, C, N, O, Si) by using monovalent phosphorus complexes [RP→M].

    PubMed

    Mathey, Francois; Duan, Zheng

    2016-02-01

    The available data on the activation of A-H sigma bonds by electrophilic terminal phosphinidene complexes are reviewed. Theoretical computations allow us to rationalize the experimental results. It appears that a successful insertion needs an initial interaction between the phosphinidene and the A-H bond, such as a donor-acceptor complex with a lone pair, a Coulombic interaction due to a negative charge on A or H, or a proximity effect.

  15. 75 FR 47608 - Agency Information Collection Activities: Application for Exportation of Articles under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-06

    ... Exportation of Articles under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... requirement concerning the: Application for Exportation of Articles under Special Bond. This request for...: Title: Application for Exportation of Articles under Special Bond. OMB Number: 1651-0004. Form...

  16. 78 FR 49761 - Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-15

    ... Exportation of Articles Under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... information collection requirement concerning the Application for Exportation of Articles under Special Bond... Articles Under Special Bond. OMB Number: 1651-0004. Form Number: CBP Form 3495. Abstract: CBP Form...

  17. 75 FR 61162 - Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-10-04

    ... Exportation of Articles Under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... Exportation of Articles under Special Bond (CBP Form 3495). This is a proposed extension of an information... Exportation of Articles under Special Bond. OMB Number: 1651-0004. Form Number: Form 3495. Abstract:...

  18. 78 FR 66038 - Agency Information Collection Activities: Application for Exportation of Articles Under Special Bond

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-11-04

    ... Exportation of Articles Under Special Bond AGENCY: U.S. Customs and Border Protection, Department of Homeland... Exportation of Articles under Special Bond (CBP Form 3495). This is a proposed extension of an information.... Title: Application for Exportation of Articles under Special Bond. OMB Number: 1651-0004. Form...

  19. Bond dissociation free energy as a general parameter for flavonoid radical scavenging activity.

    PubMed

    Stepanić, Višnja; Gall Trošelj, Koraljka; Lučić, Bono; Marković, Zoran; Amić, Dragan

    2013-11-15

    Notwithstanding multiple mechanisms of radical scavenging (RS), measured RS activities (RSA) of flavonoids are usually related to O-H bond dissociation enthalpy (BDE) for hydrogen atom transfer (HAT). For 12 flavonoids the reaction free energies were calculated for: (1) HAT, (2) single electron transfer-proton transfer (SET-PT) and (3) sequential proton loss electron transfer (SPLET) in gas and aqueous phases. Aqueous free energies, like bond dissociation (BDFEaq), ionisation (IFEaq) and deprotonation (ΔGdeprot,aq) free energies were estimated using thermochemical cycles. While in gas HAT is a RS mechanism (BDFEg

  20. Aromatic Cyanoalkylation through Double C-H Activation Mediated by Ni(III).

    PubMed

    Zhou, Wen; Zheng, Shuai; Schultz, Jason W; Rath, Nigam P; Mirica, Liviu M

    2016-05-11

    Herein we report an atom- and step-economic aromatic cyanoalkylation reaction that employs nitriles as building blocks and proceeds through Csp(2)-H and Csp(3)-H bond activation steps mediated by Ni(III). In addition to cyanomethylation with MeCN, regioselective α-cyanoalkylation was observed with various nitrile substrates to generate secondary and tertiary nitriles. Importantly, to the best of our knowledge these are the first examples of C-H bond activation reactions occurring at a Ni(III) center, which may exhibit different reactivity and selectivity profiles than those corresponding to analogous Ni(II) centers. These studies provide guiding principles to design catalytic C-H activation and functionalization reactions involving high-valent Ni species. PMID:27120207

  1. Dynamic NMR study of the mechanisms of double, triple, and quadruple proton and deuteron transfer in cyclic hydrogen bonded solids of pyrazole derivatives.

    PubMed

    Klein, Oliver; Aguilar-Parrilla, Francisco; Lopez, Juan Miguel; Jagerovic, Nadine; Elguero, José; Limbach, Hans-Heinrich

    2004-09-22

    Using dynamic solid state (15)N CPMAS NMR spectroscopy (CP = cross polarization, MAS = magic angle spinning), the kinetics of the degenerate intermolecular double and quadruple proton and deuteron transfers in the cyclic dimer of (15)N labeled polycrystalline 3,5-diphenyl-4-bromopyrazole (DPBrP) and in the cyclic tetramer of (15)N labeled polycrystalline 3,5-diphenylpyrazole (DPP) have been studied in a wide temperature range at different deuterium fractions in the mobile proton sites. Rate constants were measured on a millisecond time scale by line shape analysis of the doubly (15)N labeled compounds, and by magnetization transfer experiments on a second timescale of the singly (15)N labeled compounds in order to minimize the effects of proton-driven (15)N spin diffusion. For DPBrP the multiple kinetic HH/HD/DD isotope effects could be directly obtained. By contrast, four rate constants k(1) to k(4) were obtained for DPP at different deuterium fractions. Whereas k(1) corresponds to the rate constant k(HHHH) of the HHHH isotopolog, an appropriate kinetic reaction model was needed for the kinetic assignment of the other rate constants. Using the model described by Limbach, H. H.; Klein, O.; Lopez Del Amo, J. M.; Elguero, J. Z. Phys. Chem. 2004,218, 17, a concerted quadruple proton-transfer mechanism as well as a stepwise consecutive single transfer mechanism could be excluded. By contrast, using the kinetic assignment k(2) approximately k(3) approximately k(HHHD) approximately k(HDHD) and k(3) approximately k(HDDD) approximately k(DDDD), the results could be explained in terms of a two-step process involving a zwitterionic intermediate. In this mechanism, each reaction step involves the concerted transfer of two hydrons, giving rise to primary kinetic HH/HD/DD isotope effects, whereas the nontransferred hydrons only contribute small secondary effects, which are not resolved experimentally. By contrast, the multiple kinetic isotope effects of the double proton

  2. Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study

    NASA Astrophysics Data System (ADS)

    Sinthika, S.; Kumar, E. Mathan; Surya, V. J.; Kawazoe, Y.; Park, Noejung; Iyakutti, K.; Thapa, Ranjit

    2015-12-01

    Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir-Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level.

  3. Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study.

    PubMed

    Sinthika, S; Kumar, E Mathan; Surya, V J; Kawazoe, Y; Park, Noejung; Iyakutti, K; Thapa, Ranjit

    2015-01-01

    Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir-Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level.

  4. Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study.

    PubMed

    Sinthika, S; Kumar, E Mathan; Surya, V J; Kawazoe, Y; Park, Noejung; Iyakutti, K; Thapa, Ranjit

    2015-01-01

    Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir-Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level. PMID:26626147

  5. Non-bonded interactions and its contribution to the NLO activity of Glycine Sodium Nitrate A vibrational approach

    NASA Astrophysics Data System (ADS)

    Vijayakumar, T.; Hubert Joe, I.; Reghunadhan Nair, C. P.; Jayakumar, V. S.

    2008-04-01

    Vibrational spectral analysis of the novel nonlinear optical (NLO) material, Glycine Sodium Nitrate (GSN) is carried out using NIR FT-Raman and FT-IR spectroscopy, supported by Density Functional Theoretical (DFT) computations to derive equilibrium geometry, vibrational wave numbers and first hyperpolarizability. The reasonable NLO efficiency, predicted for the first time in this novel compound, has been confirmed by Kurtz-Perry powder SHG experiments. The influence of Twisted Intramolecular Charge Transfer (TICT) caused by the strong ionic ground state hydrogen bonding between charged species making GSN crystal to have the non-centrosymmetric structure has been discussed. The shortening of C sbnd H bond lengths, blue-shifting of the stretching frequencies and intensity variation indicating the existence of 'blue-shift or improper' C sbnd H⋯O hydrogen bonding. The intense low wavenumber H-bond Raman vibrations due to electron-phonon coupling and non-bonded interactions in making the molecule NLO active have been analyzed based on the vibrational spectral features. The Natural Bond Orbital (NBO) analysis confirms the occurrence of a strong intra- and intermolecular N sbnd H⋯O and C sbnd H⋯O hydrogen bonds.

  6. Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study

    PubMed Central

    Sinthika, S.; Kumar, E. Mathan; Surya, V. J.; Kawazoe, Y.; Park, Noejung; Iyakutti, K.; Thapa, Ranjit

    2015-01-01

    Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir–Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level. PMID:26626147

  7. Transition metal activation and functionalization of C-H bonds. Progress report, June 1, 1983-May 31, 1986

    SciTech Connect

    Jones, W.D.

    1986-11-01

    This project has been directed towards the investigation of the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers. The major accomplishments of this past three years have been: (1) to identify a new transition metal complex capable of activating both arene and alkane C-H bonds, (2) to quantitatively evaluate the stability of the hydrido aryl and hydrido alkyl complexes towards reductive elimination, (3) to measure the kinetic selectivity of the reactive intermediate towards alkane and arene C-H bonds, (4) to quantitatively determine the thermodynamics of alkane and arene oxidative addition, (5) to demonstrate that arenes are activated by way of formation of an eta/sup 2/-arene complex, (6) to quantitatively determine the kinetic and thermodynamic preference for intra vs intermolecular activation of arene and alkane C-H bonds, (7) to measure isotope effects for the oxidative addition/reductive elimination pathways as a means of confirming the proposed mechanism of reaction, and (8) to formulate a unified theory of C-H bond activation that applies to other transition metal complexes. The specific complexes involved in these studies are derivatives of the formulation (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(R)H and (C/sub 5/Me/sub 5/)Rh(PMe/sub 2/R) (R)H.

  8. Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

    DOE PAGES

    Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.

    2014-07-04

    The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH3)2CCHCH2OH) and isoprenol (3-methyl-3-buten-1-ol, CH2C(CH3)CH2CH2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. Thesemore » results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.« less

  9. Double Bond Position Plays an Important Role in Delta-9 Desaturation and Lipogenic Properties of Trans 18:1 Isomers in Mouse Adipocytes.

    PubMed

    Vahmani, P; Meadus, W J; Mapiye, C; Duff, P; Rolland, D C; Dugan, M E R

    2015-12-01

    The objective of this research was to study the delta-9 desaturation of individual trans (t) fatty acids that can be found in ruminant fat or partially hydrogenated vegetable oils (PHVO) and determine their effects on lipogenic gene expression in adipocytes. It was hypothesized that delta-9 desaturation and lipogenic properties of t-18:1 isomers depend on the position of double bond. Differentiated 3T3-L1 adipocytes were treated with 200 µM of t6-18:1, t9-18:1, t11-18:1, t13-18:1 or t16-18:1, cis (c)-9 18:1 or bovine serum albumin (BSA) vehicle control for 48 h. Cells were then harvested for fatty acid and gene expression analyses using gas chromatography and quantitative PCR respectively. Among t-18:1 isomers, t13-18:1 and t11-8:1 had the greatest percent delta-9 desaturation (44 and 41 % respectively) followed by t16-18:1 and t6-18:1 (32 and 17 % respectively), while c9-18:1 and t9-18:1 did not undergo delta-9 desaturation. Trans9-18:1 up-regulated (P < 0.05) the expression of lipogenic genes including fatty acid synthase and stearoyl-CoA desaturase-1 (P < 0.05), whereas the expression of these genes were not affected with other t-18:1 isomers (P > 0.05). Consistent with gene expression results, t9-18:1 increased the de novo lipogenic index (16:0/18:2n-6) compared with control cells and increased delta-9 desaturation index (c9-16:1/18:0) compared to other t-18:1 isomers (P < 0.05). The current study provides further evidence that the predominant trans fatty acid in PHVO (t9-18:1) has isomer specific lipogenic properties. PMID:26476931

  10. Double Bond Position Plays an Important Role in Delta-9 Desaturation and Lipogenic Properties of Trans 18:1 Isomers in Mouse Adipocytes.

    PubMed

    Vahmani, P; Meadus, W J; Mapiye, C; Duff, P; Rolland, D C; Dugan, M E R

    2015-12-01

    The objective of this research was to study the delta-9 desaturation of individual trans (t) fatty acids that can be found in ruminant fat or partially hydrogenated vegetable oils (PHVO) and determine their effects on lipogenic gene expression in adipocytes. It was hypothesized that delta-9 desaturation and lipogenic properties of t-18:1 isomers depend on the position of double bond. Differentiated 3T3-L1 adipocytes were treated with 200 µM of t6-18:1, t9-18:1, t11-18:1, t13-18:1 or t16-18:1, cis (c)-9 18:1 or bovine serum albumin (BSA) vehicle control for 48 h. Cells were then harvested for fatty acid and gene expression analyses using gas chromatography and quantitative PCR respectively. Among t-18:1 isomers, t13-18:1 and t11-8:1 had the greatest percent delta-9 desaturation (44 and 41 % respectively) followed by t16-18:1 and t6-18:1 (32 and 17 % respectively), while c9-18:1 and t9-18:1 did not undergo delta-9 desaturation. Trans9-18:1 up-regulated (P < 0.05) the expression of lipogenic genes including fatty acid synthase and stearoyl-CoA desaturase-1 (P < 0.05), whereas the expression of these genes were not affected with other t-18:1 isomers (P > 0.05). Consistent with gene expression results, t9-18:1 increased the de novo lipogenic index (16:0/18:2n-6) compared with control cells and increased delta-9 desaturation index (c9-16:1/18:0) compared to other t-18:1 isomers (P < 0.05). The current study provides further evidence that the predominant trans fatty acid in PHVO (t9-18:1) has isomer specific lipogenic properties.

  11. Crucial Role of the Double Bond Isomerism in the Steroid B-Ring on the Membrane Properties of Sterols. Grazing Incidence X-Ray Diffraction and Brewster Angle Microscopy Studies.

    PubMed

    Flasiński, Michał; Wydro, Paweł; Broniatowski, Marcin; Hąc-Wydro, Katarzyna; Fontaine, Philippe

    2015-07-01

    Three cholesterol precursors-desmosterol, zymosterol, and lanosterol-were comprehensively characterized in monolayers formed at the air/water interface. The studies were based on registration of the surface pressure (π)-area (A) isotherms complemented with in situ analysis performed with application of modern physicochemical techniques: grazing incidence X-ray diffraction (GIXD) and Brewster angle microscopy (BAM). In this approach we were interested in the correlation between molecular structures of the studied sterols found in the cholesterol biosynthetic pathway and their membrane properties. Our results revealed that only desmosterol behaves in Langmuir monolayers comparably to cholesterol, the molecules of which arrange in the monolayers into a hexagonal lattice, while the two remaining sterols possess extremely different properties. We found that molecules of both zymosterol and lanosterol are organized on the water surface in the two-dimensional oblique unit cells despite the fact that they are oriented perpendicular to the monolayer plane. The comparison of chemical structures of the investigated sterols leads to the conclusion that the only structural motive that can be responsible for such unusual behavior is the double bond in the B sterol ring, which is located in desmosterol in a different position from in the other two sterols. This issue, which was neglected in the scientific literature, seems to have crucial importance for sterol activity in biomembranes. We showed that this structural modification in sterol molecules is directly responsible for their adaptation to proper functioning in biomembranes.

  12. Properties of Ce-activated alkali-lutetium double phosphate scintillators

    SciTech Connect

    Wiśniewski, D.; Wojtowicz, A. J.; Boatner, Lynn A

    2010-01-01

    The scintillation properties of Ce-activated alkali-lutetium double phosphate single crystals that vary with the alkali ion type and activation level are summarized and compared. The materials investigated here have been identified as fast and efficient scintillators for the detection of x-ray and radiation, and in case of Li3Lu(PO4)2:Ce, for thermal neutron detection as well.

  13. Physical mechanisms of active control of sound transmission through rib stiffened double-panel structure

    NASA Astrophysics Data System (ADS)

    Ma, Xiyue; Chen, Kean; Ding, Shaohu; Yu, Haoxin

    2016-06-01

    This paper presents an analytical investigation on physical mechanisms of actively controlling sound transmission through a rib stiffened double-panel structure using point source in the cavity. The combined modal expansion and vibro-acoustic coupling methods are applied to establish the theoretical model of such active structure. Under the condition of minimizing radiated power of the radiating ribbed plate, the physical mechanisms are interpreted in detail from the point of view of modal couplings similar as that used in existed literatures. Results obtained demonstrate that the rule of sound energy transmission and the physical mechanisms for the rib stiffened double-panel structure are all changed, and affected by the coupling effects of the rib when compared with the analytical results obtained for unribbed double-panel case. By taking the coupling effects of the rib into considerations, the cavity modal suppression and rearrangement mechanisms obtained in existed investigations are modified and supplemented for the ribbed plate case, which gives a clear interpretation for the physical nature involved in the active rib stiffened double-panel structure.

  14. Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions.

    PubMed

    Esteruelas, Miguel A; López, Ana M; Oliván, Montserrat

    2016-08-10

    The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B-H, C-H, Si-H, N-H, O-H, C-C, C-N, and C-F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future.

  15. Annealing effects on recombinative activity of nickel at direct silicon bonded interface

    SciTech Connect

    Kojima, Takuto Ohshita, Yoshio; Yamaguchi, Masafumi

    2015-09-15

    By performing capacitance transient analyses, the recombination activity at a (110)/(100) direct silicon bonded (DSB) interface contaminated with nickel diffused at different temperatures, as a model of grain boundaries in multicrystalline silicon, was studied. The trap level depth from the valence band, trap density of states, and hole capture cross section peaked at an annealing temperature of 300 °C. At temperatures ⩾400 °C, the hole capture cross section increased with temperature, but the density of states remained unchanged. Further, synchrotron-based X-ray analyses, microprobe X-ray fluorescence (μ-XRF), and X-ray absorption near edge structure (XANES) analyses were performed. The analysis results indicated that the chemical phase after the sample was annealed at 200 °C was a mixture of NiO and NiSi{sub 2}.

  16. Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions.

    PubMed

    Esteruelas, Miguel A; López, Ana M; Oliván, Montserrat

    2016-08-10

    The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B-H, C-H, Si-H, N-H, O-H, C-C, C-N, and C-F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future. PMID:27268136

  17. Role of peptide bond in the realization of biological activity of short peptides.

    PubMed

    Khavinson, V Kh; Tarnovskaya, S I; Lin'kova, N S; Chervyakova, N A; Nichik, T E; Elashkina, E V; Chalisova, N I

    2015-02-01

    We performed a comparative analysis of biological activity of Lys-Glu peptide and its amino acid constituents. It was established that Lys-Glu stimulated proliferation of splenic cells in organotypic culture, while the mixture of glutamic acid and lysine inhibited culture growth. Using the method of molecular docking, we showed that glutamic acid, lysine, and Lys-Glu peptide can interact with different DNA sequences. The energy of interaction and the most beneficial localization of glutamic acid, lysine, and Lys-Glu peptide in DNA molecule was calculated. We demonstrated the interaction of the peptide and amino acids with DNA along the minor groove. The energy of DNA interaction with the peptide is higher than with individual amino acids. The peptide bonds increase the interaction of Lys-Glu peptide with DNA, which potentiates the biological effect on cell proliferation in organotypic culture of splenic cells.

  18. An internal disulfide bond acts as a switch for intein activity

    PubMed Central

    Nicastri, Michael C.; Xega, Kristina; Li, Lingyun; Xie, Jian; Wang, Chunyu; Linhardt, Robert J.; Reitter, Julie N.; Mills, Kenneth V.

    2013-01-01

    Inteins are intervening polypeptides that catalyze their own removal from flanking exteins, concomitant to the ligation of the exteins. The intein that interrupts the DP2 (large) subunit of DNA Polymerase II from Methanoculleus marisnigri (Mma) can promote protein splicing. However, protein splicing can be prevented or reduced by over-expression under non-reducing conditions, due to the formation of a disulfide bond between two internal intein Cys residues. This redox sensitivity leads to differential activity in different strains of E. coli as well as in different cell compartments. The redox-dependent control of in vivo protein splicing in an intein derived from an anaerobe that can occupy multiple environments hints at a possible physiological role for protein splicing. PMID:23906287

  19. A C–H bond activation-based catalytic approach to tetrasubstituted chiral allenes

    PubMed Central

    Wu, Shangze; Huang, Xin; Wu, Wangteng; Li, Pengbin; Fu, Chunling; Ma, Shengming

    2015-01-01

    Enantioselective synthesis of fully substituted allenes has been a challenge due to the non-rigid nature of the axial chirality, which spreads over three carbon atoms. Here we show the commercially available simple Rh complex may catalyse the CMD (concerted metalation/deprotonation)-based reaction of the readily available arenes with sterically congested tertiary propargylic carbonates at ambient temperature affording fully substituted allenes. It is confirmed that the excellent designed regioselectivity for the C–C triple bond insertion is induced by the coordination of the carbonyl group in the directing carbonate group as well as the steric effect of the tertiary O-linked carbon atom. When an optically active carbonate was used, surprisingly high efficiency of chirality transfer was realized, affording fully substituted allenes in excellent enantiomeric excess (ee). PMID:26246391

  20. Oxygen activation and intramolecular C-H bond activation by an amidate-bridged diiron(II) complex.

    PubMed

    Jones, Matthew B; Hardcastle, Kenneth I; Hagen, Karl S; MacBeth, Cora E

    2011-07-18

    A diiron(II) complex containing two μ-1,3-(κN:κO)-amidate linkages has been synthesized using the 2,2',2''-tris(isobutyrylamido)triphenylamine (H(3)L(iPr)) ligand. The resulting diiron complex, 1, reacts with dioxygen (or iodosylbenzene) to effect intramolecular C-H bond activation at the methine position of the ligand isopropyl group. The ligand-activated product, 2, has been isolated and characterized by a variety of methods including X-ray crystallography. Electrospray ionization mass spectroscopy of 2 prepared from(18)O(2) was used to confirm that the oxygen atom incorporated into the ligand framework is derived from molecular oxygen.

  1. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase.

    PubMed

    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A

    2016-07-13

    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  2. Cross-Couplings Using Aryl Ethers via C-O Bond Activation Enabled by Nickel Catalysts.

    PubMed

    Tobisu, Mamoru; Chatani, Naoto

    2015-06-16

    Arene synthesis has been revolutionized by the invention of catalytic cross-coupling reactions, wherein aryl halides can be coupled with organometallic and organic nucleophiles. Although the replacement of aryl halides with phenol derivatives would lead to more economical and ecological methods, success has been primarily limited to activated phenol derivatives such as triflates. Aryl ethers arguably represent one of the most ideal substrates in terms of availability, cost, safety, and atom efficiency. However, the robust nature of the C(aryl)-O bonds of aryl ethers renders it extremely difficult to use them in catalytic reactions among the phenol derivatives. In 1979, Wenkert reported a seminal work on the nickel-catalyzed cross-coupling of aryl ethers with Grignard reagents. However, it was not until 2004 that the unique ability of a low-valent nickel species to activate otherwise unreactive C(aryl)-O bonds was appreciated with Dankwardt's identification of the Ni(0)/PCy3 system, which significantly expanded the efficiency of the Wenkert reaction. Application of the nickel catalyst to cross-couplings with other nucleophiles was first accomplished in 2008 by our group using organoboron reagents. Later on, several other nucleophiles, including organozinc reagents, amines, hydrosilane, and hydrogen were shown to be coupled with aryl ethers under nickel catalysis. Despite these advances, progress in this field is relatively slow because of the low reactivity of benzene derivatives (e.g., anisole) compared with polyaromatic substrates (e.g., methoxynaphthalene), particularly when less reactive and synthetically useful nucleophiles are used. The "naphthalene problem" has been overcome by the use of N-heterocyclic carbene (NHC) ligands bearing bulky N-alkyl substituents, which enables a wide range of aryl ethers to be coupled with organoboron nucleophiles. Moreover, the use of N-alkyl-substituted NHC ligands allows the use of alkynylmagnesium reagents, thereby realizing

  3. β-Boomerang Antimicrobial and Antiendotoxic Peptides: Lipidation and Disulfide Bond Effects on Activity and Structure

    PubMed Central

    Mohanram, Harini; Bhattacharjya, Surajit

    2014-01-01

    Drug-resistant Gram-negative bacterial pathogens and endotoxin- or lipopolysaccharide (LPS)-mediated inflammations are among some of the most prominent health issues globally. Antimicrobial peptides (AMPs) are eminent molecules that can kill drug-resistant strains and neutralize LPS toxicity. LPS, the outer layer of the outer membrane of Gram-negative bacteria safeguards cell integrity against hydrophobic compounds, including antibiotics and AMPs. Apart from maintaining structural integrity, LPS, when released into the blood stream, also induces inflammatory pathways leading to septic shock. In previous works, we have reported the de novo design of a set of 12-amino acid long cationic/hydrophobic peptides for LPS binding and activity. These peptides adopt β-boomerang like conformations in complex with LPS. Structure-activity studies demonstrated some critical features of the β-boomerang scaffold that may be utilized for the further development of potent analogs. In this work, β-boomerang lipopeptides were designed and structure-activity correlation studies were carried out. These lipopeptides were homo-dimerized through a disulfide bridge to stabilize conformations and for improved activity. The designed peptides exhibited potent antibacterial activity and efficiently neutralized LPS toxicity under in vitro assays. NMR structure of C4YI13C in aqueous solution demonstrated the conserved folding of the lipopeptide with a boomerang aromatic lock stabilized with disulfide bond at the C-terminus and acylation at the N-terminus. These lipo-peptides displaying bacterial sterilization and low hemolytic activity may be useful for future applications as antimicrobial and antiendotoxin molecules. PMID:24756162

  4. A single mutation Gln142Lys doubles the catalytic activity of VPR, a cold adapted subtilisin-like serine proteinase.

    PubMed

    Óskarsson, Kristinn R; Nygaard, Mads; Ellertsson, Brynjar Ö; Thorbjarnardottir, Sigríður H; Papaleo, Elena; Kristjánsson, Magnús M

    2016-10-01

    Structural comparisons of the cold adapted subtilase VPR and its thermophilic homologue, aqualysin I (AQUI) indicated the presence of additional salt bridges in the latter. Few of those appear to contribute significantly to thermal stability of AQUI. This includes a putative salt bridge between residues Lys142 and Glu172 as its deletion did not have any significant effect on its stability or activity (Jónsdóttir et al. (2014)). Insertion of this putative salt bridge into the structure of VPR, in a double mutant (VPRΔC_Q142K/S172E), however was detrimental to the stability of the enzyme. Incorporation of either the Q142K or S172E mutations into VPR, were found to significantly affect the catalytic properties of the enzyme. The single mutation Q142K was highly effective, as it increased the kcat and kcat/Km more than twofold. When the Q142K mutation was inserted into a thermostabilized, but a low activity mutant of VPR (VPRΔC_N3P/I5P), the activity increased about tenfold in terms of kcat and kcat/Km, while retaining the stability of the mutant. Molecular dynamics simulations of the single mutants were carried out to provide structural rationale for these experimental observations. Based on root mean square fluctuation (RMSF) profiles, the two mutants were more flexible in certain regions of the structure and the Q142K mutant had the highest overall flexibility of the three enzymes. The results suggest that weakening of specific H-bonds resulting from the mutations may be propagated over some distance giving rise to higher flexibility in the active site regions of the enzyme, causing higher catalytic activity in the mutants. PMID:27456266

  5. Activation of amide N-H bonds by organotransition metal complexes

    SciTech Connect

    Schaad, D.R.

    1992-01-01

    This research was aimed at developing new homogeneous transition metal hydroamination catalysts, specifically for hydroamination reactions involving the addition of amides to olefins. New iron-, ruthenium-, palladium- and platinum-amido complexes were formed via amide N-H bond activation reactions to zerovalent and divalent organotransition metal complexes. Complexes of the general formula trans-MW(amido) (diphosphine)[sub 2] were synthesized by reaction of amides with FeH(C[sub 6]H[sub 4]PPhCH[sub 2]CH[sub 2]PPh[sub 2]) (dppe) and cis-RuHNp(dmpe)[sub 2]. Photolysis of cis-FeH[sub 2](dmpe)[sub 2] or Pt(C[sub 2]O[sub 4] (PEt[sub 3])[sub 2] in the presence of amides yielded trans-FeH(amido)(dmple)[sub 2] and trans-PtH (amido) IPEt[sub 3]) products. Reactions of amides with cis-M(PEtt[sub 3])[sub 2]Me[sub 2] yielded compounds with the general formula M(amido)Me(PEt[sub 3])[sub 2] (M = Pd, Pt). The reaction of M(diphosphine)Me[sub 2] complexes with amides produced compounds with the general formula M(amido)Me(diphosphine) (M = Pd, Pt). Reaction of amides with PtMe[sub 2](COD) yielded complexes with the general formula PtMe(amido)(COD). The compounds were characterized by multinuclear NMR spectroscopy. The reactions were proposed to occur by two routes: oxidative addition of the amid eN-H bond to the metal complex or direct protonation of the metal complex by the N-H bond of the amide. The rate of formation and the stability of the metal-amido products depended on the nature of the metal complex and the amide employed. Only acidic amides reacted with the iron complexes. For the thermal reactions of amides with the metal complexes, the reactions proceeded to completion faster as the acidity of the amide was increased. The new iron-, ruthenium-, palladium- and platinum-amido complexes were inert to further reaction.

  6. Plastic-PDMS bonding for high pressure hydrolytically stable active microfluidics.

    PubMed

    Lee, Kevin S; Ram, Rajeev J

    2009-06-01

    We explore the application of organofunctional silanes for bonding plastic substrates to PDMS membranes. Such devices would enable actuated membrane microfluidics in plastic devices. Bond strength degradation in aqueous environments can be reduced by using bis-silanes with larger alkoxy end groups to promote organofunctional bond formation with the plastic substrate. Hydrolytic failure can also result from low silane crosslink density or interface hydrophilicity. A test device consisting of three-valve peristaltic pumps is fabricated out of polycarbonate (PC) and bonded to PDMS through isopropoxy modified bis-trimethoxy-silyl-propyl-amine. Valves operated up to 60 psi in aqueous environments without failure. Solutions of DI water and 1 M HCl were also pumped through the device via peristaltic actuation at 18 psi for 2 weeks without bond failure. 1 M NaOH was also tested but resulted in bond failure after 115 hours.

  7. Possible interstellar formation of glycine through a concerted mechanism: a computational study on the reaction of CH2[double bond, length as m-dash]NH, CO2 and H2.

    PubMed

    Nhlabatsi, Zanele P; Bhasi, Priya; Sitha, Sanyasi

    2016-07-27

    Glycine being the simplest amino acid and also having significant astrobiological implications, has meant that intensive investigations have been carried out in the past, starting from its detection in the interstellar medium (ISM) to analysis of meteorites and cometary samples and laboratory synthesis, as well as computational studies on the possible reaction paths. In this present work quantum chemical calculations have been performed to investigate the possible interstellar formation of glycine via two different paths; (1) in a two-step process via a dihydroxy carbene intermediate and (2) through a one-step concerted mechanism, starting from reactants like CH2[double bond, length as m-dash]NH, CO, CO2, H2O and H2. For the two reactions representing the carbene route, it was observed that the formation of dihydroxy carbene from either CO + H2O or CO2 + H2 is highly endothermic with large barrier heights, whereas the subsequent step of interaction of this carbene with CH2[double bond, length as m-dash]NH to give glycine is exothermic and the barrier is below the reactants. Based on this observation it is suggested that the formation of glycine via the carbene route is a least favourable or even unfavourable path. On the other hand, the two reactions CH2[double bond, length as m-dash]NH + CO + H2O and CH2[double bond, length as m-dash]NH + CO2 + H2 representing the concerted paths were found to be favourable in leading to the formation of glycine. After an extensive study on the first concerted reaction in our previous work (Phys. Chem. Chem. Phys., 2016, 18, 375-381), in this work a detailed investigation has been carried out for the second concerted reaction, CH2[double bond, length as m-dash]NH + CO2 + H2, which can possibly lead to the interstellar formation of glycine. It was observed that this reaction proceeds through a large barrier and at the same time the transition state shows prominent hydrogen dynamics, indicating a tunnelling possibility for this

  8. Possible interstellar formation of glycine through a concerted mechanism: a computational study on the reaction of CH2[double bond, length as m-dash]NH, CO2 and H2.

    PubMed

    Nhlabatsi, Zanele P; Bhasi, Priya; Sitha, Sanyasi

    2016-07-27

    Glycine being the simplest amino acid and also having significant astrobiological implications, has meant that intensive investigations have been carried out in the past, starting from its detection in the interstellar medium (ISM) to analysis of meteorites and cometary samples and laboratory synthesis, as well as computational studies on the possible reaction paths. In this present work quantum chemical calculations have been performed to investigate the possible interstellar formation of glycine via two different paths; (1) in a two-step process via a dihydroxy carbene intermediate and (2) through a one-step concerted mechanism, starting from reactants like CH2[double bond, length as m-dash]NH, CO, CO2, H2O and H2. For the two reactions representing the carbene route, it was observed that the formation of dihydroxy carbene from either CO + H2O or CO2 + H2 is highly endothermic with large barrier heights, whereas the subsequent step of interaction of this carbene with CH2[double bond, length as m-dash]NH to give glycine is exothermic and the barrier is below the reactants. Based on this observation it is suggested that the formation of glycine via the carbene route is a least favourable or even unfavourable path. On the other hand, the two reactions CH2[double bond, length as m-dash]NH + CO + H2O and CH2[double bond, length as m-dash]NH + CO2 + H2 representing the concerted paths were found to be favourable in leading to the formation of glycine. After an extensive study on the first concerted reaction in our previous work (Phys. Chem. Chem. Phys., 2016, 18, 375-381), in this work a detailed investigation has been carried out for the second concerted reaction, CH2[double bond, length as m-dash]NH + CO2 + H2, which can possibly lead to the interstellar formation of glycine. It was observed that this reaction proceeds through a large barrier and at the same time the transition state shows prominent hydrogen dynamics, indicating a tunnelling possibility for this

  9. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    SciTech Connect

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  10. Direct functionalization of nitrogen heterocycles via Rh-catalyzed C-H bond activation.

    PubMed

    Lewis, Jared C; Bergman, Robert G; Ellman, Jonathan A

    2008-08-01

    [Reaction: see text]. Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct functionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes our work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. We initially discovered an intramolecular Rh-catalyzed C-2 alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. We then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, we discovered that a novel substrate-derived Rh- N-heterocyclic carbene (NHC) complex was involved as an intermediate. We then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy 3)2] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazoline, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy 3) 2 fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid cocatalysts accelerate the alkylation, we developed conditions that efficiently and intermolecularly alkylate a variety of

  11. Discovery of amide (peptide) bond synthetic activity in Acyl-CoA synthetase.

    PubMed

    Abe, Tomoko; Hashimoto, Yoshiteru; Hosaka, Hideaki; Tomita-Yokotani, Kaori; Kobayashi, Michihiko

    2008-04-25

    Acyl-CoA synthetase, which is one of the acid-thiol ligases (EC 6.2.1), plays key roles in metabolic and regulatory processes. This enzyme forms a carbon-sulfur bond in the presence of ATP and Mg(2+), yielding acyl-CoA thioesters from the corresponding free acids and CoA. This enzyme belongs to the superfamily of adenylate-forming enzymes, whose three-dimensional structures are analogous to one another. We here discovered a new reaction while studying the short-chain acyl-CoA synthetase that we recently reported (Hashimoto, Y., Hosaka, H., Oinuma, K., Goda, M., Higashibata, H., and Kobayashi, M. (2005) J. Biol. Chem. 280, 8660-8667). When l-cysteine was used as a substrate instead of CoA, N-acyl-l-cysteine was surprisingly detected as a reaction product. This finding demonstrated that the enzyme formed a carbon-nitrogen bond (EC 6.3.1 acid-ammonia (or amide) ligase (amide synthase); EC 6.3.2 acid-amino acid ligase (peptide synthase)) comprising the amino group of the cysteine and the carboxyl group of the acid. N-Acyl-d-cysteine, N-acyl-dl-homocysteine, and N-acyl-l-cysteine methyl ester were also synthesized from the corresponding cysteine analog substrates by the enzyme. Furthermore, this unexpected enzyme activity was also observed for acetyl-CoA synthetase and firefly luciferase, indicating the generality of the new reaction in the superfamily of adenylate-forming enzymes.

  12. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    NASA Astrophysics Data System (ADS)

    Lichtenberger, D. L.

    1987-12-01

    Results are reported in the following areas: fundamental principles of ionization energy/bond energy relationships; relative strengths of early transition metal M-H and M-C bonds in substituted niobocenes and tantalocenes. Thermodynamic trends and electronic factors of olefin insertion into a metal-hydride bond; additivity of ligand electronic effects. Complete phosphine substitution of Group VI metal hexacarbonyls; organometallic methylene-bridged metal dimers; delocalization of metal electron density in metallacycle formation; metal-heteroatom and metal-alkylidyne multiple bonds; the electronic factors favoring intermediates in acetylene metathesis and polymerization; improvements in an electron energy analyzer.

  13. Effect of three adhesive primers on the bond strengths of four light-activated opaque resins to noble alloy.

    PubMed

    Yoshida, K; Kamada, K; Taira, Y; Atsuta, M

    2001-02-01

    The effect of commercial adhesive primers for noble metals on the bond strength of light-activated opaque resin has not been determined. This study evaluated the effect of three adhesive primers on the shear bond strengths of each of the four light-activated opaque resins to silver--palladium--copper--gold (Ag--Pd--Cu--Au) alloy. The adhesive primers Alloy Primer (AP), Metal Primer II (MPII) and Metaltite(MT) were used. Four commercial light-activated opaque resins (Axis (AX), Cesead II (CEII), Dentacolor(DE) and Solidex (SO) were used to bond a light-activated resin-veneered composite to Ag--Pd--Cu--Au alloy. The specimens were stored in water at 37 degrees C for 24 h and then immersed alternatively in water baths at 4 and 60 degrees C for 1 min each for up to 20,000 thermal cycles before shear mode testing at a cross-head speed of 0.5 mm min(-1). All the primers examined improved the shear bond strength between opaque resin and Ag--Pd--Cu--Au alloy compared with non-primed specimens prior to thermal cycling. After 20,000 thermal cycles, the bond strengths of combined use of AP and DE and that of MT and each of AX, CE or DE were significantly greater than any other groups. Significant difference was observed between the bond strengths at thermal cycles 0 and 20,000, with the combined use of MT and DE. With the combination of appropriate adhesive metal primers and light-activated opaque resins, complicated surface preparations of metal frameworks of resin-veneered prostheses that are composed of casting Ag-Pd-Cu-Au alloy may be negligible.

  14. Benchmark study of the performance of density functional theory for bond activations with (ni,pd)-based transition-metal catalysts.

    PubMed

    Steinmetz, Marc; Grimme, Stefan

    2013-06-01

    The performance of 23 density functionals, including one LDA, four GGAs, three meta-GGAs, three hybrid GGAs, eight hybrid meta-GGAs, and ten double-hybrid functionals, was investigated for the computation of activation energies of various covalent main-group single bonds by four catalysts: Pd, PdCl(-), PdCl2, and Ni (all in the singlet state). A reactant complex, the barrier, and reaction energy were considered, leading to 164 energy data points for statistical analysis. Extended Gaussian AO basis sets were used in all calculations. The best functional for the complete benchmark set relative to estimated CCSD(T)/CBS reference data is PBE0-D3, with an MAD value of 1.1 kcal mol(-1) followed by PW6B95-D3, the double hybrid PWPB95-D3, and B3LYP-D3 (1.9 kcal mol(-1) each). The other tested hybrid meta-GGAs perform less well (M06-HF: 7.0 kcal mol(-1); M06-2X: 6.3 kcal mol(-1); M06: 4.9 kcal mol(-1)) for the investigated reactions. In the Ni case, some double hybrids show larger errors due to partial breakdown of the perturbative treatment for the correlation energy in cases with difficult electronic structures (partial multi-reference character). Only double hybrids either with very low amounts of perturbative correlation (e.g., PBE0-DH) or that use the opposite-spin correlation component only (e.g., PWPB95) seem to be more robust. We also investigated the effect of the D3 dispersion correction. While the barriers are not affected by this correction, significant and mostly positive results were observed for reaction energies. Furthermore, six very recently proposed double-hybrid functionals were analyzed regarding the influence of the amount of Fock exchange as well as the type of perturbative correlation treatment. According to these results, double hybrids with <50-60 % of exact exchange and ∼30 % perturbative correlation perform best.

  15. Active Metal Brazing and Adhesive Bonding of Titanium to C/C Composites for Heat Rejection System

    NASA Technical Reports Server (NTRS)

    Singh, M.; Shpargel, Tarah; Cerny, Jennifer

    2006-01-01

    Robust assembly and integration technologies are critically needed for the manufacturing of heat rejection system (HRS) components for current and future space exploration missions. Active metal brazing and adhesive bonding technologies are being assessed for the bonding of titanium to high conductivity Carbon-Carbon composite sub components in various shapes and sizes. Currently a number of different silver and copper based active metal brazes and adhesive compositions are being evaluated. The joint microstructures were examined using optical microscopy, and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). Several mechanical tests have been employed to ascertain the effectiveness of different brazing and adhesive approaches in tension and in shear that are both simple and representative of the actual system and relatively straightforward in analysis. The results of these mechanical tests along with the fractographic analysis will be discussed. In addition, advantages, technical issues and concerns in using different bonding approaches will also be presented.

  16. Active site structure in cytochrome c peroxidase and myoglobin mutants: effects of altered hydrogen bonding to the proximal histidine.

    PubMed

    Sinclair, R; Hallam, S; Chen, M; Chance, B; Powers, L

    1996-11-26

    The globins and peroxidases, while performing completely different chemistry, share features of the iron heme active site: a protoporphyrin IX prosthetic group is linked to the protein by the proximal histidine residue. X-ray absorption spectroscopy provides a method to determine the local structure of iron heme active sites in proteins. Our previous studies using X-ray absorption spectroscopy revealed a significant difference in the Fe-N epsilon bond length between the peroxidases and the globins [for a review, see Powers, L. (1994) Molecular Electronics and Molecular Electronic Devices, Vol. 3, p 211 CRC Press Inc., Boca Raton, FL]. Globins typically have an Fe-N epsilon distance close to 2.1 A while the Fe-N epsilon distance in the peroxidases is closer to 1.9 A. We have proposed [Sinclair, R., Powers, L., Bumpus, J., Albo, A., & Brock, B. (1992) Biochemistry 31, 4892] that strong hydrogen bonding to the proximal histidine is responsible for the shorter bond length in the peroxidases. Here we use site-specific mutagenesis to eliminate the strong proximal hydrogen bonding in cytochrome c peroxidase and to introduce strong proximal hydrogen bonding in myoglobin. Consistent with our hypothesis, elimination of the Asp235-His175 hydrogen bond in CcP results in elongation of Fe-N epsilon from approximately 1.9 to approximately 2.1 A. Conversely, introduction of a similar strong proximal hydrogen bond in myoglobin shortens Fe-N epsilon from approximately 2.1 to approximately 1.9 A. These results correlate well with other biochemical data.

  17. Influence of spacer moiety and length of end chain for the phase stability in complementary, double hydrogen bonded liquid crystals, MA:nOBAs

    NASA Astrophysics Data System (ADS)

    Ashok Kumar, A. V. N.; Chalapathi, P. V.; Srinivasulu, M.; Muniprasad, M.; Potukuchi, D. M.

    2015-01-01

    Supra molecular liquid crystals formed by the Hydrogen Bonding interaction between a non-mesogenic aliphatic dicarboxylic acid viz., COOHsbnd CH2sbnd COOH (Malonic Acid, MA); and mesogenic aromatic, N-(p-n-alkoxy benzoic)Acids, (i.e., nOBAs) for n = 3, 4, 5, 7, 8, 9, 10, 11 and 12, labeled as nOBA:COOHsbnd [CH2]msbnd COOH:nOBAs, abbreviated as MA:nOBAs are reported. 1H NMR and 13C NMR studies confirm the formation of HBLC complexes. Infrared (IR) studies confirm the complementary, double, alternative type of HB. Polarized Optical Microscopy (POM) and Differential Scanning Calorimetry (DSC) studies infer N, SmC, SmX, SmCRE, SmF, SmG LC phase variance. SmX phase exhibiting finger print texture grows in MA:nOBAs for n = 10, 11 and 12 by the interruption of SmC phase with decreasing temperature. Re-Entrant SmC (SmCRE) grows by the cooling of SmX. I-N, N-C, X-CRE, C-G, CRE-F, F-G and G-Solid transitions exhibit first order nature. C-X is found to be second order nature in n = 10 and 11. C-X in n = 12 and X-CRE and CRE-F transitions are found to be weak first order nature. Influence of lengths of end chain (n) and spacer (m) for the overall LC phase [ΔT]LC; tilted phase [ΔT]Tilt; SmC phase [ΔT]C and SmX phase [ΔT]X stabilities is discussed in the wake of data on other HBLCs with similar molecular structure. Prevalence of SmX phase in MA:nOBAs with m = 1 infers repulsive interaction between the π-electronic cloud of aromatic boards of nOBAs. Model molecule predicts a twisted configuration of π-cloud around the molecular long axis. Finger print texture of SmX validates the model.

  18. Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

    SciTech Connect

    Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.

    2014-07-04

    The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH3)2CCHCH2OH) and isoprenol (3-methyl-3-buten-1-ol, CH2C(CH3)CH2CH2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. These results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce

  19. Approach to In- Situ Producing Reinforcing Phase Within an Active-Transient Liquid Phase Bond Seam for Aluminum Matrix Composite

    NASA Astrophysics Data System (ADS)

    Zhang, Guifeng; Liao, Xianjin; Chen, Bo; Zhang, Linjie; Zhang, Jianxun

    2015-06-01

    To optimize the braze composition design route for aluminum matrix composite, the feasibility of in situ producing reinforcing phase within the transient liquid phase bond seam matrix, by adding active melting point increaser (MPI, e.g., Ti) together with general melting point depressant (MPD, e.g., Cu) into the interlayer, was demonstrated. For SiC p /A356 composite, by comparing the wettability, joint microstructure, joint shear strength, and fracture path for the developed Al-19Cu-1Ti, Al-19Cu, Al-33Cu-1Ti, Al-33Cu (wt pct), and commercial Cu foils as interlayer, the feasibility of in situ producing reinforcing phase within the bond seam by adding Ti was demonstrated. Especially for Al-19Cu-1Ti active braze, small and dispersed ternary aluminide of Al-Si-Ti phase was obtained within the bond seam as in situ reinforcement, leading to a favorable fracture path within SiC p /A356, not along the initial interface or within the bond seam. For the formation mechanism of the in situ reinforcing phase of MPI-containing intermetallic compound within the bond seam, a model of repeating concentration-precipitation-termination-engulfment during isothermal solidification is proposed.

  20. The role of short-range Cys171-Cys178 disulfide bond in maintaining cutinase active site integrity: A molecular dynamics simulation

    SciTech Connect

    Matak, Mehdi Youssefi; Moghaddam, Majid Erfani

    2009-12-11

    Understanding structural determinants in enzyme active site integrity can provide a good knowledge to design efficient novel catalytic machineries. Fusarium solani pisi cutinase with classic triad Ser-His-Asp is a promising enzyme to scrutinize these structural determinants. We performed two MD simulations: one, with the native structure, and the other with the broken Cys171-Cys178 disulfide bond. This disulfide bond stabilizes a turn in active site on which catalytic Asp175 is located. Functionally important H-bonds and atomic fluctuations in catalytic pocket have been changed. We proposed that this disulfide bond within active site can be considered as an important determinant of cutinase active site structural integrity.

  1. Exocyclic push-pull conjugated compounds. Part 3. An experimental NMR and theoretical MO ab initio study of the structure, the electronic properties and barriers to rotation about the exocyclic partial double bond in 2- exo-methylene- and 2-cyanoimino-quinazolines and -benzodiazepines

    NASA Astrophysics Data System (ADS)

    Benassi, R.; Bertarini, C.; Hilfert, L.; Kempter, G.; Kleinpeter, E.; Spindler, J.; Taddei, F.; Thomas, S.

    2000-03-01

    The structure of a number of 2- exo-methylene substituted quinazolines and benzodiazepines, respectively, 1, 3a, b, 4( X=-CN, -COOEt ) and their 2-cyanoimino substituted analogues 2, 3c, d( X=-CN, -SO 2C 6H 4-Me (p) was completely assigned by the whole arsenal of 1D and 2D NMR spectroscopic methods. The E/ Z isomerism at the exo-cyclic double bond was determined by both NMR spectroscopy and confirmed by ab initio quantum chemical calculations; the Z isomer is the preferred one, its amount proved dependent on steric hindrance. Due to the push-pull effect in this part of the molecules the restricted rotation about the partial C 2,C 11 and C 2,N 11 double bonds, could also be studied and the barrier to rotation measured by dynamic NMR spectroscopy. The free energies of activation of this dynamic process proved very similar along the compounds studied but being dependent on the polarity of the solvent. Quantum chemical calculations at the ab initio level were employed to prove the stereochemistry at the exo-cyclic partial double bonds of 1- 4, to calculate the barriers to rotation but also to discuss in detail both the ground and the transition state of the latter dynamic process in order to better understand electronic, inter- and intramolecular effects on the barrier to rotation which could be determined experimentally. In the cyanoimino substituted compounds 2, 3c, d, the MO ab initio calculations evidence the isomer interconversion to be better described by the internal rotation process than by the lateral shift mechanism.

  2. Palladium-catalyzed oxidative arylalkylation of activated alkenes: dual C-H bond cleavage of an arene and acetonitrile.

    PubMed

    Wu, Tao; Mu, Xin; Liu, Guosheng

    2011-12-23

    Not one but two: The title reaction proceeds through the dual C-H bond cleavage of both aniline and acetonitrile. The reaction affords a variety of cyano-bearing indolinones in excellent yield. Mechanistic studies demonstrate that this reaction involves a fast arylation of the olefin and a rate-determining C-H activation of the acetonitrile.

  3. Consequences of metal-oxide interconversion for C-H bond activation during CH4 reactions on Pd catalysts.

    PubMed

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-10-16

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH4 react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to H-abstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cation-lattice oxygen pairs (Pd(2+)-O(2-)) in PdO. The charges in the CH3 and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*-covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd(2+)-O(2-) pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H3C···Pd···H)(‡) transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3(•)···*OH)(‡) that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd(2+) and vicinal O(2-), Pd(ox)-O(ox), cleave C-H bonds heterolytically via σ-bond metathesis, with Pd(2+) adding to the C-H bond, while O(2-) abstracts the H-atom to form a four-center (H3C(δ-)···Pd(ox)···H(δ+)···O(ox))(‡) transition state without detectable Pd(ox) reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH4 oxidation turnover rates at oxygen chemical potentials leading to Pd to PdO transitions. These distinct mechanistic pathways for C-H bond activation, inferred from theory

  4. Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH₄ Reactions on Pd Catalysts

    SciTech Connect

    Chin, Ya-Huei; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-10-01

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH₄ react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to Habstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cationlattice oxygen pairs (Pd2+-O2-) in PdO. The charges in the CH₃ and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*- covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd2+-O2- pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H₃C···Pd···H)‡ transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3 •···*OH)‡ that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd2+ and vicinal O2-, Pdox-Oox, cleave C-H bonds heterolytically via σ-bond metathesis, with Pd2+ adding to the C-H bond, while O2- abstracts the H-atom to form a four-center (H3Cδ-···Pdox···Hδ+···Oox) transition state without detectable Pdox reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH₄ oxidation turnover rates at oxygen chemical

  5. Electrochemical reduction of carbon fluorine bond in 4-fluorobenzonitrile Mechanistic analysis employing Marcus Hush quadratic activation-driving force relation

    NASA Astrophysics Data System (ADS)

    Muthukrishnan, A.; Sangaranarayanan, M. V.

    2007-10-01

    The reduction of carbon-fluorine bond in 4-fluorobenzonitrile in acetonitrile as the solvent, is analyzed using convolution potential sweep voltammetry and the dependence of the transfer coefficient on potential is investigated within the framework of Marcus-Hush quadratic activation-driving force theory. The validity of stepwise mechanism is inferred from solvent reorganization energy estimates as well as bond length calculations using B3LYP/6-31g(d) method. A novel method of estimating the standard reduction potential of the 4-fluorobenzonitrile in acetonitrile is proposed.

  6. Neutral redox-active hydrogen- and halogen-bonding [2]rotaxanes for the electrochemical sensing of chloride.

    PubMed

    Lim, Jason Y C; Cunningham, Matthew J; Davis, Jason J; Beer, Paul D

    2014-12-14

    The first examples of redox-active ferrocene-functionalised neutral [2]rotaxanes have been synthesised via chloride anion templation. (1)H NMR spectroscopic titrations reveal that these [2]rotaxane host systems recognize chloride selectively over other halides and oxoanions in highly-competitive aqueous media. By replacing the hydrogen bonding prototriazole units of the rotaxane axle component with iodotriazole halogen bond-donor groups, the degree of chloride selectivity of the [2]rotaxanes is modulated. Electrochemical voltammetric experiments demonstrate that the rotaxanes can sense chloride via cathodic perturbations of the respective rotaxanes' ferrocene-ferrocenium redox-couple upon anion addition.

  7. Activation of electroplated-Cu surface via plasma pretreatment for low temperature Cu-Sn bonding in 3D interconnection

    NASA Astrophysics Data System (ADS)

    Wang, Junqiang; Wang, Qian; Liu, Ziyu; Wu, Zijian; Cai, Jian; Wang, Dejun

    2016-10-01

    The pretreatment with Ar mixed 5% H2 plasma was applied to improve surface properties of electroplated Cu for low temperature Cu-Sn bonding in 3D interconnection. Measurement results revealed that the Ar(5% H2) plasma effectively increased the surface activity by reducing oxygen content of the Cu surface. Lower surface roughness obtained by optimizing the pretreatment condition could help to suppress oxygen adsorption. Relationships between surface energy and surface oxygen content, surface oxygen content and surface roughness were also established. Evaluation of low temperature (200 °C) Cu-Sn bonding with optimal plasma pretreatment exhibited a defect-free interface and high shear strength.

  8. B-H, C-H, and B-C bond activation: the role of two adjacent agostic interactions.

    PubMed

    Cassen, Audrey; Gloaguen, Yann; Vendier, Laure; Duhayon, Carine; Poblador-Bahamonde, Amalia; Raynaud, Christophe; Clot, Eric; Alcaraz, Gilles; Sabo-Etienne, Sylviane

    2014-07-14

    Tuning the nature of the linker in a L~BHR phosphinoborane compound led to the isolation of a ruthenium complex stabilized by two adjacent, δ-C-H and ε-B(sp2)-H, agostic interactions. Such a unique coordination mode stabilizes a 14-electron "RuH2P2" fragment through connected σ-bonds of different polarity, and affords selective B-H, C-H, and B-C bond activation as illustrated by reactivity studies with H2 and boranes. PMID:24990456

  9. Coordination and activation of Al-H and Ga-H bonds.

    PubMed

    Abdalla, Joseph A B; Riddlestone, Ian M; Turner, Joshua; Kaufman, Paul A; Tirfoin, Remi; Phillips, Nicholas; Aldridge, Simon

    2014-12-22

    The modes of interaction of donor-stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14- and 16-electron transition-metal fragments. More electron-rich N-heterocyclic carbene-stabilized alanes/gallanes of the type NHC⋅EH3 (E=Al or Ga) exclusively generate κ(2) complexes of the type [M(CO)4 (κ(2)-H3 E⋅NHC)] with [M(CO)4 (COD)] (M=Cr, Mo), including the first κ(2) σ-gallane complexes. β-Diketiminato ('nacnac')-stabilized systems, {HC(MeCNDipp)2 }EH2 , show more diverse reactivity towards Group 6 carbonyl reagents. For {HC(MeCNDipp)2 }AlH2, both κ(1) and κ(2) complexes were isolated, while [Cr(CO)4 (κ(2)-H2 Ga{(NDippCMe)2 CH})] is the only simple κ(2) adduct of the nacnac-stabilized gallane which can be trapped, albeit as a co-crystallite with the (dehydrogenated) gallylene system [Cr(CO)5 (Ga{(NDippCMe)2 CH})]. Reaction of [Co2 (CO)8] with {HC(MeCDippN)2 }AlH2 generates [(OC)3 Co(μ-H)2 Al{(NdippCme)2 CH}][Co(CO)4] (12), which while retaining direct AlH interactions, features a hitherto unprecedented degree of bond activation in a σ-alane complex. PMID:25358970

  10. CHEMICAL ACTIVATION OF MOLECULES BY METALS: EXPERIMENTAL STUDIES OF ELECTRON DISTRIBUTIONS AND BONDING

    SciTech Connect

    LICHTENBERGER, DENNIS L.

    2002-03-26

    This research program is directed at obtaining detailed experimental information on the electronic interactions between metals and organic molecules. These interactions provide low energy pathways for many important chemical and catalytic processes. A major feature of the program is the continued development and application of our special high-resolution valence photoelectron spectroscopy (UPS), and high-precision X-ray core photoelectron spectroscopy (XPS) instrumentation for study of organometallic molecules in the gas phase. The study involves a systematic approach towards understanding the interactions and activation of bound carbonyls, C-H bonds, methylenes, vinylidenes, acetylides, alkenes, alkynes, carbenes, carbynes, alkylidenes, alkylidynes, and others with various monometal, dimetal, and cluster metal species. Supporting ligands include -aryls, alkoxides, oxides, and phosphines. We are expanding our studies of both early and late transition metal species and electron-rich and electron-poor environments in order to more completely understand the electronic factors that serve to stabilize particular organic fragments and intermediates on metals. Additional new directions for this program are being taken in ultra-high vacuum surface UPS, XPS, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) experiments on both physisorbed and chemisorbed organometallic thin films. The combination of these methods provides additional electronic structure information on surface-molecule and molecule-molecule interactions. A very important general result emerging from this program is the identification of a close relationship between the ionization energies of the species and the thermodynamics of the chemical and catalytic reactions of these systems.

  11. Inhibition of APOBEC3G activity impedes double-stranded DNA repair.

    PubMed

    Prabhu, Ponnandy; Shandilya, Shivender M D; Britan-Rosich, Elena; Nagler, Adi; Schiffer, Celia A; Kotler, Moshe

    2016-01-01

    The cellular cytidine deaminase APOBEC3G (A3G) was first described as an anti-HIV-1 restriction factor, acting by directly deaminating reverse transcripts of the viral genome. HIV-1 Vif neutralizes the activity of A3G, primarily by mediating degradation of A3G to establish effective infection in host target cells. Lymphoma cells, which express high amounts of A3G, can restrict Vif-deficient HIV-1. Interestingly, these cells are more stable in the face of treatments that result in double-stranded DNA damage, such as ionizing radiation and chemotherapies. Previously, we showed that the Vif-derived peptide (Vif25-39) efficiently inhibits A3G deamination, and increases the sensitivity of lymphoma cells to ionizing radiation. In the current study, we show that additional peptides derived from Vif, A3G, and APOBEC3F, which contain the LYYF motif, inhibit deamination activity. Each residue in the Vif25-39 sequence moderately contributes to the inhibitory effect, whereas replacing a single residue in the LYYF motif completely abrogates inhibition of deamination. Treatment of A3G-expressing lymphoma cells exposed to ionizing radiation with the new inhibitory peptides reduces double-strand break repair after irradiation. Incubation of cultured irradiated lymphoma cells with peptides that inhibit double-strand break repair halts their propagation. These results suggest that A3G may be a potential therapeutic target that is amenable to peptide and peptidomimetic inhibition.

  12. DOUBLE-PEAKED NARROW-LINE ACTIVE GALACTIC NUCLEI. II. THE CASE OF EQUAL PEAKS

    SciTech Connect

    Smith, K. L.; Shields, G. A.; Salviander, S.; Stevens, A. C.; Rosario, D. J. E-mail: shields@astro.as.utexas.edu E-mail: acs0196@mail.utexas.edu

    2012-06-10

    Active galactic nuclei (AGNs) with double-peaked narrow lines (DPAGNs) may be caused by kiloparsec-scale binary AGNs, bipolar outflows, or rotating gaseous disks. We examine the class of DPAGNs in which the two narrow-line components have closely similar intensity as being especially likely to involve disks or jets. Two spectroscopic indicators support this likelihood. For DPAGNs from Smith et al., the 'equal-peaked' objects (EPAGNs) have [Ne V]/[O III]ratios lower than for a control sample of non-double-peaked AGNs. This is unexpected for a pair of normal AGNs in a galactic merger, but may be consistent with [O III] emission from a rotating ring with relatively little gas at small radii. Also, [O III]/H{beta} ratios of the redshifted and blueshifted systems in the EPAGN are more similar to each other than in a control sample, suggestive of a single ionizing source and inconsistent with the binary interpretation.

  13. Role of P225 and the C136-C201 disulfide bond in tissue plasminogen activator.

    PubMed Central

    Vindigni, A.; Di Cera, E.

    1998-01-01

    The protease domain of tissue plasminogen activator (tPA), a key fibrinolytic enzyme, was expressed in Escherichia coli with a yield of 1 mg per liter of media. The recombinant protein was titrated with the Erythrina caraffa trypsin inhibitor (ETI) and characterized in its interaction with plasminogen and the natural inhibitor plasminogen activator inhibitor-1 (PAI-1). Analysis of the catalytic properties of tPA using a library of chromogenic substrates carrying substitutions at P1, P2, and P3 reveals a strong preference for Arg over Lys at P1, unmatched by other serine proteases like thrombin or trypsin. In contrast to these proteases and plasmin, tPA shows little or no preference for Pro over Gly at P2. A specific inhibition of tPA by Cu2+ was discovered. The divalent cation presumably binds to H188 near D189 in the primary specificity pocket and inhibits substrate binding in a competitive manner with a Kd = 19 microM. In an attempt to engineer Na+ binding and enhanced catalytic activity in tPA, P225 was replaced with Tyr, the residue present in Na+-dependent allosteric serine proteases. The P225Y mutation did not result in cation binding, but caused a significant loss of specificity (up to 100-fold) toward chromogenic substrates and plasminogen and considerably reduced the inhibition by PAI-1 and ETI. Interestingly, the P225Y substitution enhanced the ability of Cu2+ to inhibit the enzyme. Elimination of the C136-C201 disulfide bond, that is absent in all Na+-dependent allosteric serine proteases, significantly enhanced the yield (5 mg per liter of media) of expression in E. coli, but caused no changes in the properties of the enzyme whether residue 225 was Pro or Tyr. These findings point out an unanticipated crucial role for residue 225 in controlling the catalytic activity of tPA, and suggest that engineering of a Na+-dependent allosteric enhancement of catalytic activity in this enzyme, must involve substantial changes in the region homologous to the Na

  14. Origin of the catalytic activity of bovine seminal ribonuclease against double-stranded RNA

    NASA Technical Reports Server (NTRS)

    Opitz, J. G.; Ciglic, M. I.; Haugg, M.; Trautwein-Fritz, K.; Raillard, S. A.; Jermann, T. M.; Benner, S. A.

    1998-01-01

    Bovine seminal ribonuclease (RNase) binds, melts, and (in the case of RNA) catalyzes the hydrolysis of double-stranded nucleic acid 30-fold better under physiological conditions than its pancreatic homologue, the well-known RNase A. Reported here are site-directed mutagenesis experiments that identify the sequence determinants of this enhanced catalytic activity. These experiments have been guided in part by experimental reconstructions of ancestral RNases from extinct organisms that were intermediates in the evolution of the RNase superfamily. It is shown that the enhanced interactions between bovine seminal RNase and double-stranded nucleic acid do not arise from the increased number of basic residues carried by the seminal enzyme. Rather, a combination of a dimeric structure and the introduction of two glycine residues at positions 38 and 111 on the periphery of the active site confers the full catalytic activity of bovine seminal RNase against duplex RNA. A structural model is presented to explain these data, the use of evolutionary reconstructions to guide protein engineering experiments is discussed, and a new variant of RNase A, A(Q28L K31C S32C D38G E111G), which contains all of the elements identified in these experiments as being important for duplex activity, is prepared. This is the most powerful catalyst within this subfamily yet observed, some 46-fold more active against duplex RNA than RNase A.

  15. Nuclear Quadrupole Double Resonance Investigation of the Anomalous Temperature Coefficients of the Strong Hydrogen Bonds in Sodium and Potassium Deuterium Diacetate.

    NASA Astrophysics Data System (ADS)

    Shaw, Eric Max

    This thesis was directed at learning more about the unusual electronic environment near hydrogen within strong hydrogen bonds. "Strong" hydrogen bonds are unique in that the hydrogen atom is symmetrically located, or nearly so, between two electronegative atoms; the bond energies are relatively large. In a "normal" hydrogen bond the hydrogen atom is bonded to, and thus physically closer to, a parent atom, and only weakly attracted to another electronegative atom; bond energies are typically small. To examine these bonds, deuterium was substituted for hydrogen and the electric quadrupole coupling constant (QCC) of deuterium was measured using field cycling nuclear magnetic resonance. The electric quadrupole moment of deuterium is sensitive to changes in the surrounding electric field gradient, and is thus a good probe of the immediate electronic structure. The results show that the temperature dependence of the QCC is opposite to, and much larger than, what one would normally expect to observe for deuterium. The QCC is found to decrease strongly with decreasing temperature. This project was the first to study in detail the temperature dependence of deuterium QCCs in strong hydrogen bonds. The magnitude of the deuterium QCCs for the diacetates was found to be strongly depressed relative to typical values for deuterium. These results parallel large shifts in the infrared vibrational frequencies observed in many molecules which contain strong hydrogen bonds. The asymmetry parameter, which is a measure of the departure from axial symmetry of the electric field gradient (EFG) at deuterium, was found to be unusually large for what are known to be linear, or nearly linear, three-center bonds. Based on ab initio Hartree-Fock calculations aimed at determining the EFG at H in the archetypal bifluoride ion, F-H-F^-, the electronic charge density is drastically depleted at H. It is believed that the large reduction in the charge density allows the deuterium EFG to be highly

  16. Metal-organic cooperative catalysis in C-H and C-C bond activation and its concurrent recovery.

    PubMed

    Park, Young Jun; Park, Jung-Woo; Jun, Chul-Ho

    2008-02-01

    The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic

  17. Bond Activation by Metal-Carbene Complexes in the Gas Phase.

    PubMed

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-03-15

    "Bare" metal-carbene complexes, when generated in the gas phase and exposed to thermal reactions under (near) single-collision conditions, exhibit rather unique reactivities in addition to the well-known metathesis and cyclopropanation processes. For example, at room temperature the unligated [AuCH2](+) complex brings about efficient C-C coupling with methane to produce C2Hx (x = 4, 6), and the couple [TaCH2](+)/CO2 gives rise to the generation of the acetic acid equivalent CH2═C═O. Entirely unprecedented is the thermal extrusion of a carbon atom from halobenzenes (X = F, Cl, Br, I) by [MCH2](+) (M = La, Hf, Ta, W, Re, Os) and its coupling with the methylene ligand to deliver C2H2 and [M(X)(C5H5)](+). Among the many noteworthy C-N bond-forming processes, the formation of CH3NH2 from [RhCH2](+)/NH3, the generation of CH2═NH2(+) from [MCH2](+)/NH3 (M = Pt, Au), and the production of [PtCH═NH2](+) from [PtCH2](+)/NH3 are of particular interest. The latter species are likely to be involved as intermediates in the platinum-mediated large-scale production of HCN from CH4/NH3 (the DEGUSSA process). In this context, a few examples are presented that point to the operation of co-operative effects even at a molecular level. For instance, in the coupling of CH4 with NH3 by the heteronuclear clusters [MPt](+) (M = coinage metal), platinum is crucial for the activation of methane, while the coinage metal M controls the branching ratio between the C-N bond-forming step and unwanted soot formation. For most of the gas-phase reactions described in this Account, detailed mechanistic insight has been derived from extensive computational work in conjunction with time-honored labeling and advanced mass-spectrometry-based experiments, and often a coherent description of the experimental findings has been achieved. As for some transition metals, in particular those from the third row, the metal-carbene complexes can be formed directly from methane, coupling of the so

  18. Study on the d state of platinum in Pt/SiO sub 2 and Na/Pt/SiO sub 2 catalysts under C double bond C hydrogenation conditions by X-ray absorption near-edge structure spectroscopy

    SciTech Connect

    Yoshitake, Hideaki; Iwasawa, Yasuhiro )

    1991-09-19

    The change in the d-electron density of platinum during D{sub 2} + CH{sub 2}{double bond}CHX reactions on Pt/SiO{sub 2} and Na/Pt/SiO{sub 2} catalysts and its influence on the catalysis were studied by X-ray absorption near-edge structure (XANES) spectroscopy, kinetics and FT-IR. It was demonstrated from the change of the white lines in XANES spectra at Pt L{sub 2} and L{sub 3} edges that CH{sub 2}{double bond}CHX (X = H, CH{sub 3}, COCH{sub 3}, CF{sub 3}, and CN) is adsorbed on the Pt surface and extracts the electrons of the d state. Hence, the deuterogenation rate is reduced as the value of Hammett's {sigma}{sub P} increases. The linear free energy relationship between the reaction rate and {sigma}{sub P} was observed for the deuterogenation of CH{sub 2}{double bond}CHX. The rate of ethene deuterogenation was promoted by Na{sub 2}O addition. The electron density of unoccupied d states of pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. The electron density of unoccupied d states of Pt under vacuum decreased by Na{sub 2}O addition, indicating the electron donation from Na{sub 2}O addition. However, most of these additional electrons were observed to move to ethene under reaction conditions. The acceptor of the electrons was suggested by di-{sigma}-ethene by the shift of {upsilon}(C-H). The kinetic parameters are discussed in relation to the change in the d state of Pt as a function of {sigma}{sub P} and Na quantity.

  19. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    SciTech Connect

    Lichtenberger, D.L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of ({eta}{sup 5}-C{sub 5}H{sub 4}X)Rh(CO){sub 2} complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C{sub 60} molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C{sub 60} reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs.

  20. Exploration of earth-abundant transition metals (Fe, Co, and Ni) as catalysts in unreactive chemical bond activations.

    PubMed

    Su, Bo; Cao, Zhi-Chao; Shi, Zhang-Jie

    2015-03-17

    Activation of inert chemical bonds, such as C-H, C-O, C-C, and so on, is a very important area, to which has been drawn much attention by chemists for a long time and which is viewed as one of the most ideal ways to produce valuable chemicals. Under modern chemical bond activation logic, many conventionally viewed "inert" chemical bonds that were intact under traditional conditions can be reconsidered as novel functionalities, which not only avoids the tedious synthetic procedures for prefunctionalizations and the emission of undesirable wastes but also inspires chemists to create novel synthetic strategies in completely different manners. Although activation of "inert" chemical bonds using stoichiometric amounts of transition metals has been reported in the past, much more attractive and challenging catalytic transformations began to blossom decades ago. Compared with the broad application of late and noble transition metals in this field, the earth-abundant first-row transition-metals, such as Fe, Co, and Ni, have become much more attractive, due to their obvious advantages, including high abundance on earth, low price, low or no toxicity, and unique catalytic characteristics. In this Account, we summarize our recent efforts toward Fe, Co, and Ni catalyzed "inert" chemical bond activation. Our research first unveiled the unique catalytic ability of iron catalysts in C-O bond activation of both carboxylates and benzyl alcohols in the presence of Grignard reagents. The benzylic C-H functionalization was also developed via Fe catalysis with different nucleophiles, including both electron-rich arenes and 1-aryl-vinyl acetates. Cobalt catalysts also showed their uniqueness in both aromatic C-H activation and C-O activation in the presence of Grignard reagents. We reported the first cobalt-catalyzed sp(2) C-H activation/arylation and alkylation of benzo[h]quinoline and phenylpyridine, in which a new catalytic pathway via an oxidative addition process was demonstrated

  1. Shear bond strength of metallic brackets photo-activated with light-emitting diode (LED) at different exposure times.

    PubMed

    Rêgo, Emanuel Braga; Romano, Fábio Lourenço

    2007-10-01

    The purpose of this study was to compare the shear bond strength of orthodontic metallic brackets photo-activated with two different light-curing sources at different exposure times: halogen light (XL 1500, 3M ESPE) and LED light (Ortholux, 3M Unitek). Sixty bovine permanent lower incisors were inserted into PVC tubes containing plaster. The buccal surfaces were cleaned with pumice and water, and then etched with 37% phosphoric acid gel. The XT Primer bonding agent (3M Unitek) was applied to the enamel surfaces and the metallic pre-coated brackets (Transbond APC II system, 3M Unitek) were attached to upper central incisors. The teeth were randomly divided into four groups (n=15). In Group I (Control), halogen light was used for 40 seconds, while in Groups II, III, and IV were light-cured with LED light unit for 40, 10, and 5 seconds, respectively. The teeth were stored in distilled water at 37 degrees C for 24 hours. The brackets were submitted to shear bond strength test in universal testing machine (Instron) at a crosshead speed of 0.5 mm/minute. Shear bond strength means (MPa) were 4.87 for Group I; 5.89 for Group II; 4.83 for Group III, and 4.39 for Group IV. Tukey's test detected no statistically significant differences among the groups regarding the shear bond strength (p>0.05). Neither of the types of light-curing sources or exposure times influenced the shear bond strength of metallic brackets. PMID:19089170

  2. SHEAR BOND STRENGTH OF METALLIC BRACKETS PHOTO-ACTIVATED WITH LIGHT-EMITTING DIODE (LED) AT DIFFERENT EXPOSURE TIMES

    PubMed Central

    Rêgo, Emanuel Braga; Romano, Fábio Lourenço

    2007-01-01

    The purpose of this study was to compare the shear bond strength of orthodontic metallic brackets photo-activated with two different light-curing sources at different exposure times: halogen light (XL 1500, 3M ESPE) and LED light (Ortholux, 3M Unitek). Sixty bovine permanent lower incisors were inserted into PVC tubes containing plaster. The buccal surfaces were cleaned with pumice and water, and then etched with 37% phosphoric acid gel. The XT Primer bonding agent (3M Unitek) was applied to the enamel surfaces and the metallic pre-coated brackets (Transbond APC II system, 3M Unitek) were attached to upper central incisors. The teeth were randomly divided into four groups (n=15). In Group I (Control), halogen light was used for 40 seconds, while in Groups II, III, and IV were light-cured with LED light unit for 40, 10, and 5 seconds, respectively. The teeth were stored in distilled water at 37°C for 24 hours. The brackets were submitted to shear bond strength test in universal testing machine (Instron) at a crosshead speed of 0.5 mm/minute. Shear bond strength means (MPa) were 4.87 for Group I; 5.89 for Group II; 4.83 for Group III, and 4.39 for Group IV. Tukey's test detected no statistically significant differences among the groups regarding the shear bond strength (p>0.05). Neither of the types of light-curing sources or exposure times influenced the shear bond strength of metallic brackets. PMID:19089170

  3. C-O and O-H Bond Activation of Methanole by Lanthanum

    NASA Astrophysics Data System (ADS)

    Silva, Ruchira; Hewage, Dilrukshi; Yang, Dong-Sheng

    2012-06-01

    The interaction between methanol (CH_3OH) molecules and laser-vaporized La atoms resulted in the cleavage of C-O and O-H bonds and the formation of three major products, LaH_2O_2, LaCH_4O_2 and LaC_2H_6O_2, in a supersonic molecular beam. These products were identified by time-of-flight mass spectrometry, and their electronic spectra were obtained using mass-analyzed threshold ionization (MATI) spectroscopy. From the MATI spectra, adiabatic ionization energies of the three complexes were measured to be 40136 (5), 39366 (5) and 38685 (5) cm-1 for LaH_2O_2, LaCH_4O_2 and LaC_2H_6O_2, respectively. The ionization energies of these complexes decrease as the size of the coordinated organic fragments increases. The most active vibrational transitions of all three complexes were observed to be the M-O stretches in the ionic state. A metal-ligand bending mode with a frequency of 127 cm-1 was also observed for [LaH_2O_2]^+. However, the spectra of the other two complexes were less resolved, due to the existence of a large number of low frequency modes, which could be thermally excited even in the supersonic molecular beams, and of multiple rotational isomers formed by the free rotation of the methyl group in these systems. The electronic transitions responsible for the observed spectra were identified as ^1A_1 (C2v) ← ^2A_1 (C2v) for LaH_2O_2 and ^1A (C_1) ← ^2A (C_1) for LaCH_4O_2 and LaC_2H_6O_2.

  4. Electrophilic, Ambiphilic, and Nucleophilic C-H bond Activation. Understanding the electronic continuum of C-H bond activation through transition-state and reaction pathway interaction energy decompositions

    SciTech Connect

    Ess, Daniel H.; Goddard, William A.; Periana, Roy A.

    2010-10-29

    The potential energy and interaction energy profiles for metal- and metal-ligand-mediated alkane C-H bond activation were explored using B3LYP density functional theory (DFT) and the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA). The set of complexes explored range from late transition metal group 10 (Pt and Pd) and group 11 (Au) metal centers to group 7-9 (Ir, Rh, Ru, and W) metal centers as well as a group 3 Sc complex. The coordination geometries, electron metal count (d8, d6, d4, and d0), and ligands (N-heterocycles, O-donor, phosphine, and Cp*) are also diverse. Quantitative analysis using ALMO-EDA of both directions of charge-transfer stabilization (occupied to unoccupied orbital stabilization) energies between the metal-ligand fragment and the coordinated C-H bond in the transition state for cleavage of the C-H bond allows classification of C-H activation reactions as electrophilic, ambiphilic, or nucleophilic on the basis of the net direction of charge-transfer energy stabilization. This bonding pattern transcends any specific mechanistic or bonding paradigm, such as oxidative addition, σ-bond metathesis, or substitution. Late transition metals such as Au(III), Pt(II), Pd(II), and Rh(III) metal centers with N-heterocycle, halide, or O-donor ligands show electrophilically dominated reaction profiles with forward charge-transfer from the C-H bond to the metal, leading to more stabilization than reverse charge transfer from the metal to the C-H bond. Transition states and reaction profiles for d6 Ru(II) and Ir(III) metals with Tp and acac ligands were found to have nearly equal forward and reverse charge-transfer energy stabilization. This ambiphilic region also includes the classically labeled electrophilic cationic species Cp*(PMe3)Ir(Me). Nucleophilic character, where the metal to C-H bond charge-transfer interaction is most stabilizing, was found in

  5. Luminescence properties of some double-activated zinc-sulphide-type phosphors

    NASA Astrophysics Data System (ADS)

    Popovici, Elisabeth-Jeanne; Aneculaese, Maria; Ursu, Veronica

    1998-07-01

    Silver and copper double activated phosphor samples were synthesized from zinc sulphide prepared by thiosulphate method and with a NaCl-MgCl2 mixture as flux. The thermal treatment was performed in a protective atmosphere at 900 - 1100 degree(s)C. The samples were characterized by crystalline structure (XRD patterns) and luminescent properties (emission spectra, decay curves). An intensification effect of the copper green fluorescence by silver ions was put in evidence. Conditions for a good green emitting phosphor were established.

  6. Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: new insights into C-F bond formation and activation.

    PubMed

    Milner, Lucy M; Hall, Lewis M; Pridmore, Natalie E; Skeats, Matthew K; Whitwood, Adrian C; Lynam, Jason M; Slattery, John M

    2016-01-28

    Metal vinylidene complexes are widely encountered, or postulated, as intermediates in a range of important metal-mediated transformations of alkynes. However, fluorovinylidene complexes have rarely been described and their reactivity is largely unexplored. By making use of the novel outer-sphere electrophilic fluorination (OSEF) strategy we have developed a rapid, robust and convenient method for the preparation of fluorovinylidene and trifluoromethylvinylidene ruthenium complexes from non-fluorinated alkynes. Spectroscopic investigations (NMR and UV/Vis), coupled with TD-DFT studies, show that fluorine incorporation results in significant changes to the electronic structure of the vinylidene ligand. The reactivity of fluorovinylidene complexes shows many similarities to non-fluorinated analogues, but also some interesting differences, including a propensity to undergo unexpected C-F bond cleavage reactions. Heating fluorovinylidene complex [Ru(η(5)-C5H5)(PPh3)2(C[double bond, length as m-dash]C{F}R)][BF4] led to C-H activation of a PPh3 ligand to form an orthometallated fluorovinylphosphonium ligand. Reaction with pyridine led to nucleophilic attack at the metal-bound carbon atom of the vinylidene to form a vinyl pyridinium species, which undergoes both C-H and C-F activation to give a novel pyridylidene complex. Addition of water, in the presence of chloride, leads to anti-Markovnikov hydration of a fluorovinylidene complex to form an α-fluoroaldehyde, which slowly rearranges to its acyl fluoride isomer. Therefore, fluorovinylidenes ligands may be viewed as synthetic equivalents of 1-fluoroalkynes providing access to reactivity not possible by other routes. PMID:26701305

  7. Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: new insights into C-F bond formation and activation.

    PubMed

    Milner, Lucy M; Hall, Lewis M; Pridmore, Natalie E; Skeats, Matthew K; Whitwood, Adrian C; Lynam, Jason M; Slattery, John M

    2016-01-28

    Metal vinylidene complexes are widely encountered, or postulated, as intermediates in a range of important metal-mediated transformations of alkynes. However, fluorovinylidene complexes have rarely been described and their reactivity is largely unexplored. By making use of the novel outer-sphere electrophilic fluorination (OSEF) strategy we have developed a rapid, robust and convenient method for the preparation of fluorovinylidene and trifluoromethylvinylidene ruthenium complexes from non-fluorinated alkynes. Spectroscopic investigations (NMR and UV/Vis), coupled with TD-DFT studies, show that fluorine incorporation results in significant changes to the electronic structure of the vinylidene ligand. The reactivity of fluorovinylidene complexes shows many similarities to non-fluorinated analogues, but also some interesting differences, including a propensity to undergo unexpected C-F bond cleavage reactions. Heating fluorovinylidene complex [Ru(η(5)-C5H5)(PPh3)2(C[double bond, length as m-dash]C{F}R)][BF4] led to C-H activation of a PPh3 ligand to form an orthometallated fluorovinylphosphonium ligand. Reaction with pyridine led to nucleophilic attack at the metal-bound carbon atom of the vinylidene to form a vinyl pyridinium species, which undergoes both C-H and C-F activation to give a novel pyridylidene complex. Addition of water, in the presence of chloride, leads to anti-Markovnikov hydration of a fluorovinylidene complex to form an α-fluoroaldehyde, which slowly rearranges to its acyl fluoride isomer. Therefore, fluorovinylidenes ligands may be viewed as synthetic equivalents of 1-fluoroalkynes providing access to reactivity not possible by other routes.

  8. A double-panel active segmented partition module using decoupled analog feedback controllers: numerical model.

    PubMed

    Sagers, Jason D; Leishman, Timothy W; Blotter, Jonathan D

    2009-06-01

    Low-frequency sound transmission has long plagued the sound isolation performance of lightweight partitions. Over the past 2 decades, researchers have investigated actively controlled structures to prevent sound transmission from a source space into a receiving space. An approach using active segmented partitions (ASPs) seeks to improve low-frequency sound isolation capabilities. An ASP is a partition which has been mechanically and acoustically segmented into a number of small individually controlled modules. This paper provides a theoretical and numerical development of a single ASP module configuration, wherein each panel of the double-panel structure is independently actuated and controlled by an analog feedback controller. A numerical model is developed to estimate frequency response functions for the purpose of controller design, to understand the effects of acoustic coupling between the panels, to predict the transmission loss of the module in both passive and active states, and to demonstrate that the proposed ASP module will produce bidirectional sound isolation.

  9. Luminescence properties of europium?terbium double activated calcium tungstate phosphor*1

    NASA Astrophysics Data System (ADS)

    Nazarov, M. V.; Jeon, D. Y.; Kang, J. H.; Popovici, E.-J.; Muresan, L.-E.; Zamoryanskaya, M. V.; Tsukerblat, B. S.

    2004-08-01

    Double incorporation of Eu 3+ and Tb 3+ ions into a CaWO 4 crystalline lattice modifies the luminescence spectrum due to the formation of new emission centers. Depending on the activators concentration and nature, as well as on the interaction between the activators themselves, the luminescence color can be varied within the entire range of the visible spectrum. Variable luminescence was obtained when CaWO 4:Eu,Tb phosphors with 0-5 mol% activator ions were exposed to relatively low excitation energies as UV (365 and 254 nm). Under high energy excitation such as VUV (147 nm) radiation or electron beam, white light has been observed. This material with controlled properties seems to be promising for the applications in fluorescent lamps, colored lightning for advertisement industries, and other optoelectronic devices.

  10. Quantitative evaluation on activated property-tunable bulk liquid water with reduced hydrogen bonds using deconvoluted Raman spectroscopy.

    PubMed

    Chen, Hsiao-Chien; Mai, Fu-Der; Yang, Kuang-Hsuan; Chen, Liang-Yih; Yang, Chih-Ping; Liu, Yu-Chuan

    2015-01-01

    Interesting properties of water with distinguishable hydrogen-bonding structure on interfacial phase or in confined environment have drawn wide attentions. However, these unique properties of water are only found within the interfacial phase and confined environment, thus, their applications are limited. In addition, quantitative evaluation on these unique properties associating with the enhancement of water's physical and chemical activities represents a notable challenge. Here we report a practicable production of free-standing liquid water at room temperature with weak hydrogen-bonded structure naming Au nanoparticles (NPs)-treated (AuNT) water via treating by plasmon-induced hot electron transfer occurred on resonantly illuminated gold NPs (AuNPs). Compared to well-known untreated bulk water (deionized water), the prepared AuNT water exhibits many distinct activities in generally physical and chemical reactions, such as high solubilities to NaCl and O2. Also, reducing interaction energy within water molecules provides lower overpotential and higher efficiency in electrolytic hydrogen production. In addition, these enhanced catalytic activities of AuNT water are tunable by mixing with deionized water. Also, most of these tunable activities are linearly proportional to its degree of nonhydrogen-bonded structure (DNHBS), which is derived from the O-H stretching in deconvoluted Raman spectrum. PMID:25471522

  11. Bond dissociation enthalpies calculated by the PM3 method confirm activity cliffs in radical scavenging of flavonoids.

    PubMed

    Amić, Dragan; Lucić, Bono; Kovacević, Goran; Trinajstić, Nenad

    2009-02-01

    Radical scavenging potency of flavonoids is associated with activity cliffs, i.e., small chemical modifications on flavonoid core can have a significant effect on activity. The presence or absence of the 3',4'-diOH and/or 3-OH group may serve as an activity switch for radical scavenging. The physicochemical background of such an indicator variable, defined previously (Amić et al. (2003) Croat Chem Acta 76:55-61), is confirmed by computation of bond dissociation enthalpies and selecting the minimal of all values relating to flavonoid OH groups. Bond dissociation enthalpies for hydrogen abstraction from OH groups for 29 flavonoids were calculated by the PM3 method. Minimal bond dissociation enthalpy values were obtained for OH groups attached to C-3, C-3' and C-4' positions, and they correspond to the previously introduced indicator variable. Taking into account some driving forces of the radical scavenging mechanism, it is possible to relate structural characteristics of flavonoids to their radical scavenging potency as well as to develop reliable structure-activity models.

  12. Quantitative evaluation on activated property-tunable bulk liquid water with reduced hydrogen bonds using deconvoluted Raman spectroscopy.

    PubMed

    Chen, Hsiao-Chien; Mai, Fu-Der; Yang, Kuang-Hsuan; Chen, Liang-Yih; Yang, Chih-Ping; Liu, Yu-Chuan

    2015-01-01

    Interesting properties of water with distinguishable hydrogen-bonding structure on interfacial phase or in confined environment have drawn wide attentions. However, these unique properties of water are only found within the interfacial phase and confined environment, thus, their applications are limited. In addition, quantitative evaluation on these unique properties associating with the enhancement of water's physical and chemical activities represents a notable challenge. Here we report a practicable production of free-standing liquid water at room temperature with weak hydrogen-bonded structure naming Au nanoparticles (NPs)-treated (AuNT) water via treating by plasmon-induced hot electron transfer occurred on resonantly illuminated gold NPs (AuNPs). Compared to well-known untreated bulk water (deionized water), the prepared AuNT water exhibits many distinct activities in generally physical and chemical reactions, such as high solubilities to NaCl and O2. Also, reducing interaction energy within water molecules provides lower overpotential and higher efficiency in electrolytic hydrogen production. In addition, these enhanced catalytic activities of AuNT water are tunable by mixing with deionized water. Also, most of these tunable activities are linearly proportional to its degree of nonhydrogen-bonded structure (DNHBS), which is derived from the O-H stretching in deconvoluted Raman spectrum.

  13. Tautomerization lowers the activation barriers for N-glycosidic bond cleavage of protonated uridine and 2'-deoxyuridine.

    PubMed

    Wu, R R; Rodgers, M T

    2016-09-21

    The gas-phase conformations of protonated uridine, [Urd+H](+), and its 2'-deoxy form, protonated 2'-deoxyuridine, [dUrd+H](+), have been examined in detail previously by infrared multiple photon dissociation action spectroscopy techniques. Both 2,4-dihydroxy tautomers and O4 protonated conformers of [Urd+H](+) and [dUrd+H](+) were found to coexist in the experiments with the 2,4-dihydroxy tautomers dominating the population. In the present study, the kinetic energy dependence of the collision-induced dissociation behavior of [Urd+H](+) and [dUrd+H](+) are examined using a guided ion beam tandem mass spectrometer to probe the mechanisms and energetics for activated dissociation of these protonated nucleosides. The primary dissociation pathways observed involve N-glycosidic bond cleavage leading to competitive elimination of protonated or neutral uracil. The potential energy surfaces (PESs) for these N-glycosidic bond cleavage pathways are mapped out via electronic structure calculations for the mixture of 2,4-dihydroxy tautomers and O4 protonated conformers of [Urd+H](+) and [dUrd+H](+) populated in the experiments. The calculated activation energies (AEs) and heats of reaction (ΔHrxns) for N-glycosidic bond cleavage at both the B3LYP and MP2(full) levels of theory are compared to the measured values. The agreement between experiment and theory indicates that B3LYP provides better estimates of the energetics of the species along the PESs for N-glycosidic bond cleavage than MP2, and that the 2,4-dihydroxy tautomers, which are stabilized by strong hydrogen-bonding interactions, predominantly influence the observed threshold dissociation behavior of [Urd+H](+) and [dUrd+H](+). PMID:27536972

  14. Endonucleolytic activity directed towards 8-(2-hydroxy-2-propyl) purines in double-stranded DNA.

    PubMed

    Livneh, Z; Elad, D; Sperling, J

    1979-11-01

    Photoalkylation of circular covalently closed DNA from phage PM2 with isopropyl alcohol by using a free radical photoinitiator and UV light of lambda greater than 305 nm led to the specific 8-substitution of purine moieties in the DNA, yielding 8-(2-hydroxy-2-propyl)adenine and 8-(2-hydroxy-2-propyl)guanine as the only detectable damage in the DNA. Using this specifically photoalkylated DNA as a substrate, we discovered in extracts of Micrococcus luteus an endonucleolytic activity that is directed towards 8-(2-hydroxy-2-propyl) purines in DNA. The activity is not a combination of a DNA-glycosylase and an apurinic site endonuclease. It is not inhibited by single-stranded DNA, by UV- or gamma-irradiated single-stranded DNA, or by normal or depurinated double-stranded DNA. however, gamma- or UV-(254 nm) irradiated double-stranded DNAs to inhibit the activity, hinting at the possibility of a common type of lesion in these damaged DNAs. Divalent cations are not required for the incising activity, and it is fully active in 1 mM EDTA, whereas caffeine and ATP cause inhibition. Extracts of mutant M. luteus lacking pyrimidine-dimer-directed endonucleases were found to contain the endonucleolytic activity in levels comparable to those present in the wild type. After the incision, we could demonstrate the specific excision of the 8-alkylated purines from the damaged DNA. The special conformational consequences of the 8-alkylation of purines, at the nucleotide level, namely their nonregular syn conformation, suggest that it is the distortion in the DNA that is recognized by the endonuclease. PMID:293658

  15. Conversion of Amides to Esters by the Nickel-Catalyzed Activation of Amide C–N Bonds

    PubMed Central

    Hie, Liana; Fine Nathel, Noah F.; Shah, Tejas K.; Baker, Emma L.; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K. N.; Garg, Neil K.

    2015-01-01

    Amides are common functional groups that have been well studied for more than a century.1 They serve as the key building blocks of proteins and are present in an broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to resonance stability of the amide bond.1,2 Whereas Nature can easily cleave amides through the action of enzymes, such as proteases,3 the ability to selectively break the C–N bond of an amide using synthetic chemistry is quite difficult. In this manuscript, we demonstrate that amide C–N bonds can be activated and cleaved using nickel catalysts. We have used this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory (DFT) calculations provide insight into the thermodynamics and catalytic cycle of this unusual transformation. Our results provide a new strategy to harness amide functional groups as synthons and are expected fuel the further use of amides for the construction of carbon–heteroatom or carbon–carbon bonds using non-precious metal catalysis. PMID:26200342

  16. Conversion of amides to esters by the nickel-catalysed activation of amide C-N bonds.

    PubMed

    Hie, Liana; Fine Nathel, Noah F; Shah, Tejas K; Baker, Emma L; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K N; Garg, Neil K

    2015-08-01

    Amides are common functional groups that have been studied for more than a century. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond. Although amides can readily be cleaved by enzymes such as proteases, it is difficult to selectively break the carbon-nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon-nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon-heteroatom or carbon-carbon bonds using non-precious-metal catalysis. PMID:26200342

  17. Conversion of amides to esters by the nickel-catalysed activation of amide C-N bonds

    NASA Astrophysics Data System (ADS)

    Hie, Liana; Fine Nathel, Noah F.; Shah, Tejas K.; Baker, Emma L.; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K. N.; Garg, Neil K.

    2015-08-01

    Amides are common functional groups that have been studied for more than a century. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond. Although amides can readily be cleaved by enzymes such as proteases, it is difficult to selectively break the carbon-nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon-nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon-heteroatom or carbon-carbon bonds using non-precious-metal catalysis.

  18. Diffusion bonding aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, G. A.; Broughton, T.

    1988-10-01

    The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

  19. The biologically active form of the sea urchin egg receptor for sperm is a disulfide-bonded homo-multimer

    PubMed Central

    1994-01-01

    Since many cell surface receptors exist in their active form as oligomeric complexes, we have investigated the subunit composition of the biologically active sperm receptor in egg plasma membranes from Strongylocentrotus purpuratus. Electrophoretic analysis of the receptor without prior reduction of disulfide bonds revealed that the surface receptor exists in the form of a disulfide-bonded multimer, estimated to be a tetramer. These findings are in excellent agreement with the fact that the NH2-terminus of the extracellular domain of the sperm receptor is rich in cysteine residues. Studies with cross-linking agents of various length and hydrophobicity suggest that no other major protein is tightly associated with the receptor. Given the multimeric structure of the receptor, we investigated the effect of disulfide bond reduction on its biological activity. Because in quantitative bioassays fertilization was found to be inhibited by treatment of eggs with 5 mM dithiothreitol, we undertook more direct studies of the effect of reduction on properties of the receptor. First, we studied the effect of addition of isolated, pure receptor on fertilization. Whereas the non-reduced, native receptor complex inhibited fertilization in a dose- dependent manner, the reduced and alkylated receptor was inactive. Second, we tested the ability of the isolated receptor to mediate binding of acrosome-reacted sperm to polystyrene beads. Whereas beads coated with native receptor bound sperm, those containing reduced and alkylated receptor did not. Thus, these results demonstrate that the biologically active form of the sea urchin sperm receptor consists only of 350 kD subunits and that these must be linked as a multimer via disulfide bonds to produce a complex that is functional in sperm recognition and binding. PMID:8188748

  20. Insertion of phosphinidene complexes into the P-H bond of secondary phosphine oxides: a new version of the phospha-Wittig synthesis of P=C double bonds.

    PubMed

    Hao, Yanwei; Wu, Di; Tian, Rongqiang; Duan, Zheng; Mathey, François

    2016-01-21

    Terminal phosphinidene complexes [RP-W(CO)5], as generated at 60 °C in the presence of copper chloride from the appropriate 7-phosphanorbornadiene complexes, react with secondary phosphine oxides Ar2P(O)H to give the insertion products into the P-H bonds. After metalation with NaH, these products react with aldehydes to give the corresponding phosphaalkenes which are trapped by dimethylbutadiene. PMID:26661055

  1. Visualizing repetitive diffusion activity of double-strand RNA binding proteins by single molecule fluorescence assays.

    PubMed

    Koh, Hye Ran; Wang, Xinlei; Myong, Sua

    2016-08-01

    TRBP, one of double strand RNA binding proteins (dsRBPs), is an essential cofactor of Dicer in the RNA interference pathway. Previously we reported that TRBP exhibits repetitive diffusion activity on double strand (ds)RNA in an ATP independent manner. In the TRBP-Dicer complex, the diffusion mobility of TRBP facilitates Dicer-mediated RNA cleavage. Such repetitive diffusion of dsRBPs on a nucleic acid at the nanometer scale can be appropriately captured by several single molecule detection techniques. Here, we provide a step-by-step guide to four different single molecule fluorescence assays by which the diffusion activity of dsRBPs on dsRNA can be detected. One color assay, termed protein induced fluorescence enhancement enables detection of unlabeled protein binding and diffusion on a singly labeled RNA. Two-color Fluorescence Resonance Energy Transfer (FRET) in which labeled dsRBPs is applied to labeled RNA, allows for probing the motion of protein along the RNA axis. Three color FRET reports on the diffusion movement of dsRBPs from one to the other end of RNA. The single molecule pull down assay provides an opportunity to collect dsRBPs from mammalian cells and examine the protein-RNA interaction at single molecule platform. PMID:27012177

  2. 77 FR 15378 - Agency Information Collection Activities: Application for Withdrawal of Bonded Stores for Fishing...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-15

    ... previously published in the Federal Register (77 FR 1497) on January 10, 2012, allowing for a 60-day comment... permission of the CBP port director for the withdrawal and lading of bonded merchandise (especially alcoholic beverages) for use on board fishing vessels involved in international trade. The applicant must certify...

  3. Chelation-assisted regioselective C-O bond clevage reactions

    SciTech Connect

    Sue-Min Yeh; yu-Huei Chen; Ruey-Min Chen

    1995-12-31

    Chelation demonstrates a unique role to direct the chemo- and regioselectivity on a variety of fascinating transformations. The strategy has been extensively employed in the regioselective intramolecular addition of an organometallic species to a coordinated double bond and in the activation of a neighboring C-H bond. In this paper, the authors present the recent progress on applications of the chelation-assisted C-O bond cleavage reactions in acetals. Thus, treatments of various acetonides of monosaccharide and inositol derivatives with the Grignard reagent afford regioselectively the corresponding products having only one free hydroxy group.

  4. A double-blind placebo-controlled trial of methylprednisolone pulse therapy in active rheumatoid disease.

    PubMed

    Williams, I A; Baylis, E M; Shipley, M E

    1982-07-31

    To confirm the findings of uncontrolled trials that methylprednisolone pulse therapy (MPPT) is a safe treatment for active rheumatoid disease, a double-blind trial was conducted in which 20 patients with active rheumatoid disease were randomly allocated to receive an infusion of either 1 g methylprednisolone or placebo. Methylprednisolone produced significant improvement in all clinical variables measured, a benefit which was sustained for at least 6 weeks. The placebo produced only transient improvement in some of the clinical variables measured. when the 10 placebo groups patients were later given an infusion of 1 g methylprednisolone, they too showed significant clinical benefit. The methylprednisolone also gave rise to improvements in some haematological and biochemical variables. PMID:6124671

  5. Chromospherically active stars. 13: HD 30957: A double lined K dwarf binary

    NASA Technical Reports Server (NTRS)

    Fekel, Francis C.; Dadonas, Virgilijus; Sperauskas, Julius; Vaccaro, Todd R.; Patterson, L. Ronald

    1994-01-01

    HD 30957 is a double-lined spectroscopic binary with a period of 44.395 days and a modest eccentricity of 0.09. The spectral types of the components are K2-3 V and K5 V. The measured v sin i for both components is less than or equal to 3 km/s and the orbital inclination is estimated to be 69 deg. The system is relatively nearby with a parallax of 0.025 sec or a distance of 40 pc. Space motions of the system indicate that it does not belong to any of the known moving groups. Absolute surface fluxes of the Ca II H and K lines have been recomputed and indicate only modest chromospheric activity. If the stars are rotating pseudosynchronously, the lack of light variability is consistent with the value of the critical Rossby number for starspot activity.

  6. Bond strength of Epiphany™ Sealer combined with different adhesive systems photo-activated with LED and QTH

    NASA Astrophysics Data System (ADS)

    Minto, A. M. P.; Bandéca, M. C.; Borges, A. H.; Nadalin, M. R.; Thomé, L. H. C.

    2009-08-01

    The Epiphany™ Sealer is a new dual-curing resin-based sealer and has been introduced as an alternative to gutta-percha and traditional root canal sealers. The canal filling is claimed to create a seal with the dentinal tubules within the root canal system producing a ‘monoblock’ effect between the sealer and dentinal tubules. Therefore, considering the possibility to incorporate the others adhesive systems, it is important to study the bond strength of the resulting cement. Forty-eight root mandibular canines were sectioned 8-mm below CEJ. The dentine discs were prepared using a tapered diamond bur and irrigated with 1% NaOCl and 17% EDTA. Previous the application Epiphany™ Sealer, the Epiphany™ Primer, AdheSE, and One Up Bond F were applied to the root canal walls. The LED and QTH (Quartz Tungsten Halogen) were used to photo-activation during 45 s with power density of 400 and 720 mW/cm2, respectively. The specimens were performed on a universal testing machine at a cross-head speed of 1 mm/min until bond failure occurred. The force was recorded and the debonding values were used to calculate Push-out bond strength. The analysis of variance (ANOVA) and Tukey’s post-hoc tests showed significant statistical differences ( P < 0.05) to Epiphany™ Sealer/Epiphany™ Primer/QTH and EpiphanyTM Sealer/AdheSE/QTH, which had the highest mean values of bond strength. The efficiency of resin-based filling materials are dependent the type of light curing unit used including the power density, the polymerization characteristics of these resin-based filling materials, depending on the primer/adhesive used.

  7. Ultrahigh Enzyme Activity Assembled in Layered Double Hydroxides via Mg(2+)-Allosteric Effector.

    PubMed

    Wang, Min; Huang, Shu-Wan; Xu, Dan; Bao, Wen-Jing; Xia, Xing-Hua

    2015-06-01

    It is well-known that some metal ions could be allosteric effectors of allosteric enzymes to activate/inhibit the catalytic activities of enzymes. In nanobiocatalytic systems constructed based on the positive metal ion-induced allosteric effect, the incorporated enzymes will be activated and thus exhibit excellent catalytic performance. Herein, we present an environmentally friendly strategy to construct a novel allosteric effect-based β-galactosidase/Mg-Al layered double hydroxide (β-gal/Mg-Al-LDH) nanobiocatalytic system via the delamination-reconstruction method. The intercalated β-gal in the LDH galleries changes its conformation significantly due to the Mg(2+)-induced allosteric interactions and other weak interactions, which causes the activation of enzymatic activity. The β-gal/Mg-Al-LDH nanobiocatalytic system shows much higher catalytic activity and affinity toward its substrate and about 30 times higher catalytic reaction velocity than the free β-gal, which suggests that Mg(2+)-induced allosteric effect plays a vital role in the improvement of enzymatic performance.

  8. A germanium isocyanide complex featuring (n → π*) back-bonding and its conversion to a hydride/cyanide product via C-H bond activation under mild conditions.

    PubMed

    Brown, Zachary D; Vasko, Petra; Fettinger, James C; Tuononen, Heikki M; Power, Philip P

    2012-03-01

    Reaction of the diarylgermylene Ge(Ar(Me(6)))(2) [Ar(Me(6)) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(CH(3))(3))(2)] with tert-butyl isocyanide gave the Lewis adduct species (Ar(Me(6)))(2)GeCNBu(t), in which the isocyanide ligand displays a decreased C-N stretching frequency consistent with an n → π* back-bonding interaction. Density functional theory confirmed that the HOMO is a Ge-C bonding combination between the lone pair of electrons on the germanium atom and the C-N π* orbital of the isocyanide ligand. The complex undergoes facile C-H bond activation to produce a new diarylgermanium hydride/cyanide species and isobutene via heterolytic cleavage of the N-Bu(t) bond.

  9. A high fraction of double-peaked narrow emission lines in powerful active galactic nuclei

    NASA Astrophysics Data System (ADS)

    Lyu, Yang; Liu, Xin

    2016-11-01

    1 per cent of redshift z ˜ 0.1 active galactic nuclei (AGNs) show velocity splitting of a few hundred km s-1 in the narrow emission lines in spatially integrated spectra. Such line profiles have been found to arise from the bulk motion of ionized gas clouds associated with galactic-scale outflows, merging pairs of galaxies each harbouring a supermassive black hole (SMBH), and/or galactic-scale disc rotation. It remains unclear, however, how the frequency of narrow-line velocity splitting may depend on AGN luminosity. Here we study the correlation between the fraction of Type 2 AGNs with double-peaked narrow emission lines and AGN luminosity as indicated by [O III] λ5007 emission-line luminosity L_[O III]. We combine the sample of Liu et al. at z ˜ 0.1 with a new sample of 178 Type 2 AGNs with double-peaked [O III] emission lines at z ˜ 0.5. We select the new sample from a parent sample of 2089 Type 2 AGNs from the SDSS-III/Baryon Oscillation Spectroscopic Survey. We find a statistically significant (˜4.2σ) correlation between L_[O III] and the fraction of objects that exhibit double-peaked narrow emission lines among all Type 2 AGNs, corrected for selection bias and incompleteness due to [O III] line width, equivalent width, splitting velocity, and/or equivalent width ratio between the two velocity components. Our result suggests that galactic-scale outflows and/or merging pairs of SMBHs are more prevalent in more powerful AGNs, although spatially resolved follow-up observations are needed to resolve the origin(s) for the narrow-line velocity splitting for individual AGNs.

  10. Photon efficient double-helix PSF microscopy with application to 3D photo-activation localization imaging

    PubMed Central

    Grover, Ginni; Quirin, Sean; Fiedler, Callie; Piestun, Rafael

    2011-01-01

    We present a double-helix point spread function (DH-PSF) based three-dimensional (3D) microscope with efficient photon collection using a phase mask fabricated by gray-level lithography. The system using the phase mask more than doubles the efficiency of current liquid crystal spatial light modulator implementations. We demonstrate the phase mask DH-PSF microscope for 3D photo-activation localization microscopy (PM-DH-PALM) over an extended axial range. PMID:22076263

  11. Equilibrium CO bond lengths

    NASA Astrophysics Data System (ADS)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  12. Interfacial chemical bonding effect on the photocatalytic activity of TiO2-SiO2 nanocoupling systems.

    PubMed

    Fujishima, Musashi; Takatori, Hiroaki; Tada, Hiroaki

    2011-09-15

    TiO(2) nanoparticles (NPs) were deposited on the surfaces of SiO(2) microspheres with a mesoporous structure prepared by a hydrolysis-controlled sol-gel technique. The TiO(2) NPs were firmly combined on the surfaces of SiO(2) microspheres through the interfacial Si-O-Ti bonds. The coupling causes the bandgap widening up to 3.37 eV, enhancing the photocatalytic activity for the decomposition of acetaldehyde under illumination of UV-light (330 < λ < 400 nm). Density functional theory calculations for model clusters suggested that the observed results are derived from the lowering in the valence band edge energy with the interfacial bond formation.

  13. Coordinated nuclease activities counteract Ku at single-ended DNA double-strand breaks

    PubMed Central

    Chanut, Pauline; Britton, Sébastien; Coates, Julia; Jackson, Stephen P.; Calsou, Patrick

    2016-01-01

    Repair of single-ended DNA double-strand breaks (seDSBs) by homologous recombination (HR) requires the generation of a 3′ single-strand DNA overhang by exonuclease activities in a process called DNA resection. However, it is anticipated that the highly abundant DNA end-binding protein Ku sequesters seDSBs and shields them from exonuclease activities. Despite pioneering works in yeast, it is unclear how mammalian cells counteract Ku at seDSBs to allow HR to proceed. Here we show that in human cells, ATM-dependent phosphorylation of CtIP and the epistatic and coordinated actions of MRE11 and CtIP nuclease activities are required to limit the stable loading of Ku on seDSBs. We also provide evidence for a hitherto unsuspected additional mechanism that contributes to prevent Ku accumulation at seDSBs, acting downstream of MRE11 endonuclease activity and in parallel with MRE11 exonuclease activity. Finally, we show that Ku persistence at seDSBs compromises Rad51 focus assembly but not DNA resection. PMID:27641979

  14. A PCR-free fluorescence strategy for detecting telomerase activity via double amplification strategy.

    PubMed

    Zhang, Xiafei; Cheng, Rui; Shi, Zhilu; Jin, Yan

    2016-01-15

    As a universal tumor biomarker, research on the activity and inhibition of telomerase is of great importance for cancer diagnosis and therapy. Although the telomeric repeat amplification protocol (TRAP) has served as a powerful assay for detecting telomerase activity, its application has been significantly limited by amplification related errors and time-consuming procedure. To address the limitations of PCR-based protocol, a dual amplification fluorescence assay was developed for PCR-free detecting telomerase activity. Briefly, we designed an arch-structure DNA probe to specifically control strand displacement reaction and subsequent enzyme-aided amplification. Telomerase substrate (TS) primer was extended by telomerase to form long elongation products which contain several TTAGGG repeat units. So, one elongation product can release more than one trigger DNA (t-DNA) via strand displacement reaction to realize first amplification. Subsequently, t-DNA specifically opened molecular beacon (MB) to restore the fluorescence of MB. Meanwhile, t-DNA was recycled by the aid of nicking endonuclease to continuously open more and more MBs, leading to a second amplification. Owing to the double amplification strategy, the proposed method allowed the measurement of telomerase activity in crude cell extracts equivalent to 5 HeLa cells and 10 CCRF-CEM cells without PCR amplification. Besides, the influence of telomere-binding ligands on the telomerase activity demonstrated that the proposed method holds the potential to evaluate the inhibition efficiency of telomerase inhibitors.

  15. Coordinated nuclease activities counteract Ku at single-ended DNA double-strand breaks.

    PubMed

    Chanut, Pauline; Britton, Sébastien; Coates, Julia; Jackson, Stephen P; Calsou, Patrick

    2016-01-01

    Repair of single-ended DNA double-strand breaks (seDSBs) by homologous recombination (HR) requires the generation of a 3' single-strand DNA overhang by exonuclease activities in a process called DNA resection. However, it is anticipated that the highly abundant DNA end-binding protein Ku sequesters seDSBs and shields them from exonuclease activities. Despite pioneering works in yeast, it is unclear how mammalian cells counteract Ku at seDSBs to allow HR to proceed. Here we show that in human cells, ATM-dependent phosphorylation of CtIP and the epistatic and coordinated actions of MRE11 and CtIP nuclease activities are required to limit the stable loading of Ku on seDSBs. We also provide evidence for a hitherto unsuspected additional mechanism that contributes to prevent Ku accumulation at seDSBs, acting downstream of MRE11 endonuclease activity and in parallel with MRE11 exonuclease activity. Finally, we show that Ku persistence at seDSBs compromises Rad51 focus assembly but not DNA resection. PMID:27641979

  16. Absorption of the selenite anion from aqueous solutions by thermally activated layered double hydroxide.

    PubMed

    Liu, Rui; Frost, Ray L; Martens, Wayde N

    2009-03-01

    The presence of selenite or selenate in potable water is a health hazard especially when consumed over a long period of time. Its removal from potable water is of importance. This paper reports technology for the removal of selenite from water through the use of thermally activated layered double hydroxides. Mg/Al hydrotalcites with selenite in the interlayer were prepared at different times from 0.5 to 20 h through ion exchange. X-ray diffraction of the MgAlSeO3 hydrotalcites indicates that the selenite anion entered the interlayer spacing of Mg/Al hydrotalcite and MgAlSeO3 hydrotalcite was formed. Raman spectra proved the presence of selenite anion in the hydrotalcite interlayer as the counter anion. The band intensity and width of MgAlSeO3 hydrotalcite in the region of 3800-3000 cm(-1) increase with the adsorption of selenite by the Mg/Al hydrotalcite. The characteristic bands of free selenite anions in the MgAlSeO3 hydrotalcites are located between the region between 850 and 800 cm(-1). The Raman spectra of the lower wave number region of 550-500 cm(-1) show a shift toward higher wave numbers with adsorption of the selenite. An estimation of the amount of selenite anion removed by the thermally activated layered double hydroxide was obtained through the measurement of the intensity of the selenite Raman bands at 814 and 835 cm(-1) resulting from the amount of selenite anion remaining in solution. Thermally activated LDHs provide a mechanism for removing selenite anions from aqueous solutions.

  17. A unique quinolineboronic acid-based supramolecular structure that relies on double intermolecular B-N bonds for self-assembly in solid state and in solution.

    PubMed

    Zhang, Yanling; Li, Minyong; Chandrasekaran, Sekar; Gao, Xingming; Fang, Xikui; Lee, Hsiau-Wei; Hardcastle, Kenneth; Yang, Jenny; Wang, Binghe

    2007-04-16

    The boronic acid functional group plays very important roles in sugar recognition, catalysis, organic synthesis, and supramolecular assembly. Therefore, understanding the unique properties of this functional group is very important. 8-Quinolineboronic acid (8-QBA) is found to be capable of self-assembling in solid state through a unique intermolecular B-N bond mechanism reinforced by intermolecular boronic anhydride formation, π-π stacking, and hydrogen bond formation. NMR NOE and diffusion studies indicate that intermolecular B-N interaction also exists in solution with 8-QBA. In contrast, a positional isomer of 8-QBA, 5-quinolineboronic acid (5-QBA) showed very different behaviors in crystal packing and in solution and therefore different supramolecular network. Understanding the structural features of this unique 8-QBA assembly could be very helpful for the future design of new sugar sensors, molecular catalysts, and supramolecular assemblies. PMID:18414645

  18. A unique quinolineboronic acid-based supramolecular structure that relies on double intermolecular B-N bonds for self-assembly in solid state and in solution

    PubMed Central

    Zhang, Yanling; Li, Minyong; Chandrasekaran, Sekar; Gao, Xingming; Fang, Xikui; Lee, Hsiau-Wei; Hardcastle, Kenneth; Yang, Jenny; Wang, Binghe

    2007-01-01

    The boronic acid functional group plays very important roles in sugar recognition, catalysis, organic synthesis, and supramolecular assembly. Therefore, understanding the unique properties of this functional group is very important. 8-Quinolineboronic acid (8-QBA) is found to be capable of self-assembling in solid state through a unique intermolecular B-N bond mechanism reinforced by intermolecular boronic anhydride formation, π-π stacking, and hydrogen bond formation. NMR NOE and diffusion studies indicate that intermolecular B-N interaction also exists in solution with 8-QBA. In contrast, a positional isomer of 8-QBA, 5-quinolineboronic acid (5-QBA) showed very different behaviors in crystal packing and in solution and therefore different supramolecular network. Understanding the structural features of this unique 8-QBA assembly could be very helpful for the future design of new sugar sensors, molecular catalysts, and supramolecular assemblies. PMID:18414645

  19. [Transition metal activation and functionalization of carbon-hydrogen bonds]. Progress report, December 1, 1992--November 30, 1993

    SciTech Connect

    Not Available

    1993-12-01

    A method was developed for synthesizing a new complex for studying C-H activation, (HBPz*{sub 3})Rh(CNCH{sub 2}CMe{sub 3})(PhN=C=NCH{sub 2}CMe{sub 3}). This complex loses the carbodiimide ligand, thereby serving as a precursor for a 16-electron Rh(I) fragment which activates (via oxidative addition) a wide range of aromatic and aliphatic C-H bonds. Mechanism of activation of benzene by this fragment was studied. Reaction of [Tp`Rh(CNR)] fragment with aliphatic hydrocarbons was also studied. A study of C-H bond activation by the complex MnH{sub 3}(dmpe){sub 2} was completed. Reactions of [Ru(dmpe){sub 2}] with several small molecules were also investigated. Effects of fluorine substituents on aromatic ring on C-H activation were looked at. Studies of {eta}{sup 2}-arene coordination with [(C{sub 5}Me{sub 5})Rh(PMe{sub 3})] were completed; studies of reaction of this complex with 1,3-disubstituted benzenes are in progress.

  20. Bonding thermoplastic polymers

    DOEpatents

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.

    2008-06-24

    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  1. Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

    PubMed

    Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

    2016-05-24

    Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems. PMID:27124717

  2. Development of Active Gas-Gap Heat Switch for Double-Stage Adiabatic Demagnetization Refrigerators

    NASA Astrophysics Data System (ADS)

    Ishisaki, Y.; Henmi, K.; Akamatsu, H.; Enoki, T.; Ohashi, T.; Hoshino, A.; Shinozaki, K.; Matsuo, H.; Okada, N.; Oshima, T.

    2012-06-01

    We designed and fabricated an active gas-gap heat switch (AGGHS), which ON/OFF the heat conduction between the 1st stage (0.05-2 K) and the 2nd stage (1-4 K) of a double-stage adiabatic demagnetization refrigerator (DADR). Our design geometrically separates two components which dominates the ON or OFF performance, and achieved heat conductivity of 6 mW/K (ON) or 4 μW/K (OFF) at 2 K. The ON/OFF is controlled by a heater attached to the charcoal box to adsorb/deadsorb 4He gas inside. We introduced the AGGHS to the DADR and successfully cooled the detector stage down to 60 mK, working properly more than a year.

  3. Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

    PubMed

    Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

    2016-05-24

    Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

  4. Preferential Repair of DNA Double-strand Break at the Active Gene in Vivo*

    PubMed Central

    Chaurasia, Priyasri; Sen, Rwik; Pandita, Tej K.; Bhaumik, Sukesh R.

    2012-01-01

    Previous studies have demonstrated transcription-coupled nucleotide/base excision repair. We report here for the first time that DNA double-strand break (DSB) repair is also coupled to transcription. We generated a yeast strain by introducing a homing (Ho) endonuclease cut site followed by a nucleotide sequence for multiple Myc epitopes at the 3′ end of the coding sequence of a highly active gene, ADH1. This yeast strain also contains the Ho cut site at the nearly silent or poorly active mating type α (MATα) locus and expresses Ho endonuclease under the galactose-inducible GAL1 promoter. Using this strain, DSBs were generated at the ADH1 and MATα loci in galactose-containing growth medium that induced HO expression. Subsequently, yeast cells were transferred to dextrose-containing growth medium to stop HO expression, and the DSB repair was monitored at the ADH1 and MATα loci by PCR, using the primer pairs flanking the Ho cut sites. Our results revealed a faster DSB repair at the highly active ADH1 than that at the nearly silent MATα locus, hence implicating a transcription-coupled DSB repair at the active gene in vivo. Subsequently, we extended this study to another gene, PHO5 (carrying the Ho cut site at its coding sequence), under transcriptionally active and inactive growth conditions. We found a fast DSB repair at the active PHO5 gene in comparison to its inactive state. Collectively, our results demonstrate a preferential DSB repair at the active gene, thus supporting transcription-coupled DSB repair in living cells. PMID:22910905

  5. 26 CFR 1.144-1 - Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... student loan bonds, and qualified redevelopment bonds. (a) Overview. Interest on a private activity bond... 26 Internal Revenue 2 2010-04-01 2010-04-01 false Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds. 1.144-1 Section 1.144-1 Internal Revenue...

  6. 26 CFR 1.144-1 - Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... student loan bonds, and qualified redevelopment bonds. (a) Overview. Interest on a private activity bond... 26 Internal Revenue 2 2012-04-01 2012-04-01 false Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds. 1.144-1 Section 1.144-1 Internal Revenue...

  7. 26 CFR 1.144-1 - Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... student loan bonds, and qualified redevelopment bonds. (a) Overview. Interest on a private activity bond... 26 Internal Revenue 2 2014-04-01 2014-04-01 false Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds. 1.144-1 Section 1.144-1 Internal Revenue...

  8. 26 CFR 1.144-1 - Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... student loan bonds, and qualified redevelopment bonds. (a) Overview. Interest on a private activity bond... 26 Internal Revenue 2 2011-04-01 2011-04-01 false Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds. 1.144-1 Section 1.144-1 Internal Revenue...

  9. 26 CFR 1.144-1 - Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... student loan bonds, and qualified redevelopment bonds. (a) Overview. Interest on a private activity bond... 26 Internal Revenue 2 2013-04-01 2013-04-01 false Qualified small issue bonds, qualified student loan bonds, and qualified redevelopment bonds. 1.144-1 Section 1.144-1 Internal Revenue...

  10. A major peroxiredoxin-induced activation of Yap1 transcription factor is mediated by reduction-sensitive disulfide bonds and reveals a low level of transcriptional activation.

    PubMed

    Tachibana, Tsuyoshi; Okazaki, Shoko; Murayama, Asako; Naganuma, Akira; Nomoto, Akio; Kuge, Shusuke

    2009-02-13

    Redox reactions involving cysteine thiol-disulfide exchange are crucial for the intracellular monitoring of hydrogen peroxide (H(2)O(2)). Yap1, the master transcription factor for the oxidative stress response in budding yeast, is activated by the formation of disulfide bonds in response to H(2)O(2). Gpx3 (glutathione peroxidase-like protein 3) acts as a receptor for H(2)O(2), and Ybp1 (Yap1-binding protein 1) is crucial for Gpx3-dependent disulfide bond formation in Yap1. We previously reported that Tsa1, a major peroxiredoxin in yeast cells, is required for activation of Yap1 in a widely used yeast strain, W303-1b, carrying the ybp1-1 mutant allele encoding a truncated Ybp1 protein. In the present study, we show that Tsa1 can interact with Yap1 via disulfide linkages and induce the formation of intramolecular disulfide bonds in Yap1 in ybp1-1 cells. The results provide evidence that Prx can have intrinsic activity as an H(2)O(2) receptor and can relay H(2)O(2) as a signal to the Prx target proteins in terms of formation of disulfide linkage. Furthermore, our data reveal that there is more of the reduction-resistant active form of Yap1 (i.e. Yap1 (oxII)) when it is partnered with Gpx3 than with Tsa1. These data support our hypothesis that changes in the redox status of Yap1 to reduction-resistant forms by multiple disulfide bond formation are important for determining the level and duration of Yap1 activity in the dynamic equilibrium of redox reactions in cells exposed to H(2)O(2). PMID:19106090

  11. Computational study on the mechanism and selectivity of C-H bond activation and dehydrogenative functionalization in the synthesis of rhazinilam.

    PubMed

    Ellis, Corey S; Ess, Daniel H

    2011-09-01

    The key platinum mediated C-H bond activation and functionalization steps in the synthesis of (-)-rhazinilam (Johnson, J. A.; Li, N.; Sames, D. J. Am. Chem. Soc. 2002, 124, 6900) were investigated using the M06 and B3LYP density functional approximation methods. This computational study reveals that ethyl group dehydrogenation begins with activation of a primary C-H bond in preference to a secondary C-H bond in an insertion/methane elimination pathway. The C-H activation step is found to be reversible while the methane elimination (reductive elimination) transition state controls rate and diastereoselectivity. The chiral oxazolinyl ligand induces ethyl group selectivity through stabilizing weak interactions between its phenyl group (or cyclohexyl group) and the carboxylate group. After C-H activation and methane elimination steps, Pt-C bond functionalization occurs through β-hydride elimination to give the alkene platinum hydride complex. PMID:21812492

  12. A Highly Reactive Mononuclear Non-Heme Manganese(IV)-Oxo Complex That Can Activate the Strong C-H Bonds of Alkanes

    SciTech Connect

    Wu, Xiujuan; Seo, Mi Sook; Davis, Katherine M; Lee, Yong-Min; Chen, Junying; Cho, Kyung-Bin; Pushkar, Yulia N; Nam, Wonwoo

    2012-03-15

    A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of ~4.4 in the oxidation of para-substituted thioanisoles.

  13. Ce-PROMOTED Bond Activation of Propene Probed by Mass-Analyzed Threshold Ionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Yuchen; Kumari, Sudesh; Yang, Dong-Sheng

    2016-06-01

    The reaction of Ce + propene (CH2=CH-CH3) was carried out in a laser-ablation supersonic molecular beam source. CeC_2H_2, CeC_3H_4, CeC_3H_6, CeC_4H_6, CeC_6H10, and CeC_6H12 were identified by photoionization time-of-flight mass spectrometric measurements, and their structures and electronic states were investigated with mass-analyzed threshold ionization (MATI) spectroscopy and theoretical calculations. The metal complexes containing two or three carbon atoms were formed by the C-C bond breakage (CeC_2H_2), dehydrogenation (CeC_3H_4), or metal insertion into a C-H bond (CeC_3H_6) of a propene molecule. The larger complexes with four to six carbons are formed through secondary reactions involving C-C bond coupling and dehydrogenation. The ground electronic states of the neutral CeC_2H_2, CeC_3H_4, CeC_3H_6, and CeC_4H_6 complexes are triplets with a 4f16s1 electron configuration on the Ce center, and those of the corresponding ions are doublet with a 4f1 configuration. Their MATI spectra are much more complex than those of the corresponding La species formed in the La + propene reaction previously observed by our group. The spectral complexity arises from possibly multiple electronic transitions due to the existence of a 4f electron of the Ce atom which could be located in any one of the seven f-atomic orbitals or involved in considerable spin-orbit interactions.

  14. Simple Bond Cleavage

    SciTech Connect

    Gary S. Groenewold

    2005-08-01

    Simple bond cleavage is a class of fragmentation reactions in which a single bond is broken, without formation of new bonds between previously unconnected atoms. Because no bond making is involved, simple bond cleavages are endothermic, and activation energies are generally higher than for rearrangement eliminations. The rate of simple bond cleavage reactions is a strong function of the internal energy of the molecular ion, which reflects a loose transition state that resembles reaction products, and has a high density of accessible states. For this reason, simple bond cleavages tend to dominate fragmentation reactions for highly energized molecular ions. Simple bond cleavages have negligible reverse activation energy, and hence they are used as valuable probes of ion thermochemistry, since the energy dependence of the reactions can be related to the bond energy. In organic mass spectrometry, simple bond cleavages of odd electron ions can be either homolytic or heterolytic, depending on whether the fragmentation is driven by the radical site or the charge site. Simple bond cleavages of even electron ions tend to be heterolytic, producing even electron product ions and neutrals.

  15. General and facile method for exo-methlyene synthesis via regioselective C-C double-bond formation using a copper-amine catalyst system.

    PubMed

    Nishikata, Takashi; Nakamura, Kimiaki; Itonaga, Kohei; Ishikawa, Shingo

    2014-11-01

    In this study, for distal-selective β-hydride elimination to produce exomethylene compounds with a newly formed Csp(3)-Csp(3) bond between tertiary alkyl halides and α-alkylated styrenes, a combination of a Cu(I) salt and a pyridine-based amine ligand (TPMA) is found to be a very efficient catalyst system. The yields and regioselectivities were high, and the regioselectivity was found to be dependent on the structure of the alkyl halide, with bulky alkyl halides showing the highest distal selectivities. PMID:25315319

  16. Colochiroside E, an Unusual Non-holostane Triterpene Sulfated Trioside from the Sea Cucumber Colochirus robustus and Evidence of the Impossibility of a 7(8)-Double Bond Migration in Lanostane Derivatives having an 18(16)-Lactone.

    PubMed

    Silchenko, Alexandra S; Kalinovsky, Anatoly I; Avilov, Sergey A; Andryjaschenko, Pelageya V; Dmitrenok, Pavel S; Yurchenko, Ekaterina A; Dolmatov, Igor Yu; Dautov, Salim Sh; Stonik, Valentin A; Kalinin, Vladimir I

    2016-06-01

    The unusual non-holostane triterpene glycoside, colochiroside E (1) was isolated from the sea cucumber Colochirus robustus (Cucumariidae, Dendrochirotida). The structure of 1 was established by analysis of 1D, 2D NMR and HRESI MS data. Colochiroside E (1) belongs to a rare group of glycosylated 9β-H-lanosta-18(16)-lactones and has an unprecedented sulfated trisaccharide carbohydrate chain consisting of two glucose and one xylose units. In contrast with (9β-H)-7(8)-unsaturated holostane glycosides, the 7(8)-double bond in the having (9β-H)-configuration aglycone of colochiroside E is not capable of migration into the 8(9)- and then into the 9(11)-position on treatment with HCl. The formation of a chlorine derivative of 1 was observed under these conditions. PMID:27534106

  17. Colochiroside E, an Unusual Non-holostane Triterpene Sulfated Trioside from the Sea Cucumber Colochirus robustus and Evidence of the Impossibility of a 7(8)-Double Bond Migration in Lanostane Derivatives having an 18(16)-Lactone.

    PubMed

    Silchenko, Alexandra S; Kalinovsky, Anatoly I; Avilov, Sergey A; Andryjaschenko, Pelageya V; Dmitrenok, Pavel S; Yurchenko, Ekaterina A; Dolmatov, Igor Yu; Dautov, Salim Sh; Stonik, Valentin A; Kalinin, Vladimir I

    2016-06-01

    The unusual non-holostane triterpene glycoside, colochiroside E (1) was isolated from the sea cucumber Colochirus robustus (Cucumariidae, Dendrochirotida). The structure of 1 was established by analysis of 1D, 2D NMR and HRESI MS data. Colochiroside E (1) belongs to a rare group of glycosylated 9β-H-lanosta-18(16)-lactones and has an unprecedented sulfated trisaccharide carbohydrate chain consisting of two glucose and one xylose units. In contrast with (9β-H)-7(8)-unsaturated holostane glycosides, the 7(8)-double bond in the having (9β-H)-configuration aglycone of colochiroside E is not capable of migration into the 8(9)- and then into the 9(11)-position on treatment with HCl. The formation of a chlorine derivative of 1 was observed under these conditions.

  18. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    SciTech Connect

    Hoskins, J.T.; Zhou, Z.; Harding, P.A.

    2008-10-31

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser{sub 108/121}, HB-EGF-Cys/Ser{sub 116/132}, and HB-EGF-Cys/Ser{sub 134/143}) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with M{sub r} of 6.5, 21 and 24 kDa were observed from lysates of HB-EGF and each HB-EGF disulfide analogue. HB-EGF immunohistochemical analyses of each HB-EGF stable cell line demonstrated ubiquitous protein expression except HB-EGF-Cys/Ser{sub 108/121} and HB-EGF-Cys/Ser{sub 116/132} stable cell lines which exhibited accumulated expression immediately outside the nucleus. rHB-EGF, HB-EGF, and HB-EGF{sub 134/143} proteins competed with {sup 125}I-EGF in an A431 competitive binding assay, whereas HB-EGF-Cys/Ser{sub 108/121} and HB-EGF-Cys/Ser{sub 116/132} failed to compete. Each HB-EGF disulfide analogue lacked the ability to stimulate tyrosine phosphorylation of the 170 kDa EGFR. These results suggest that HB-EGF-Cys/Ser{sub 134/143} antagonizes EGFRs.

  19. Rationale of the effects from dopants on C-H bond activation for sp2 hybridized nanostructured carbon catalysts

    NASA Astrophysics Data System (ADS)

    Mao, Shanjun; Sun, Xiaoying; Li, Bo; Su, Dang Sheng

    2015-10-01

    Doping has become an effective way to tune the catalytic properties of nanostructured carbon catalysts. Taking C-H activation as an example, first-principles calculations propose that the relative energy level and the BEP rule might be applicable to explain the observed doping effects. Moreover, boron doping is proposed as an effective way to enhance the catalytic performance.Doping has become an effective way to tune the catalytic properties of nanostructured carbon catalysts. Taking C-H activation as an example, first-principles calculations propose that the relative energy level and the BEP rule might be applicable to explain the observed doping effects. Moreover, boron doping is proposed as an effective way to enhance the catalytic performance. Electronic supplementary information (ESI) available: The computational setup, the doping positions for B, N and S doping, the definition of the binding energy and dissociation energy for C2H5 and C2H6 respectively, the transition state and dissociation state structures for the C-H bond activation of C2H6 in the undoped case, and the lengths of the C-H bond of C2H6 at the transition states for both the undoped and doped cases. See DOI: 10.1039/c5nr05759k

  20. Comparison of carbon-sulfur and carbon-amine bond in therapeutic drug: 4β-S-aromatic heterocyclic podophyllum derivatives display antitumor activity

    PubMed Central

    Li, Jian-Long; Zhao, Wei; Zhou, Chen; Zhang, Ya-Xuan; Li, Hong-Mei; Tang, Ya-Ling; Liang, Xin-Hua; Chen, Tao; Tang, Ya-Jie

    2015-01-01

    Herein is a first effort to systematically study the significance of carbon-sulfur (C-S) and carbon-amine (C-NH) bonds on the antitumor proliferation activity of podophyllum derivatives and their precise mechanism of apoptosis. Compared with the derivative modified by a C-NH bond, the derivative modified by a C-S bond exhibited superior antitumor activity, the inhibition activity of target proteins tubulin or Topo II, cell cycle arrest, and apoptosis induction. Antitumor mechanistic studies showed that the death receptor and the mitochondrial apoptotic pathways were simultaneously activated by the C-S bond modified aromatic heterocyclic podophyllum derivatives with a higher cellular uptake percentage of 60–90% and induction of a higher level of reactive oxygen species (ROS). Only the mitochondrial apoptotic pathway was activated by the C-NH bond modified aromatic heterocyclic podophyllum derivatives, with a lower cellular uptake percentage of 40–50%. This study provided insight into effects of the C-S and C-NH bond modification on the improvement of the antitumor activity of Podophyllum derivatives. PMID:26443888

  1. Comparison of carbon-sulfur and carbon-amine bond in therapeutic drug: 4β-S-aromatic heterocyclic podophyllum derivatives display antitumor activity.

    PubMed

    Li, Jian-Long; Zhao, Wei; Zhou, Chen; Zhang, Ya-Xuan; Li, Hong-Mei; Tang, Ya-Ling; Liang, Xin-Hua; Chen, Tao; Tang, Ya-Jie

    2015-10-07

    Herein is a first effort to systematically study the significance of carbon-sulfur (C-S) and carbon-amine (C-NH) bonds on the antitumor proliferation activity of podophyllum derivatives and their precise mechanism of apoptosis. Compared with the derivative modified by a C-NH bond, the derivative modified by a C-S bond exhibited superior antitumor activity, the inhibition activity of target proteins tubulin or Topo II, cell cycle arrest, and apoptosis induction. Antitumor mechanistic studies showed that the death receptor and the mitochondrial apoptotic pathways were simultaneously activated by the C-S bond modified aromatic heterocyclic podophyllum derivatives with a higher cellular uptake percentage of 60-90% and induction of a higher level of reactive oxygen species (ROS). Only the mitochondrial apoptotic pathway was activated by the C-NH bond modified aromatic heterocyclic podophyllum derivatives, with a lower cellular uptake percentage of 40-50%. This study provided insight into effects of the C-S and C-NH bond modification on the improvement of the antitumor activity of Podophyllum derivatives.

  2. C-H bond activation of benzene by unsaturated η2-cyclopropene and η2-benzyne complexes of niobium.

    PubMed

    Boulho, Cédric; Oulié, Pascal; Vendier, Laure; Etienne, Michel; Pimienta, Véronique; Locati, Abel; Bessac, Fabienne; Maseras, Feliu; Pantazis, Dimitrios A; McGrady, John E

    2010-10-13

    We report the synthesis of a niobium cyclopropyl complex, Tp(Me2)NbMe(c-C(3)H(5))(MeCCMe), and show that thermal loss of methane from this compound generates an intermediate that is capable of activating both aliphatic and aromatic C-H bonds. Isotopic labeling, trapping studies, a detailed kinetic analysis, and density functional theory all suggest that the active intermediate is an η(2)-cyclopropene complex formed via β-hydrogen abstraction rather than an isomeric cyclopropylidene species. C-H activation chemistry of this type represents a rather unusual reactivity pattern for η(2)-alkene complexes but is favored in this case by the strain in the C(3) ring which prevents the decomposition of the key intermediate via loss of cyclopropene.

  3. Bonding aerogels with polyurethanes

    SciTech Connect

    Matthews, F.M.; Hoffman, D.M.

    1989-11-01

    Aerogels, porous silica glasses with ultra-fine cell size (30nm), are made by a solution gelation (sol-gel) process. The resulting gel is critical point dried to densities from 0.15--0.60 g/cc. This material is machinable, homogeneous, transparent, coatable and bondable. To bond aerogel an adhesive should have long cure time, no attack on the aerogel structure, and high strength. Several epoxies and urethanes were examined to determine if they satisfied these conditions. Bond strengths above 13 psi were found with double bubble and DP-110 epoxies and XI-208/ODA-1000 and Castall U-2630 urethanes. Hardman Kalex Tough Stuff'' A-85 hardness urethane gave 18 psi bond strength. Hardman A-85, Tuff-Stuff'' was selected for further evaluation because it produced bond strengths comparable to the adherend cohesive strength. 5 refs., 2 figs.

  4. An electrochemical double layer capacitor using an activated carbon electrode with gel electrolyte binder

    SciTech Connect

    Osaka, Tetsuya, Liu, X.; Nojima, Masashi; Momma, Toshiyuki

    1999-05-01

    An electric double layer capacitor (EDLC) was prepared with an activated carbon powder electrode with poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) based gel electrolyte. Ethylene carbonate (EC) and propylene carbonate (PC) were used as plasticizer and tetraethylammonium tetrafluoroborate (TEABF{sub 4}) was used as the supporting electrolyte. An optimized gel electrolyte of PVdF-HFP/PC/EC/TEABF{sub 4} - 23/31/35/11 mass ratio exhibited high ionic conductivity of 5 {times} 10{sup {minus}3} S/cm, high electrode capacitance, and good mechanical strength. An electrode consisting of activated carbon (AC) with the gel electrolyte as the binder (AC/PVdF-HFP based gel, 7/3 mass ratio) showed a higher specific capacitance and a lower ion diffusion resistance within the electrode than a carbon electrode, prepared with PVdF-HFP binder without plasticizer. This suggests that an electrode mixed with the gel electrolyte has a lower ion diffusion resistance inside the electrode. The highest specific capacitance of 123 F/g was achieved with an electrode containing AC with a specific surface area of 2500 m{sup 2}/g. A coin-type EDLC cell with optimized components showed excellent cycleability exceeding 10{sup 4} cycles with ca. 100% coulombic efficiency achieved when charging and discharging was repeated between 1.0 and 2.5 V at 1.66 mA/cm{sup 2}.

  5. Cockayne syndrome group B protein regulates DNA double-strand break repair and checkpoint activation

    PubMed Central

    Batenburg, Nicole L; Thompson, Elizabeth L; Hendrickson, Eric A; Zhu, Xu-Dong

    2015-01-01

    Mutations of CSB account for the majority of Cockayne syndrome (CS), a devastating hereditary disorder characterized by physical impairment, neurological degeneration and segmental premature aging. Here we report the generation of a human CSB-knockout cell line. We find that CSB facilitates HR and represses NHEJ. Loss of CSB or a CS-associated CSB mutation abrogating its ATPase activity impairs the recruitment of BRCA1, RPA and Rad51 proteins to damaged chromatin but promotes the formation of 53BP1-Rif1 damage foci in S and G2 cells. Depletion of 53BP1 rescues the formation of BRCA1 damage foci in CSB-knockout cells. In addition, knockout of CSB impairs the ATM- and Chk2-mediated DNA damage responses, promoting a premature entry into mitosis. Furthermore, we show that CSB accumulates at sites of DNA double-strand breaks (DSBs) in a transcription-dependent manner. The kinetics of DSB-induced chromatin association of CSB is distinct from that of its UV-induced chromatin association. These results reveal novel, important functions of CSB in regulating the DNA DSB repair pathway choice as well as G2/M checkpoint activation. PMID:25820262

  6. Analysis and Simple Circuit Design of Double Differential EMG Active Electrode.

    PubMed

    Guerrero, Federico Nicolás; Spinelli, Enrique Mario; Haberman, Marcelo Alejandro

    2016-06-01

    In this paper we present an analysis of the voltage amplifier needed for double differential (DD) sEMG measurements and a novel, very simple circuit for implementing DD active electrodes. The three-input amplifier that standalone DD active electrodes require is inherently different from a differential amplifier, and general knowledge about its design is scarce in the literature. First, the figures of merit of the amplifier are defined through a decomposition of its input signal into three orthogonal modes. This analysis reveals a mode containing EMG crosstalk components that the DD electrode should reject. Then, the effect of finite input impedance is analyzed. Because there are three terminals, minimum bounds for interference rejection ratios due to electrode and input impedance unbalances with two degrees of freedom are obtained. Finally, a novel circuit design is presented, including only a quadruple operational amplifier and a few passive components. This design is nearly as simple as the branched electrode and much simpler than the three instrumentation amplifier design, while providing robust EMG crosstalk rejection and better input impedance using unity gain buffers for each electrode input. The interference rejection limits of this input stage are analyzed. An easily replicable implementation of the proposed circuit is described, together with a parameter design guideline to adjust it to specific needs. The electrode is compared with the established alternatives, and sample sEMG signals are obtained, acquired on different body locations with dry contacts, successfully rejecting interference sources. PMID:26841414

  7. CpG oligodeoxynucleotides with double stem-loops show strong immunostimulatory activity.

    PubMed

    Yang, Liang; Wu, Xiuli; Wan, Min; Yu, Yue; Yu, Yongli; Wang, Liying

    2013-01-01

    Based on the current understanding of TLR9 recognition of CpG ODN, we have tried to design a series of CpG ODNs that display double stem-loops when being analyzed for their secondary structures using 'mfold web server'. Proliferation of human PBMC and bioassay for IFN production were used as technical platforms in primary screening. Interestingly, two of them, designated as DSL01 and D-SL03, belonging to B class CpG ODN and C class CpG ODN respectively, showed vigorous immunostimulatory activity and were chosen for further tests. Flow cytometry analysis showed that both of them could activate human B cells, NK cells, mononuclear cells and T cells and up-regulate expression of CD80, CD86 and HLA-DR on the surface of subsets in human PBMCs. Furthermore, we demonstrated that those two ODNs potently stimulated proliferation of PBMC/splenocytes obtained from diverse vertebrate species. Noticeably, both of them displayed anti-breast cancer effect in mice when administered by peritumoral injection. PMID:23142503

  8. Analysis and Simple Circuit Design of Double Differential EMG Active Electrode.

    PubMed

    Guerrero, Federico Nicolás; Spinelli, Enrique Mario; Haberman, Marcelo Alejandro

    2016-06-01

    In this paper we present an analysis of the voltage amplifier needed for double differential (DD) sEMG measurements and a novel, very simple circuit for implementing DD active electrodes. The three-input amplifier that standalone DD active electrodes require is inherently different from a differential amplifier, and general knowledge about its design is scarce in the literature. First, the figures of merit of the amplifier are defined through a decomposition of its input signal into three orthogonal modes. This analysis reveals a mode containing EMG crosstalk components that the DD electrode should reject. Then, the effect of finite input impedance is analyzed. Because there are three terminals, minimum bounds for interference rejection ratios due to electrode and input impedance unbalances with two degrees of freedom are obtained. Finally, a novel circuit design is presented, including only a quadruple operational amplifier and a few passive components. This design is nearly as simple as the branched electrode and much simpler than the three instrumentation amplifier design, while providing robust EMG crosstalk rejection and better input impedance using unity gain buffers for each electrode input. The interference rejection limits of this input stage are analyzed. An easily replicable implementation of the proposed circuit is described, together with a parameter design guideline to adjust it to specific needs. The electrode is compared with the established alternatives, and sample sEMG signals are obtained, acquired on different body locations with dry contacts, successfully rejecting interference sources.

  9. Chronic glial activation, neurodegeneration, and APP immunoreactive deposits following acute administration of double-stranded RNA.

    PubMed

    Melton, Lisa M; Keith, Alexander B; Davis, Sue; Oakley, Arthur E; Edwardson, James A; Morris, Christopher M

    2003-10-01

    Several neurodegenerative disorders, including Alzheimer's and Parkinson's diseases, are associated with immunocompetent microglia, leading to the suggestion that chronic glial-mediated inflammation contributes to the neurodegeneration seen in these diseases. Little direct evidence supports this hypothesis, and no suitable rodent models exist that do not involve the use of blunt trauma or ischaemia, events that are infrequently encountered in the human disease state. In the present study, we report that administration of double-stranded RNA, a classical inducer of interferon-gamma (IFN-gamma), causes rapid and persistent activation of microglia and astrocytes, as well as induction of interleukin-1beta (IL-beta) and nitric oxide synthase. In close temporal succession to glial activation, there is neurodegeneration, with neuron loss involving apoptosis in selected brain regions including the septal nucleus, hippocampus, cortex and thalamus, along with hippocampal atrophy. This neuronal loss is accompanied by punctate deposits of material that are immunoreactive for amyloid precursor protein, beta-amyloid peptide (Abeta), and apolipoprotein E. The findings may have clinical relevance, since the administration of the nonsteroidal antiinflammatory agent (NSAID) ibuprofen markedly reduces the neurodegeneration observed in the absence of significant glial inhibition. These findings may be relevant to the pathogenesis of Alzheimer's disease in particular, and to other neurodegenerative diseases involving inflammation.

  10. Unprecedented structural variations in trinuclear mixed valence Co(II/III) complexes: theoretical studies, pnicogen bonding interactions and catecholase-like activities.

    PubMed

    Hazari, Alokesh; Kanta Das, Lakshmi; Kadam, Ramakant M; Bauzá, Antonio; Frontera, Antonio; Ghosh, Ashutosh

    2015-02-28

    Three new mixed valence trinuclear Co(II/III) compounds cis-[Co3L2(MeOH)2(N3)2(μ1,1-N3)2] (1), trans-[Co3L2(H2O)2(N3)2(μ1,1-N3)2]·(H2O)2 (2) and [Co3L(R)2(N3)3(μ1,3-N3)] (3) have been synthesized by reacting a di-Schiff base ligand (H2L) or its reduced form [H2LR] (where H2L= N,N'-bis(salicylidene)-1,3-propanediamine and H2LR= N,N'-bis(2-hydroxybenzyl)-1,3-propanediamine) with cobalt perchlorate hexahydrate and sodium azide. All three products have been characterized by IR, UV-Vis and EPR spectroscopies, ESI-MS, elemental, powder and single crystal X-ray diffraction analyses. Complex 2 is an angular trinuclear species in which two terminal octahedral Co(III)N2O4 centers coordinate to the central octahedral cobalt(II) ion through μ2-phenoxido oxygen and μ1,1-azido nitrogen atoms along with two mutually cis-oxygen atoms of methanol molecules. On the other hand, in linear trinuclear complex , in addition to the μ2-phenoxido and μ1,1-azido bridges with terminal octahedral Co(III) centres, the central Co(II) is bonded with two mutually trans-oxygen atoms of water molecules. Thus the cis-trans configuration of the central Co(II) is solvent dependent. In complex 3, the two terminal octahedral Co(III)N2O4 centers coordinate to the central penta-coordinated Co(II) ion through double phenoxido bridges along with the nitrogen atom of a terminal azido ligand. In addition, the two terminal Co(III) are connected through a μ1,3-azido bridge that participates in pnicogen bonding interactions (intermolecular N-N interaction) as an acceptor. Both the cis and trans isomeric forms of 1 and 2 have been optimized using density functional theory (DFT) calculations and it is found that the cis configuration is energetically more favorable than the trans one. However, the trans configuration of 2 is stabilized by the hydrogen bonding network involving a water dimer. The pnicogen bonding interactions have been demonstrated using MEP surfaces and CSD search which support the counter

  11. Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and "green" catalysis.

    PubMed

    Gunanathan, Chidambaram; Milstein, David

    2011-08-16

    In view of global concerns regarding the environment and sustainable energy resources, there is a strong need for the discovery of new, green catalytic reactions. For this purpose, fresh approaches to catalytic design are desirable. In recent years, complexes based on "cooperating" ligands have exhibited remarkable catalytic activity. These ligands cooperate with the metal center by undergoing reversible structural changes in the processes of substrate activation and product formation. We have discovered a new mode of metal-ligand cooperation, involving aromatization-dearomatization of ligands. Pincer-type ligands based on pyridine or acridine exhibit such cooperation, leading to unusual bond activation processes and to novel, environmentally benign catalysis. Bond activation takes place with no formal change in the metal oxidation state, and so far the activation of H-H, C-H (sp(2) and sp(3)), O-H, and N-H bonds has been demonstrated. Using this approach, we have demonstrated a unique water splitting process, which involves consecutive thermal liberation of H(2) and light-induced liberation of O(2), using no sacrificial reagents, promoted by a pyridine-based pincer ruthenium complex. An acridine pincer complex displays unique "long-range" metal-ligand cooperation in the activation of H(2) and in reaction with ammonia. In this Account, we begin by providing an overview of the metal-ligand cooperation based on aromatization-dearomatization processes. We then describe a range of novel catalytic reactions that we developed guided by these new modes of metal-ligand cooperation. These reactions include the following: (1) acceptorless dehydrogenation of secondary alcohols to ketones, (2) acceptorless dehydrogenative coupling of alcohols to esters, (3) acylation of secondary alcohols by esters with dihydrogen liberation, (4) direct coupling of alcohols and amines to form amides and polyamides with liberation of dihydrogen, (5) coupling of esters and amines to form amides

  12. An activated triple bond linker enables ‘click’ attachment of peptides to oligonucleotides on solid support

    PubMed Central

    Wenska, Malgorzata; Alvira, Margarita; Steunenberg, Peter; Stenberg, Åsa; Murtola, Merita; Strömberg, Roger

    2011-01-01

    A general procedure, based on a new activated alkyne linker, for the preparation of peptide–oligonucleotide conjugates (POCs) on solid support has been developed. With this linker, conjugation is effective at room temperature (RT) in millimolar concentration and submicromolar amounts. This is made possible since the use of a readily attachable activated triple bond linker enhances the Cu(I) catalyzed 1,3-dipolar cycloaddition (‘click’ reaction). The preferred scheme for conjugate preparation involves sequential conjugation to oligonucleotides on solid support of (i) an H-phosphonate-based aminolinker; (ii) the triple bond donor p-(N-propynoylamino)toluic acid (PATA); and (iii) azido-functionalized peptides. The method gives conversion of oligonucleotide to the POC on solid support, and only involves a single purification step after complete assembly. The synthesis is flexible and can be carried out without the need for specific automated synthesizers since it has been designed to utilize commercially available oligonucleotide and peptide derivatives on solid support or in solution. Methodology for the ready conversion of peptides into ‘clickable’ azidopeptides with the possibility of selecting either N-terminus or C-terminus connection also adds to the flexibility and usability of the method. Examples of synthesis of POCs include conjugates of oligonucleotides with peptides known to be membrane penetrating and nuclear localization signals. PMID:21795380

  13. Heat treatment of bovine alpha-lactalbumin results in partially folded, disulfide bond shuffled states with enhanced surface activity.

    PubMed

    Wijesinha-Bettoni, Ramani; Gao, Chunli; Jenkins, John A; Mackie, Alan R; Wilde, Peter J; Mills, E N Clare; Smith, Lorna J

    2007-08-28

    Prolonged heating of holo bovine alpha-lactalbumin (BLA) at 80 degrees C in pH 7 phosphate buffer in the absence of a thiol initiator improves the surface activity of the protein at the air:water interface, as determined by surface tension measurements. Samples after 30, 60, and 120 min of heating were analyzed on cooling to room temperature. Size-exclusion chromatography shows sample heterogeneity that increases with the length of heating. After 120 min of heating monomeric, dimeric, and oligomeric forms of BLA are present, with aggregates formed from disulfide bond linked hydrolyzed protein fragments. NMR characterization at pH 7 in the presence of Ca2+ of the monomer species isolated from the sample heated for 120 min showed that it consisted of a mixture of refolded native protein and partially folded protein and that the partially folded protein species had spectral characteristics similar to those of the pH 2 molten globule state of the protein. Circular dichroism spectroscopy showed that the non-native species had approximately 40% of the alpha-helical content of the native state, but lacked persistent tertiary interactions. Proteomic analysis using thermolysin digestion of three predominant non-native monomeric forms isolated by high-pressure liquid chromatography indicated the presence of disulfide shuffled isomers, containing the non-native 61-73 disulfide bond. These partially folded, disulfide shuffled species are largely responsible for the pronounced improvement in surface activity of the protein on heating.

  14. Reactivity of oxygen radical anions bound to scandia nanoparticles in the gas phase: C-H bond activation.

    PubMed

    Tian, Li-Hua; Meng, Jing-Heng; Wu, Xiao-Nan; Zhao, Yan-Xia; Ding, Xun-Lei; He, Sheng-Gui; Ma, Tong-Mei

    2014-01-20

    The activation of C-H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O(-·)) is an important species in C-H activation. The mechanistic details of C-H activation by O(-·) radicals can be well understood by studying the reactions between O(-·) containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n-butane was studied by using a high-resolution time-of-flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n-butane by (Sc2O3)(N)O(-) (N=1-18) clusters was observed. The reactivity of (Sc2O3)(N)O(-) (N=1-18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13(-)) and 12 (Sc24O37(-)). Larger (Sc2O3)(N)O(-) clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)(N)O(-) (N=1-5) clusters, which were found to contain the O(-·) radicals as the active sites. The local charge environment around the O(-·) radicals was demonstrated to control the experimentally observed size-dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O(-·) containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C-H bond activation. PMID:24338790

  15. Intermolecular activation of hydrocarbon C-H bonds under ambient conditions by 16-electron neopentylidene and benzyne complexes of molybdenum.

    PubMed

    Wada, Kenji; Pamplin, Craig B; Legzdins, Peter; Patrick, Brian O; Tsyba, Irina; Bau, Robert

    2003-06-11

    CpMo(NO)(CH(2)CMe(3))(2) (1), a complex with alpha-agostic C-H.Mo interactions, evolves neopentane in neat hydrocarbon solutions at room temperature and forms the transient 16-electron alkylidene complex, CpMo(NO)(=CHCMe(3)), which subsequently activates solvent C-H bonds. Thus, it reacts with tetramethylsilane or mesitylene to form CpMo(NO)(CH(2)CMe(3))(CH(2)SiMe(3)) (2) or CpMo(NO)(CH(2)CMe(3))(eta(2)-CH(2)C(6)H(3)-3,5-Me(2)) (3), respectively, in nearly quantitative yields. Under identical conditions, 1 in p-xylene generates a mixture of sp(2) and sp(3) C-H bond activation products, namely CpMo(NO)(CH(2)CMe(3))(C(6)H(3)-2,5-Me(2)) (4, 73%) and CpMo(NO)(CH(2)CMe(3))(eta(2)-CH(2)C(6)H(4)-4-Me) (5, 27%). In benzene at room temperature, 1 transforms to a mixture of CpMo(NO)(CH(2)CMe(3))(C(6)H(5)) (6) and CpMo(NO)(C(6)H(5))(2) (7) in a sequential manner. Most interestingly, the thermal activation of 6 at ambient temperatures gives rise to two parallel modes of reactivity involving either the elimination of benzene and formation of CpMo(NO)(=CHCMe(3)) or the elimination of neopentane and formation of the benzyne complex, CpMo(NO)(eta(2)-C(6)H(4)). In pyridine, these intermediates are trapped as the isolable 18-electron adducts, CpMo(NO)(=CHCMe(3))(NC(5)H(5)) (8) and CpMo(NO)(eta(2)-C(6)H(4))(NC(5)H(5)) (9), and, in hydrocarbon solvents, they effect the intermolecular activation of aliphatic C-H bonds at room temperature to generate mixtures of neopentyl- and phenyl-containing derivatives. However, the distribution of products resulting from the hydrocarbon activations is dependent on the nature of the solvent, probably due to solvation effects and the presence of sigma- or pi-hydrocarbon complexes on the reaction coordinates of the alkylidene and the benzyne intermediates. The results of DFT calculations on these processes in the gas phase support the existence of such hydrocarbon complexes and indicate that better agreement with experimental observations is obtained

  16. Clioquinol induces DNA double-strand breaks, activation of ATM, and subsequent activation of p53 signaling.

    PubMed

    Katsuyama, Masato; Iwata, Kazumi; Ibi, Masakazu; Matsuno, Kuniharu; Matsumoto, Misaki; Yabe-Nishimura, Chihiro

    2012-09-01

    Clioquinol, a Cu²⁺/Zn²⁺/Fe²⁺ chelator/ionophor, was used extensively in the mid 1900s as an amebicide for treating indigestion and diarrhea. It was eventually withdrawn from the market because of a link to subacute myelo-optic neuropathy (SMON) in Japan. The pathogenesis of SMON, however, is not fully understood. To clarify the molecular mechanisms of clioquinol-induced neurotoxicity, a global analysis using DNA chips was carried out on human neuroblastoma cells. The global analysis and quantitative PCR demonstrated that mRNA levels of p21(Cip1), an inhibitor of cyclins D and E, and of GADD45α, a growth arrest and DNA damage-inducible protein, were significantly increased by clioquinol treatment in SH-SY5Y and IMR-32 neuroblastoma cells. Activation of p53 by clioquinol was suggested, since clioquinol induced phosphorylation of p53 at Ser15 to enhance its stabilization. The phosphorylation of p53 was inhibited by KU-55933, an inhibitor of ataxia-telangiectasia mutated kinase (ATM), but not by NU7026, an inhibitor of DNA-dependent protein kinase (DNA-PK). Clioquinol in fact induced phosphorylation of ATM and histone H2AX, a marker of DNA double-strand breaks (DSBs). These results suggest that clioquinol-induced neurotoxicity is mediated by DSBs and subsequent activation of ATM/p53 signaling. PMID:22627294

  17. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions.

    PubMed

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-01-01

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO3(2-) and DCCM/SeO3(2-) complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation. PMID:26635113

  18. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions.

    PubMed

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-12-04

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO3(2-) and DCCM/SeO3(2-) complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation.

  19. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions

    NASA Astrophysics Data System (ADS)

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-12-01

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO32- and DCCM/SeO32- complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation.

  20. The Comparative Studies of Binding Activity of Curcumin and Didemethylated Curcumin with Selenite: Hydrogen Bonding vs Acid-Base Interactions

    PubMed Central

    Liao, Jiahn-Haur; Wu, Tzu-Hua; Chen, Ming-Yi; Chen, Wei-Ting; Lu, Shou-Yun; Wang, Yi-Hsuan; Wang, Shao-Pin; Hsu, Yen-Min; Huang, Yi-Shiang; Huang, Zih-You; Lin, Yu-Ching; Chang, Ching-Ming; Huang, Fu-Yung; Wu, Shih-Hsiung

    2015-01-01

    In this report, the in vitro relative capabilities of curcumin (CCM) and didemethylated curcumin (DCCM) in preventing the selenite-induced crystallin aggregation were investigated by turbidity tests and isothermal titration calorimetry (ITC). DCCM showed better activity than CCM. The conformers of CCM/SeO32− and DCCM/SeO32− complexes were optimized by molecular orbital calculations. Results reveal that the selenite anion surrounded by CCM through the H-bonding between CCM and selenite, which is also observed via IR and NMR studied. For DCCM, the primary driving force is the formation of an acid-base adduct with selenite showing that the phenolic OH group of DCCM was responsible for forming major conformer of DCCM. The formation mechanisms of selenite complexes with CCM or DCCM explain why DCCM has greater activity than CCM in extenuating the toxicity of selenite as to prevent selenite-induced lens protein aggregation. PMID:26635113

  1. Detection of a water molecule in the active-site of bacteriorhodopsin: hydrogen bonding changes during the primary photoreaction.

    PubMed

    Fischer, W B; Sonar, S; Marti, T; Khorana, H G; Rothschild, K J

    1994-11-01

    FTIR-difference spectroscopy in combination with site-directed mutagenesis has been used to investigate the role of water during the photocycle of bacteriorhodopsin. At least one water molecule is detected which undergoes an increase in H-bonding during the primary bR-->K phototransition. Bands due to water appear in the OH stretch region of the bR-->K FTIR-difference spectrum which downshift by approximately 12 cm-1 when the sample is hydrated with H2(18)O. In contrast to 2H2O, the H2(18)O-induced shift is not complete, even after 24 h of hydration. This indicates that even though water is still able to exchange protons with the outside medium, it is partially trapped in the interior of the protein. In the mutant Y57D, these bands are absent while a new set of bands appear at much lower frequencies which undergo H2(18)O-induced shifts. It is concluded that the water molecule we detect is located inside the bR active-site and may interact with Tyr-57. The change in its hydrogen-bonding strength is most likely due to the photoinduced all-trans-->13-cis isomerization of the retinal chromophore and the associated movement of the positively charged Schiff base during the bR-->K transition. In contrast, a second water molecule, whose infrared difference bands are not affected by the Y57D mutation, appears to undergo a decrease in hydrogen bonding during the K-->L and L-->M transitions.

  2. High-capacity electric double-layer capacitor with high-density-activated carbon fiber electrodes

    SciTech Connect

    Nakagawa, Hiroyuki; Shudo, Atsushi; Miura, Kouichi

    2000-01-01

    Recently the authors have presented a method to prepare activated carbon fiber with high bulk density (HD-ACF) without using any binders. The possibility of using the HD-ACF as an electrode for electric double-layer capacitors (EDLCs) was examined in this paper. The capacitance of the EDLC with the HD-ACF electrode increased with the increase of bulk density of the HD-ACF, indicating that individual fibers are highly packed without losing their capacitance. The capacitance also increased in proportion to the size of the HD-ACF electrode. The initial discharge current of the EDLC showed little dependency on either the bulk density or the size of the HD-ACF electrode. These results clarified that the HD-ACF electrode is suitable for constructing a high-power EDLC. The initial discharge current was directly proportional to the conductivity of aqueous KCI used as the electrolyte, indicating that the resistance of the electrolyte is much higher than that of the HD-ACF electrode. This result showed that the efficiency of the HD-ACF was well above the efficiency of the electrolyte used in this study and that the improvement of the ionic conductivity of electrolyte is also necessary for developing a high-power EDLC.

  3. Numerical investigation of sound transmission through double wall cylinders with respect to active noise control

    NASA Astrophysics Data System (ADS)

    Coats, T. J.; Silcox, R. J.; Lester, H. C.

    Market pressure for more fuel efficient air travel has led to increased use of turboprop and higher bypass turbofan engines. The low frequency components of propeller, jet and boundary layer noise are difficult to attenuate with conventional passive techniques. Weight and geometric restrictions for sound absorbing meterials limit the amount and type of treatment that may be applied. An active noise control (ANC) method is providing to be an attractive alternative. The approach taken in this paper uses a numerical finite/boundary element method (FEM/BEM) that may be easilty adapted to arbitrary geometries. A double walled cylinder is modeled using commercially available software. The outer shell is modeled as an aluminum cylinder, similar to that of aircraft skins. The inner shell is modeled as a composite material representative of a lightweight, stiff trim panel. Two different inner shell materials are used. The first is representative of current trim structure, the second a much stiffer composite. The primary source is generated by an exterior acoustic monopole. Control fields are generated using normal force inputs to the inner cylindrical shell. A linear least mean square (LMS) algorithm is used to determine amplitudes of control forces that minimize the interior acoustic field. Coupling of acoustic and structural modes and noise reductions are discussed for each of the inner shell materials.

  4. DNA Double Strand Break Repair Pathway Choice Is Directed by Distinct MRE11 Nuclease Activities

    PubMed Central

    Shibata, Atsushi; Moiani, Davide; Arvai, Andrew S.; Perry, J. Jefferson P.; Harding, Shane M.; Genois, Marie-Michelle; Maity, Ranjan; van Rossum-Fikkert, Sari; Kertokalio, Aryandi; Romoli, Filippo; Ismail, Amani; Ismalaj, Ermal; Petricci, Elena; Matthew, J Neale; Bristow, Robert G; Masson, Jean-Yves; Wyman, Claire; Jeggo, Penny; Tainer, John A.

    2014-01-01

    SUMMARY MRE11 within the MRE11-RAD50-NBS1 (MRN) complex acts in DNA double-strand break repair (DSBR), detection and signaling; yet, how its endo- and exonuclease activities regulate DSB repair by non-homologous end-joining (NHEJ) versus homologous recombination (HR) remains enigmatic. Here we employed structure-based design with a focused chemical library to discover specific MRE11 endo- or exonuclease inhibitors. With these inhibitors we examined repair pathway choice at DSBs generated in G2 following radiation exposure. Whilst endo- or exonuclease inhibition impairs radiation-induced RPA chromatin binding, suggesting diminished resection, the inhibitors surprisingly direct different repair outcomes. Endonuclease inhibition promotes NHEJ in lieu of HR, whilst exonuclease inhibition confers a repair defect. Collectively, the results describe nuclease-specific MRE11 inhibitors, define distinct nuclease roles in DSB repair, and support a mechanism whereby MRE11 endonuclease initiates resection, thereby licensing HR followed by MRE11 exo and EXO1/BLM bidirectional resection towards and away from the DNA end, which commits to HR. PMID:24316220

  5. Noise-enhanced stability and double stochastic resonance of active Brownian motion

    NASA Astrophysics Data System (ADS)

    Zeng, Chunhua; Zhang, Chun; Zeng, Jiakui; Liu, Ruifen; Wang, Hua

    2015-08-01

    In this paper, we study the transient and resonant properties of active Brownian particles (ABPs) in the Rayleigh-Helmholtz (RH) and Schweitzer-Ebeling-Tilch (SET) models, which is driven by the simultaneous action of multiplicative and additive noise and periodic forcing. It is shown that the cross-correlation between two noises (λ) can break the symmetry of the potential to generate motion of the ABPs. In case of no correlation between two noises, the mean first passage time (MFPT) is a monotonic decrease depending on the multiplicative noise, however in case of correlation between two noises, the MFPT exhibits a maximum, depending on the multiplicative noise for both models, this maximum for MFPT identifies the noise-enhanced stability (NES) effect of the ABPs. By comparing with case of no correlation (λ =0.0 ), we find two maxima in the signal-to-noise ratio (SNR) depending on the cross-correlation intensity, i.e. the double stochastic resonance is shown in both models. For the RH model, the SNR exhibits two maxima depending on the multiplicative noise for small cross-correlation intensity, while in the SET model, it exhibits only a maximum depending on the multiplicative noise. Whether λ =0.0 or not, the MFPT is a monotonic decrease, and the SNR exhibits a maximum, depending on the additive noise in both models.

  6. Defluorination of perfluoroolefins by divalent lanthanoid reagents: Activating C-F bonds

    SciTech Connect

    Watson, P.L.; Tulip, T.H.; Williams, I. )

    1990-07-01

    Divalent lanthanoid complexes MCp*{sub 2} {times} L (M = Yb, Eu, Sm; L = diethyl ether or THF; Cp* = {eta}{sup 5}-pentamethylcyclopetadienyl) and YbCp{prime}{sub 2} {times} L (Cp{prime} = {eta}{sup 5}-methylcyclopentadienyl; L = tetrahydrofuran) rapidly abstract fluorine atoms from a variety of perfluoroolefins including perfluoro-2,4-dimethyl-3-ethylpent-2-ene, perfluoro-2,3-dimethylpent-2-ene, and perfluorocyclohexene. Qualitative observation shows that the relative fluorine abstraction reactivity of the four lanthanoid complexes increases with increasingly negative reduction potential for reasonably unhindered fluoroolefin substrates. The Yb(III)/Yb(II) reduction potential of YbCp{prime}{sub 2} solvated in acetonitrile is determined here to be {minus}1.65 V (relative to ferrocene) by cyclic voltammetry. The fully characterized organometallic products from the fluorine atom abstraction reactions are solvated trivalent lanthanoid fluorides MCp*{sub 2}F {times} L (M = Yb, Eu, Sm; L = diethyl ether or THF) and YbCp{prime}{sub 2}F {times} THF. The molecular structures of YbCp*{sub 2}F {times} OEt{sub 2} and YbCp*{sub 2}F {times} THF determined by X-ray crystallography reveal the first terminal lanthanoid-fluoride bonds.

  7. Bond Issues.

    ERIC Educational Resources Information Center

    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…

  8. Recycling of MSWI fly ash by means of cementitious double step cold bonding pelletization: Technological assessment for the production of lightweight artificial aggregates.

    PubMed

    Colangelo, Francesco; Messina, Francesco; Cioffi, Raffaele

    2015-12-15

    In this work, an extensive study on the recycling of municipal solid waste incinerator fly ash by means of cold bonding pelletization is presented. The ash comes from an incineration plant equipped with rotary and stoker furnaces, in which municipal, hospital and industrial wastes are treated. Fly ash from waste incineration is classified as hazardous and cannot be utilized or even landfilled without prior treatment. The pelletization process uses cement, lime and coal fly ash as components of the binding systems. This process has been applied to several mixes in which the ash content has been varied from 50% (wt.%) up to a maximum of 70%. An innovative additional pelletization step with only cementitious binder has been performed in order to achieve satisfactory immobilization levels. The obtained lightweight porous aggregates are mostly suitable for recovery in the field of building materials with enhanced sustainability properties. Density, water absorption and crushing strength ranged from 1000 to 1600 kg/m(3), 7 to 16% and 1.3 to 6.2 MPa, respectively, and the second pelletization step increased stabilization efficiency. The feasibility of the process has been analyzed by testing also concrete specimens containing the artificial aggregates, resulting in lightweight concrete of average performance. PMID:26124064

  9. Recycling of MSWI fly ash by means of cementitious double step cold bonding pelletization: Technological assessment for the production of lightweight artificial aggregates.

    PubMed

    Colangelo, Francesco; Messina, Francesco; Cioffi, Raffaele

    2015-12-15

    In this work, an extensive study on the recycling of municipal solid waste incinerator fly ash by means of cold bonding pelletization is presented. The ash comes from an incineration plant equipped with rotary and stoker furnaces, in which municipal, hospital and industrial wastes are treated. Fly ash from waste incineration is classified as hazardous and cannot be utilized or even landfilled without prior treatment. The pelletization process uses cement, lime and coal fly ash as components of the binding systems. This process has been applied to several mixes in which the ash content has been varied from 50% (wt.%) up to a maximum of 70%. An innovative additional pelletization step with only cementitious binder has been performed in order to achieve satisfactory immobilization levels. The obtained lightweight porous aggregates are mostly suitable for recovery in the field of building materials with enhanced sustainability properties. Density, water absorption and crushing strength ranged from 1000 to 1600 kg/m(3), 7 to 16% and 1.3 to 6.2 MPa, respectively, and the second pelletization step increased stabilization efficiency. The feasibility of the process has been analyzed by testing also concrete specimens containing the artificial aggregates, resulting in lightweight concrete of average performance.

  10. Enhancement of laccase activity through the construction and breakdown of a hydrogen bond at the type I copper center in Escherichia coli CueO and the deletion mutant Δα5-7 CueO.

    PubMed

    Kataoka, Kunishige; Hirota, Shun; Maeda, Yasuo; Kogi, Hiroki; Shinohara, Naoya; Sekimoto, Madoka; Sakurai, Takeshi

    2011-02-01

    CueO is a multicopper oxidase involved in a copper efflux system of Escherichia coli and has high cuprous oxidase activity but little or no oxidizing activity toward various organic substances. However, its activity toward oxidization of organic substrates was found to be considerably increased by the removal of the methionine-rich helical segment that covers the substrate-binding site (Δα5-7 CueO) [Kataoka, K., et al. (2007) J. Mol. Biol. 373, 141]. In the study presented here, mutations at Pro444 to construct a second NH-S hydrogen bond between the backbone amide and coordinating Cys500 thiolate of the type I copper are shown to result in positive shifts in the redox potential of this copper center and enhanced oxidase activity in CueO. Analogous enhancement of the activity of Δα5-7 CueO has been identified only in the Pro444Gly mutant because Pro444 mutants limit the incorporation of copper ions into the trinuclear copper center. The activities of both CueO and Δα5-7 CueO were also enhanced by mutations to break down the hydrogen bond between the imidazole group of His443 that is coordinated to the type I copper and the β-carboxy group of Asp439 that is located in the outer sphere of the type I copper center. A synergetic effect of the positive shift in the redox potential of the type I copper center and the increase in enzyme activity has been achieved by the double mutation of Pro444 and Asp439 of CueO. Absorption, circular dichroism, and resonance Raman spectra indicate that the characteristics of the Cu(II)-S(Cys) bond were only minimally perturbed by mutations involving formation or disruption of a hydrogen bond from the coordinating groups to the type I copper. This study provides widely applicable strategies for tuning the activities of multicopper oxidases.

  11. A double-blind atropine trial for active learning of autonomic function.

    PubMed

    Fry, Jeffrey R; Burr, Steven A

    2011-12-01

    Here, we describe a human physiology laboratory class measuring changes in autonomic function over time in response to atropine. Students use themselves as subjects, generating ownership and self-interest in the learning as well as directly experiencing the active link between physiology and pharmacology in people. The class is designed to concomitantly convey the importance of bias in experimentation by adopting a double-blind placebo-controlled approach. We have used this class effectively in various forms with ∼600 students receiving atropine over the last 16 yr. This class has received favorable feedback from staff and students of medicine, pharmacy, and neuroscience, and we recommend it for such undergraduates. The learning objectives that students are expected to achieve are to be able to 1) know the ethical, safety, and hygiene requirements for using human volunteers as subjects; 2) implement and explain a double-blind placebo-controlled trial; 3) design, agree, and execute a protocol for making (and accurately recording) precise reproducible measurements of pulse rate, pupil diameter, and salivary flow; 4) evaluate the importance of predose periods and measurement consistency to detect effects (including any reversibility) after an intervention; 5) experience direct cause-and-effect relationships integrating physiology with pharmacology in people; 6) calculate appropriate summary statistics to describe the data and determine the data's statistical significance; 7) recognize normal variability both within and between subjects in baseline physiological parameters and also recognize normal variability in response to pharmacological treatment; 8) infer the distribution and role of muscarinic receptors in the autonomic nervous system with respect to the heart, eye, and mouth; 9) identify and explain the clinical significance of differences in effect due to the route and formulation of atropine; 10) produce and deliver a concise oral presentation of

  12. Experimental and analytical study of active control of energy transmission through double walls using novel piezoelectric actuators

    NASA Astrophysics Data System (ADS)

    Gao, Jianxin; Cheng, Li

    2003-10-01

    Active noise control has recently been used to increase the sound transmission loss of double wall structures. Vibration energy transmission through a double-plates system is investigated experimentally and analytically in this paper. Novel high performance actuators which use two curved THUNDER actuators as active driving components are developed and mounted between the two plates to control the energy transmission in the double-plates system. The Rayleigh-Ritz method and eigenfunction expansion theorem are used to resolve arbitrary boundary conditions of plates, and the feedforward control strategy is employed in this paper. The time average power transmission between the source, actuators and receiver plate are discussed and utilized as a cost function to obtain optimal control. The optimal control voltages for actuators are obtained by minimizing the cost function. A double-plates system connected by four actuators is set up experimentally in order to verify the models and formulations by comparing with analytical results. The analytical and experimental data show that the new actuator exhibits excellent performance on active control of power transmission.

  13. Cooperativity between Al Sites Promotes Hydrogen Transfer and Carbon–Carbon Bond Formation upon Dimethyl Ether Activation on Alumina

    PubMed Central

    2015-01-01

    The methanol-to-olefin (MTO) process allows the conversion of methanol/dimethyl ether into olefins on acidic zeolites via the so-called hydrocarbon pool mechanism. However, the site and mechanism of formation of the first carbon–carbon bond are still a matter of debate. Here, we show that the Lewis acidic Al sites on the 110 facet of γ-Al2O3 can readily activate dimethyl ether to yield CH4, alkenes, and surface formate species according to spectroscopic studies combined with a computational approach. The carbon–carbon forming step as well as the formation of methane and surface formate involves a transient oxonium ion intermediate, generated by a hydrogen transfer between surface methoxy species and coordinated methanol on adjacent Al sites. These results indicate that extra framework Al centers in acidic zeolites, which are associated with alumina, can play a key role in the formation of the first carbon–carbon bond, the initiation step of the industrial MTO process. PMID:27162986

  14. Intermolecular disulfide bonds are not required for the expression of the dimeric state and functional activity of the transferrin receptor.

    PubMed Central

    Alvarez, E; Gironès, N; Davis, R J

    1989-01-01

    The human transferrin receptor is expressed as a disulfide-linked dimer at the cell surface. The sites of intermolecular disulfide bonds are Cys-89 and Cys-98. We have examined the functional significance of the covalent dimeric structure of the transferrin receptor by substitution of Cys-89 and Cys-98 with serine residues. Wild-type and mutated transferrin receptors were expressed in Chinese hamster ovary cells (clone TF-) that lack detectable endogenous transferrin receptors. The rates of receptor endocytosis and recycling were measured and the accumulation of iron by cells incubated with [59Fe]diferric transferrin was investigated. No significant differences between these rates were observed when cells expressing wild-type and mutated receptors were compared. The structure of the mutant receptor lacking intermolecular disulfide bonds was investigated. The presence of a population of mutant receptors with a non-covalent dimeric structure was indicated by cross-linking studies using diferric [125I]transferrin and the bifunctional reagent disuccinimidyl suberimidate. However, sucrose density gradient sedimentation analysis of Triton X-100 solubilized transferrin receptors demonstrated that the mutant receptor existed as a monomer in the absence of diferric transferrin and as an apparent dimer in the presence of this receptor ligand. We conclude that the covalent dimeric structure of the transferrin receptor is not required for the expression of the dimeric state and functional activity of the receptor. Images PMID:2507316

  15. Formation of a Double-decker Magnetic Flux Rope in the Sigmoidal Solar Active Region 11520

    NASA Astrophysics Data System (ADS)

    Cheng, X.; Ding, M. D.; Zhang, J.; Sun, X. D.; Guo, Y.; Wang, Y. M.; Kliem, B.; Deng, Y. Y.

    2014-07-01

    In this paper, we address the formation of a magnetic flux rope (MFR) that erupted on 2012 July 12 and caused a strong geomagnetic storm event on July 15. Through analyzing the long-term evolution of the associated active region observed by the Atmospheric Imaging Assembly and the Helioseismic and Magnetic Imager on board the Solar Dynamics Observatory, it is found that the twisted field of an MFR, indicated by a continuous S-shaped sigmoid, is built up from two groups of sheared arcades near the main polarity inversion line a half day before the eruption. The temperature within the twisted field and sheared arcades is higher than that of the ambient volume, suggesting that magnetic reconnection most likely works there. The driver behind the reconnection is attributed to shearing and converging motions at magnetic footpoints with velocities in the range of 0.1-0.6 km s-1. The rotation of the preceding sunspot also contributes to the MFR buildup. Extrapolated three-dimensional non-linear force-free field structures further reveal the locations of the reconnection to be in a bald-patch region and in a hyperbolic flux tube. About 2 hr before the eruption, indications of a second MFR in the form of an S-shaped hot channel are seen. It lies above the original MFR that continuously exists and includes a filament. The whole structure thus makes up a stable double-decker MFR system for hours prior to the eruption. Eventually, after entering the domain of instability, the high-lying MFR impulsively erupts to generate a fast coronal mass ejection and X-class flare; while the low-lying MFR remains behind and continuously maintains the sigmoidicity of the active region.

  16. Formation of a double-decker magnetic flux rope in the sigmoidal solar active region 11520

    SciTech Connect

    Cheng, X.; Ding, M. D.; Zhang, J.; Guo, Y.; Sun, X. D.; Wang, Y. M.; Kliem, B.; Deng, Y. Y.

    2014-07-10

    In this paper, we address the formation of a magnetic flux rope (MFR) that erupted on 2012 July 12 and caused a strong geomagnetic storm event on July 15. Through analyzing the long-term evolution of the associated active region observed by the Atmospheric Imaging Assembly and the Helioseismic and Magnetic Imager on board the Solar Dynamics Observatory, it is found that the twisted field of an MFR, indicated by a continuous S-shaped sigmoid, is built up from two groups of sheared arcades near the main polarity inversion line a half day before the eruption. The temperature within the twisted field and sheared arcades is higher than that of the ambient volume, suggesting that magnetic reconnection most likely works there. The driver behind the reconnection is attributed to shearing and converging motions at magnetic footpoints with velocities in the range of 0.1-0.6 km s{sup –1}. The rotation of the preceding sunspot also contributes to the MFR buildup. Extrapolated three-dimensional non-linear force-free field structures further reveal the locations of the reconnection to be in a bald-patch region and in a hyperbolic flux tube. About 2 hr before the eruption, indications of a second MFR in the form of an S-shaped hot channel are seen. It lies above the original MFR that continuously exists and includes a filament. The whole structure thus makes up a stable double-decker MFR system for hours prior to the eruption. Eventually, after entering the domain of instability, the high-lying MFR impulsively erupts to generate a fast coronal mass ejection and X-class flare; while the low-lying MFR remains behind and continuously maintains the sigmoidicity of the active region.

  17. A mechanism for weak double layers and coherent low-frequency electrostatic wave activity in the solar wind

    NASA Astrophysics Data System (ADS)

    Singh Lakhina, Gurbax; Singh, Satyavir

    2016-07-01

    A mechanism for the weak double layers and coherent low-frequency electrostatic wave activity observed by Wind spacecraft in the solar wind at 1 AU is proposed in terms of ion-acoustic solitons and double layers. The solar wind plasma is modelled by a three component plasma consisting of fluid hot protons, hot alpha particles streaming with respect to protons, and suprathermal electrons having κ- distribution. This system supports two types of, slow and fast, ion-acoustic solitary waves. The fast ion-acoustic mode is similar to the ion-acoustic mode of proton-electron plasma, and can support only positive potential solitons. The slow ion-acoustic mode is a new mode that occurs due to the presence of alpha particles. This mode can support both positive and negative solitons and double layers. An increase of the κ- index leads to an increase in the critical Mach number, maximum Mach number and the maximum amplitude of both slow and fast ion-acoustic solitons. The slow ion-acoustic double layer can explain the amplitudes and widths, but not shapes, of the weak double layers (WDLs) observed in the solar wind at 1 AU by Wind spacecraft. The Fourier transform of the slow ion-acoustic solitons/double layers would produce broadband low-frequency electrostatic waves having main peaks between 0.35 kHz to 1.6 kHz, with electric field in the range of E = (0.01 - 0.7 ) mV/m, in excellent agreement with the observed low-frequency electrostatic wave activity in the solar wind at 1 AU.

  18. An admittance function of active piezoelectric elements bonded on a cracked beam

    NASA Astrophysics Data System (ADS)

    Kuang, You-Di; Li, Guo-Qing; Chen, Chuan-Yao

    2006-11-01

    The electric admittance function of the piezoelectric patches bonded on a beam with an open crack is presented, for the purpose of theoretically evaluating the health conditions of the cracked beam. At first, a sandwich beam with two layers of piezoelectric actuators is regarded as a piezoelectric bimorph, and the dynamics of the bimorph is represented by a 5×5 piezoelectric impedance matrix. Secondly, the dynamics of the elastic beam is also represented by a 4×4 impedance matrix, which is a degenerative form of piezoelectric impedance. Thirdly, the open crack is modeled as rotational massless spring and an expression of the equivalent stiffness is adopted, then the spring is used to connect the adjacent elastic beam segments. Furthermore, the cracked beam is represented by three elastic beam segments and one piezoelectric bimorph segment together with one spring. The admittance function of the piezoelectric elements is obtained by solving the linear impedance equations considering the mechanical-electric boundary conditions and the continuum conditions between the beam segments and the spring. Lastly, the effects of the crack depth and location on the admittance are examined in two numeric examples. It is found that the frequency changes and the admittance amplitude changes of the beam due to the crack can be predicted by the piezoelectric admittance function, and the modal frequencies calculated by the proposed method are accord with the results obtained by experiments and other methods. The possible application of the admittance function to detect the crack on the beam is discussed at the end of the paper as well.

  19. Effects of Peptide Backbone Amide-to-Ester Bond Substitution on the Cleavage Frequency in Electron Capture Dissociation and Collision-Activated Dissociation

    NASA Astrophysics Data System (ADS)

    Kjeldsen, Frank; Zubarev, Roman A.

    2011-08-01

    Probing the mechanism of electron capture dissociation on variously modified model peptide polycations has resulted in discovering many ways to prevent or reduce {{N}} - {{{C}}_α } bond fragmentation. Here we report on a rare finding of how to increase the backbone bond dissociation rate. In a number of model peptides, amide-to-ester backbone bond substitution increased the frequency of {{O}} - {{{C}}_α } bond cleavage (an analogue of {{N}} - {{{C}}_α } bonds in normal peptides) by several times, at the expense of reduced frequency of cleavages of the neighboring {{N}} - {{{C}}_α } bonds. In contrast, the ester linkage was only marginally broken in collisional dissociation. These results further highlight the complementarity of the reaction mechanisms in electron capture dissociation (ECD) and collision-activated dissociation (CAD). It is proposed that the effects of amide-to-ester bond substitution on fragmentation are mainly due to the differences in product ion stability (ECD, CAD) as well as proton affinity (CAD). This proposal is substantiated by calculations using density functional theory. The implications of these results in relation to the current understanding of the mechanisms of electron capture dissociation and electron transfer dissociation are discussed.

  20. Multiple bonds between transition metals and main-group elements. 73. Synthetic routes to rhenium(V) alkyl and rhenium(VII) alkylidyne complexes. X-ray crystal structures of (. eta. sup 5 -C sub 5 Me sub 5 )Re( double bond O)(CH sub 3 )(CH sub 2 C(CH sub 3 ) sub 3 ) and (. eta. sup 5 -C sub 5 Me sub 5 )(Br) sub 3 Re triple bond CC(CH sub 3 ) sub 3

    SciTech Connect

    Herrmann, W.A.; Felixberger, J.K.; Anwander, R.; Herdtweck, E.; Kiprof, P.; Riede, J. )

    1990-05-01

    Dialkyloxo({eta}{sup 5}pentamethylcyclopentadienyl)rhenium(V) complexes ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(CH{sub 3})R{prime}(R{prime} = C{sub 2}H{sub 5}, CH{sub 2}Si(CH{sub 3}){sub 3}, CH{sub 2}C(CH{sub 3}){sub 3}), 1c-e, have become accessible through alkylation of ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(Cl)(CH{sub 3}) (7) with R{prime}MgCl. 1c-e are the first rhenium complexes containing different alkyl ligands. The neopentyl derivative 1e (R{prime} = CH{sub 2}C(CH{sub 3}){sub 3}) crystallizes in the orthorhombic space group Pbca with a = 960.7 (2), b = 2.844.5 (4), c = 1,260.7 (2) pm, and Z = 8. The X-ray crystal structure was refined to R{sub W} = 3.9%. The chiral molecule shows a distorted tetrahedral geometry around the rhenium center. The tribromide 3b has been structurally characterized. Brown crystals of 3b belong to space group P2{sub 1}/c with unit cell dimensions a = 1,311.5 (2), b = 723.0 (1), c = 1,901.6 (2) pm, {beta} = 92.68 (1){degree}, and Z = 4. The structure exhibits a four-legged piano stool geometry with no trans influence of the neopentylidyne ligand to the bromine atom.

  1. Xalpha-DVM investigation of double water molecule interactions with active sites of alpha- and beta-subunits of hemoglobin

    NASA Astrophysics Data System (ADS)

    Yuryeva, Elmira I.

    In this work, the results of Xalpha-discrete variation method calculations of the electronic structure and interatomic parameters of chemical bonding between iron (II) and oxygen molecule with and without extra electrons and protons in active site (AS) of alpha- and beta-subunits of oxyhemoglobin are presented. The Skulachev model of O2 molecule existing in respiration medium in the 2H2O form was used. The introduction of extra electrons does not change considerably the interaction of the iron atom with the O2 oxygen molecule, but strengthens the repulsion in the Fe bond N bonds. In this case, the estimated effective charge of the iron atom is +1.8/1.5e for AS of alpha-/beta-subunits of oxyhemoglobin, and the magnetic moment of iron atoms becomes zero. The deoxygenation effect of the AS of the alpha- and beta-subunits of oxyhemoglobin is due to the ability of extra protons to break down covalent attraction between the iron atom and the nearest oxygen atom and also to weakening of the repulsive component of the covalent Fe bond N interactions.

  2. Athermal fracture of covalent bonds

    SciTech Connect

    Gilman, J.J.

    1999-08-01

    Most fracture is athermal. Either because it occurs at low temperatures or because it occurs too fast for thermal activation to be effective. Thus it must be directly activated by applied stresses. This can occur via quantum tunneling when the chemical bonding of a solid resides in localized (covalent) bonds. Then applied stresses can cause the bonding electrons to become delocalized (anti-bonded) through quantum tunneling. That is, the bonds become broken. The process is related to the Zener tunneling process that is thought to be responsible for dielectric breakdown in semiconductors. Under a driving force, bonding electrons tunnel at constant energy from their bonding states into anti-bonding states through the forbidden gap in the bonding energy spectrum.

  3. Photo-deactivation pathways of a double H-bonded photochromic Schiff base investigated by combined theoretical calculations and experimental time-resolved studies.

    PubMed

    Randino, Carlos; Ziółek, Marcin; Gelabert, Ricard; Organero, Juan Angel; Gil, Michal; Moreno, Miquel; Lluch, José M; Douhal, Abderrazzak

    2011-09-01

    The photophysics of N,N'-bis(salicylidene)-p-phenylenediamine (BSP) is analyzed both theoretically and experimentally. The alternative intramolecular proton-transfer reactions lead to three different tautomers. We performed DFT and TDDFT calculations to analyze the topography of the reactions connecting the three tautomers. Deactivation paths through a Conical Intersection (CI) region are also analyzed to explain the low fluorescence quantum yield of the phototautomers. The complex molecular structure of BSP provides a large number of deactivation paths, almost all of them energetically available following the initial photoexcitation. Femtosecond (fs) time-resolved emission studies in solution and flash photolysis experiments (nano to millisecond regime) were performed to get detailed information on the time domain of the full photocycle. The picture that emerges by combining theoretical and experimental results shows a very fast (less than 100 fs) photoinduced single proton transfer process leading to a phototautomer where a single proton has moved. This species may deactivate through a low-energy CI leading in about 20 ps to a rotameric form in the ground state that has a lifetime of several tens of microseconds in solution. This process competes with another deactivation path taking place prior to the proton-transfer reaction which involves a low-energy CI leading to a rotamer of the enol structure. In the flash photolysis studies, the rotamer of the enol structure was directly identified by the positive transient absorption band in the 250-260 nm and its lifetime in n-hexane (10 ms) is almost 3 orders of magnitude longer than the lifetime of the photochrome (around 40 μs). Our findings do not exclude a double proton transfer reaction in the excited enol form to give a tautomer in less than 100 fs during the first (impulsive) phase of the reaction which reverts back to the photoproducts of the simple proton transfer in 1-3 ps.

  4. High performance flexible double-sided micro-supercapacitors with an organic gel electrolyte containing a redox-active additive.

    PubMed

    Kim, Doyeon; Lee, Geumbee; Kim, Daeil; Yun, Junyeong; Lee, Sang-Soo; Ha, Jeong Sook

    2016-08-25

    In this study, we report the fabrication of a high performance flexible micro-supercapacitor (MSC) with an organic gel electrolyte containing a redox-active additive, referred to as poly(methyl methacrylate)-propylene carbonate-lithium perchlorate-hydroquinone (PMMA-PC-LiClO4-HQ). Hexagonal MSCs fabricated on thin polyethylene terephthalate (PET) films had interdigitated electrodes made of spray-coated multi-walled carbon nanotubes (MWNTs) on Au. The addition of HQ as a redox-active additive enhanced not only the specific capacitance but also the energy density of the MSCs dramatically, which is approximately 35 times higher than that of MSCs without the HQ additive. In addition, both areal capacitance and areal energy density could be doubled by fabrication of double-sided MSCs, where two MSCs are connected in parallel. The double-sided MSCs exhibited stable electrochemical performance during repeated deformation by bending. By dry-transferring the double-sided MSCs based on PMMA-PC-LiClO4-HQ on a deformable polymer substrate, we fabricated a stretchable MSC array, which also retained its electrochemical performance during a uniaxial strain of 40%. Furthermore, a wearable energy storage bracelet made of such an MSC array could operate a μ-LED on the wrist. PMID:27511060

  5. Architecture engineering toward highly active palladium integrated titanium dioxide yolk-double-shell nanoreactor for catalytic applications

    NASA Astrophysics Data System (ADS)

    Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun

    2014-09-01

    Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd2+ ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus

  6. Modifications on the hydrogen bond network by mutations of Escherichia coli copper efflux oxidase affect the process of proton transfer to dioxygen leading to alterations of enzymatic activities

    SciTech Connect

    Kajikawa, Takao; Kataoka, Kunishige; Sakurai, Takeshi

    2012-05-25

    Highlights: Black-Right-Pointing-Pointer Proton transfer pathway to dioxygen in CueO was identified. Black-Right-Pointing-Pointer Glu506 is the key amino acid to transport proton. Black-Right-Pointing-Pointer The Ala mutation at Glu506 formed a compensatory proton transfer pathway. Black-Right-Pointing-Pointer The Ile mutation at Glu506 shut down the hydrogen bond network. -- Abstract: CueO has a branched hydrogen bond network leading from the exterior of the protein molecule to the trinuclear copper center. This network transports protons in the four-electron reduction of dioxygen. We replaced the acidic Glu506 and Asp507 residues with the charged and uncharged amino acid residues. Peculiar changes in the enzyme activity of the mutants relative to the native enzyme indicate that an acidic amino acid residue at position 506 is essential for effective proton transport. The Ala mutation resulted in the formation of a compensatory hydrogen bond network with one or two extra water molecules. On the other hand, the Ile mutation resulted in the complete shutdown of the hydrogen bond network leading to loss of enzymatic activities of CueO. In contrast, the hydrogen bond network without the proton transport function was constructed by the Gln mutation. These results exerted on the hydrogen bond network in CueO are discussed in comparison with proton transfers in cytochrome oxidase.

  7. A highly efficient ADH-coupled NADH-recycling system for the asymmetric bioreduction of carbon-carbon double bonds using enoate reductases.

    PubMed

    Tauber, Katharina; Hall, Melanie; Kroutil, Wolfgang; Fabian, Walter M F; Faber, Kurt; Glueck, Silvia M

    2011-06-01

    The asymmetric bioreduction of activated alkenes catalyzed by flavin-dependent enoate reductases from the OYE-family represents a powerful method for the production of optically active compounds. For its preparative-scale application, efficient and economic NADH-recycling is crucial. A novel enzyme-coupled NADH-recycling system is proposed based on the concurrent oxidation of a sacrificial sec-alcohol catalyzed by an alcohol dehydrogenase (ADH-A). Due to the highly favorable position of the equilibrium of ene-reduction versus alcohol-oxidation, the cosubstrate is only required in slight excess.

  8. APCAP - activated protein C in acute pancreatitis: a double-blind randomized human pilot trial

    PubMed Central

    2010-01-01

    Introduction Previous human studies have shown low activity of protein C (APC) in severe acute pancreatitis (SAP). This, together with the findings in animal models, suggests that activated protein C (APC) may protect against pancreatic injury and ameliorate the disease. We, therefore, evaluated its effect on multiple organ dysfunction (MOD) measured by the SOFA (Sequential Organ Failure Assessment) and on organ-failure-free days, and the safety of APC in SAP. Methods A prospective double blind randomized pilot study was use. The study occurred in one university hospital tertiary intensive care unit (ICU) with eight beds. The patients were chosen according to the following inclusion criteria: 1) Those admitted to the hospital < 96 h from the onset of pain, 2) Those who had a three-fold increase in serum amylase over normal upper range or/and in whom computed tomography (CT) verification of SAP was noted, 3) Those who had one or more organ dysfunction (OD), and 4) Those in whom less than 48 hours had passed since their first OD. Of a total of 215 adult patients with SAP screened between June 2003 and August 2007, 158 fulfilled the study inclusion criteria. After exclusions 32 patients were randomized to the study. The intervention consisted of APC (N = 16) administered intravenously for 96 hours with a dose of 24 μg/kg/hour or placebo (N = 16) with a similar infusion rate. The sample size for the study was calculated according to the primary end-point: the change in SOFA during study drug infusion (Days 0 and 5). Comparisons between the study groups were performed using patient-related changes and calculation of difference in means (DIM, 95% CIs) and regarding categorical variables with Fisher's exact test. For all comparisons P < 0.05 was considered significant. Results No serious bleeding was detected clinically or by CT scans in either group. No significant difference in SOFA score change between the APC and placebo groups was found (difference in means (DIM) +2

  9. Topological hydrogen-bond definition to characterize the structure and dynamics of liquid water.

    PubMed

    Henchman, Richard H; Irudayam, Sheeba Jem

    2010-12-23

    A definition that equates a hydrogen bond topologically with a local energy well in the potential energy surface is used to study the structure and dynamics of liquid water. We demonstrate the robustness of this hydrogen-bond definition versus the many other definitions which use fixed, arbitrary parameters, do not account for variable molecular environments, and cannot effectively resolve transition states. Our topology definition unambiguously shows that most water molecules are double acceptors but sizable proportions are single or triple acceptors. Almost all hydrogens are found to take part in hydrogen bonds. Broken hydrogen bonds only form when two molecules try to form two hydrogen bonds between them. The double acceptors have tetrahedral geometry, lower potential energy, entropy, and density, and slower dynamics. The single and triple acceptors have trigonal and trigonal bipyramidal geometry and when considered together have higher density, potential energy, and entropy, faster dynamics, and a tendency to cluster. These calculations use an extended theory for the entropy of liquid water that takes into account the variable number of hydrogen bonds. Hydrogen-bond switching is shown to depend explicitly on the variable number of hydrogen bonds accepted and the presence of interstitial water molecules. Transition state theory indicates that the switching of hydrogen bonds is a mildly activated process, requiring only a moderate distortion of hydrogen bonds. Three main types of switching events are observed depending on whether the donor and acceptor are already sharing a hydrogen bond. The switch may proceed with no intermediate or via a bifurcated-oxygen or cyclic dimer, both of which have a broken hydrogen bond and symmetric and asymmetric forms. Switching is found to be strongly coupled to whole-molecule vibration, particularly for the more mobile single and triple acceptors. Our analysis suggests that even though water is heterogeneous in terms of the

  10. Organo- and Organometallic-Catalytic Intramolecular [1,5]-Hydride Transfer/Cyclization Process through C(sp(3) )-H Bond Activation.

    PubMed

    Kwon, Su Jin; Kim, Dae Young

    2016-06-01

    The direct functionalization of C(sp(3) )-H bonds is one of the most synthetically powerful research areas in current organic synthesis. Organocatalytic C(sp(3) )-H bond activation reactions have recently been developed in addition to the traditional metal-catalyzed C(sp(3) )-H activation reactions. In this review, we aim to give a brief overview of organo- and organometallic internal redox cascade reactions with respect to the mechanism, the reactivity of hydrogen donors and acceptors, and the migration modes of hydrogen. PMID:27062480

  11. Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers.

    PubMed

    Kanavarioti, A; Rosenbach, M T

    1991-01-01

    Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles). PMID:11538282

  12. Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Rosenbach, M. T.

    1991-01-01

    Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

  13. Bridge-bonded formate: active intermediate or spectator species in formic acid oxidation on a Pt film electrode?

    PubMed

    Chen, Y-X; Heinen, M; Jusys, Z; Behm, R J

    2006-12-01

    We present and discuss the results of an in situ IR study on the mechanism and kinetics of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection (ATR) flow cell configuration under controlled mass transport conditions, which specifically aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction. Potentiodynamic measurements show a complex interplay between formation and desorption/oxidation of COad and formate species and the total Faradaic current. The notably faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in transient measurements at constant potential, but with different formic acid concentrations, reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction pathway. If being reactive intermediate at all, the contribution of formate adsorption/decomposition to the reaction current decreases with increasing formic acid concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast dynamic adsorption-desorption equilibrium with the electrolyte, and that formate desorption is much faster than its decomposition. The results corroborate the proposal of a triple pathway reaction mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway, as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an active intermediate.

  14. Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

    SciTech Connect

    Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.

    2008-01-30

    The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

  15. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding. Progress report, March 1, 1992--September 30, 1992

    SciTech Connect

    Lichtenberger, D.L.

    1992-11-01

    Purpose of this research program is to obtain experimental information on the different fundamental ways metals bond and activate organic molecules. Our approach has been to directly probe the electronic interactions between metals and molecules through a wide variety of ionization spectroscopies and other techniques, and to investigate the relationships with bonding modes, structures, and chemical behavior. During this period, we have (1) characterized the electronic features of diphosphines and monophosphines in their coordination to metals, (2) carried out theoretical and experimental investigations of the bonding capabilities of C{sub 60} to transition metals, (3) developed techniques for the imaging of single molecules on gold substrates that emphasizes the electronic backbonding from the metal to the molecule, (4) obtained the high resolution photoelectron spectrum of pure C{sub 70} in the gas phase, (5) compared the bonding of {eta}{sup 3}- acetylide ligands to the bonding of other small organic molecules with metals, and (6) reported the photoelectron spectra and bonding of {eta}{sup 3}-cyclopropenyl groups to metals.

  16. A Systematic Study of Structure and E-H Bond Activation Chemistry by Sterically Encumbered Germylene Complexes.

    PubMed

    Usher, Matthew; Protchenko, Andrey V; Rit, Arnab; Campos, Jesús; Kolychev, Eugene L; Tirfoin, Rémi; Aldridge, Simon

    2016-08-01

    A series of new germylene compounds has been synthesized offering systematic variation in the σ- and π-capabilities of the α-substituent and differing levels of reactivity towards E-H bond activation (E=H, B, C, N, Si, Ge). Chloride metathesis utilizing [(terphenyl)GeCl] proves to be an effective synthetic route to complexes of the type [(terphenyl)Ge(ERn )] (1-6: ERn =NHDipp, CH(SiMe3 )2 , P(SiMe3 )2 , Si(SiMe3 )3 or B(NDippCH)2 ; terphenyl=C6 H3 Mes2 -2,6=Ar(Mes) or C6 H3 Dipp2 -2,6=Ar(Dipp) ; Dipp=C6 H3 iPr2 -2,6, Mes=C6 H2 Me3 -2,4,6), while the related complex [{(Me3 Si)2 N}Ge{B(NDippCH)2 }] (8) can be accessed by an amide/boryl exchange route. Metrical parameters have been probed by X-ray crystallography, and are consistent with widening angles at the metal centre as more bulky and/or more electropositive substituents are employed. Thus, the widest germylene units (θ>110°) are found to be associated with strongly σ-donating boryl or silyl ancillary donors. HOMO-LUMO gaps for the new germylene complexes have been appraised by DFT calculations. The aryl(boryl)-germylene system [Ar(Mes) Ge{B(NDippCH)2 }] (6-Mes), which features a wide C-Ge-B angle (110.4(1)°) and (albeit relatively weak) ancillary π-acceptor capabilities, has the smallest HOMO-LUMO gap (119 kJ mol(-1) ). These features result in 6-Mes being remarkably reactive, undergoing facile intramolecular C-H activation involving one of the mesityl ortho-methyl groups. The related aryl(silyl)-germylene system, [Ar(Mes) Ge{Si(SiMe3 )3 }] (5-Mes) has a marginally wider HOMO-LUMO gap (134 kJ mol(-1) ), rendering it less labile towards decomposition, yet reactive enough to oxidatively cleave H2 and NH3 to give the corresponding dihydride and (amido)hydride. Mixed aryl/alkyl, aryl/amido and aryl/phosphido complexes are unreactive, but amido/boryl complex 8 is competent for the activation of E-H bonds (E=H, B, Si) to give hydrido, boryl and silyl products. The results of these reactivity studies

  17. A Systematic Study of Structure and E-H Bond Activation Chemistry by Sterically Encumbered Germylene Complexes.

    PubMed

    Usher, Matthew; Protchenko, Andrey V; Rit, Arnab; Campos, Jesús; Kolychev, Eugene L; Tirfoin, Rémi; Aldridge, Simon

    2016-08-01

    A series of new germylene compounds has been synthesized offering systematic variation in the σ- and π-capabilities of the α-substituent and differing levels of reactivity towards E-H bond activation (E=H, B, C, N, Si, Ge). Chloride metathesis utilizing [(terphenyl)GeCl] proves to be an effective synthetic route to complexes of the type [(terphenyl)Ge(ERn )] (1-6: ERn =NHDipp, CH(SiMe3 )2 , P(SiMe3 )2 , Si(SiMe3 )3 or B(NDippCH)2 ; terphenyl=C6 H3 Mes2 -2,6=Ar(Mes) or C6 H3 Dipp2 -2,6=Ar(Dipp) ; Dipp=C6 H3 iPr2 -2,6, Mes=C6 H2 Me3 -2,4,6), while the related complex [{(Me3 Si)2 N}Ge{B(NDippCH)2 }] (8) can be accessed by an amide/boryl exchange route. Metrical parameters have been probed by X-ray crystallography, and are consistent with widening angles at the metal centre as more bulky and/or more electropositive substituents are employed. Thus, the widest germylene units (θ>110°) are found to be associated with strongly σ-donating boryl or silyl ancillary donors. HOMO-LUMO gaps for the new germylene complexes have been appraised by DFT calculations. The aryl(boryl)-germylene system [Ar(Mes) Ge{B(NDippCH)2 }] (6-Mes), which features a wide C-Ge-B angle (110.4(1)°) and (albeit relatively weak) ancillary π-acceptor capabilities, has the smallest HOMO-LUMO gap (119 kJ mol(-1) ). These features result in 6-Mes being remarkably reactive, undergoing facile intramolecular C-H activation involving one of the mesityl ortho-methyl groups. The related aryl(silyl)-germylene system, [Ar(Mes) Ge{Si(SiMe3 )3 }] (5-Mes) has a marginally wider HOMO-LUMO gap (134 kJ mol(-1) ), rendering it less labile towards decomposition, yet reactive enough to oxidatively cleave H2 and NH3 to give the corresponding dihydride and (amido)hydride. Mixed aryl/alkyl, aryl/amido and aryl/phosphido complexes are unreactive, but amido/boryl complex 8 is competent for the activation of E-H bonds (E=H, B, Si) to give hydrido, boryl and silyl products. The results of these reactivity studies

  18. One-Pot Amide Bond Formation from Aldehydes and Amines via a Photoorganocatalytic Activation of Aldehydes.

    PubMed

    Papadopoulos, Giorgos N; Kokotos, Christoforos G

    2016-08-19

    A mild, one-pot, and environmentally friendly synthesis of amides from aldehydes and amines is described. Initially, a photoorganocatalytic reaction of aldehydes with di-isopropyl azodicarboxylate leads to an intermediate carbonyl imide, which can react with a variety of amines to afford the desired amides. The initial visible light-mediated activation of a variety of monosubstituted or disubstituted aldehydes is usually fast, occurring in a few hours. Following the photocatalytic reaction, addition of the primary amine at room temperature or the secondary amine at elevated temperatures leads to the corresponding amide from moderate to excellent yields without epimerization. This methodology was applied in the synthesis of Moclobemide, a drug against depression and social anxiety. PMID:27227271

  19. Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures

    NASA Astrophysics Data System (ADS)

    Christopher, Phillip; Xin, Hongliang; Marimuthu, Andiappan; Linic, Suljo

    2012-12-01

    The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝intensityn, with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

  20. Asymmetric Desymmetrization via Metal-Free C-F Bond Activation: Synthesis of 3,5-Diaryl-5-fluoromethyloxazolidin-2-ones with Quaternary Carbon Centers.

    PubMed

    Tanaka, Junki; Suzuki, Satoru; Tokunaga, Etsuko; Haufe, Günter; Shibata, Norio

    2016-08-01

    We disclose the first asymmetric activation of a non-activated aliphatic C-F bond in which a conceptually new desymmetrization of 1,3-difluorides by silicon-induced selective C-F bond scission is a key step. The combination of a cinchona alkaloid based chiral ammonium bifluoride catalyst and N,O-bis(trimethylsilyl)acetoamide (BSA) as the silicon reagent enabled the efficient catalytic cycle of asymmetric Csp3 -F bond cleavage under mild conditions with high enantioselectivities. The ortho effect of the aryl group at the prostereogenic center is remarkable. This concept was applied for the asymmetric synthesis of promising agrochemical compounds, 3,5-diaryl-5-fluoromethyloxazolidin-2-ones bearing a quaternary carbon center.

  1. Single-Tailed Lipidoids Enhance the Transfection Activity of Their Double-Tailed Counterparts.

    PubMed

    Wu, Yihang; Li, Linxian; Chen, Qing; Su, Yi; Levkin, Pavel A; Davidson, Gary

    2016-01-11

    Cationic lipid-like molecules (lipidoids) are widely used for in vitro and in vivo gene delivery. Nearly all lipidoids developed to date employ double-tail or multiple-tail structures for transfection. Single-tail lipidoids are seldom considered for transfection as they have low efficiency in gene delivery. So far, there is no detailed study on the contribution to transfection efficiency of single-tail lipidoids when combined with standard double-tail lipidoids. Here, we use combinatorial chemistry to synthesize 17 double-tail and 17 single-tail lipidoids using thiol-yne and thiol-ene click chemistry, respectively. HEK 293T cells were used to analyze transfection efficiency by fluorescence microscopy and calculated based on the percentage of cells transfected. The size and zeta potential of liposomes and lipoplexes were characterized by dynamic light scattering (DLS). Intracellular DNA delivery and trafficking was further examined using confocal microscopy. Our study shows that combining single with double-tail lipidoids increases uptake of lipoplexes, as well as cellular transfection efficiency.

  2. Active vibration reduction of a flexible structure bonded with optimised piezoelectric pairs using half and quarter chromosomes in genetic algorithms

    NASA Astrophysics Data System (ADS)

    Daraji, A. H.; Hale, J. M.

    2012-08-01

    The optimal placement of sensors and actuators in active vibration control is limited by the number of candidates in the search space. The search space of a small structure discretized to one hundred elements for optimising the location of ten actuators gives 1.73 × 1013 possible solutions, one of which is the global optimum. In this work, a new quarter and half chromosome technique based on symmetry is developed, by which the search space for optimisation of sensor/actuator locations in active vibration control of flexible structures may be greatly reduced. The technique is applied to the optimisation for eight and ten actuators located on a 500×500mm square plate, in which the search space is reduced by up to 99.99%. This technique helps for updating genetic algorithm program by updating natural frequencies and mode shapes in each generation to find the global optimal solution in a greatly reduced number of generations. An isotropic plate with piezoelectric sensor/actuator pairs bonded to its surface was investigated using the finite element method and Hamilton's principle based on first order shear deformation theory. The placement and feedback gain of ten and eight sensor/actuator pairs was optimised for a cantilever and clamped-clamped plate to attenuate the first six modes of vibration, using minimization of linear quadratic index as an objective function.

  3. Mechanistic insights into the C-H bond activation of hydrocarbons by chromium(IV) oxo and chromium(III) superoxo complexes.

    PubMed

    Cho, Kyung-Bin; Kang, Hyeona; Woo, Jaeyoung; Park, Young Jun; Seo, Mi Sook; Cho, Jaeheung; Nam, Wonwoo

    2014-01-01

    The mechanism of the C-H bond activation of hydrocarbons by a nonheme chromium(IV) oxo complex bearing an N-methylated tetraazamacrocyclic cyclam (TMC) ligand, [Cr(IV)(O)(TMC)(Cl)](+) (2), has been investigated experimentally and theoretically. In experimental studies, reaction rates of 2 with substrates having weak C-H bonds were found to depend on the concentration and bond dissociation energies of the substrates. A large kinetic isotope effect value of 60 was determined in the oxidation of dihydroanthracene (DHA) and deuterated DHA by 2. These results led us to propose that the C-H bond activation reaction occurs via a H-atom abstraction mechanism, in which H-atom abstraction of substrates by 2 is the rate-determining step. In addition, formation of a chromium(III) hydroxo complex, [Cr(III)(OH)(TMC)(Cl)](+) (3), was observed as a decomposed product of 2 in the C-H bond activation reaction. The Cr(III)OH product was characterized unambiguously with various spectroscopic methods and X-ray crystallography. Density functional theory (DFT) calculations support the experimental observations that the C-H bond activation by 2 does not occur via the conventional H-atom-abstraction/oxygen-rebound mechanism and that 3 is the product formed in this C-H bond activation reaction. DFT calculations also propose that 2 may have some Cr(III)O(•-) character. The oxidizing power of 2 was then compared with that of a chromium(III) superoxo complex bearing the identical TMC ligand, [Cr(III)(O2)(TMC)(Cl)](+) (1), in the C-H bond activation reaction. By performing reactions of 1 and 2 with substrates under identical conditions, we were able to demonstrate that the reactivity of 2 is slightly greater than that of 1. DFT calculations again support this experimental observation, showing that the rate-limiting barrier for the reaction with 2 is slightly lower than that of 1.

  4. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    NASA Astrophysics Data System (ADS)

    Yik, Edwin Shyn-Lo

    convergence to a single phase is expected and predictable from thermodynamics at a given temperature and sulfur chemical potential, metastability of two phases can exist. We demonstrate, through extensive characterization and kinetic evidence, such behaviors exist in Re, where structural disparities between its phases lead to kinetic hurdles that prevent interconversions between layered ReSx nanostructures and sulfur-covered Re metal clusters. Such features allowed, for the first time, direct comparisons of reaction rates at identical conditions on two disparate phases of the same transition metal identity. Rigorous assessments of kinetic and selectivity data indicated that more universal mechanistic features persist across all catalysts studied, suggesting that differences in their catalytic activity were the result of different densities of HDS sites, which appeared to correlate with their respective metal-sulfur bond energies. Kinetic responses and product distributions indicated that the consumption of thiophene proceeds by the formation of a partially-hydrogenated surface intermediate, which subsequently produces tetrahydrothiophene (THT) and butene/butane (C4) via primary routes on similar types of sites. These sites are formed from desorption of weakly-bound sulfur adatoms on sulfur-covered metal surfaces, which can occur when the heat of sulfur adsorption is sufficiently low at high sulfur coverage as a result of increased sulfur-sulfur repulsive interactions. Relative stabilities and differences in the molecularity of the respective transition states that form THT and C4 dictate product distributions. THT desulfurization to form C4 occurs via readsorption and subsequent dehydrogenation, evidenced by secondary rates that exhibited negative H2 dependences. These behaviors suggest that C-S bond activation occurs on a partially (un)saturated intermediate, analogous to behaviors observed in C-C bond scission reactions of linear and cycloalkanes on hydrogen-covered metal

  5. Structure-Based Insight into the Asymmetric Bioreduction of the C=C Double Bond of α,β-Unsaturated Nitroalkenes by Pentaerythritol Tetranitrate Reductase

    PubMed Central

    Toogood, Helen S.; Fryszkowska, Anna; Hare, Victoria; Fisher, Karl; Roujeinikova, Anna; Leys, David; Gardiner, John M.; Stephens, Gill M.; Scrutton, Nigel S.

    2009-01-01

    Biocatalytic reduction of α- or β-alkyl-β-arylnitroalkenes provides a convenient and efficient method to prepare chiral substituted nitroalkanes. Pentaerythritol tetranitrate reductase (PETN reductase) from Enterobacter cloacae st. PB2 catalyses the reduction of nitroolefins such as 1-nitrocyclohexene (1) with steady state and rapid reaction kinetics comparable to other old yellow enzyme homologues. Furthermore, it reduces 2-aryl-1-nitropropenes (4a-d) to their equivalent (S)-nitropropanes 9a-d. The enzyme shows a preference for the (Z)-isomer of substrates 4a-d, providing almost pure enantiomeric products 9a-d (ees up to > 99%) in quantitative yield, whereas the respective (E)-isomers are reduced with lower enantioselectivity (63-89% ee) and lower product yields. 1-Aryl-2-nitropropenes (5a, b) are also reduced efficiently, but the products (R)-10 have lower optical purities. The structure of the enzyme complex with 1-nitrocyclohexene (1) was determined by X-ray crystallography, revealing two substrate-binding modes, with only one compatible with hydride transfer. Models of nitropropenes 4 and 5 in the active site of PETN reductase predicted that the enantioselectivity of the reaction was dependent on the orientation of binding of the (E)- and (Z)-substrates. This work provides a structural basis for understanding the mechanism of asymmetric bioreduction of nitroalkenes by PETN reductase. PMID:20396603

  6. Propane σ-Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary C-H Bonds.

    PubMed

    Zhang, Feng; Pan, Li; Choi, Juhee; Mehar, Vikram; Diulus, John T; Asthagiri, Aravind; Weaver, Jason F

    2015-11-16

    Achieving selective C-H bond cleavage is critical for developing catalytic processes that transform small alkanes to value-added products. The present study clarifies the molecular-level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C-H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ-complexes preferentially adopt geometries on PdO(101) in which only primary C-H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H-Pd dative bond forms at each CH3 group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C-H bonds. PMID:26420576

  7. Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

    PubMed

    Meng, Guangrong; Szostak, Michal

    2016-06-15

    The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

  8. Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

    PubMed

    Meng, Guangrong; Szostak, Michal

    2016-06-15

    The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined (). PMID:26864384

  9. Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles.

    PubMed

    Elias, Joseph S; Risch, Marcel; Giordano, Livia; Mansour, Azzam N; Shao-Horn, Yang

    2014-12-10

    We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M(3+) and M(2+)) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M(3+) and M(2+) in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu(3+), as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu(3+) is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts. PMID:25406101

  10. Cerium-activated rare-earth orthophosphate and double-phosphate scintillators for x-and gamma-ray detection

    SciTech Connect

    Boatner, Lynn A; Keefer, Lara A; Farmer, James Matthew; Wisniewski, D.; Wojtowicz, A. J.

    2004-01-01

    When activated with an appropriate rare-earth ion (e.g., Ce or Nd), rare-earth orthophosphates of the form REPO4 (where RE = a rare-earth cation) and alkali rare-earth double phosphates of the form A{sub 3}RE(PO{sub 4}){sub 2} (where A = K, Rb, or Cs) are characterized by light yields and decay times that make these materials of interest for radiation-detection applications. Crystals of the compound Rb{sub 3}Lu(PO{sub 4}){sub 2} when activated with {approx}0.1 mol % Ce exhibit a light yield that is {approx}250% that of BGO with a decay time on the order of {approx}40 nsec. The cerium-activated rare-earth orthophosphate LuPO{sub 4}:Ce is also characterized by a high light yield and a relatively fast decay time of {approx}25 nsec. Additionally, the rare-earth orthophosphates are extremely chemically, physically, and thermally durable hosts that recover easily from radiation damage effects. The properties of the rare-earth orthophosphates and double phosphates that pertain to their use as X- and gamma-ray detectors are reviewed. This review includes information related to the use of Nd-doped LuPO{sub 4} as a scintillator with a sufficiently energetic, short-wavelength output ({lambda} = 90 nm) so that it can be used in conjunction with appropriately activated proportional counters. Information is presented on the details of the synthesis, structure, and luminescence properties of lanthanide double phosphates that, when activated with cerium, are efficient scintillators with output wavelengths that are sufficiently long to be well matched to the response of silicon photodiode detectors.

  11. Metal-free nitro-carbocyclization of activated alkenes: a direct approach to synthesize oxindoles by cascade C-N and C-C bond formation.

    PubMed

    Shen, Tao; Yuan, Yizhi; Jiao, Ning

    2014-01-18

    A novel and direct metal-free nitro-carbocyclization of activated alkenes leading to valuable nitro-containing oxindoles via cascade C-N and C-C bond formation has been developed. The mechanistic study indicates that the initial NO and NO2 radical addition and the following C-H functionalization processes are involved in this transformation.

  12. Catalytic C-H bond activation at nanoscale Lewis acidic aluminium fluorides: H/D exchange reactions at aromatic and aliphatic hydrocarbons.

    PubMed

    Prechtl, Martin H G; Teltewskoi, Michael; Dimitrov, Anton; Kemnitz, Erhard; Braun, Thomas

    2011-12-16

    Nanoscopic amorphous Lewis acidic aluminium fluorides, such as aluminium chlorofluoride (ACF) and high-surface aluminium fluoride (HS-AlF(3)), are capable of activating C-H bonds of aliphatic hydrocarbons. H/D exchange reactions are catalysed under mild conditions (40 °C).

  13. Energy-efficient green catalysis: supported gold nanoparticle-catalyzed aminolysis of esters with inert tertiary amines by C-O and C-N bond activations.

    PubMed

    Bao, Yong-Sheng; Baiyin, Menghe; Agula, Bao; Jia, Meilin; Zhaorigetu, Bao

    2014-07-18

    Catalyzed by supported gold nanoparticles, an aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of tertiary amides. Comparison studies indicated that the gold nanoparticles could perform energy-efficient green catalysis at room temperature, whereas Pd(OAc)2 could not.

  14. Implementation and Evaluation of Web-Based Learning Activities on Bonding and the Structure of Matter for 10-th Grade Chemistry

    NASA Astrophysics Data System (ADS)

    Frailich, Marcel

    This study deals with the development, implementation, and evaluation of web-based activities associated with the topic of chemical bonding , as taught in 10th grade chemistry. A website was developed entitled: "Chemistry and the Chemical Industry in the Service of Mankind", its URL is: http://stwww.weizmann.ac.il/g-chem/learnchem (Kesner, Frailich, & Hofstein, 2003). The main goal of this study was to assess the educational effectiveness of website activities dealing with the chemical bonding concept. These activities include visualization tools, as well as topics relevant to daily life and industrial applications. The study investigated the effectiveness of a web-based learning environment regarding the understanding of chemical bonding concepts, students' perceptions of the classroom learning environment, their attitudes regarding the relevance of learning chemistry to everyday life, and their interest in chemistry studies. As mentioned before, in the present study we focused on activities (from the website), all of which deal with chemical bonding concept. The following are the reasons for the decision to focus on this topic: (1) Chemical bonding is a key concept that is taught in 10th grade chemistry in high school. It provides the basis for many other chemistry topics that are taught later, and (2) Chemical bonding is a difficult for students using existing tools (e. g., static models in books, ball-and- stick models), which are insufficient to demonstrate the abstract nature phenomena associated with this topic. The four activities developed for this study are (1) models of the atomic structure, (2) metals -- structure and properties, (3) ionic substances in everyday life and in industry, and (4) molecular substances -- structure, properties, and uses. The study analyzed both quantitative and qualitative research. The quantitative tools of the study included: A Semantic Differential questionnaire and a Chemistry Classroom Web-Based Learning Environment

  15. Cyclometallation of arylimines and nitrogen-containing heterocycles via room-temperature C-H bond activation with arene ruthenium(II) acetate complexes.

    PubMed

    Li, Bin; Roisnel, Thierry; Darcel, Christophe; Dixneuf, Pierre H

    2012-08-28

    The reaction of [RuCl(2)(p-cymene)](2) with arylimines and 4 equiv. of KOAc in methanol at room temperature produces stable (N^C)-cyclometallated ruthenium(II) complexes via C-H bond activation/deprotonation. This method can be applied also to nitrogen-containing molecules: N-phenylpyrazole, 2-phenyl-2-oxazoline and benzo[h]quinoline. N-Phenyl-pyrazole, [RuCl(2)(p-cymene)](2) and diphenylacetylene directly lead to alkyne insertion into the metallacycle C-Ru bond. PMID:22890507

  16. The Effect of Artificial Aging on The Bond Strength of Heat-activated Acrylic Resin to Surface-treated Nickel-chromium-beryllium Alloy

    PubMed Central

    Al Jabbari, Youssef S.; Zinelis, Spiros; Al Taweel, Sara M.; Nagy, William W.

    2016-01-01

    Purpose The debonding load of heat-activated polymethylmethacrylate (PMMA) denture base resin material to a nickel-chromium-beryllium (Ni-Cr-Be) alloy conditioned by three different surface treatments and utilizing two different commercial bonding systems was investigated. Materials and Methods Denture resin (Lucitone-199) was bonded to Ni-Cr-Be alloy specimens treated with Metal Primer II, the Rocatec system with opaquer and the Rocatec system without opaquer. Denture base resin specimens bonded to non-treated sandblasted Ni-Cr-Be alloy were used as controls. Twenty samples for each treatment condition (80 specimens) were tested. The 80 specimens were divided into two categories, thermocycled and non-thermocycled, containing four groups of ten specimens each. The non-thermocycled specimens were tested after 48 hours’ storage in room temperature water. The thermocycled specimens were tested after 2,000 cycles in 4°C and 55°C water baths. The debonding load was calculated in Newtons (N), and collected data were subjected by non parametric test Kruskal-Wallis One Way Analysis of Variance on Ranks and Dunn’s post hoc test at the α = 0.05. Results The Metal Primer II and Rocatec system without opaquer groups produced significantly higher bond strengths (119.9 and 67.6 N), respectively, than did the sandblasted and Rocatec system with opaquer groups, where the bond strengths were 2.6 N and 0 N, respectively. The Metal Primer II was significantly different from all other groups (P<0.05). The bond strengths of all groups were significantly decreased (P<0.05) after thermocycling. Conclusions Although thermocycling had a detrimental effect on the debonding load of all surface treatments tested, the Metal Primer II system provided higher values among all bonding systems tested, before and after thermocycling. PMID:27335613

  17. Geometric and Electronic Structure of [{Cu(MeAN)}2(μ-η2:η2(O22−))]2+ with an Unusually Long O–O Bond: O–O Bond Weakening vs Activation for Reductive Cleavage

    PubMed Central

    Park, Ga Young; Qayyum, Munzarin F.; Woertink, Julia; Hodgson, Keith O.; Hedman, Britt; Narducci Sarjeant, Amy A.; Solomon, Edward I.; Karlin, Kenneth D.

    2012-01-01

    Certain side-on peroxo dicopper(II) species with particularly low υO–O (710–730 cm−1) have been found in equilibrium with their bis-μ-oxo dicopper(III) isomer. An issue is whether such side-on peroxo bridges are further activated for O–O cleavage. In a previous study (Liang, H.-C., et al., J. Am. Chem. Soc. 2002, 124, 4170–4171), we showed that oxygenation of the three-coordinate complex [CuI(MeAN)]+ (MeAN=N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) leads to a low-temperature stable [{CuII(MeAN)}2(μ-η2:η2-O22−)]2+ peroxo species with low υO–O (721 cm−1), as characterized by UV-Vis absorption and resonance Raman (rR) spectroscopies. Here, this complex has been crystallized as its SbF6− salt and an X-ray structure indicates the presence of an unusually long O–O bond (1.540(5) Å) consistent with the low υO–O. EXAFS and rR spectroscopic and reactivity studies indicate the exclusive formation of [{CuII(MeAN)}2(μ-η2:η2-O22−)]2+ without any bis-μ-oxo-dicopper(III) isomer present. This is the first structure of a side-on peroxo dicopper(II) species with a significantly long and weak O–O bond. DFT calculations show that the weak O–O bond results from strong σ donation from the MeAN ligand to Cu that is compensated by a decrease in the extent of peroxo to Cu charge transfer. Importantly, the weak O–O bond does not reflect an increase in backbonding into the σ* orbital of the peroxide. Thus, although the O–O bond is unusually weak, this structure is not further activated for reductive cleavage to form a reactive bis-μ-oxo-dicopper(III) species. These results highlight the necessity of understanding electronic structure changes associated with spectral changes for correlations to reactivity. PMID:22571744

  18. Oxidative Addition of Carbon–Carbon Bonds with a Redox-Active Bis(imino)pyridine Iron Complex

    PubMed Central

    Darmon, Jonathan M.; Stieber, S. Chantal E.; Sylvester, Kevin T.; Fernández, Ignacio; Lobkovsky, Emil; Semproni, Scott P.; Bill, Eckhard; Wieghardt, Karl; DeBeer, Serena; Chirik, Paul J.

    2013-01-01

    Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)Fe(N2)2 and [(MePDI)Fe(N2)]2(μ2-N2) (RPDI = 2,6-(2,6-R2—C6H3— N=CMe)2C5H3N; R = Me, iPr), resulted in oxidative addition of a C—C bond at ambient temperature to yield the corresponding iron biphenyl compounds, (RPDI)Fe-(biphenyl). The molecular structures of the resulting bis-(imino)pyridine iron metallacycles were established by X-ray diffraction and revealed idealized square pyramidal geometries. The electronic structures of the compounds were studied by Mössbauer spectroscopy, NMR spectroscopy, magnetochemistry, and X-ray absorption and X-ray emission spectroscopies. The experimental data, in combination with broken-symmetry density functional theory calculations, established spin crossover (low to intermediate spin) ferric compounds antiferromagnetically coupled to bis(imino)pyridine radical anions. Thus, the overall oxidation reaction involves cooperative electron loss from both the iron center and the redox-active bis(imino)pyridine ligand. PMID:23043331

  19. Supramolecular hydrogen-bonding patterns of co-crystals containing the active pharmaceutical ingredient (API) phloroglucinol and N-heterocycles.

    PubMed

    Cvetkovski, Aleksandar; Bertolasi, Valerio; Ferretti, Valeria

    2016-06-01

    The active pharmaceutical ingredient phloroglucinol (PHL) has been taken as an illustrative molecule to explore the intermolecular interactions which can be established with other molecular entities to build PHL pharmaceutical co-crystals. The crystal structures of five newly synthesized co-crystals are reported, where PHL is crystallized with N-heterocycles, namely 2-hydroxy-6-methylpyridine (1), 2,4-dimethyl-6-hydroxypyrimidine (2), 4-phenylpyridine (3), 2-hydroxypyridine (4) and 2,3,5,6-tetramethylpyrazine (5). The structural characteristics of these co-crystals, as far as the hydrogen-bonding networks and the crystalline architectures are concerned, are strongly dependent on the chemical features of the coformer molecules, as well as on their size and shape. A detailed analysis of the intermolecular interactions established in all the PHL co-crystals of known structures has allowed the recognition of some regularities in the packing modes that can be useful in the design of new supramolecular adducts forming predictable structural motifs.

  20. Supramolecular hydrogen-bonding patterns of co-crystals containing the active pharmaceutical ingredient (API) phloroglucinol and N-heterocycles.

    PubMed

    Cvetkovski, Aleksandar; Bertolasi, Valerio; Ferretti, Valeria

    2016-06-01

    The active pharmaceutical ingredient phloroglucinol (PHL) has been taken as an illustrative molecule to explore the intermolecular interactions which can be established with other molecular entities to build PHL pharmaceutical co-crystals. The crystal structures of five newly synthesized co-crystals are reported, where PHL is crystallized with N-heterocycles, namely 2-hydroxy-6-methylpyridine (1), 2,4-dimethyl-6-hydroxypyrimidine (2), 4-phenylpyridine (3), 2-hydroxypyridine (4) and 2,3,5,6-tetramethylpyrazine (5). The structural characteristics of these co-crystals, as far as the hydrogen-bonding networks and the crystalline architectures are concerned, are strongly dependent on the chemical features of the coformer molecules, as well as on their size and shape. A detailed analysis of the intermolecular interactions established in all the PHL co-crystals of known structures has allowed the recognition of some regularities in the packing modes that can be useful in the design of new supramolecular adducts forming predictable structural motifs. PMID:27240764

  1. Iridium-mediated Bond Activation and Water Oxidation as an Exemplary Case of CARISMA, A European Network for the Development of Catalytic Routines for Small Molecule Activation.

    PubMed

    Licini, Giulia; Albrecht, Martin

    2015-01-01

    CARISMA is a currently running COST Action that pools leading European experts in computational and experimental chemistry to foster synergies for developing new catalytic processes for the transformation of abundant small molecules such as water, carbon dioxide, or ammonia into high-value chemicals and energy-relevant products. CARISMA promotes new collaborations, exchange of knowledge and skills, frontier training to young as well as established researchers, and a platform for the advancement of theoretical and experimental research in an iterative process, comprised of expertise in various connate domains including synthesis, catalysis, spectroscopy, kinetics, and computational chemistry. These interactions stimulate the discovery of new and efficient catalytic processes, illustrated in the second part of this contribution with the collaborative development of powerful iridium-based complexes for bond activation and water oxidation catalysis.

  2. Density function theoretical study on the complex involved in Th atom-activated C–C bond in C2H6

    NASA Astrophysics Data System (ADS)

    Qing-Qing, Wang; Peng, Li; Tao, Gao; Hong-Yan, Wang; Bing-Yun, Ao

    2016-06-01

    Density functional theory (DFT) calculations are performed to investigate the reactivity of Th atom toward ethane C–C bond activation. A comprehensive description of the reaction mechanisms leading to two different reaction products is presented. We report a complete exploration of the potential energy surfaces by taking into consideration different spin states. In addition, the intermediate and transition states along the reaction paths are characterized. Total, partial, and overlap population density of state diagrams and analyses are also presented. Furthermore, the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function (ELF) and Mayer bond order. Infrared spectrum (IR) is obtained and further discussed based on the optimized geometries. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160, 21401173, and 11364023).

  3. Prevalence of Bimolecular Routes in the Activation of Diatomic Molecules with Strong Chemical Bonds (O2, NO, CO, N2) on Catalytic Surfaces.

    PubMed

    Hibbitts, David; Iglesia, Enrique

    2015-05-19

    Dissociation of the strong bonds in O2, NO, CO, and N2 often involves large activation barriers on low-index planes of metal particles used as catalysts. These kinetic hurdles reflect the noble nature of some metals (O2 activation on Au), the high coverages of co-reactants (O2 activation during CO oxidation on Pt), or the strength of the chemical bonds (NO on Pt, CO and N2 on Ru). High barriers for direct dissociations from density functional theory (DFT) have led to a consensus that "defects", consisting of low-coordination exposed atoms, are required to cleave such bonds, as calculated by theory and experiments for model surfaces at low coverages. Such sites, however, bind intermediates strongly, rendering them unreactive at the high coverages prevalent during catalysis. Such site requirements are also at odds with turnover rates that often depend weakly on cluster size or are actually higher on larger clusters, even though defects, such as corners and edges, are most abundant on small clusters. This Account illustrates how these apparent inconsistencies are resolved through activations of strong bonds assisted by co-adsorbates on crowded low-index surfaces. Catalytic oxidations occur on Au clusters at low temperatures in spite of large activation barriers for O2 dissociation on Au(111) surfaces, leading to proposals that O2 activation requires low-coordination Au atoms or Au-support interfaces. When H2O is present, however, O2 dissociation proceeds with low barriers on Au(111) because chemisorbed peroxides (*OOH* and *HOOH*) form and weaken O-O bonds before cleavage, thus allowing activation on low-index planes. DFT-derived O2 dissociation barriers are much lower on bare Pt surfaces, but such surfaces are nearly saturated with CO* during CO oxidation. A dearth of vacant sites causes O2* to react with CO* to form *OOCO* intermediates that undergo O-O cleavage. NO-H2 reactions occur on Pt clusters saturated with NO* and H*; direct NO* dissociation requires vacant

  4. Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation.

    PubMed

    Jia, Teng; Zhao, Chongyang; He, Ruoyu; Chen, Hui; Wang, Congyang

    2016-04-18

    Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step.

  5. Yttrium-Assisted C-H and C-C Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Jong Hyun; Yang, Dong-Sheng

    2016-06-01

    The reaction between Y atom and ethylene (CH2=CH2) was performed in a laser-ablation supersonic molecular beam source. Y(C2H2), Y(C2H4), and Y(C4H6) were observed by time-of-flight mass spectrometry and investigated with mass-analyzed threshold ionization (MATI) spectroscopy and theoretical calculations. Y(C2H2) is formed by hydrogen elimination, Y(C2H4) by simple association, and La(C4H6) by C-C bond coupling and dehydrogenation. Both Y(C2H2) and Y(C2H4) have a C2v triangular structure with a C=C double bond in Y(C2H2) and a C-C single bond in Y(C2H4). Y(C4H6) has a five-membered metallacyclic structure (Cs) with Y binding to the two terminal carbon atoms of butene, which is the exactly same as that of Y(C4H6) formed in the Y + 1-butene reaction. For all three complexes, ionization has a small effect on the metal-carbon bond lengths because the rejected electron has basically a Y 5s character. The adiabatic ionization energies are measured to be 45679(5) wn for Y(C2H2), 45603(5) wn for Y(C2H4) and 43475(5) wn for Y(C4H6). The metal-ligand stretching frequencies of the three complexes are also measured from the MATI spectra.

  6. Double-bed-type extraction needle packed with activated-carbon-based sorbents for very volatile organic compounds.

    PubMed

    Ueta, Ikuo; Samsudin, Emi Liana; Mizuguchi, Ayako; Takeuchi, Hayato; Shinki, Takumi; Kawakubo, Susumu; Saito, Yoshihiro

    2014-01-01

    A novel needle-type sample preparation device was developed for the determination of very volatile organic compounds (VVOCs) in gaseous samples by gas chromatography-mass spectrometry (GC-MS). Two types of activated-carbon-based sorbents, Carbopack X and a carbon molecular sieve (CMS), were investigated as the extraction medium. A double-bed-type extraction needle showed successful extraction and desorption performance for all investigated VVOCs, including acetaldehyde, isoprene, pentane, acetone, and ethanol. Sensitive and reliable determination of VVOCs was achieved by systematically optimizing several desorption conditions. In addition, the effects of sample humidity on the extraction and desorption of analytes were investigated with the needle-type extraction devices. Only the CMS packed extraction needle was adversely affected by sample humidity during the desorption process; on the other hand the double-bed-type extraction needle was unaffected by sample humidity. Finally, the developed double-bed-type extraction needle was successfully applied to the analysis of breath VVOCs of healthy subjects. PMID:24176747

  7. Organic chemistry: No double bond left behind

    NASA Astrophysics Data System (ADS)

    Sarlah, David

    2016-03-01

    Alkenyl halides are some of the most useful building blocks for synthesizing small organic molecules. A catalyst has now allowed their direct preparation from widely available alkenes using the cross-metathesis reaction. See Article p.459

  8. Rate of steroid double-bond reduction catalysed by the human steroid 5β-reductase (AKR1D1) is sensitive to steroid structure: implications for steroid metabolism and bile acid synthesis.

    PubMed

    Jin, Yi; Chen, Mo; Penning, Trevor M

    2014-08-15

    Human AKR1D1 (steroid 5β-reductase/aldo-keto reductase 1D1) catalyses the stereospecific reduction of double bonds in Δ4-3-oxosteroids, a unique reaction that introduces a 90° bend at the A/B ring fusion to yield 5β-dihydrosteroids. AKR1D1 is the only enzyme capable of steroid 5β-reduction in humans and plays critical physiological roles. In steroid hormone metabolism, AKR1D1 serves mainly to inactivate the major classes of steroid hormones. AKR1D1 also catalyses key steps of the biosynthetic pathway of bile acids, which regulate lipid emulsification and cholesterol homoeostasis. Interestingly, AKR1D1 displayed a 20-fold variation in the kcat values, with steroid hormone substrates (e.g. aldosterone, testosterone and cortisone) having significantly higher kcat values than steroids with longer side chains (e.g. 7α-hydroxycholestenone, a bile acid precursor). Transient kinetic analysis revealed striking variations up to two orders of magnitude in the rate of the chemistry step (kchem), which resulted in different rate determining steps for the fast and slow substrates. By contrast, similar Kd values were observed for representative fast and slow substrates, suggesting similar rates of release for different steroid products. The release of NADP+ was shown to control the overall turnover for fast substrates, but not for slow substrates. Despite having high kchem values with steroid hormones, the kinetic control of AKR1D1 is consistent with the enzyme catalysing the slowest step in the catabolic sequence of steroid hormone transformation in the liver. The inherent slowness of the conversion of the bile acid precursor by AKR1D1 is also indicative of a regulatory role in bile acid synthesis.

  9. UNUSUAL CENTRAL ENGINE ACTIVITY IN THE DOUBLE BURST GRB 110709B

    SciTech Connect

    Zhang Binbin; Burrows, David N.; Meszaros, Peter; Falcone, Abraham D.; Zhang Bing; Wang Xiangyu; Stratta, Giulia; D'Elia, Valerio; Frederiks, Dmitry; Golenetskii, Sergey; Cummings, Jay R.; Barthelmy, Scott D.; Gehrels, Neil; Norris, Jay P.

    2012-04-01

    The double burst, GRB 110709B, triggered the Swift/Burst Alert Telescope (BAT) twice at 21:32:39 UT and 21:43:45 UT, respectively, on 2011 July 9. This is the first time we observed a gamma-ray burst (GRB) with two BAT triggers. In this paper, we present simultaneous Swift and Konus-WIND observations of this unusual GRB and its afterglow. If the two events originated from the same physical progenitor, their different time-dependent spectral evolution suggests they must belong to different episodes of the central engine, which may be a magnetar-to-BH accretion system.

  10. Unusual Central Engine Activity in the Double Burst GRB 110709B

    NASA Technical Reports Server (NTRS)

    Zhang, Bin-Bin; Burrows, David N.; Zhang, Bing; Meszaros, Peter; Stratta, Giulia; D'Elia, Valerio; Frederiks, Dmitry; Golenetskii, S.; Cummings, Jay R.; Wang, Xiang-Yu; Falcone, Abraham D.; Barthelmy, Scott D.; Gehrels, Neil

    2011-01-01

    The double burst, GRB 110709B, triggered Swift/BAT twice at 21:32:39 UT and 21:43:45 UT, respectively, on 9 July 2011. This is the first time we observed a GRB with two BAT triggers. In this paper, we present simultaneous Swift and Konus-WIND observations of this unusual GRB and its afterglow. If the two events are from the same physical origin, their different time-dependent spectral evolution suggest they must belong to different episodes of the central engine, which may be a magnetar-to-BH accretion system.

  11. Immobilizing highly catalytically active Pt nanoparticles inside the pores of metal-organic framework: a double solvents approach.

    PubMed

    Aijaz, Arshad; Karkamkar, Abhi; Choi, Young Joon; Tsumori, Nobuko; Rönnebro, Ewa; Autrey, Tom; Shioyama, Hiroshi; Xu, Qiang

    2012-08-29

    Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework, MIL-101, without aggregation of Pt nanoparticles on the external surfaces of framework by using a "double solvents" method. TEM and electron tomographic measurements clearly demonstrated the uniform three-dimensional distribution of the ultrafine Pt NPs throughout the interior cavities of MIL-101. The resulting Pt@MIL-101 composites represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis, solid-phase ammonia borane thermal dehydrogenation, and gas-phase CO oxidation. PMID:22888976

  12. Active-Transient Liquid Phase (A-TLP) Bonding of Pure Aluminum Matrix Composite Reinforced with Short Alumina Fiber Using Al-12Si- xTi Foils as Active Interlayer

    NASA Astrophysics Data System (ADS)

    Zhang, Guifeng; Su, Wei; Suzumura, Akio

    2016-06-01

    To optimize both the interlayer composition design route and pressure for joining aluminum matrix composite reinforced with short alumina fiber (as-cast 30 vol pct Al2O3sf/Al), traditional transient liquid phase (TLP) bonding using Al-12Si and Cu interlayer and active-TLP (A-TLP) bonding using an active Ti-containing interlayer (Al-12Si- xTi, x = 0.1, 0.5, and 1 wt pct) under the same condition [883 K (610 °C) × 30 minutes × 1 or 0.015 MPa in flowing argon] were compared in terms of interfacial wettability, bond seam microstructure, shear strength, and fracture path. It was found that not only the Ti content but also the pressure are critical factors affecting interfacial wettability and bond seam microstructure. The improvement in wettability by adding Ti as an active element were confirmed by reduction of expulsion of liquid interlayer, elimination of interfacial gap, higher shear strength and favorable fracture path (partially through bond seam and the composite). Because of the incubation period for wetting, reducing the pressure after melting of the interlayer could further increase joint shear strength by thickening the remaining bond seam of solid-solution matrix and decreasing fraction of the in situ newly formed Al-Si-Ti IMC phase (short bar shape) within the bond seam. The maximum shear strength of 88.6 MPa (99 pct of the as-cast composite) was obtained by adding trace Ti content (0.5 Ti wt pct) addition and using low pressure (0.015 MPa). The results showed that suitable combination of Ti content and pressure pattern is required for improving both wettability and bond seam microstructure.

  13. GaInAsP/silicon-on-insulator hybrid laser with ring-resonator-type reflector fabricated by N2 plasma-activated bonding

    NASA Astrophysics Data System (ADS)

    Hayashi, Yusuke; Suzuki, Junichi; Inoue, Satoshi; Tanvir Hasan, Shovon Muhammad; Kuno, Yuki; Itoh, Kazuto; Amemiya, Tomohiro; Nishiyama, Nobuhiko; Arai, Shigehisa

    2016-08-01

    III-V/Si hybrid integration with direct bonding is an attractive method of realizing an electrophotonic convergence router with a small size and a low power consumption. Plasma-activated bonding (PAB) is an effective approach for reducing thermal stress during the bonding process because PAB achieves a high bonding strength with low-temperature annealing. This time, the fabrication of a GaInAsP/silicon-on-insulator (SOI) hybrid laser with Si ring-resonator-type reflectors was demonstrated by N2 PAB. By measuring the lasing spectra, we confirmed the reflective characteristics resulting from the cascaded Si ring resonators. We also investigated kink characteristics, which occur around the threshold current, of the current-light output (I-L) characteristics, and successfully approximated the kink characteristics by considering saturable absorption occurring at the III-V/Si taper tip. The taper structure was investigated in terms of a passive device as well as an active device, and a structure for eliminating saturable absorption was proposed.

  14. GaInAsP/silicon-on-insulator hybrid laser with ring-resonator-type reflector fabricated by N2 plasma-activated bonding

    NASA Astrophysics Data System (ADS)

    Hayashi, Yusuke; Suzuki, Junichi; Inoue, Satoshi; Tanvir Hasan, Shovon Muhammad; Kuno, Yuki; Itoh, Kazuto; Amemiya, Tomohiro; Nishiyama, Nobuhiko; Arai, Shigehisa

    2016-08-01

    III–V/Si hybrid integration with direct bonding is an attractive method of realizing an electrophotonic convergence router with a small size and a low power consumption. Plasma-activated bonding (PAB) is an effective approach for reducing thermal stress during the bonding process because PAB achieves a high bonding strength with low-temperature annealing. This time, the fabrication of a GaInAsP/silicon-on-insulator (SOI) hybrid laser with Si ring-resonator-type reflectors was demonstrated by N2 PAB. By measuring the lasing spectra, we confirmed the reflective characteristics resulting from the cascaded Si ring resonators. We also investigated kink characteristics, which occur around the threshold current, of the current–light output (I–L) characteristics, and successfully approximated the kink characteristics by considering saturable absorption occurring at the III–V/Si taper tip. The taper structure was investigated in terms of a passive device as well as an active device, and a structure for eliminating saturable absorption was proposed.

  15. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    NASA Astrophysics Data System (ADS)

    Yik, Edwin Shyn-Lo

    convergence to a single phase is expected and predictable from thermodynamics at a given temperature and sulfur chemical potential, metastability of two phases can exist. We demonstrate, through extensive characterization and kinetic evidence, such behaviors exist in Re, where structural disparities between its phases lead to kinetic hurdles that prevent interconversions between layered ReSx nanostructures and sulfur-covered Re metal clusters. Such features allowed, for the first time, direct comparisons of reaction rates at identical conditions on two disparate phases of the same transition metal identity. Rigorous assessments of kinetic and selectivity data indicated that more universal mechanistic features persist across all catalysts studied, suggesting that differences in their catalytic activity were the result of different densities of HDS sites, which appeared to correlate with their respective metal-sulfur bond energies. Kinetic responses and product distributions indicated that the consumption of thiophene proceeds by the formation of a partially-hydrogenated surface intermediate, which subsequently produces tetrahydrothiophene (THT) and butene/butane (C4) via primary routes on similar types of sites. These sites are formed from desorption of weakly-bound sulfur adatoms on sulfur-covered metal surfaces, which can occur when the heat of sulfur adsorption is sufficiently low at high sulfur coverage as a result of increased sulfur-sulfur repulsive interactions. Relative stabilities and differences in the molecularity of the respective transition states that form THT and C4 dictate product distributions. THT desulfurization to form C4 occurs via readsorption and subsequent dehydrogenation, evidenced by secondary rates that exhibited negative H2 dependences. These behaviors suggest that C-S bond activation occurs on a partially (un)saturated intermediate, analogous to behaviors observed in C-C bond scission reactions of linear and cycloalkanes on hydrogen-covered metal

  16. A double-stranded RNA unwinding activity introduces structural alterations by means of adenosine to inosine conversions in mammalian cells and Xenopus eggs.

    PubMed Central

    Wagner, R W; Smith, J E; Cooperman, B S; Nishikura, K

    1989-01-01

    Amphibian eggs and embryos as well as mammalian cells have been reported to contain an activity that unwinds double-stranded RNA. We have now found that adenosine residues have been modified in the RNA products of this unwinding activity. Although the modified RNA remains double-stranded, the modification causes the RNA to be susceptible to single-strand-specific RNase and to migrate as a retarded smear on a native polyacrylamide electrophoresis gel. The modification is specific for double-stranded RNA. At least 40% of the adenosine residues can be modified in vitro in a given random sequence RNA molecule. By using standard two-dimensional TLC and HPLC analyses, the modified base has been identified as inosine. Mismatched base-pairing between inosine and uridine appears to be responsible for the observed characteristics of the unwound RNA. The biological significance of this modifying activity and also of the modified double-stranded RNA is discussed. Images PMID:2704740

  17. Conjugation-Driven "Reverse Mars-van Krevelen"-Type Radical Mechanism for Low-Temperature C-O Bond Activation.

    PubMed

    Mironenko, Alexander V; Vlachos, Dionisios G

    2016-07-01

    C-O bond activation on monofunctional catalysts (metals, carbides, and oxides) is challenging due to activity constraints imposed by energy scaling relationships. Yet, contrary to predictions, recently discovered multifunctional metal/metal oxide catalysts (e.g., Rh/ReOx, Rh/MoOx, Ir/VOx) demonstrate unusually high C-O scission activity at moderate temperatures. Herein, we use extensive density functional theory calculations, first-principles microkinetic modeling, and electronic structure analysis to elucidate the metal/metal oxide synergy in the Ru/RuO2 catalyst, which enables up to 76% yield of the C-O scission product (2-methyl furan) in catalytic transfer hydrogenolysis of furfural at low temperatures. Our key mechanistic finding is a facile radical-mediated C-O bond activation on RuO2 oxygen vacancies, which directly leads to a weakly bound final product. This is the first time the radical reduction mechanism is reported in heterogeneous catalysis at temperatures <200 °C. We attribute the unique catalytic properties to the formation of a conjugation-stabilized furfuryl radical upon C-O bond scission, the strong hydroxyl affinity of oxygen vacancies due to the metallic character of RuO2, and the acid-base heterogeneity of the oxide surface. The conjugation-driven radical-assisted C-O bond scission applies to any catalytic surface that preserves the π-electron system of the reactant and leads to C-O selectivity enhancement, with notable examples including Cu, H-covered Pd, self-assembled monolayers on Pd, and oxygen-covered Mo2C. Furthermore, we reveal the cooperativity of active sites in multifunctional catalysts. The mechanism is fully consistent with kinetic studies and isotopic labeling experiments, and the insights gained might prove useful more broadly in overcoming activity constraints induced by energy scaling relationships.

  18. Conjugation-Driven "Reverse Mars-van Krevelen"-Type Radical Mechanism for Low-Temperature C-O Bond Activation.

    PubMed

    Mironenko, Alexander V; Vlachos, Dionisios G

    2016-07-01

    C-O bond activation on monofunctional catalysts (metals, carbides, and oxides) is challenging due to activity constraints imposed by energy scaling relationships. Yet, contrary to predictions, recently discovered multifunctional metal/metal oxide catalysts (e.g., Rh/ReOx, Rh/MoOx, Ir/VOx) demonstrate unusually high C-O scission activity at moderate temperatures. Herein, we use extensive density functional theory calculations, first-principles microkinetic modeling, and electronic structure analysis to elucidate the metal/metal oxide synergy in the Ru/RuO2 catalyst, which enables up to 76% yield of the C-O scission product (2-methyl furan) in catalytic transfer hydrogenolysis of furfural at low temperatures. Our key mechanistic finding is a facile radical-mediated C-O bond activation on RuO2 oxygen vacancies, which directly leads to a weakly bound final product. This is the first time the radical reduction mechanism is reported in heterogeneous catalysis at temperatures <200 °C. We attribute the unique catalytic properties to the formation of a conjugation-stabilized furfuryl radical upon C-O bond scission, the strong hydroxyl affinity of oxygen vacancies due to the metallic character of RuO2, and the acid-base heterogeneity of the oxide surface. The conjugation-driven radical-assisted C-O bond scission applies to any catalytic surface that preserves the π-electron system of the reactant and leads to C-O selectivity enhancement, with notable examples including Cu, H-covered Pd, self-assembled monolayers on Pd, and oxygen-covered Mo2C. Furthermore, we reveal the cooperativity of active sites in multifunctional catalysts. The mechanism is fully consistent with kinetic studies and isotopic labeling experiments, and the insights gained might prove useful more broadly in overcoming activity constraints induced by energy scaling relationships. PMID:27281043

  19. Double-stranded RNA-dependent RNase activity associated with human immunodeficiency virus type 1 reverse transcriptase.

    PubMed Central

    Ben-Artzi, H; Zeelon, E; Gorecki, M; Panet, A

    1992-01-01

    Early events in the retroviral replication cycle include the conversion of viral genomic RNA into linear double-stranded DNA. This process is mediated by the reverse transcriptase (RT), a multifunctional enzyme that possesses RNA-dependent DNA polymerase, DNA-dependent DNA polymerase, and RNase H activities. In the course of studies of a recombinant RT of human immunodeficiency virus type 1 (HIV-1), we observed an additional, unexpected activity of the enzyme. The purified RT catalyzes a specific cleavage in HIV-1 RNA hybridized to tRNALys, the primer for HIV-1 reverse transcription. The cleavage at the primer binding site (PBS) of HIV RNA is dependent on the double-stranded structure of the HIV RNA-tRNALys complex. This RNase activity appears to be distinct from the RNase H activity of HIV-1 RT, as the substrate specificity and the products of the two activities are different. Moreover, Escherichia coli RNase H and avian myeloblastosis virus RT are unable to cleave the HIV RNA-tRNALys complex. We refer to this unusual activity as RNase D. Two lines of evidence indicate that the specific RNase D activity is an integral part of recombinant HIV RT. The specific RNase D activity comigrates with the other RT activities, DNA polymerase, and RNase H upon filtration on a Superose 6 gel column or chromatography on a phosphocellulose column. Moreover, three recombinant HIV-1 RT preparations expressed and purified in different laboratories by various procedures exhibit RNase D activity. Sequence analysis indicated that RNase D activity cleaves the substrate HIV-1 RNA-tRNALys at two distinct sites within the PBS sequence 5'-UGGCGCCCGA decreases ACAG decreases GGAC-3'. The sequence specificity of RNase D activity suggests that it might be involved in two stages during the reverse transcription process: displacement of the PBS to enable copying of tRNALys sequences into plus-strand DNA or to facilitate the second template switch, which was postulated to occur at the PBS

  20. A Substrate-Assisted Mechanism of Nucleophile Activation in a Ser-His-Asp Containing C-C Bond Hydrolase

    SciTech Connect

    Ruzzini, Antonio C.; Bhowmik, Shiva; Ghosh, Subhangi; Yam, Katherine C.; Bolin, Jeffrey T.; Eltis, Lindsay D.

    2013-11-12

    The meta-cleavage product (MCP) hydrolases utilize a Ser–His–Asp triad to hydrolyze a carbon–carbon bond. Hydrolysis of the MCP substrate has been proposed to proceed via an enol-to-keto tautomerization followed by a nucleophilic mechanism of catalysis. Ketonization involves an intermediate, ESred, which possesses a remarkable bathochromically shifted absorption spectrum. We investigated the catalytic mechanism of the MCP hydrolases using DxnB2 from Sphingomonas wittichii RW1. Pre-steady-state kinetic and LC ESI/MS evaluation of the DxnB2-mediated hydrolysis of 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid to 2-hydroxy-2,4-pentadienoic acid and benzoate support a nucleophilic mechanism catalysis. In DxnB2, the rate of ESred decay and product formation showed a solvent kinetic isotope effect of 2.5, indicating that a proton transfer reaction, assigned here to substrate ketonization, limits the rate of acylation. For a series of substituted MCPs, this rate was linearly dependent on MCP pKa2nuc ~ 1). Structural characterization of DxnB2 S105A:MCP complexes revealed that the catalytic histidine is displaced upon substrate-binding. The results provide evidence for enzyme-catalyzed ketonization in which the catalytic His–Asp pair does not play an essential role. The data further suggest that ESred represents a dianionic intermediate that acts as a general base to activate the serine nucleophile. This substrate-assisted mechanism of nucleophilic catalysis distinguishes MCP hydrolases from other serine hydrolases.

  1. Distinguishing Bonds.

    PubMed

    Rahm, Martin; Hoffmann, Roald

    2016-03-23

    The energy change per electron in a chemical or physical transformation, ΔE/n, may be expressed as Δχ̅ + Δ(VNN + ω)/n, where Δχ̅ is the average electron binding energy, a generalized electronegativity, ΔVNN is the change in nuclear repulsions, and Δω is the change in multielectron interactions in the process considered. The last term can be obtained by the difference from experimental or theoretical estimates of the first terms. Previously obtained consequences of this energy partitioning are extended here to a different analysis of bonding in a great variety of diatomics, including more or less polar ones. Arguments are presented for associating the average change in electron binding energy with covalence, and the change in multielectron interactions with electron transfer, either to, out, or within a molecule. A new descriptor Q, essentially the scaled difference between the Δχ̅ and Δ(VNN + ω)/n terms, when plotted versus the bond energy, separates nicely a wide variety of bonding types, covalent, covalent but more correlated, polar and increasingly ionic, metallogenic, electrostatic, charge-shift bonds, and dispersion interactions. Also, Q itself shows a set of interesting relations with the correlation energy of a bond.

  2. Activation Energies for Dissociation of Double Strand Oligonucleotide Anions: Evidence for Watson–Crick Base Pairing in Vacuo

    PubMed Central

    Schnier, Paul D.; Klassen, John S.; Strittmatter, Eric F.; Williams*, Evan R.

    2005-01-01

    The dissociation kinetics of a series of complementary and noncomplementary DNA duplexes, (TGCA)23−, (CCGG)23−, (AATTAAT)23−, (CCGGCCG)23−, A7·T73−, A7·A73−, T7·T73−, and A7·C73− were investigated using blackbody infrared radiative dissociation in a Fourier transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Activation energies range from 1.2 to 1.7 eV, and preexponential factors range from 1013 to 1019 s−1. Dissociation of the duplexes results in cleavage of the noncovalent bonds and/or cleavage of covalent bonds leading to loss of a neutral nucleobase followed by backbone cleavage producing sequence-specific (a – base) and w ions. Four pieces of evidence are presented which indicate that Watson–Crick (WC) base pairing is preserved in complementary DNA duplexes in the gas phase: i. the activation energy for dissociation of the complementary dimer, A7·T73−, to the single strands is significantly higher than that for the related noncomplementary A7·A73− and T7·T73− dimers, indicating a stronger interaction between strands with a specific base sequence, ii. extensive loss of neutral adenine occurs for A7·A73− and A7·C73− but not for A7·T73− consistent with this process being shut down by WC hydrogen bonding, iii. a correlation is observed between the measured activation energy for dissociation to single strands and the dimerization enthalpy (−ΔHd) in solution, and iv. molecular dynamics carried out at 300 and 400 K indicate that WC base pairing is preserved for A7·T73− duplex, although the helical structure is essentially lost. In combination, these results provide strong evidence that WC base pairing can exist in the complete absence of solvent. PMID:16498487

  3. Halogen Bonding in Organic Synthesis and Organocatalysis.

    PubMed

    Bulfield, David; Huber, Stefan M

    2016-10-01

    Halogen bonding is a noncovalent interaction similar to hydrogen bonding, which is based on electrophilic halogen substituents. Hydrogen-bonding-based organocatalysis is a well-established strategy which has found numerous applications in recent years. In light of this, halogen bonding has recently been introduced as a key interaction for the design of activators or organocatalysts that is complementary to hydrogen bonding. This Concept features a discussion on the history and electronic origin of halogen bonding, summarizes all relevant examples of its application in organocatalysis, and provides an overview on the use of cationic or polyfluorinated halogen-bond donors in halide abstraction reactions or in the activation of neutral organic substrates.

  4. A Double WAP Domain-Containing Protein Es-DWD1 from Eriocheir sinensis Exhibits Antimicrobial and Proteinase Inhibitory Activities

    PubMed Central

    Guo, Xiao-Nv; Yu, Ai-Qing; Wu, Min-Hao; Tan, Shang-Jian; Zhu, You-Ting; Li, Wei-Wei; Wang, Qun

    2013-01-01

    Whey acidic proteins (WAP) belong to a large gene family of antibacterial peptides, which are critical in the host immune response against microbial invasion. The common feature of these proteins is a single WAP domain maintained by at least one four-disulfide core (4-DSC) structure rich in cysteine residues. In this study, a double WAP domain (DWD)-containing protein, Es-DWD1, was first cloned from the Chinese mitten crab (Eriocheirsinensis). The full-length Es-DWD1cDNA was 1193 bp, including a 411 bp open reading frame (ORF) encoding 136 amino acids with a signal peptide of 22 amino acids in the N-terminus. A comparison with other reported invertebrate and vertebrate sequences revealed the presence of WAP domains characteristic of WAP superfamilies. As determined by quantitative real-time RT-PCR, Es-DWD1 transcripts were ubiquitously expressed in all tissues, but it was up-regulated in hemocytes post-challenge with pathogen-associated molecular patterns (PAMPs). The mature recombinant Es-DWD1 (rEs-DWD1) protein exhibited different binding activities to bacteria and fungus. Moreover, rEs-DWD1 could exert agglutination activities against Bacillus subtilis and Pichiapastoris and demonstrated inhibitory activities against the growth of Staphylococcus aureus, Aeromonas hydrophila and P. pastoris. Furthermore, rEs-DWD1 showed a specific protease inhibitory activity in B. subtilis. Coating of rEs-DWD1 onto agarose beads enhanced encapsulation of the beads by crab hemocytes. Collectively, the results suggest that Es-DWD1 is a double WAP domain containing protein with antimicrobial and proteinase inhibitory activities, which play significant roles in the immunity of crustaceans. PMID:23967346

  5. Antihirsutism activity of Fennel (fruits of Foeniculum vulgare) extract. A double-blind placebo controlled study.

    PubMed

    Javidnia, K; Dastgheib, L; Mohammadi Samani, S; Nasiri, A

    2003-01-01

    Idiopathic hirsutism is defined as the occurrence of excessive male pattern hair growth in women who have a normal ovulatory menstrual cycle and normal levels of serum androgens. It may be a disorder of peripheral androgen metabolism. In this study we evaluated the clinical response of idiopathic hirsutism to topical Fennel extract. Fennel, Foeniculum vulgare, is a plant, which has been used as an estrogenic agent. The ethanolic extract of Fennel was obtained by using a soxhlete apparatus. In a double blind study, 38 patients were treated with creams containing 1%, 2% of Fennel extract and placebo. Hair diameter was measured and rate of growth was considered. The efficacy of treatment with the cream containing 2% Fennel is better than the cream containing 1% Fennel and these two were more potent than placebo. The mean values of hair diameter reduction was 7.8%, 18.3% and -0.5% for patients receiving the creams containing 1%, 2% and 0% (placebo) respectively.

  6. Isolating the effect of pore size distribution on electrochemical double-layer capacitance using activated fluid coke

    NASA Astrophysics Data System (ADS)

    Zuliani, Jocelyn E.; Tong, Shitang; Kirk, Donald W.; Jia, Charles Q.

    2015-12-01

    Electrochemical double-layer capacitors (EDLCs) use physical ion adsorption in the capacitive electrical double layer of high specific surface area (SSA) materials to store electrical energy. Previous work shows that the SSA-normalized capacitance increases when pore diameters are less than 1 nm. However, there still remains uncertainty about the charge storage mechanism since the enhanced SSA-normalized capacitance is not observed in all microporous materials. In previous studies, the total specific surface area and the chemical composition of the electrode materials were not controlled. The current work is the first reported study that systematically compares the performance of activated carbon prepared from the same raw material, with similar chemical composition and specific surface area, but different pore size distributions. Preparing samples with similar SSAs, but different pores sizes is not straightforward since increasing pore diameters results in decreasing the SSA. This study observes that the microporous activated carbon has a higher SSA-normalized capacitance, 14.1 μF cm-2, compared to the mesoporous material, 12.4 μF cm-2. However, this enhanced SSA-normalized capacitance is only observed above a threshold operating voltage. Therefore, it can be concluded that a minimum applied voltage is required to induce ion adsorption in these sub-nanometer micropores, which increases the capacitance.

  7. Retinoblastoma-binding protein 1 has an interdigitated double Tudor domain with DNA binding activity.

    PubMed

    Gong, Weibin; Wang, Jinfeng; Perrett, Sarah; Feng, Yingang

    2014-02-21

    Retinoblastoma-binding protein 1 (RBBP1) is a tumor and leukemia suppressor that binds both methylated histone tails and DNA. Our previous studies indicated that RBBP1 possesses a Tudor domain, which cannot bind histone marks. In order to clarify the function of the Tudor domain, the solution structure of the RBBP1 Tudor domain was determined by NMR and is presented here. Although the proteins are unrelated, the RBBP1 Tudor domain forms an interdigitated double Tudor structure similar to the Tudor domain of JMJD2A, which is an epigenetic mark reader. This indicates the functional diversity of Tudor domains. The RBBP1 Tudor domain structure has a significant area of positively charged surface, which reveals a capability of the RBBP1 Tudor domain to bind nucleic acids. NMR titration and isothermal titration calorimetry experiments indicate that the RBBP1 Tudor domain binds both double- and single-stranded DNA with an affinity of 10-100 μM; no apparent DNA sequence specificity was detected. The DNA binding mode and key interaction residues were analyzed in detail based on a model structure of the Tudor domain-dsDNA complex, built by HADDOCK docking using the NMR data. Electrostatic interactions mediate the binding of the Tudor domain with DNA, which is consistent with NMR experiments performed at high salt concentration. The DNA-binding residues are conserved in Tudor domains of the RBBP1 protein family, resulting in conservation of the DNA-binding function in the RBBP1 Tudor domains. Our results provide further insights into the structure and function of RBBP1.

  8. Double-stranded RNA-activated protein kinase regulates early innate immune responses during respiratory syncytial virus infection.

    PubMed

    Minor, Radiah A Corn; Limmon, Gino V; Miller-DeGraff, Laura; Dixon, Darlene; Andrews, Danica M K; Kaufman, Randal J; Imani, Farhad

    2010-04-01

    Respiratory syncytial virus (RSV) is the most common cause of childhood viral bronchiolitis and lung injury. Inflammatory responses significantly contribute to lung pathologies during RSV infections and bronchiolitis but the exact mechanisms have not been completely defined. The double-stranded RNA-activated protein kinase (PKR) functions to inhibit viral replication and participates in several signaling pathways associated with innate inflammatory immune responses. Using a functionally defective PKR (PKR(-/-)) mouse model, we investigated the role of this kinase in early events of RSV-induced inflammation. Our data showed that bronchoalveolar lavage (BAL) fluid from infected PKR(-/-) mice had significantly lower levels of several innate inflammatory cytokines and chemokines. Histological examinations revealed that there was less lung injury in infected PKR(-/-) mice as compared to the wild type. A genome-wide analysis showed that several early antiviral and immune regulatory genes were affected by PKR activation. These data suggest that PKR is a signaling molecule for immune responses during RSV infections.

  9. Determining water content in activated carbon for double-layer capacitor electrodes

    NASA Astrophysics Data System (ADS)

    Egashira, Minato; Izumi, Takuma; Yoshimoto, Nobuko; Morita, Masayuki

    2016-09-01

    Karl-Fisher titration is used to estimate water contents in activated carbon and the distribution of impurity-level water in an activated carbon-solvent system. Normalization of the water content of activated carbon is attempted using vacuum drying after immersion in water was controlled. Although vacuum drying at 473 K and 24 h can remove large amounts of water, a substantial amount of water remains in the activated carbon. The water release to propylene carbonate is less than that to acetonitrile. The degradation of capacitor cell capacitance for activated carbon with some amount of water differs according to the electrolyte solvent type: acetonitrile promotes greater degradation than propylene carbonate does.

  10. Theoretical study of optical activity of 1:1 hydrogen bond complexes of water with S-warfarin

    NASA Astrophysics Data System (ADS)

    Dadsetani, Mehrdad; Abdolmaleki, Ahmad; Zabardasti, Abedin

    2016-11-01

    The molecular interaction between S-warfarin (SW) and a single water molecule was investigated using the B3LYP method at 6-311 ++G(d,p) basis set. The vibrational spectra of the optimized complexes have been investigated for stabilization checking. Quantum theories of atoms in molecules, natural bond orbitals, molecular electrostatic potentials and energy decomposition analysis methods have been applied to analyze the intermolecular interactions. The intermolecular charge transfer in the most stable complex is in the opposite direction from those in the other complexes. The optical spectra and the hyperpolarizabilities of SW-water hydrogen bond complexes have been computed.

  11. Theoretical study of optical activity of 1:1 hydrogen bond complexes of water with S-warfarin.

    PubMed

    Dadsetani, Mehrdad; Abdolmaleki, Ahmad; Zabardasti, Abedin

    2016-11-01

    The molecular interaction between S-warfarin (SW) and a single water molecule was investigated using the B3LYP method at 6-311++G(d,p) basis set. The vibrational spectra of the optimized complexes have been investigated for stabilization checking. Quantum theories of atoms in molecules, natural bond orbitals, molecular electrostatic potentials and energy decomposition analysis methods have been applied to analyze the intermolecular interactions. The intermolecular charge transfer in the most stable complex is in the opposite direction from those in the other complexes. The optical spectra and the hyperpolarizabilities of SW-water hydrogen bond complexes have been computed. PMID:27294546

  12. Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

    PubMed Central

    Tian, Panpan; Feng, Chao; Loh, Teck-Peng

    2015-01-01

    Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present a RhIII-catalysed tandem C–H/C–F activation for the synthesis of (hetero)arylated monofluoroalkenes. The use of readily available gem-difluoroalkenes as electrophiles provides a highly efficient and operationally simple method for the introduction of α-fluoroalkenyl motifs onto (hetero)arenes under oxidant-free conditions. Furthermore, the employment of alcoholic solvent and the in-situ generated hydrogen fluoride are found to be beneficial in this transformation, indicating the possibility of the involvement of hydrogen bond activation mode with regards to the C–F bond cleavage step. PMID:26081837

  13. Comparison of the kinetics of S-S bond, secondary structure, and active site formation during refolding of reduced denatured hen egg white lysozyme.

    PubMed Central

    Roux, P.; Ruoppolo, M.; Chaffotte, A. F.; Goldberg, M. E.

    1999-01-01

    To investigate the role of some tertiary interactions, the disulfide bonds, in the early stages of refolding of hen lysozyme, we report the kinetics of reoxidation of denatured and reduced lysozyme under the same refolding conditions as those previously used to investigate the kinetics of regain of its circular dichroism (CD), fluorescence, and activity. At different stages of the refolding, the oxidation of the protein was blocked by alkylation of the free cysteines with iodoacetamide and the various oxidation states present in the samples were identified by electrospray-mass spectrometry. Thus, it was possible to monitor the appearance and/or disappearance of the species with 0 to 4 disulfide bonds. Using a simulation program, these kinetics were compared with those of regain of far-UV CD, fluorescence, and enzymatic activity and were discussed in terms of a refined model for the refolding of reduced hen egg white lysozyme. PMID:10631992

  14. Synthesis, structure, and C-H bond activation chemistry of ([eta][sup 6]-arene)Ru(H)[sub 2](SiMe[sub 3])[sub 2] complexes

    SciTech Connect

    Djurovich, P.I.; Carroll, P.J.; Berry, D.H. )

    1994-07-01

    The ([eta][sup 6]-arene)Ru(H)[sub 2](SiMe[sub 3])[sub 2] arene = C[sub 6]-Me[sub 6] (1a), p-cymene (1b), C[sub 6]H[sub 6] (1c) complexes have been prepared and characterized. The complexes activate both aromatic and aliphatic C-H bonds and catalyze H/D exchange in alkylsilanes upon thermolysis in benzene-d[sub 6]. A mechanism based on oxidative-addition/reductive-elimination steps which utilizes a Ru(II)-Ru(IV) cycle is proposed to account for the C-H bond activation and H/D exchange reactions. It is further proposed that H/D exchange into sites adjacent to silicon in alkylsilanes is due to the intermediacy of an [eta][sup 2]-silene complex generated by [beta]-hydrogen elimination from the silyl group. 19 refs., 1 fig.

  15. The Comparative Evaluation of Antibacterial Activity of Methacryloxydodecyl Pyridinium Bromide and Non-methacryloxydodecyl Pyridinium Bromide Dentin Bonding Systems Using Two Different Techniques: An In vitro Study

    PubMed Central

    Deshpande, Prashanth; Nainan, Mohan Thomas; Metta, Kiran Kumar; Shivanna, Vasundhara; Ravi, Ramkrishna; Prashanth, B R

    2014-01-01

    Background: Adhesive systems have enabled clinicians to preserve more tooth structure by changing cavity designs. However, because of the polymerization shrinkage adhesive systems are not capable of totally prohibiting the gap formation between the cavity and restorative material of composite resin leading to colonization of oral microorganisms from saliva. One possible solution for this serious problem is to use dental materials with antibacterial properties. So the development of such agents has initiated for successful restorations. Hence, the purpose of this study was to compare the antibacterial activities of two dentin bonding systems: Clearfil protect bond (CPB) and prime & bond NT using agar well technique and tooth cavity model. Materials and Methods: CPB and prime and bond NT (PBNT) were evaluated in this study using agar well technique and tooth cavity model. In the agar well technique, the materials were filled in the wells of Muller-Hinton agar plates inoculated with Streptococcus mutans NCTC 10449M and the diameter of inhibition zones produced around the materials were measured after 24 h of incubation. For the tooth cavity model test, 3 cavities (of diameter - 1 mm and depth - 2 mm) were prepared in the flat occlusal dentin of human extracted molar. After sterilization, the teeth were left in the culture of broth of S. mutans at 37°C for 72 h for allowing bacteria to invade the cavity for 72 h. The dentin bonding systems were applied separately to each of the two infected cavities, and the third cavity was not applied and used as control. After sealing the occlusal surfaces, the teeth were kept in sterile physiological saline at 37°C for 72 h. The standardized amounts of dentin chips (120 + 5 mg) were obtained from the cavity walls, and the numbers of bacteria recovered were determined. The results were analyzed using one-way ANOVA, Kruskal–Wallis and Mann–Whitney’s U-tests. Results: The primer of CPB and PBNT produced similar inhibition

  16. Molecular structure, Normal Coordinate Analysis, harmonic vibrational frequencies, Natural Bond Orbital, TD-DFT calculations and biological activity analysis of antioxidant drug 7-hydroxycoumarin

    NASA Astrophysics Data System (ADS)

    Sebastian, S.; Sylvestre, S.; Jayarajan, D.; Amalanathan, M.; Oudayakumar, K.; Gnanapoongothai, T.; Jayavarthanan, T.

    2013-01-01

    In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis of Umbelliferone also known as 7-hydroxycoumarin (7HC). The optimized geometric bond lengths and bond angles obtained by computation (monomer and dimmer) shows good agreement with experimental XRD data. Harmonic frequencies of 7HC were determined and analyzed by DFT utilizing 6-311+G(d,p) as basis set. The assignments of the vibrational spectra have been carried out with the help of Normal Coordinate Analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). The change in electron density (ED) in the σ* and π* antibonding orbitals and stabilization energies E(2) have been calculated by Natural Bond Orbital (NBO) analysis to give clear evidence of stabilization originating in the hyperconjugation of hydrogen-bonded interaction. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) complements with the experimental findings. The simulated spectra satisfactorily coincides with the experimental spectra. Microbial activity of studied compounds was tested against Staphylococcus aureus, Streptococcus pyogenes, Bacillus subtilis, Escherichia coli, Psuedomonas aeruginosa, Klebsiella pneumoniae, Proteus mirabilis, Shigella flexneri, Salmonella typhi and Enterococcus faecalis.

  17. Non-actively controlled double-inverted-pendulum-like dynamics can minimize center of mass acceleration during human quiet standing.

    PubMed

    Suzuki, Yasuyuki; Morimoto, Hiroki; Kiyono, Ken; Morasso, Pietro; Nomura, Taishin

    2015-08-01

    Multiple joint movements during human quiet standing exhibit characteristic inter-joint coordination, shortly referred to as reciprocal relationship, in which angular acceleration of the hip joint is linearly and negatively correlated with that of the ankle joint (antiphase coordination) and, moreover, acceleration of the center of mass (CoM) of the double-inverted-pendulum (DIP) model of the human body is close to zero constantly. A question considered in this study is whether the reciprocal relationship is established by active neural control of the posture, or rather it is a biomechanical consequence of non-actively controlled body dynamics. To answer this question, we consider a DIP model of quiet standing, and show that the reciprocal relationship always holds by Newton's second law applied to the DIP model with human anthropometric dimensions, regardless of passive and active joint torque patterns acting on the ankle and hip joints. We then show that characteristic frequencies included in experimental sway trajectories with the reciprocal relationship match with harmonics of the eigenfrequency of the stable antiphase eigenmode of the non-actively controlled DIP-like unstable body dynamics. The results suggest that non-actively controlled DIP-like mechanical dynamics is a major cause of the minimization of the CoM acceleration during quiet standing, which is consistent with a type of control strategy that allows switching off active neural control intermittently for suitable periods of time during quiet standing.

  18. Non-actively controlled double-inverted-pendulum-like dynamics can minimize center of mass acceleration during human quiet standing.

    PubMed

    Suzuki, Yasuyuki; Morimoto, Hiroki; Kiyono, Ken; Morasso, Pietro; Nomura, Taishin

    2015-08-01

    Multiple joint movements during human quiet standing exhibit characteristic inter-joint coordination, shortly referred to as reciprocal relationship, in which angular acceleration of the hip joint is linearly and negatively correlated with that of the ankle joint (antiphase coordination) and, moreover, acceleration of the center of mass (CoM) of the double-inverted-pendulum (DIP) model of the human body is close to zero constantly. A question considered in this study is whether the reciprocal relationship is established by active neural control of the posture, or rather it is a biomechanical consequence of non-actively controlled body dynamics. To answer this question, we consider a DIP model of quiet standing, and show that the reciprocal relationship always holds by Newton's second law applied to the DIP model with human anthropometric dimensions, regardless of passive and active joint torque patterns acting on the ankle and hip joints. We then show that characteristic frequencies included in experimental sway trajectories with the reciprocal relationship match with harmonics of the eigenfrequency of the stable antiphase eigenmode of the non-actively controlled DIP-like unstable body dynamics. The results suggest that non-actively controlled DIP-like mechanical dynamics is a major cause of the minimization of the CoM acceleration during quiet standing, which is consistent with a type of control strategy that allows switching off active neural control intermittently for suitable periods of time during quiet standing. PMID:26736538

  19. Iodine-catalyzed [Formula: see text] C-H bond activation by selenium dioxide: synthesis of diindolylmethanes and di(3-indolyl)selanides.

    PubMed

    Naidu, P Seetham; Majumder, Swarup; Bhuyan, Pulak J

    2015-11-01

    An efficient reaction protocol was developed for the synthesis of several diindolylmethane derivatives via the [Formula: see text] C-H bond activation of aryl methyl ketones by [Formula: see text] and indoles in the presence of catalytic amounts of [Formula: see text] at 80 [Formula: see text] using dioxane as solvent. Unexpectedly, an interesting class of di(3-indolyl)selenide compounds was isolated when the reaction was carried out at room temperature.

  20. Activation of C-F bonds in fluoroarenes by N-heterocyclic carbenes as an effective route to synthesize abnormal NHC complexes.

    PubMed

    Kim, Youngsuk; Lee, Eunsung

    2016-09-18

    IPr (1a) reacts with octafluorotoluene by an unexpected sequential substitution of fluorides in two separate rings. The resulting tetrasubstituted imidazolium salt was isolated and elaborated into Ag(i) and Au(i) complexes with a novel abnormal NHC ligand. Both IPr (1a) and IMes (1b) were also found to be moderately reactive by nucleophilic substitution of the aromatic C-F bond in a weakly-activated fluoroarene, 1-fluoro-4-trifluoromethylbenzene (5). PMID:27533338