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Sample records for alkyl side groups

  1. Probing the effects of the ester functional group, alkyl side chain length and anions on the bulk nanostructure of ionic liquids: a computational study.

    PubMed

    Fakhraee, Mostafa; Gholami, Mohammad Reza

    2016-04-14

    The effects of ester addition on nanostructural properties of biodegradable ILs composed of 1-alkoxycarbonyl-3-alkyl-imidazolium cations ([C1COOCnC1im](+), n = 1, 2, 4) combined with [Br](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) were explored by using the molecular dynamics (MD) simulations and quantum theory of atoms in molecules (QTAIM) analysis at 400 K. Various thermodynamic properties of these ILs were extensively computed in our earlier work (Ind. Eng. Chem. Res., 2015, 54, 11678-11700). Nano-scale segregation analysis demonstrates the formation of a small spherical island-like hydrocarbon within the continuous ionic domain for ILs with short alkyl side chain ([C1COOC1C1im]), and a sponge-like nanostructure for the compound with long alkyl side chain ([C1COOC4C1im]). Ester-functionalized ILs with ethyl side chain ([C1COOC2C1im]) are the turning point between two different morphologies. Non-polar channels were observed for [C1COOC4C1im] ILs composed of smaller anions such as [Br] and [NO3], whereas clustering organization was found for the other anions. Formation of the spherical micelle-like nanostructure was seen for lengthened cations. Finally, the incorporation of an ester group into the alkyl side chain of the cation leads to stronger segregation between charged and uncharged networks, which consequently increased the possibility of self-assembly and micelle formation. PMID:27001746

  2. Polyimides with pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1982-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  3. Polyimide characterization studies - Effect of pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1984-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  4. Combustion pathways of the alkylated heteroaromatics: bond dissociation enthalpies and alkyl group fragmentations

    SciTech Connect

    Hayes, C.J.; Hadad, C.M.

    2009-11-15

    The bond dissociation enthalpies (BDEs) of the alkyl groups of the alkyl-substituted heterocycles have been studied and compiled using DFT methodology, with the intent of modeling the larger heterocyclic functionalities found in coal. DFT results were calibrated against CBS-QB3 calculations, and qualitative trends were reproduced between these methods. Loss of hydrogen at the benzylic position provided the most favorable route to radical formation, for both the azabenzenes and five-membered heterocycles. The ethyl derivatives had lower BDE values than the methyl derivatives due to increased stabilization of the corresponding radicals. Calculated spin densities correlated well with bond dissociation enthalpies for these compounds, while geometric effects were minimal with respect to the heterocycles themselves. Temperature effects on the bond dissociation enthalpies were minor, ranging by about 5 kcal/mol from 298 to 2000 K; the free energies of reaction dropped significantly over the same range due to entropic effects. Monocyclic heteroaromatic rings were seen to replicate the chemistry of multicyclic heteroaromatic systems.

  5. Distance-Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups.

    PubMed

    Hwang, Jungwun; Li, Ping; Smith, Mark D; Shimizu, Ken D

    2016-07-01

    The stabilizing and destabilizing effects of alkyl groups on an aromatic stacking interaction were experimentally measured in solution. The size (Me, Et, iPr, and tBu) and position (meta and para) of the alkyl groups were varied in a molecular balance model system designed to measure the strength of an intramolecular aromatic interaction. Opposite stability trends were observed for alkyl substituents at different positions on the aromatic rings. At the closer meta-position, smaller groups were stabilizing and larger groups were destabilizing. Conversely, at the farther para-position, the larger alkyl groups were systematically more stabilizing with the bulky tBu group forming the strongest stabilizing interaction. X-ray crystal structures showed that the stabilizing interactions of the small meta-alkyl and large para-alkyl groups were due to their similar distances and van der Waals contact areas with the edge of opposing aromatic ring. PMID:27159670

  6. Comprehensive Study on the Impact of the Cation Alkyl Side Chain Length on the Solubility of Water in Ionic Liquids

    PubMed Central

    Kurnia, Kiki A.; Neves, Catarina M. S. S.; Freire, Mara G.; Santos, Luís M. N. B. F.; Coutinho, João A. P.

    2015-01-01

    A comprehensive study on the phase behaviour of two sets of ionic liquids (ILs) and their interactions with water is here presented through combining experimental and theoretical approaches. The impact of the alkyl side chain length and the cation symmetry on the water solubility in the asymmetric [CN-1C1im][NTf2] and symmetric [CN-1CN-1im][NTf2] series of ILs (N up to 22), from 288.15 K to 318.15 K and at atmospheric pressure, was studied. The experimental data reveal that the solubility of water in ILs with an asymmetric cation is higher than in those with the symmetric isomer. Several trend shifts on the water solubility as a function of the alkyl side chain length were identified, namely at [C6C1im][NTf2] for asymmetric ILs and at [C4C4im][NTf2] and [C7C7im][NTf2] for the symmetric ILs. To complement the experimental data and to further investigate the molecular-level mechanisms behind the dissolution process, Density Functional Theory calculations, using the Conductor-like Screening Model for Real Solvents (COSMO-RS) and the Electrostatic potential-derived CHelpG, were performed. The COSMO-RS model is able to qualitatively predict water solubility as function of temperature and alkyl chain lengths of both symmetric and asymmetric cations. Furthermore, the model is also capable to predict the somewhat higher water solubility in the asymmetric cation, as well as the trend shift as function of alkyl chain lengths experimentally observed. Both COSMO-RS and the electrostatic potential-derived CHelpG show that the interactions of water and the IL cation take place on the IL polar region, namely on the aromatic head and adjacent methylene groups what explains the differences in water solubility observed for cations with different chain lengths. Furthermore, the CHelpG calculations for the isolated cations in the gas phase indicates that the trend shift of water solubility as function of alkyl chain lengths and the difference of water solubility in symmetric may also

  7. Triazatriangulenium adlayers on Au(111): Superstructure as a function of alkyl side chain length

    NASA Astrophysics Data System (ADS)

    Lemke, Sonja; Ulrich, Sandra; Claußen, Frauke; Bloedorn, Andreas; Jung, Ulrich; Herges, Rainer; Magnussen, Olaf M.

    2015-02-01

    The structure of organic adlayers, formed by self-assembly of molecular platforms of triazatriangulenium ions on Au(111), was systematically studied by scanning tunneling microscopy as a function of the length of the lateral ligands for alkyl side chains from propyl to dodecyl. A series of hexagonally-ordered adlayers with spacings from 10.7 Å (propyl) to 13.6 Å (dodecyl) was found which are commensurate to the Au(111) substrate lattice, indicating localized bonding of the molecules to the metal.

  8. Helix-Coil Transition and Association Behavior of Water-Soluble Polypeptides Having Hydrophobic Alkyl Side Chains

    NASA Astrophysics Data System (ADS)

    Inomata, Katsuhiro; Takai, Tomokazu; Ohno, Noriyoshi; Yamaji, Yoshiaki; Yamada, Erina; Sugimoto, Hideki; Nakanishi, Eiji

    Water soluble polypeptide, poly[N 5-(2-hydroxyethyl) L-glutamine] (PHEG), was hydrophobiocally modified partially along the main chain by long alkyl groups -(CH2) n-1CH3 (Cn) as side chains. Association and viscoelastic behavior of solutions of these self-assembling polymers (PHEG-g-Cn, n = 12, 16 and 18) were investigated by means of steady-flow viscosity and linear dynamic viscoelasticity measurements. In the mixed solvent of water/ethylene glycol (EG), the main chain of PHEG-g-Cn changed its conformation from flexible random coil to rodlike α-helix with the increase in EG content of the solvent. When the solvent was pure water, existence of the associative alkyl chains induced a drastic increase in shear flow viscosity (η) than PHEG homopolymer, probably because of formation of self-assembled large aggregates via intermolecular association. When EG was used as solvent, η and the elastic storage modulus (G') of the solution revealed a unique concentration dependence, i.e., η and G' of PHEG-g-C18 solution at 20 wt% were smaller than those at 15 wt%. These viscoelastic behaviors may be described by the α-helical rodlike conformation of PHEG main chain, which is suitable to form an ordered anisotropic phase like lyotropic liquid crystal, with destruction of a physically crosslinked network structure.

  9. Layered structure and Xe sorption and diffusion properties of low-density liquid-crystalline polyesters with n-alkyl side chains

    NASA Astrophysics Data System (ADS)

    Yoshimizu, Hiroaki; Tsukahara, Mitsuhiro; Suzuki, Tomoyuki; Toida, Jiro; Ando, Aisuke; Watanabe, Junji; Tsujita, Yoshiharu

    2005-04-01

    Four low-density liquid-crystalline polyesters with n-alkyl side chains, B-C n ( n is a carbon number of n-alkyl group), were synthesized from the 1,4-di-( n-alkyl ester) of 1,2,4,5-benzenetetracarboxylic acid and 4,4'-biphenol, to clarify the effect of side chain length on higher ordered structure in the solid state and gas sorption and diffusion properties of these polyesters. All the B-C n ( n=6, 10, 14, 18) samples behaved as a thermotropic liquid crystal and formed a layered structure composed of alternating rigid aromatic main chain layers and flexible n-alkyl side chain layers. In the crystal phase, the distance between the rigid aromatic main chain layers, namely the layer spacing, linearly increased with n, indicating that the conformational feature of n-alkyl side chains was trans-rich. This finding was supported from the 13C NMR chemical shift values of methylene carbons in B-C14 and B-C18. Xe sorption of B-C n was restricted to the side chain layer, which is almost a liquid-like environment, and these sorption isotherms obeyed Henry's law. The density of side chain layers was estimated from experimental values of layer spacing and density, under some speculate assumptions, but that determined individually by 129Xe NMR spectroscopy was coincidence. The estimated density of side chain layers became higher with increasing n, as well as n-alkane liquid, and closed to that of the polyethylene in rubbery state. Xe solubility coefficient corrected with the estimated side chain layer's density decreased with increasing n. On the other hand, the diffusion coefficient of Xe in B-C n increased with n, and this was supported from the NMR spectral width of the 129Xe in B-C n. These results also indicate that the main chain layers of B-C n were very dense and could not sorb Xe.

  10. Side chain variations radically alter the diffusion of poly(2-alkyl-2-oxazoline) functionalised nanoparticles through a mucosal barrier.

    PubMed

    Mansfield, Edward D H; de la Rosa, Victor R; Kowalczyk, Radoslaw M; Grillo, Isabelle; Hoogenboom, Richard; Sillence, Katy; Hole, Patrick; Williams, Adrian C; Khutoryanskiy, Vitaliy V

    2016-08-16

    Functionalised nanomaterials are gaining popularity for use as drug delivery vehicles and, in particular, mucus penetrating nanoparticles may improve drug bioavailability via the oral route. To date, few polymers have been investigated for their muco-penetration, and the effects of systematic structural changes to polymer architectures on the penetration and diffusion of functionalised nanomaterials through mucosal tissue have not been reported. We investigated the influence of poly(2-oxazoline) alkyl side chain length on nanoparticle diffusion; poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), and poly(2-n-propyl-2-oxazoline) were grafted onto the surface of thiolated silica nanoparticles and characterised by FT-IR, Raman and NMR spectroscopy, thermogravimetric analysis, and small angle neutron scattering. Diffusion coefficients were determined in water and in a mucin dispersion (using Nanoparticle Tracking Analysis), and penetration through a mucosal barrier was assessed using an ex vivo fluorescence technique. The addition of a single methylene group in the side chain significantly altered the penetration and diffusion of the materials in both mucin dispersions and mucosal tissue. Nanoparticles functionalised with poly(2-methyl-2-oxazoline) were significantly more diffusive than particles with poly(2-ethyl-2-oxazoline) while particles with poly(2-n-propyl-2-oxazoline) showed no significant increase compared to the unfunctionalised particles. These data show that variations in the polymer structure can radically alter their diffusive properties with clear implications for the future design of mucus penetrating systems. PMID:27400181

  11. Catalytic synthesis of n-alkyl arenes through alkyl group cross-metathesis.

    PubMed

    Dobereiner, Graham E; Yuan, Jian; Schrock, Richard R; Goldman, Alan S; Hackenberg, Jason D

    2013-08-28

    n-Alkyl arenes were prepared in a one-pot tandem dehydrogenation/olefin metathesis/hydrogenation sequence directly from alkanes and ethylbenzene. Excellent selectivity was observed when ((tBu)PCP)IrH2 was paired with tungsten monoaryloxide pyrrolide complexes such as W(NAr)(C3H6)(pyr)(OHIPT) (1a) [Ar = 2,6-i-Pr2C6H3; pyr = pyrrolide; OHIPT = 2,6-(2,4,6-i-Pr3C6H2)2C6H3O]. Complex 1a was also especially active in n-octane self-metathesis, providing the highest product concentrations reported to date. The thermal stability of selected olefin metathesis catalysts allowed elevated temperatures and extended reaction times to be employed. PMID:23909821

  12. High-performance polymer semiconducting heterostructure devices by nitrene-mediated photocrosslinking of alkyl side chains.

    PubMed

    Png, Rui-Qi; Chia, Perq-Jon; Tang, Jie-Cong; Liu, Bo; Sivaramakrishnan, Sankaran; Zhou, Mi; Khong, Siong-Hee; Chan, Hardy S O; Burroughes, Jeremy H; Chua, Lay-Lay; Friend, Richard H; Ho, Peter K H

    2010-02-01

    Heterostructures are central to the efficient manipulation of charge carriers, excitons and photons for high-performance semiconductor devices. Although these can be formed by stepwise evaporation of molecular semiconductors, they are a considerable challenge for polymers owing to re-dissolution of the underlying layers. Here we demonstrate a simple and versatile photocrosslinking methodology based on sterically hindered bis(fluorophenyl azide)s. The photocrosslinking efficiency is high and dominated by alkyl side-chain insertion reactions, which do not degrade semiconductor properties. We demonstrate two new back-infiltrated and contiguous interpenetrating donor-acceptor heterostructures for photovoltaic applications that inherently overcome internal recombination losses by ensuring path continuity to give high carrier-collection efficiency. This provides the appropriate morphology for high-efficiency polymer-based photovoltaics. We also demonstrate photopatternable polymer-based field-effect transistors and light-emitting diodes, and highly efficient separate-confinement-heterostructure light-emitting diodes. These results open the way to the general development of high-performance polymer semiconductor heterostructures that have not previously been thought possible. PMID:19966791

  13. Polymer containing pendant tertiary alkyl amine groups useful in enhanced oil recovery using

    SciTech Connect

    Irani, C.A.; Harris, T.V.; Pretzer, W.R.

    1990-08-07

    This patent describes an improvement in a method for recovering oil from an underground oil-bearing earth formation penetrated by an injection well and a producing well, in which method carbon dioxide is injected into the formation to displace oil towards the producing well from which oil is produced to the surface. It comprises: injecting into the formation carbon dioxide, the viscosity of which is increased at least three-fold by the presence of a sufficient amount of a polymer containing pendant tertiary alkyl amine groups and a sufficient amount of a cosolvent to form a solution of the polymer in the carbon dioxide, wherein the minimum solubility parameter of the polymer is reduced to 6.85 (cal/cc)1/2 or less by control of the number of pendant tertiary alkyl amine groups and by the selection of the tertiary alkyl amine groups.

  14. Synthesis and Photophysical Properties of Soluble Low-Bandgap Thienothiophene Polymers with Various Alkyl Side-Chain Lengths

    SciTech Connect

    Bae, W. J.; Scilla, C.; Duzhko, V. V.; Jo, Jang; Coughlin, E. B.

    2011-05-27

    We report the facile synthesis and characterization of a class of thienothiophene polymers with various lengths of alkyl side chains. A series of 2-alkylthieno[3,4-b]thiophene monomers (Ttx) have been synthesized in a two-step protocol in an overall yield of 28–37%. Poly(2-alkylthieno[3,4-b]thiophenes) (PTtx, alkyl: pentyl, hexyl, heptyl, octyl, and tridecyl) were synthesized by oxidative polymerization with FeCl₃ or via Grignard metathesis (GRIM) polymerization methods. The polymers are readily soluble in common organic solvents. The polymers synthesized by GRIM polymerization method (PTtx-G) have narrower molecular weight distribution (Ð) with lower molecular weight (Mn) than those synthesized by oxidative polymerization (PTtx-O). The band structures of the polymers with various lengths of alkyl side chains were investigated by UV–vis spectroscopy, cyclic voltammetry, and ultraviolet photoelectron spectroscopy. These low-bandgap polymers are good candidates for organic transistors, organic light-emitting diodes, and organic photovoltaic cells.

  15. Effect of alkyl side-chain length on the photophysical, morphology and photoresponse properties of poly(3-alkylthiophene)

    NASA Astrophysics Data System (ADS)

    Xu, Wei-Long; Yang, Xiao-Yu; Zheng, Fei; Jin, Han-Dong; Hao, Xiao-Tao

    2015-12-01

    The effect of alkyl side-chain length on the photophysical, morphology and photoresponse properties of poly (3-alkylthiophene) (P3AT) has been investigated. Butyl, hexyl, octyl, decyl, and dodecyl side chains have been studied. In solution state, the average lifetime of poly (3-octylthiophene) (P3OT) is the shortest among P3AT solution owing to the strong intrachain interaction. The fluorescence lifetime of P3AT solution increases with the side-chain length increasing. A similar trend occurs in the P3AT films. This phenomenon illustrates conformation ‘memory’ property evolving from solution state to solid film. The four lifetimes represent different photophysical processes and have been systematically analyzed. The photodetector based on P3DDT is a suitable candidate for practical application owing to the fast, reversible photoresponse and photostability. The high performance of P3DDT-based photodetector is correlated to the optimized morphology and strong interchain interaction which promotes the exciton delocalization.

  16. Antiallergic activity of rosmarinic acid esters is modulated by hydrophobicity, and bulkiness of alkyl side chain.

    PubMed

    Zhu, Fengxian; Xu, Zhongming; Yonekura, Lina; Yang, Ronghua; Tamura, Hirotoshi

    2015-01-01

    Methyl, propyl and hexyl esters of rosmarinic, caffeic and p-coumaric acids were tested for antiallergic activity, and rosmarinic acid propyl ester exhibited the greatest β-hexosaminidase release suppression (IC50, 23.7 μM). Quadratic correlations between pIC50 and cLogP (r(2) = 0.94, 0.98, and 1.00, respectively) were observed in each acid ester series. The antiallergic activity is modulated by hydrophobicity, and alkyl chain bulkiness. PMID:25686361

  17. Mesoporous organosilicas functionalized by alkyl groups: Synthesis, structure and adsorption properties

    NASA Astrophysics Data System (ADS)

    Barczak, M.; Dąbrowski, A.; Iwan, M.; Rzączyńska, Z.

    2009-01-01

    Mesoporous organosilicas were synthesized by sol-gel co-condensation of tetraethoxysilane and appropriate alkoxysilanes in the presence of Pluronic P123 surfactant. Hexyl, dodecyl, and octadecyl alkyl chains have been incorporated into mesopores by such co-condensation. Obtained materials were characterized by X-ray diffraction, FTIR spectroscopy, nitrogen adsorption measurements and thermogravimetry. Two resulted materials have highly ordered SBA-15 structure (p6m symmetry), other two are less ordered. All the materials exhibit well-developed porous structure (surface areas 500 to 830m2/g, pore volumes 0.65-1.32 cm3/g) and a high content of organic pendant groups introduced during co-condensation. All materials are thermally stable to 180°C, after that thermal decomposition of alkyl pendant groups starts.

  18. Liquid crystal alignment on ion-beam-treated polyimide with a long alkyl side chain: near edge X-ray absorption fine structure spectroscopy analysis.

    PubMed

    Seo, Joo-Hong; Hwang, Soo Won; Song, Dong Han; Shin, Jae Hoon; Yoon, Tae-Hoon; Kim, Jae Chang; Yi, Mi Hye

    2009-02-19

    Liquid crystal alignment on ion-beam-treated polyimides with a long alkyl side chain was investigated using near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The long alkyl side chains and the asymmetric distribution and orientational order of the pi-bonds of the polyimide surface can be determined by analyzing the angular dependent resonance intensities of the NEXAFS measurements. Herein, we demonstrate that the pretilt angle of the LC cell made by our method decreases as more long alkyl side chains are destroyed. Additionally, the tilt direction of the LC molecules can be determined from the asymmetric distribution of pi-bonds of the polyimide created by the ion beam irradiation. PMID:19161281

  19. Cholesterol Analogs with Degradation-resistant Alkyl Side Chains Are Effective Mycobacterium tuberculosis Growth Inhibitors.

    PubMed

    Frank, Daniel J; Zhao, Yan; Wong, Siew Hoon; Basudhar, Debashree; De Voss, James J; Ortiz de Montellano, Paul R

    2016-04-01

    Cholest-4-en-3-one, whether added exogenously or generated intracellularly from cholesterol, inhibits the growth ofMycobacterium tuberculosiswhen CYP125A1 and CYP142A1, the cytochrome P450 enzymes that initiate degradation of the sterol side chain, are disabled. Here we demonstrate that a 16-hydroxy derivative of cholesterol, which was previously reported to inhibit growth ofM. tuberculosis, acts by preventing the oxidation of the sterol side chain even in the presence of the relevant cytochrome P450 enzymes. The finding that (25R)-cholest-5-en-3β,16β,26-triol (1) (and its 3-keto metabolite) inhibit growth suggests that cholesterol analogs with non-degradable side chains represent a novel class of anti-mycobacterial agents. In accord with this, two cholesterol analogs with truncated, fluorinated side chains have been synthesized and shown to similarly block the growth in culture ofM. tuberculosis. PMID:26833565

  20. Solubility of n-butane and 2-methylpropane (isobutane) in 1-alkyl-3-methylimidazolium-based ionic liquids with linear and branched alkyl side-chains.

    PubMed

    Pison, Laure; Shimizu, Karina; Tamas, George; Lopes, José Nuno Canongia; Quitevis, Edward L; Gomes, Margarida F Costa

    2015-11-11

    The solubility of n-butane and 2-methylpropane (isobutane) in three ionic liquids - 1-(2-methylpropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [(2mC3)C1im][Ntf2], 1-(3-methylbutyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [(3mC4)C1im][Ntf2] and 1-methyl-3-pentylimidazolium bis(trifluoromethylsulfonyl)imide [C5C1im][Ntf2] - has been measured at atmospheric pressure from 303 to 343 K. Isobutane is less soluble than n-butane in all the ionic liquids. Henry's constant values range from 13.8 × 10(5) Pa for n-butane in [C5C1im][Ntf2] at 303 K to 64.5 × 10(5) Pa for isobutane in [(2mC3)C1im][Ntf2] at 343 K. The difference in solubility between the two gases can be explained by a more negative enthalpy of solvation for n-butane. A structural analysis of the pure solvents and of the solutions of the gases, probed by molecular dynamics simulations, could explain the differences found in the systems: (i) the nonpolar domains of the ionic liquids accommodate better the long and more flexible n-butane solute; (ii) the small differences in solubility of each gas in the ionic liquids with the same number of carbon atoms in the alkyl side-chains are explained by the absence of large structural differences in the pure solvents. In all cases, the structural analysis of the four ionic liquids confirms that the studied gases can act as probes of the molecular structure of the ionic liquids, the simulations being always compatible with the experimental solubility data. PMID:26506981

  1. Effect of alkyl chain length and hydroxyl group functionalization on the surface properties of imidazolium ionic liquids.

    PubMed

    Pensado, Alfonso S; Costa Gomes, Margarida F; Canongia Lopes, José N; Malfreyt, Patrice; Pádua, Agílio A H

    2011-08-14

    Properties of the surface of ionic liquids, such as surface tension, ordering, and charge and density profiles, were studied using molecular simulation. Two types of modification in the molecular structure of imidazolium cations were studied: the length of the alkyl side chain and the presence of a polar hydroxyl group at the end of the side chain. Four ionic liquids were considered: 1-ethyl-3-methylimidazolium tetrafluoroborate, [C(2)C(1)im][BF(4)]; 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate, [C(2)OHC(1)im][BF(4)]; 1-octyl-3-methylimidazolium tetrafluoroborate, [C(8)C(1)im][BF(4)] and 1-(8-hydroxyoctyl)-3-methylimidazolium tetrafluoroborate, [C(8)OHC(1)im][BF(4)]. The surface tension was calculated using both mechanical and thermodynamic definitions, with consistent treatment of the long-range corrections. The simulations reproduce the available experimental values of surface tension with a maximum deviation of ±10%. This energetic characterization of the interface is completed by microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface. The presence of the hydroxyl group modifies the local structure at the interface, leading to a less organized liquid phase. The results allow us to relate the surface tension to the structural ordering at the liquid-vacuum interface. PMID:21643581

  2. Side-chain-to-tail cyclization of ribosomally derived peptides promoted by aryl and alkyl amino-functionalized unnatural amino acids.

    PubMed

    Frost, John R; Wu, Zhijie; Lam, Yick Chong; Owens, Andrew E; Fasan, Rudi

    2016-06-28

    A strategy for the production of side-chain-to-tail cyclic peptides from ribosomally derived polypeptide precursors is reported. Two genetically encodable unnatural amino acids, bearing either an aryl or alkyl amino group, were investigated for their efficiency toward promoting the formation of medium to large-sized peptide macrocycles via intein-mediated side-chain-to-C-terminus cyclization. While only partial cyclization was observed with precursor proteins containing para-amino-phenylalanine, efficient peptide macrocyclization could be achieved using O-2-aminoethyl-tyrosine as the reactive moiety. Conveniently, the latter was generated upon quantitative, post-translational reduction of the azido-containing counterpart, O-2-azidoethyl-tyrosine, directly in E. coli cells. This methodology could be successfully applied for the production of a 12 mer cyclic peptide with enhanced binding affinity for the model target protein streptavidin as compared to the acyclic counterpart (KD: 5.1 μM vs. 22.4 μM), thus demonstrating its utility toward the creation and investigation of novel, functional macrocyclic peptides. PMID:27064594

  3. Influence of Alkoxy Groups on the Photoinduced Dynamics of Organic Molecules Exemplified on Alkyl Vinyl Ethers.

    PubMed

    Schalk, O; Stenrup, M; Geng, T; Lindh, R; Thomas, R D; Feifel, R; Hansson, T

    2015-11-12

    A series of different alkyl vinyl ethers is investigated to decipher the possible reaction channels upon photoexcitation to the π3s-Rydberg and the ππ*-valence state at 200 nm using time-resolved photoelectron spectroscopy and on-the-fly time-dependent density functional theory dynamics simulations. The results indicate two possible relaxation pathways: (1) a radiationless decay through the ππ*-state back to the ground state via torsion of the C═C double bond, in accordance with the dynamics found in ethylene; and (2) a fast dissociation of the C-O bond between the alkyl and the vinoxy group in the πσ*-state. The latter state can be accessed only after excitation to the π3s-Rydberg state (quantum yield of ∼50% according to the dynamics simulations). Additionally, the excited state barrier leading to formation of a vinyl radical was found to be too high to be crossed. These results indicate that the dynamics of ethers crucially depend on the excitation wavelength and that the πσ*-state constitutes an important competitive reaction channel that leads to dissociation of the molecules. PMID:26490385

  4. 25. SECOND FLOOR EAST SIDE APARTMENT KITCHEN INTERIOR SHOWING GROUP ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    25. SECOND FLOOR EAST SIDE APARTMENT KITCHEN INTERIOR SHOWING GROUP OF THREE 6-LIGHT WOOD-FRAME CASEMENT WINDOWS OVER THE SINK, AND OPEN DOORWAY TO TOP OF EXTERIOR STAIR LANDING AND WALKWAY AT REAR OF HOUSE. WALKWAY IS VISIBLE THROUGH KITCHEN WINDOWS. VIEW TO SOUTH. - Lee Vining Creek Hydroelectric System, Triplex Cottage, Lee Vining Creek, Lee Vining, Mono County, CA

  5. Potential long-acting anticonvulsants. 1; Synthesis and activity of succinimides containing an alkylating group at the 2 position.

    PubMed

    Kornet, M J; Crider, A M; Magarian, E O

    1977-03-01

    The synthesis of succinimide derivatives in which alkylating groups have been attached to the 2 positions of the ring or to the para position of the 2-phenyl substituent is described. The alkylating groups used were (a) alpha-haloacetyl, (b) alpha-haloacetamido, (c) maleimido, and (d) maleamyl. These compounds were prepared as potential long-acting anticonvulsants. Several of these derivatives exhibited activity against metrazole-induced seizures comparable to phensuximde, The maleimide 16 and the bromoacetamido derivative 23 exhibited a duration of action of at least 3.5 h. PMID:845873

  6. High Efficiency Antimicrobial Thiazolium and Triazolium Side-Chain Polymethacrylates Obtained by Controlled Alkylation of the Corresponding Azole Derivatives.

    PubMed

    Tejero, Rubén; López, Daniel; López-Fabal, Fátima; Gómez-Garcés, José L; Fernández-García, Marta

    2015-06-01

    Two series of antimicrobial polymethacrylates (PMTAs) bearing mono and bis-cationic quaternary ammonium cations (QUATs) were prepared by controlled N-alkylation of 1,3-thiazole and 1,2,3-triazole pendant groups with butyl iodide (PMTAs-BuI). The degree of quaternization (DQ) of the azole heterocycles was monitored by (1)H NMR spectroscopy over a wide range of reaction times. Spectra analysis of the (1)H NMR aromatic region allowed to characterize and quantify the different species involved and, therefore, to control the chemical composition distribution of the amphiphilic polycations. The polymer charge density and the hydrodynamic sizes were measured by zeta potential and dynamic light scattering (DLS), respectively. Consequently, the relationship between structure and antibacterial properties and toxicity was studied. Interestingly, these polyelectrolytes present excellent selective toxicity against bacteria being nonhemolytic even at low values of DQ. Furthermore, they were also evaluated for their microbial time-killing efficiency, presenting a 3 log-reduction in only 15 min. Additionally, the bacteria cell morphology treated with PMTAs-BuI was analyzed. PMID:25944495

  7. Potential long-acting anticonvulsants. 2. Synthesis and activity of succinimides containing an alkylating group on nitrogen or at the 3 position.

    PubMed

    Kornet, M J; Crider, A M; Magarian, E O

    1977-09-01

    The synthesis of succinimide derivatives in which alkylating groups have been attached to the imide nitrogen or to the 3 position of the ring is described. The synthesis of one bis-alkylating derivative 19 is also described. The alkylating groups used were (a) alpha-haloacetyl, (b) alpha-haloacetamido, (c) maleamyl, and (d) maleimido. These compounds were prepared as potential long-acting anticonvulsants. None of the compounds showed activity against maximal electroshock or metrazole-induced seizures. PMID:926123

  8. Effects of alkyl groups in the rate determining step of the Baeyer-Villiger reaction of phenyl alkyl ketones: a quantum chemistry study.

    PubMed

    Reyes, Lino; Díaz-Sánchez, Celestino; Iuga, Cristina

    2012-07-26

    In this work, we have studied the substituent effect of several alkyl groups in the rate-determining step of the catalyzed Baeyer-Villiger (BV) reaction of phenyl alkyl ketones with performic (PFA) and trifluoroperacetic (TFPAA) acids, using quantum chemistry methods. Our results reveal that the substituent effect is more pronounced in the migration step barriers than in the corresponding addition step; that could change the rate-determining step (RDS) of the reaction, as observed in the oxidation of phenyl tert-butyl ketone with both peracids. In addition, the effect of the acid/peracid pairs used is also analyzed. We have demonstrated that the addition step is less susceptible to the acid/peracid nature since the acid strength and the nucleophilicity of the peracid have opposite effects. The effect of the acid/peracid pair is much more pronounced in the migration step because it only depends on the leaving ability of the acid, which in turn depends on its strength. These observations are relevant for understanding the effects of the substrate, the peracid, and the catalyst on the switching of the RDS in the BV reaction. PMID:22738150

  9. Effect of fluorination and size of the alkyl side-chain on the solubility of carbon dioxide in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids.

    PubMed

    Almantariotis, D; Gefflaut, T; Pádua, A A H; Coxam, J-Y; Costa Gomes, M F

    2010-03-18

    It is proven in this work that it is possible to significantly increase the carbon dioxide uptake by an ionic liquid relying on physical interactions only. The solubility and thermodynamics of solvation of carbon dioxide in the ionic liquids 1-octyl-3-methylimidazolium bis[trifluoromethylsulfonyl]amide [C(8)mim][Ntf(2)], 1-decyl-3-methylimidazolium bis[trifluoromethylsulfonyl]amide [C(10)mim][Ntf(2)], and 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-3-methylimidazolium bis[trifluoromethylsulfonyl]amide [C(8)H(4)F(13)mim][Ntf(2)] were determined experimentally between 298 and 343 K at pressures close to atmospheric. The solubility of carbon dioxide is significantly higher in the fluorine-substituted ionic liquid with Henry's law constants at 303 K of 33.3 and 30.7 bar for [C(8)mim][Ntf(2)] and [C(10)mim][Ntf(2)], respectively, and of 28.0 bar for [C(8)H(4)F(13)mim][Ntf(2)]. Molecular simulation was used for interpreting the molecular mechanisms of solvation of carbon dioxide in the studied ionic liquids and coherent molecular mechanisms of solvation are proposed in light of the solute-solvent radial distribution functions. It is shown that the increase of the size of the hydrogenated or fluorinated alkyl chain in the imidazolium cation does not lead to a steady augmentation of the gaseous uptake by the liquid probably due to an increase of the nonpolar domains of the ionic liquid, carbon dioxide being solvated preferentially in the charged regions of the solvent. PMID:20178327

  10. Peculiarities of the signals of the protons of the alkyl group at the boron atom in the PMR spectra

    SciTech Connect

    Kuznetsov, V.V.; Gren, A.I.; Zakharov, K.S.

    1985-05-01

    The authors note the peculiarities of the resonance signals of the alkyl group bonded to the boron atom. They present two charts of data gathered by the use of PMR spectroscopy. Analyzing these data, they conclude that observed peculiarities are probably due to chemical shifts of the protons of the methyl groups and of the methine proton, but they aver that a more profound analysis of the anomaly is impossible without a precise calculation of the spectra under discussion.

  11. How Does the Ionic Liquid Organizational Landscape Change when Nonpolar Cationic Alkyl Groups Are Replaced by Polar Isoelectronic Diethers?

    SciTech Connect

    Kashyap, Hemant K.; Santos, Cherry S.; Daly, Ryan P.; Hettige, Jeevapani J.; Murthy, N. Sanjeeva; Shirota, Hideaki; Edward W. Castner Jr.; Margulis, Claudio J.

    2012-12-21

    The X-ray scattering experiments and molecular dynamics simulations have been performed to investigate the structure of four room temperature ionic liquids (ILs) comprising the bis(trifluoromethylsulfonyl)amide (NTf2) anion paired with the triethyloctylammonium (N2228+) and triethyloctylphosphonium (P2228+) cations and their isoelectronic diether analogs, the (2-ethoxyethoxy)ethyltriethylammonium (N222(2O2O2)+) and (2-ethoxyethoxy)ethyltriethylphosphonium (P222(2O2O2)+) cations. Agreement between simulations and experiments is good and permits a clear interpretation of the important topological differences between these systems. The first sharp diffraction peak (or prepeak) in the structure function S(q) that is present in the case of the liquids containing the alkyl-substituted cations is absent in the case of the diether substituted analogs. Using different theoretical partitioning schemes for the X-ray structure function, we show that the prepeak present in the alkyl-substituted ILs arises from polarity alternations between charged groups and nonpolar alkyl tails. In the case of the diether substituted ILs, we find considerable curling of tails. Anions can be found with high probability in two different environments: close to the cationic nitrogen (phosphorus) and also close to the two ether groups. Moreover, for the two diether systems, anions are found in locations from which they are excluded in the alkyl-substituted systems. This removes the longer range (polar/nonpolar) pattern of alternation that gives rise to the prepeak in alkyl-substituted systems.

  12. An efficient nitration of light alkanes and the alkyl side-chain of aromatic compounds with nitrogen dioxide and nitric acid catalyzed by N-hydroxyphthalimide.

    PubMed

    Nishiwaki, Yoshiki; Sakaguchi, Satoshi; Ishii, Yasutaka

    2002-08-01

    Nitration of light alkanes and the alkyl side-chain of aromatic compounds with NO(2) and HNO(3) was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a catalyst under relatively mild conditions. For example, the nitration of propane with NO(2) catalyzed by NHPI at 100 degrees C for 14 h gave 2-nitropropane in good yield without formation of 1-nitropropane and cleaved products such as nitroethane and nitromethane. Various aliphatic nitroalkanes, which are difficult to prepare by conventional methods, could be selectively obtained by means of the present methodology by using NHPI as the key catalyst. In addition, the side-chain nitration of alkylbenzenes such as toluene was selectively carried out to lead to alpha-nitrotoluene without the ring nitration. The present reaction provides an efficient selective method for the nitration of light alkanes and alkylbenzenes, which has been very difficult to carry out so far. PMID:12153265

  13. Pd-Catalyzed C-H Alkylation of Arenes Using PyrDipSi, a Transformable and Removable Silicon-Tethered Directing Group.

    PubMed

    Sarkar, Dhruba; Gevorgyan, Vladimir

    2016-08-01

    An efficient Pd-catalyzed ortho-C-H alkylation reaction of arenes using a transformable and removable Si-tethered pyridyldiisopropylsilyl (PyrDipSi) directing group has been developed. In addition, the PyrDipSi directing group allows for an efficient sequential double-fold C-H alkylation/oxygenation of arenes to produce meta-alkylated phenols. This directing group can easily be removed or converted into valuable functionalities, such as aryl, iodo, boronic ester, or phenol. PMID:27272930

  14. Effect of side-chain asymmetry on the intermolecular structure and order-disorder transition in alkyl-substituted polyfluorenes

    NASA Astrophysics Data System (ADS)

    Knaapila, M.; Stepanyan, R.; Torkkeli, M.; Haase, D.; Fröhlich, N.; Helfer, A.; Forster, M.; Scherf, U.

    2016-04-01

    We study relations among the side-chain asymmetry, structure, and order-disorder transition (ODT) in hairy-rod-type poly(9,9-dihexylfluorene) (PF6) with two identical side chains and atactic poly(9-octyl-9-methyl-fluorene) (PF1-8) with two different side chains per repeat. PF6 and PF1-8 organize into alternating side-chain and backbone layers that transform into an isotropic phase at TODT(PF 6 ) and TbiODT(PF 1 -8 ) . We interpret polymers in terms of monodisperse and bidisperse brushes and predict scenarios TODTside-chain length above or below the average grafting distance). Calorimetry and x-ray scattering indicate the condition TODT(PF 6 ) ˜TbiODT(PF 1 -8 ) following the low grafting prediction. PF6 side chains coming from the alternating backbone layers appear as two separate layers with thickness H (PF 6 ) , whereas PF1-8 side chains appear as an indistinguishable bilayer with a half thickness Hbilayer(PF 1 -8 ) /2 ≈H (PF 6 ) . The low grafting density region is structurally possible but not certain for PF6 and confirmed for PF1-8.

  15. Comparative analysis of the conformations of symmetrically and asymmetrically deca- and undecasubstituted porphyrins bearing meso-alkyl or -aryl groups

    SciTech Connect

    Senge, M.O.; Medforth, C.J.; Forsyth, T.P.

    1997-03-12

    Conformational analysis of highly substituted porphyrins, has potential implications for modeling the behavior of macrocycles in tetrapyrrole-containing protein complexes and during catalytic reactions. In order to study the influence of different substituent patterns of the conformation of the porphyrin macrocycle, a series of metal free and nickel(II) decasubstituted porphyrins bearing aryl or ethyl groups at opposite meso positions and alkyl groups at the pyrrole positions have been synthesized and characterized by X-ray crystallography. Crystal structures of the free-base porphyrins with 5,15-diaryl substituents showed negligible out-of-plane distortion but a large amount of in-plane distortion along the 5,15-axis accompanied by large bond angle changes similar to those previously seen for related porphyrins with 5,15-dialkyl substituents. Nickel(II) complexes of the 5,15-diaryl-substituted porphyrins show planar or modestly nonplanar conformations, suggesting that these complexes are not intrinsically nonplanar, whereas a complex with 5,15-diethyl substituents has a very ruffled conformation similar to those observed for related complexes with other metals. The nickel(II) complexes are also elongated along the 5,15-axis in a qualitatively similar but less dramatic fashion than are the free-base porphyrins. Spectroscopic studies ({sup 1}H NMR, optical, and resonance Raman spectroscopy) suggest that conformations similar to those determined by X-ray crystallography are present in solution for the 5,15-disubstituted porphyrins containing both aryl and alkyl mesosubstituents were also investigated. Metal-free 5,15-dialkyl- and 5,15-diaryl-substituted porphyrins. Several asymmetric nickel(II) and metal-free deca- and undecasubstituted porphyrins containing both aryl and alkyl mesosubstituents were also investigated.

  16. Mechanism of copper(I)-catalyzed allylic alkylation of phosphorothioate esters: influence of the leaving group on α regioselectivity.

    PubMed

    Sheng, Wenhao; Wang, Mian; Lein, Matthias; Jiang, Linbin; Wei, Wanxing; Wang, Jianyi

    2013-10-11

    The mechanism of Cu(I) -catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2 ; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2 Cu](-) prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α- or γ-selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α- and γ-substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α- and γ-substituted products are 2.75 kcal mol(-1) with SPO(OiPr)2 , 2.44 kcal mol(-1) with SPiv, 2.33 kcal mol(-1) with OPiv, and 1.98 kcal mol(-1) with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2 >SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2 , SPiv, OPiv, and Cl groups on the Cu group. PMID:24038319

  17. Ultrasonic spectrometry of aqueous solutions of alkyl maltosides: kinetics of micelle formation and head-group isomerization.

    PubMed

    Haller, Julian; Kaatze, Udo

    2009-10-19

    At frequencies between 100 kHz and 400 MHz, ultrasonic attenuation spectra are measured at 25 degrees C for aqueous solutions of hexyl-, heptyl-, octyl-, nonyl-, and decyl-beta-D-maltopyranoside as well as of decyl-alpha-D-maltopyranoside. The spectra with surfactant concentration c above the relevant critical micelle concentration (cmc) display three relaxation terms with discrete relaxation times. That with a relaxation time between 0.1 and 1.2 micros is due to exchange of monomers between micelles and the suspending phase. It is discussed in the light of the Teubner-Kahlweit-Aniansson-Wall model of the formation/decay kinetics of systems with Gaussian size distribution of micelles. The relaxation parameters are compared to those for solutions of other non-ionic surfactants, such as alkyl monoglycosides and poly(ethylene glycol) monoalkyl ethers. At c < cmc this low-frequency relaxation term is missing and at c approximately = cmc it is broadened, as is characteristic of solutions of oligomeric molecular structures rather than proper micelles. The relaxation terms with relaxation times between 6 and 15 ns and 0.7 and 2.3 ns reveal head-group rotations around glycosidic angles and isomerization of the exocyclic hydroxymethyl group, respectively. These unimolecular reactions are also examined with a view to solutions of alkyl monoglycosides as well as of glucose and maltose. PMID:19760695

  18. Anionic group 6B metal carbonyls as homogeneous catalysts for carbon dioxide/hydrogen activation: the production of alkyl formates

    SciTech Connect

    Darensbourg, D.J.; Ovalles, C.

    1984-06-27

    The production of alkyl formates from the hydrocondensation of carbon dioxide in alcohols utilizing anionic group 6B carbonyl hydrides as catalysts is herein reported. HM(CO)/sub 5//sup -/ (M = Cr, W; derived from ..mu..-H(M/sub 2/(CO)/sub 10/)/sup -/) and their products of carbon dioxide insertion, HCO/sub 2/M(CO)/sub 5//sup -/, have been found to be effective catalysts for the hydrogenation of CO/sub 2/ in alcohols under rather mild conditions (loading pressures of CO/sub 2/ and H/sub 2/, 250 psi each, and 125/sup 0/C) to provide alkyl formates. The only metal carbonyl species detected in solution via spectroscopy, both at the end of a catalytic period and during catalysis, were M(CO)/sub 6/ and HCO/sub 2/M(CO)/sub 5//sup -/. The metal hexacarbonyls were independently shown to be catalytically inactive. A catalytic cycle is proposed which initially involves release of formic acid from the metal center, either by reductive elimination of the hydrido formato ligands or ligand-assisted heterolytic splitting of dihydrogen with loss of formic acid. In a rapid subsequent process HCOOH reacts with alcohols to yield HCOOR. The addition of carbon monoxide retards alkyl formate production, strongly implying CO/sub 2/ to be the primary source of the carboxylic carbon atom in HCOOR. This was verified by carrying out reactions in the presence of HCO/sub 2/W(/sup 13/CO)/sub 5//sup -/ which provided only H/sup 12/COOR after short reaction periods. However, in the absence of hydrogen and carbon dioxide ..mu..-H(M/sub 2/(CO)/sub 10/)/sup -/ species were observed to be effective catalyst precursors for converting CO and methanol into methyl formate. 36 references, 2 figures, 2 tables.

  19. Dielectric properties of liquid-crystal azomethine polymer with a side alkyl-substituted chain, doped with fullerene C60

    NASA Astrophysics Data System (ADS)

    Kovalev, D. S.; Kostromin, S. V.; Musteaţa, V.; Cozan, V.; Bronnikov, S. V.

    2016-04-01

    We studied the actual and imaginary components of the dielectric constant of liquid-crystal azomethine polymer with a side chain, doped with 0.5 wt % of fullerene C60, over a wide range of temperatures and frequencies; measurements were made by means of dielectric spectroscopy. By analyzing the frequency dependence of the dielectric constant, we detected the relaxation processes (α, β1, and β2) in the nanocomposite, corresponding to certain modes of molecular motion and described them by the Arrhenius equations (β1- and β2-processes) and the Vogel-Fulcher-Tamman equation (α-process). An antiplasticization effect is discovered after doping the polymer with fullerene C60, which manifests itself in increasing the glass transition temperature of the nanocomposite compared to this parameter typical of pure polymer.

  20. Active-site-directed reductive alkylation of xanthine oxidase by imidazo[4,5-g]quinazoline-4,9-diones functionalized with a leaving group.

    PubMed

    Lee, C H; Skibo, E B

    1987-11-17

    A new class of purine antimetabolites, directed toward xanthine oxidase, was designed by employing some of the features found in the bioreductive alkylator mitomycin C. The design involved functionalizing the purine-like imidazo[4,5-g]quinazoline ring system as a quinone (4,9-dione) bearing a 2 alpha leaving group. Due to the presence of the electron-deficient quinone ring, the leaving group cannot participate in alkylation reactions. Reduction to the hydroquinone (4,9-dihydroxy) derivative, however, permits elimination of the leaving group to afford an alkylating quinone methide. In spite of the electronic differences, both quinone and hydroquinone derivatives of the imidazo[4,5-g]quinazoline system are able to enter the purine-utilizing active site of the enzyme. Thus, the hypoxanthine-like quinone derivative [2-(bromomethyl)-3-methylimidazo[4,5-g]quinazoline-4,8, 9(3H, 7H)-trione] and its hydroquinone derivative can act as reducing substrates for the enzyme, resulting in conversion to the xanthane-like 6-oxo derivatives. Hydrolysis studies described herein indicate that the hypoxanthine-like hydroquinone derivative eliminates HBr to afford an extended quinone methide species. The observed alkylation of the enzyme by this derivative may thus pertain to quinone methide generation and nucleophile trapping during enzymatic oxidation at the 6-position. Enzymatic studies indicate that the hypoxanthine-like quinone is an oxidizing suicide substrate for the enzyme. Thus, the reduced enzyme transfers electrons to this quinone, and the resulting hydroquinone inactivates the enzyme. As with mitomycin C, reduction and quinone methide formation are necessary for alkylation by the title quinone. This system is therefore an example of a purine active-site-directed reductive alkylator.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3427077

  1. The Synthesis and Properties of Solution Processable a Red Phosphorescent Iridium(III) Complex with Alkyl Group.

    PubMed

    Yang, B N; Shin, D M

    2016-03-01

    The (TMP-HT)2Ir(acac) was synthesized with 2-bromo-4-(trifluoromethyl)pyridine and 5-hexyl-2-thiopheneboronic acid pinacol ester for organic light-emitting diodes (OLEDs). This material was designed on the basis of Gaussian modeling program results. The ligands have both the electron donor and acceptor in a molecule. There are pyridyl group which decrease electron density and thiophene group which increase electron density. Therefore, it showed intramolecular charge transfer (ICT) property. For solution process, the ligand have a alkyl group which has hydrophobic property. The (TMP-HT)21r(acac) was synthesized by Suzuki coupling reaction and Nonoyama reaction. The (TMP-HT)21r(acac) emitted at approximately 600 nm. The device structures were ITO/PEDOT (500 Å)/TFB (170 Å)/PVK:PBD (40%): (TMPHT)21r(acac) (300 Å:10%)/BH:BD5% (150 Å)/L201(50 Å)/Liq(200 Å)/Al. Electroluminescent properties were observed with devices doped with various doping concentrations. PMID:27455692

  2. Oxidative addition of group 13 and 14 metal halides and Alkyls to Ga(DDP) (DDP = bulky bisimidinate).

    PubMed

    Kempter, Andreas; Gemel, Christian; Fischer, Roland A

    2008-08-18

    The oxidative addition of a variety of group 13 and group 14 halides and alkyls R aMX to the mono valent group 13 bis-imidinate Ga(DDP) (DDP = 2-{(2,6-diisopropyl-phenyl)amino}-4-{(2,6-diisopropylphenyl)imino}-2-pentene) is reported. Accordingly, the insertion of Ga(DDP) into the Ga-Me bond of GaMe 3 yield in the complexes [{(DDP)GaMe}GaMe 2] ( 1) and [{(DDP)GaMe} 2GaMe] ( 2), respectively, which show a temperature-dependent equilibrium between 1 at higher temperatures and 2 at lower temperatures. In the case of GaCl 3, the only isolable product is [{(DDP)GaCl} 2GaCl] ( 3). The related reaction of SnMe 2Cl 2 with Ga(DDP) yields the compound [Me 2Sn{ClGa(DDP)} 2] ( 4), whereas SnMe 4 behaves inert. In the case of SiCl 4, only the monoinsertion product [Cl 3Si{ClGa(DDP)}] ( 5) was observed. Finally, [(CH 3) 3C{ClGa(DDP)}] ( 6) is synthesized by insertion of Ga(DDP) into the C-Cl bond of ClC(CH 3) 3. All new compounds were fully characterized by elemental analysis, NMR-spectroscopy, and single-crystal X-ray diffraction analysis. PMID:18630902

  3. Bis(alkyl) rare-earth complexes supported by a new tridentate amidinate ligand with a pendant diphenylphosphine oxide group. Synthesis, structures and catalytic activity in isoprene polymerization.

    PubMed

    Tolpygin, Aleksei O; Glukhova, Tatyana A; Cherkasov, Anton V; Fukin, Georgy K; Aleksanyan, Diana V; Cui, Dongmei; Trifonov, Alexander A

    2015-10-01

    A new tridentate amidine 2-[Ph2P(O)]C6H4NHC(tBu)[double bond, length as m-dash]N(2,6-Me2C6H3) (1) bearing a side chain pendant Ph2P[double bond, length as m-dash]O group was synthesized and proved to be a suitable ligand for coordination to rare-earths ions. Bis(alkyl) complexes {2-[Ph2P(O)]C6H4NC(tBu)N(2,6-Me2C6H3)}Ln(CH2SiMe3)2(THF)n (Ln = Y, n = 1 (3), Ln = Er, n = 1 (4), Ln = Lu, n = 0 (5)) were prepared using alkane elimination reactions of and Ln(CH2SiMe3)3(THF)2 (Ln = Y, Er, Lu) in hexane and were isolated in 50, 70 and 75% yields respectively. The X-ray studies revealed that complexes 2-5 feature intramolecular coordination of P[double bond, length as m-dash]O groups to metal ions. The lutetium complex 5 proved to be rather stable: at 20 °C its half-life time is 1155 h, while for the yttrium analogue the half-life time was found to be 63 h. Complexes 3-5 were evaluated as precatalysts for isoprene polymerization. The systems Ln/borate/AliBu3 (Ln = 3-5, borate = [PhNHMe2][B(C6F5)4], [Ph3C][B(C6F5)4]) turned out to be highly efficient in isoprene polymerization and enable complete conversion of 1000-10,000 equivalents of monomer into polymer at 20 °C within 0.5-2.5 h affording polyisoprenes with a very high content of 1,4-cis units (up to 96.6%) and from narrow (1.49) to moderate (3.54) polydispersities. A comparative study of catalytic performance of the related bis(alkyl) yttrium complexes supported by amidinate ligands of different denticities and structures [tBuC(N-2,6iPr2C6H4)2](-), [tBuC(N-2,6-iPr2C6H4)(N-2-MeOC6H4)](-) and {2-[Ph2P(O)]C6H4NC(tBu)N(2,6-Me2C6H3)}(-) demonstrated that the introduction of a pendant donor group (2-MeOC6H4 or Ph2P(O)) into a side chain of amidinate scaffolds results in a significant increase in catalytic activity. The amidinate ligand bearing a Ph2P(O)-group provides a high isoprene polymerization rate along with excellent control over regio- and stereoselectivities and allows us to obtain polyisoprenes with a reasonable

  4. Photophysics and redox properties of rylene imide and diimide dyes alkylated ortho to the imide groups.

    PubMed

    Bullock, Joseph E; Vagnini, Michael T; Ramanan, Charusheela; Co, Dick T; Wilson, Thea M; Dicke, Jay W; Marks, Tobin J; Wasielewski, Michael R

    2010-02-11

    Ruthenium-catalyzed C-H bond activation was used to directly attach phenethyl groups derived from styrene to positions ortho to the imide groups in a variety of rylene imides and diimides including naphthalene-1,8-dicarboximide (NMI), naphthalene-1,4:5,8-bis(dicarboximide) (NI), perylene-3,4-dicarboximide (PMI), perylene-3,4:9,10-bis(dicarboximide) (PDI), and terrylene-3,4:11,12-bis(dicarboximide) (TDI). The monoimides were dialkylated, while the diimides were tetraalkylated, with the exception of NI, which could only be dialkylated due to steric hindrance. The absorption, fluorescence, transient absorption spectra, and lowest excited singlet state lifetimes of these chromophores, with the exception of NI, are nearly identical to those of their unsubstituted parent chromophores. The reduction potentials of the dialkylated chromophores are approximately 100 mV more negative and oxidation potentials are approximately 40 mV less positive than those of the parent compounds, while the corresponding potentials of the tetraalkylated compounds are approximately 200 mV more negative and approximately 100 mV less positive than those of their parent compounds, respectively. Continuous wave electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) data on the radical anion of PDI reveals spin density on the perylene-core protons as well as on the beta-protons of the phenethyl groups. The phenethyl groups enhance the otherwise poor solubility of the bis(dicarboximide) chromophores and only weakly perturb the photophysical and redox properties of the parent molecules, rendering these derivatives and related molecules of significant interest to solar energy conversion. PMID:20073517

  5. Role of alkyl group in the aromatic extraction using pyridinium-based ionic liquids.

    PubMed

    Kim, Min Ji; Shin, Seung Hoon; Kim, Young Jin; Cheong, Minserk; Lee, Je Seung; Kim, Hoon Sik

    2013-11-27

    The performance of N-alkylpyridinium-based ionic liquids with a SCN anion (PyILs) was evaluated for the selective extraction of aromatics from aliphatic hydrocarbons. The aromatic extraction ability of PyILs was greatly enhanced by the presence of a methyl group on the pyridinium ring at the 3- or 4-position, whereas the solubility of the aromatics in the PyILs decreased with increasing the number of methyl groups on the benzene ring. The FT-IR studies revealed that the solubility of an aromatic compound in a PyIL is closely correlated with the degree of aromatic C-H bending frequency shift observed during the dissolution of the aromatic compound in the PyIL: the larger the shift, the higher the solubility. The computational calculations on the dispersion interactions between aromatics and PyILs demonstrated that the anion-aromatic interaction is much more important than the cation-aromatic interaction in determining the aromatic solubility in PyILs, and such anion-aromatic interaction can be enhanced by introducing a methyl group at the carbon atom of the pyridinium ring. PMID:24180561

  6. Human platelets respond differentially to lysophosphatidic acids having a highly unsaturated fatty acyl group and alkyl ether-linked lysophosphatidic acids.

    PubMed Central

    Tokumura, Akira; Sinomiya, Junya; Kishimoto, Seishi; Tanaka, Tamotsu; Kogure, Kentaro; Sugiura, Takayuki; Satouchi, Kiyoshi; Waku, Keizo; Fukuzawa, Kenji

    2002-01-01

    Lysophosphatidic acid (LPA) is a physiological agonist that is produced by lysophospholipase D, phospholipase A(1) and phospholipase A(2) in the blood of animals. It exerts diverse biological actions on a broad range of animal cells. Specific receptors for this important agonist have been characterized. In this investigation, for the first time we prepared LPAs having a highly unsaturated fatty acyl group, such as the eicosapentaenoyl or docosahexaenoyl residue, and their acetylated derivatives. Human platelets aggregated more potently in response to the highly unsaturated acyl-LPAs than to LPAs with a C(18) fatty acyl group, such as an oleoyl group, while alkyl ether-linked LPAs (alkyl-LPA) had much stronger aggregating activity. Two positional isomers of LPAs with an arachidonoyl, eicosapentaenoyl or docosahexaenoyl group had equipotent aggregatory activity as well as the positional isomers of their acetylated analogues, indicating that putative LPA receptors could not distinguish the difference between the positional isomers. We found that platelet preparations from two individuals showed no aggregatory response to alkyl-LPAs, although they contained mRNAs for known LPA receptors in the following order of expression level: endothelial differentiation gene (Edg)-4>Edg-7>Edg-2. We also obtained evidence that 2-(p-amylcinnamoyl)amino-4-chlorobenzoic acid (ONO-RS-082), a phospholipase A(2) inhibitor, potentiated alkyl-LPA-induced platelet aggregation, but inhibited highly unsaturated acyl-LPA-induced platelet aggregation. These results indicated that human platelets express acyl-LPA-selective and alkyl-LPA-selective receptors on their plasma membrane. PMID:11982483

  7. Effect of heteroatom insertion at the side chain of 5-alkyl-1H-tetrazoles on their properties as catalysts for ester hydrolysis at neutral pH.

    PubMed

    Bhattacharya, Santanu; Vemula, Praveen Kumar

    2005-11-25

    [reaction: see text] Herein we introduce tetrazole and its suitably designed derivatives as powerful ester-cleaving reagents. By first performing a detailed ab initio computational study, we found that, in the side chain of 5-alkyl-1H-tetrazoles, introduction of a heteroatom (e.g., N, O, or S at the alpha-position of the tetrazole ring) raises the charge on the tetrazole nucleus significantly. All calculations have been performed using restricted Hartree-Fock (RHF) and hybrid ab initio/DFT (B3LYP) methods employing 6-31G* and 6-31+G* basis sets. To estimate the nucleophilicity of these reagents, the charges on conjugate bases of various tetrazole derivatives have been calculated using natural population (NBO) analysis in gas phase and in water. Free energy of protonation (fep) of the 1H-tetrazole derivatives (1-7), free energy of solvation, deltaG(aq), and the corresponding pKa values have been calculated by self-consistent reaction field (SCRF) methods applying the polarized continuum model (PCM). Since the calculation indicates that incorporation of heteroatom leads to enhanced nucleophilicity in their deprotonated anionic tetrazole forms, a series of 5-substituted 1H-tetrazole derivatives have been synthesized. These compounds indeed catalyze the hydrolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) and p-nitrophenyl hexanoate (PNPH) efficiently in cationic cetyl trimethylammonium bromide (CTABr) micelles at pH 7.0 and 25 degrees C. The pseudo-first-order rate constants (k(obs)) were determined for each catalyst against both substrates. The experimental and theoretical results show that, to achieve better k(obs) values for the cleavage of PNPDPP and PNPH under micellar conditions, charge on the N- atom (nucleophile) of conjugate base is important. Replacing the alpha-CH2 in alkyl substituent with S (3), NH (4), or O (5) enhances the accumulation of charge on N- in conjugate bases of tetrazoles and subsequently increases their intrinsic nucleophilic reactivity

  8. Dehydrocyclization of peripheral alkyl groups in porphyrins at Cu(100) and Ag(111) surfaces

    NASA Astrophysics Data System (ADS)

    Williams, Christopher G.; Wang, Miao; Skomski, Daniel; Tempas, Christopher D.; Kesmodel, Larry L.; Tait, Steven L.

    2016-11-01

    The self-assembly of organic and metal-organic species at metal surfaces is a topic of high interest for applications that can benefit from tunable surface functionalization through organic building block design. As the complexity of molecular building blocks increases to direct ordering and function, thermal stability of the adsorbate often increases opening up new surface-catalyzed reaction pathways. We report dehydrocyclization of octaethylporphyrin to tetrabenzoporphyrin on the Cu(100) and Ag(111) surfaces at 500-600 K. Dehydrocyclization of smaller species is not typically observed on these surfaces at low pressure due to short adsorption lifetimes. The dehydrocyclization of peripheral ethyl groups forms benzo groups which then undergo additional dehydrogenation. The reaction products are characterized by high resolution electron energy loss spectroscopy (HREELS), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS). These results extend our understanding of reaction pathways that may be encountered as molecular building blocks increase in size and complexity on relatively inert surfaces.

  9. Involvement of cyan and ester groups in surface interactions of aerosil-cyanophenyl alkyl benzoate systems with high silica density: Infrared investigations

    NASA Astrophysics Data System (ADS)

    Frunza, Ligia; Frunza, Stefan; Zgura, Irina; Beica, Traian; Gheorghe, Nicoleta; Ganea, Paul; Stoenescu, Daniel; Dinescu, Adrian; Schönhals, Andreas

    2010-04-01

    Composites prepared from aerosil A380 and liquid crystals (LCs) of 4- n-alkyl-4'-cyanophenyl benzoate type, with four to six carbon atoms in the alkyl chain were investigated by infrared spectroscopy. Their high silica content (of 2-7 g aerosil/1 g of LC) was given by thermogravimetric investigations and allows the observation of a rather thin LC layer on the silica particles. Several surface species onto the external surface of the grains were demonstrated. Arguments are given that monomer and dimer species are present in the bulk cyanophenyl benzoate materials while bulk-like species along with hydrogen-bonded ones coexist in the so-called surface layer of the composites. The main interaction of LC molecules with the aerosil surface is by hydrogen bonding taking place with the involvement of the cyan group. There is a contribution of ester carbonyl group to these surface interactions but this cannot be well quantified.

  10. [Secondary right-sided diaphragmatic hernia following neonatal group B Streptococcal septicaemia in a preterm infant].

    PubMed

    Vedel-Werts, F; Desandes, R; Rouabah, M; Bach, P; de Miscault, G; Hascoët, J-M; Hamon, I

    2007-07-01

    We report on a case of a secondary right-sided diaphragmatic hernia following group B streptococcal (GBS) septicaemia in a very low birth weight infant born at 30 weeks. After initial improvement, the diagnosis of a secondary right-sided diaphragmatic hernia was suspected with the persistent radiological pulmonary right-sided image on the chest x-ray and the clinical degradation. The diagnosis was confirmed by ultrasonography on day 43. The postoperative course was simple. Persistent respiratory distress in a neonate, after a GBS septicaemia associated with a right pulmonary opacity on the chest x-ray, should prompt a careful evaluation. A secondary right-sided diaphragmatic hernia should be considered. Treatment is surgery, the prognosis is good in the absence of pulmonary hypoplasia. PMID:17451917

  11. Structure and aggregation in the 1,3-dialkyl-imidazolium bis(trifluoromethylsulfonyl)imide ionic liquid family: 2. From single to double long alkyl side chains.

    PubMed

    Bernardes, Carlos E S; Shimizu, Karina; Lobo Ferreira, Ana I M C; Santos, Luís M N B F; Canongia Lopes, José N

    2014-06-19

    A systematic molecular dynamics study using large simulation boxes has been performed in order to extend the analysis of the mesoscopic segregation behavior observed in ionic liquids of the 1,3-dialkyl-imidazolium bis(trifluoromethylsulfonyl)imide homologous series, [C(n)C(mim)][Ntf2] (2 ≤ n ≤ 10, 2 ≤ m ≤ n). The analyses include the discussion of the structure factors, S(q), in the low-q range (1.6 ≤ q/nm(-1) ≤ 20); the confirmation of the periodicity of the polar network of the ionic liquid and its relation to the so-called intermediate peaks; and the characterization of the polar network and the nonpolar regions that are formed along the series using aggregate analyses by means of five different statistical tools. The analyses confirmed that the percolation of the nonpolar regions into a continuous domain occurs when the total number of carbon atoms in the alkyl chains exceeds six but that this is not a sufficient condition for the emergence of a distinct and intense prepeak. The existence of such a peak also requires that the longer alkyl chain contains more than a critical alkyl length (CAL) of five carbon atoms. PMID:24873822

  12. UV gelation of single-component polyacrylates bearing dinitrobenzoate side groups.

    PubMed

    Xie, Tongqing; Yang, Li; Sun, Xingxing; Jiang, Jun; Zhang, Xuepeng; Luo, Yi; Zhang, Guoqing

    2016-07-19

    Polyacrylates bearing dinitrobenzoate side groups undergo sol-gel-sol transformations in DMF or THF solutions regulated by alternating UV light and dark conditions. The formation and recombination of radical ionic species via photoinduced electron transfer may be responsible. PMID:27373563

  13. Concerns about contraceptive side effects among young Latinas: a focus-group approach.

    PubMed

    Gilliam, Melissa L; Warden, Meredith; Goldstein, Chava; Tapia, Beatriz

    2004-10-01

    To identify perceptions and attitudes about contraceptive side effects in young, low-income Latina adolescents through focus-group conversations. We conducted seven focus-group discussions with Latino females in an outpatient clinic and community setting. Qualitative methodology was used to analyze data. Participants were recruited from the outpatient gynecology clinic at the University of Illinois at Chicago, and from the Easter Seals Day Care Center. Women were recruited if they were Latino and between the ages of 18 and 26 years (N = 40). Participants cited both perceptions of side effects as well as personal experience with side effects as reasons for not using or discontinuing the use of contraception. Women also demonstrated incorrect knowledge about contraception, and tended to value anecdotal information over information from health professionals. These factors led to reliance on less-effective methods of contraception, placing participants at risk for unintended pregnancy. Concern about side effects, fear of health consequences and misinformation were identified as barriers to effective contraceptive use in young, low-income Latinas. Providers caring for this population should address potential concerns about side effects of contraception as well as assess patients' understanding in light of cultural and language barriers. PMID:15451334

  14. Synthesis of waterborne polyurethane containing alkoxysilane side groups and the properties of the hybrid coating films

    NASA Astrophysics Data System (ADS)

    Li, Qi; Guo, Longhai; Qiu, Teng; Xiao, Weidong; Du, Dianxing; Li, Xiaoyu

    2016-07-01

    A series of waterborne polyurethane (WPU) containing alkoxysilane side groups were synthesized by using the dihydroxy functionalized alkoxysilane. The diol with trimethoxysilane groups at the side chains was synthesized via Michael addition between 3-(methacryloxypropyl)trimethoxysilane (MAPTS) and diethanolamine (DEA). The silane diol was applied as the chain extender for the NCO-endcapped prepolymer of isophorone diisocyanate, polycarbonate diol, 2,2-bis(hydroxymethyl) butyric acid and 1,4-butanediol. The products with the silane content varied from 1.2 to 16.5 wt% were dispersed in water after neutralization. The effect of the silane diol on the particle size and morphology of the WPU dispersion was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. X-ray photoelectron spectroscopy (XPS) characterization was carried out on the coating film of the WPU, revealing that the long flexible side chain is favorable for the silane components to emigrate toward the film surface and crosslink during the film formation process. As a result, both the surface contact angle to water and water adsorption of the WPU coating films increased with the silane content. Furthermore, the mechanical properties including the modulus and tensile strength of the films were also improved by the incorporation of silane diol.

  15. Synthesis and biological effects of new hybrid compounds composed of benzylguanidines and the alkylating group of busulfan on neuroblastoma cells.

    PubMed

    Hampel, Thomas; Bruns, Marietta; Bayer, Melanie; Handgretinger, Rupert; Bruchelt, Gernot; Brückner, Reinhard

    2014-06-15

    (131)Iodine-labelled (meta-iodobenzyl)guanidine ([(131)I]-mIBG) and busulfan [butane-1,4-diylbis(methanesulfonate)] are well-established pharmaceuticals in neuroblastoma therapy. We report the design, synthesis, and testing of hybrid molecules-mBBG and pBBG-which combine key structural features of (meta-iodobenzyl)guanidine and busulfan: they contain a benzylguanidine moiety for accumulating in neuroblastoma cells via the noradrenaline transporter and, in the meta- or para-position, respectively, one of the two identical alkylating motives of busulfan for killing cells. Uptake and toxicity of hybrids mBBG and pBBG in human neuroblastoma cells compared favorably to their ancestors [(131)I]-mIBG and busulfan. PMID:24814532

  16. Nanostructured surfaces by supramolecular self-assembly of linear oligosilsesquioxanes with biocompatible side groups

    PubMed Central

    Nowacka, Maria; Makowski, Tomasz

    2015-01-01

    Summary Linear oligomeric silsesquioxanes with polar side moieties (e.g., carboxylic groups and derivatives of N-acetylcysteine, cysteine hydrochloride or glutathione) can form specific, self-assembled nanostructures when deposited on mica by dip coating. The mechanism of adsorption is based on molecule-to-substrate interactions between carboxylic groups and mica. Intermolecular cross-linking by hydrogen bonds was also observed due to the donor–acceptor character of the functional groups. The texture of supramolecular nanostructures formed by the studied materials on mica was analysed with atomic force microscopy and their specific surface energy was estimated by contact angle measurements. Significant differences in the surface roughness, thickness and the arrangement of macromolecules were noted depending on the kind of functional groups on the side chains. Specific changes in the morphology of the surface layer were observed when mica was primed with a monolayer of small organic compounds (e.g., N-acetylcysteine, citric acid, thioglycolic or acid). The adsorption of both silsesquioxane oligomers and organic primers was confirmed with attenuated total reflectance infrared spectroscopy. The observed physiochemical and textural variations in the adsorbed materials correlate with the differences in the chemical structure of the applied oligomers and primers. PMID:26734528

  17. Synthesis of brassinosteroids with a keto group in the side chain.

    PubMed

    Baradzenka, Aliona G; Barysau, Barys M; Hurski, Alaksiej L; Zhabinskii, Vladimir N; Khripach, Vladimir A

    2015-09-01

    The aim of this work was to prepare 24-epicryptolide and 22-dehydro-24-epibrassinolide as possible metabolites of 24-epibrassinolide. The main synthetic problem to be solved was the differentiation of functional groups in brassinosteroids. Distinguishing 2α,3α-diol function from another diol group in 24-epibrassinolide was achieved via selective hydrolysis of 2α,3α-cyclic carbonate or via regioselective reaction of boric acid with the functional groups in the side chain. The hydroxyl at C-23 was more reactive than the 22-OH in the oxidation with bromine in the presence of bis(tributyltin) oxide and in the benzylation reaction that resulted in the predominant formation of the corresponding α-hydroxy ketone derivatives with the ratio ranging from 4:1 to 1.5:1. PMID:26079654

  18. Shear Alignment Behavior of Nematic Solutions Induced by Ultralong Side-Group Liquid Crystal Polymers

    NASA Astrophysics Data System (ADS)

    Kempe, M. D.; Kornfield, J. A.

    2003-03-01

    Addition of a low concentration of a very long (430 kg/mol) side group liquid crystal polymer is shown to produce dramatic changes in the flow characteristics of a calamitic nematic liquid crystal. This polymer causes a typical flow-aligning nematic liquid crystal to align near the velocity gradient direction rather than near the velocity direction, corresponding to having a tumbling parameter λ<-1, for concentrations greater than 7.5% polymer. Such flow-aligning behavior has not been reported previously in a calamitic nematic. The large molecular weight of the present polymer relative to those examined in the prior literature is responsible for these new phenomena.

  19. Implementing type I & type II error spending for two-sided group sequential designs.

    PubMed

    Rudser, Kyle D; Emerson, Scott S

    2008-05-01

    Group sequential designs have become the mainstay for addressing efficacy and ethical issues when monitoring clinical trials. Several different procedures of defining stopping rules have been developed for the formulation of a sequential design, one of these being direct specification of type I and type II error spending. There are also different methods that have been proposed to fit a two-sided design for a given error spending function. Two methods that differ on when type II error begins to be spent are the flexible implementation of the unified family by Kittelson and Emerson and the method of Chang, Hwang, and Shih. Trial designs formulated by the latter are unable to mimic the boundaries of the unified family, which includes the two-sided symmetric designs of Emerson and Fleming, the two-sided designs of Pampallona and Tsiatis, and the double triangular designs of Whitehead and Stratton. Design operating characteristics of these two methods are compared over a wide range of commonly used size, power and error spending function combinations. PMID:17933592

  20. Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Elsila, Jamie E.; Dworkin, Jason P.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

  1. Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils.

    PubMed

    Wang, Shu; Robertson, Megan L

    2015-06-10

    Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between

  2. Demonstration of two functionally heterogenous groups within the activities of UDP-glucuronosyltransferase towards a series of 4-alkyl-substituted phenols.

    PubMed Central

    Wishart, G J; Campbell, M T

    1979-01-01

    1. A simple colorimetric assay for UDP-glucuronosyltransferase activities towards phenolic substrates, using Folin & Ciocalteu's phenol reagent, is described. The assay is used to measure rat liver transferase activities towards substrates from a series of 4-alkyl-substituted phenols. 2. Activities towards phenol, 4-methylphenol and 4-ethylphenol develop near-adult values before birth, are precociously stimulated by dexa methasone in utero and are stimulated 3--4-fold by 3-methylcholanthrene in adult liver. These are assigned to a "late-foetal" group of transferase activities. 3. Activities towards 4-n-propylphenol, 4-s-butylphenol and 4-t-butylphenol are negligible in late-foetal liver, developing to near-adult values in the first 4 postnatal days, and are not affected by dexamethasone or 3-methylcholanthrene. They are assigned to a "neonatal" group of transferase activities. 4. Although 4-ethylphenol and 4-n-propylphenol differ only by a single --CH2-- moiety, this is sufficient to change the acceptability of these substrates respectively from the late-foetal to the neonatal group of transferase activities. The change is distinct, with no overlapping of substrate acceptability between the two groups of transferase activities. 5. From consideration of the above and other substrates, the two groups of transferase activities do not distinguish substrates on the basis of their molecular weights or lipophilicity. The distinguishing feature appears to be the specific molecular configurations of the substrates. PMID:109087

  3. Synthesis of fluorous photolabile aldehyde and carbamate and alkyl carbamate protecting groups for carbohydrate-associated amines.

    PubMed

    Roychoudhury, Rajarshi; Pohl, Nicola L B

    2014-02-21

    Two new fluorous photolabile-protecting groups (FNBC and FNB) and a new base-labile protecting group (FOC) for the masking of amines are reported. The protecting groups survive a wide range of common reaction conditions used in oligosaccharide synthesis and render the attached molecules amenable to fluorous solid-phase extraction (FSPE). A glycosyl acceptor containing the FNB group is shown to be useful in the synthesis of carbohydrates tagged with free deactivated secondary amines. PMID:24512452

  4. Alkylation and acylation of cyclotriphosphazenes.

    PubMed

    Benson, Mark A; Zacchini, Stefano; Boomishankar, Ramamoorthy; Chan, Yuri; Steiner, Alexander

    2007-08-20

    Phosphazenes (RNH)6P3N3 (R = n-propyl, isobutyl, isopropyl, cyclohexyl, tert-butyl, benzyl) are readily alkylated at ring N sites by alkyl halides forming N-alkyl phosphazenium cations. Alkylation of two ring N sites occurred after prolonged heating in the presence of methyl iodide or immediately at room temperature with methyl triflate yielding N,N'-dimethyl phosphazenium dications. Geminal dichloro derivatives Cl2(RNH)4P3N3 are methylated by methyl iodide at the ring N site adjacent to both P centers carrying four RNH groups. X-ray crystal structures showed that the alkylation of ring N sites leads to substantial elongation of the associated P-N bonds. Both N-alkyl and N,N'-dialkyl phosphazenium salts form complex supramolecular networks in the solid state via NH...X interactions. Systems carrying less-bulky RNH groups show additional NH...N bonds between N-alkyl phosphazenium ions. N-Alkyl phosphazenium halides form complexes with silver ions upon treatment with silver nitrate. Depending on the steric demand of RNH substituents, either one or both of the vacant ring N sites engage in coordination to silver ions. Treatment of (RNH)6P3N3 (R = isopropyl) with acetyl chloride and benzoyl chloride, respectively, yielded N-acyl phosphazenium ions. X-ray crystal structures revealed that elongation of P-N bonds adjacent to the acylated ring N site is more pronounced than it is in the case of N-alkylated species. Salts containing N-alkyl phosphazenium ions are stable toward water and other mild nucleophiles, while N,N'-dialkyl and N-acyl phosphazenium salts are readily hydrolyzed. The reaction of (RNH)6P3N3 with bromoacetic acid led to N-alkylation at one ring N site in addition to formation of an amide via condensation of an adjacent RNH substituent with the carboxylic acid group. The resulting bromide salt contains mono cations of composition (RNH)5P3N3CH2CONR in which a CH2-C(O) unit is embedded between a ring N and an exocyclic N site of the phosphazene. PMID

  5. Dendronized polyimides bearing long-chain alkyl groups and their application for vertically aligned nematic liquid crystal displays.

    PubMed

    Tsuda, Yusuke; Min, Jae; Kuwahara, Renpei

    2009-11-01

    Polyimides having dendritic side chains were investigated. The terphenylene diamine monomer having a first-generation monodendron, 3,4,5-tris(n-dodecyloxy)-benzoate and the monomer having a second-generation monodendron, 3,4,5-tris[-3',4',5'-tri(n-dodecyloxy)benzyloxy]benzoate were successfully synthesized and the corresponding soluble dendritic polyimides were obtained by polycondensation with conventional tetracarboxylic dianhydride monomers such as benzophenone tertracarboxylic dianhydride (BTDA). The two-step polymerizations in NMP that is a general method for the synthesis of soluble polyimides is difficult; however, the expected dendritic polyimides can be obtained in aromatic polar solvents such as m-cresol and pyridine. The solubility of these dendoronized polyimides is characteristic; soluble in common organic solvents such as dichloromethane, chloroform, toluene and THF. These dendronized polyimides exhibited high glass transition temperatures and good thermal stability in both air and under nitrogen. Their application as alignment layers for LCDs was investigated, and it was found that these polyimides having dendritic side chains were applicable for the vertically aligned nematic liquid crystal displays (VAN-LCDs). PMID:20087476

  6. Increased efficiency of evolved group I intron spliceozymes by decreased side product formation

    PubMed Central

    Amini, Zhaleh N.; Müller, Ulrich F.

    2015-01-01

    The group I intron ribozyme from Tetrahymena was recently reengineered into a trans-splicing variant that is able to remove 100-nt introns from pre-mRNA, analogous to the spliceosome. These spliceozymes were improved in this study by 10 rounds of evolution in Escherichia coli cells. One clone with increased activity in E. coli cells was analyzed in detail. Three of its 10 necessary mutations extended the substrate binding duplexes, which led to increased product formation and reduced cleavage at the 5′-splice site. One mutation in the conserved core of the spliceozyme led to a further reduction of cleavage at the 5′-splice site but an increase in cleavage side products at the 3′-splice site. The latter was partially reduced by six additional mutations. Together, the mutations increased product formation while reducing activity at the 5′-splice site and increasing activity at the 3′-splice site. These results show the adaptation of a ribozyme that evolved in nature for cis-splicing to trans-splicing, and they highlight the interdependent function of nucleotides within group I intron ribozymes. Implications for the possible use of spliceozymes as tools in research and therapy, and as a model for the evolution of the spliceosome, are discussed. PMID:26106216

  7. Controlling Miscibility in Polyethylene-Polynorbornene Block Copolymers via Side-Group Chemistry

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Block copolymers containing a crystallizable block, such as polyethylene (PE), and an amorphous block with high glass transition temperature (Tg) are an interesting class of materials since the rigid glassy block can improve the mechanical response of the article under strain by reinforcing the crystal fold surface. However, to prepare an easily processable PE-containing block copolymer it is necessary to avoid microphase separation in the melt by selection of amorphous blocks with weak repulsive interactions against PE (low Flory interaction parameter χ or interaction energy density X) . Most such low- χ polymers are chemically similar to PE, such as copolymers of ethylene and a small amount of an α-olefin, and therefore exhibit similarly low glass transition temperatures. This work investigates a series of low- and high-Tg polymers based on substituted norbornene monomers, polymerized via ring-opening metathesis polymerization (ROMP). Hydrogenated polynorbornene derivatives possess a wide range of glass transition temperatures, and miscibility with PE can be readily tuned by the choice of substituents on the monomers (e.g. aromatic vs. aliphatic groups). Two species investigated, hydrogenated poly(cyclohexyl norbornene) and hydrogenated poly(norbornyl norbornene), have high Tg and also remain miscible with polyethylene to high molecular weight. Furthermore, we develop a set of mixing rules to qualitatively predict the solubility behavior of substituted ROMP polynorbornenes as a function of their side-groups.

  8. Hydrogen bonding motifs of protein side chains: descriptions of binding of arginine and amide groups.

    PubMed Central

    Shimoni, L.; Glusker, J. P.

    1995-01-01

    The modes of hydrogen bonding of arginine, asparagine, and glutamine side chains and of urea have been examined in small-molecule crystal structures in the Cambridge Structural Database and in crystal structures of protein-nucleic acid and protein-protein complexes. Analysis of the hydrogen bonding patterns of each by graph-set theory shows three patterns of rings (R) with one or two hydrogen bond acceptors and two donors and with eight, nine, or six atoms in the ring, designated R2(2)(8), R2(2)(9), and R1(2)(6). These three patterns are found for arginine-like groups and for urea, whereas only the first two patterns R2(2)(8) and R2(2)(9) are found for asparagine- and glutamine-like groups. In each case, the entire system is planar within 0.7 A or less. On the other hand, in macromolecular crystal structures, the hydrogen bonding patterns in protein-nucleic acid complexes between the nucleic acid base and the protein are all R2(2)(9), whereas hydrogen bonding between Watson-Crick-like pairs of nucleic acid bases is R2(2)(8). These two hydrogen bonding arrangements [R2(2)(9)] and R2(2)(8)] are predetermined by the nature of the groups available for hydrogen bonding. The third motif identified, R1(2)(6), involves hydrogen bonds that are less linear than in the other two motifs and is found in proteins. PMID:7773178

  9. Study of adjuvant effect of model surfactants from the groups of alkyl sulfates, alkylbenzene sulfonates, alcohol ethoxylates and soaps.

    PubMed

    Clausen, S K; Sobhani, S; Poulsen, O M; Poulsen, L K; Nielsen, G D

    2000-11-01

    The sodium salts of representatives of anionic surfactants, dodecylbenzene sulfonate (SDBS), dodecyl sulfate (SDS) and coconut oil fatty acids, and a nonionic surfactant, dodecyl alcohol ethoxylate, were studied for adjuvant effect on the production of specific IgE antibodies in mice. The surfactants were injected subcutaneously (sc) in concentrations of 1000, 100, 10 or 1 mg/l, respectively, together with 1 microg of ovalbumin (OVA). In addition, groups of mice received OVA in saline (control group) or in Al(OH)(3) (positive adjuvant control group). After the primary immunization the mice were boosted up to three times with OVA (0.1 microg sc) in saline. OVA-specific IgE antibodies were determined by the heterologous mouse rat passive cutaneous anaphylaxis test. The results were confirmed by a specific ELISA method. After the first booster, the Al(OH)(3) group and the 10 mg/l SDS group showed a statistically significant increase in OVA specific IgE levels. After two boosters, a statistically significant suppression in OVA-specific IgE production occurred with SDS (1000 mg/l), SDBS (1000 and 100 mg/l), coconut soap (1000 mg/l) and the alcohol ethoxylate (10 mg/l). This study suggests that a limited number of surfactants possess an adjuvant effect whereas all surfactants at certain levels can suppress specific IgE production. PMID:11038243

  10. Rectifying Properties of Oligo(Phenylene Ethynylene) Heterometallic Molecular Junctions: Molecular Length and Side Group Effects

    PubMed Central

    Fu, Xiao-Xiao; Zhang, Rui-Qin; Zhang, Guang-Ping; Li, Zong-Liang

    2014-01-01

    The rectifying properties of α,ω-dithiol terminated oligo(phenylene ethynylene) molecules sandwiched between heterometallic electrodes, including the molecular length and side group effects, are theoretically investigated using the fully self-consistent nonequilibrium Green's function method combined with density functional theory. The results show nonlinear variation with changes in molecule length: when the molecule becomes longer, the current decreases at first and then increases while the rectification shifts in the opposite direction. This stems from the change in molecular eigenstates and the coupling between the molecule and electrodes caused by different molecular lengths. The rectifying behavior of heterometallic molecular junctions can be attributed to the asymmetric molecule-electrode contacts, which lead to asymmetric electronic tunneling spectra, molecular eigenvalues, molecular orbitals, and potential drop at reversed equivalent bias voltages. Our results provide a fundamental understanding of the rectification of heterometallic molecular junction, and a prediction of rectifiers with different rectification properties from those in the experiment, using electrodes with reduced sizes. PMID:25220880

  11. Hydrocarbon binding by proteins: structures of protein binding sites for ≥C10 linear alkanes or long-chain alkyl and alkenyl groups.

    PubMed

    Park, Jiyong; Pham, Hung V; Mogensen, Kristian; Solling, Theis Ivan; Bennetzen, Martin Vad; Houk, K N

    2015-01-16

    In order to identify potential de novo enzyme templates for the cleavage of C–C single bonds in long-chain hydrocarbons, we analyzed protein structures that bind substrates containing alkyl and alkenyl functional groups. A survey of ligand-containing protein structures deposited in the Protein Data Bank resulted in 874 entries, consisting of 194 unique ligands that have ≥10 carbons in a linear chain. Fatty acids and phospholipids are the most abundant types of ligands. Hydrophobic amino acids forming α-helical structures frequently line the binding pockets. Occupation of these binding sites was evaluated by calculating both the buried surface area and volume employed by the ligands; these quantities are similar to those computed for drug–protein complexes. Surface complementarity is relatively low due to the nonspecific nature of the interaction between the long-chain hydrocarbons and the hydrophobic amino acids. The selected PDB structures were annotated on the basis of their SCOP and EC identification numbers, which will facilitate design template searches based on structural and functional homologies. Relatively low surface complementarity and ∼55% volume occupancy, also observed in synthetic-host, alkane-guest systems, suggest general principles for the recognition of long-chain linear hydrocarbons. PMID:25526284

  12. Microbial degradation of n-alkyl tetrahydrothiophenes found in petroleum.

    PubMed Central

    Fedorak, P M; Payzant, J D; Montgomery, D S; Westlake, D W

    1988-01-01

    Although n-alkyl-substituted tetrahydrothiophenes are found in nonbiodegraded petroleums, they are not found in petroleums which have undergone biodegradation in their reservoirs. These observations suggested that this group of compounds with alkyl chain lengths from approximately C10 to at least C30 is biodegradable. Two of these sulfides, 2-n-dodecyltetrahydrothiophene (DTHT) and 2-n-undecyltetrahydrothiophene, were synthesized, and their biodegradabilities were tested by using five gram-positive, n-alkane-degrading bacterial isolates. The alkyl side chains of these compounds were oxidized, and the major intermediates found in 2-n-undecyltetrahydrothiophene- and DTHT-metabolizing cultures were 2-tetrahydrothiophenecarboxylic acid (THTC) and 2-tetrahydrothiopheneacetic acid (THTA), respectively. Four n-alkane-degrading fungi were also shown to degrade DTHT, yielding both THTA and THTC. Quantitation of tetrahydrothiophene ring-containing products in 28-day-old bacterial and fungal cultures suggested that THTC and THTA were metabolized further to unidentified products. In addition, two of the bacterial isolates were shown to degrade a mixture of n-alkyl tetrahydrothiophenes isolated from Bellshill Lake crude oil. PMID:3389816

  13. Catalytic alkylation apparatus

    SciTech Connect

    Hann, P.D.; VanPool, J.

    1989-09-05

    This patent describes an apparatus. It comprises alkylation reactor means for producing alkylate product; acid catalyst settler means having an upper portion, an intermediate portion and a lower portion; means for withdrawing alkylate product from the alkylation reactor means and for providing alkylate product from the alkylation reactor means to a point of introduction in the intermediate portion of the acid catalyst settler means; and means for establishing a temperature gradient in the upper the gas lines to the detector so that a flow rate of a sample gas passing through the detector is constant.

  14. Stabilized dialkyl aluminum complexes as alkylating agents

    SciTech Connect

    Blum, J.; Baidossi, W.; Rosenfeld, A.

    1995-12-31

    Although trialkylaluminum derivatives are widely used as Ziegler-Natta polymerization co-catalysts, their application as routine alkylating agents is limited owing to their pyrophoric nature. The authors have now found that substitution of one of the alkyl moieties by a chelating group reduces the sensitivity of the organoaluminum compounds to air, and enables one to utilize them under normal laboratory conditions.

  15. Model photo-responsive elastomers based on the self-assembly of side group liquid crystal triblock copolymers (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Kurji, Zuleikha; Kornfield, Julia A.; Kuzyk, Mark G.

    2015-10-01

    We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that form uniform and highly reproducible elastomers by self-assembly. To serve as actuators to (non-invasively) steer a fiber optic, for example in deep brain stimulation, the polymers are designed to become monodomain "single liquid crystal" elastomers during the fiber-draw process and to have a large stress/strain response to stimulation with either light or heat. A fundamental scientific question that we seek to answer is how the interplay between the concentration of photoresponsive mesogens and the proximity to the nematic-isotropic transition governs the sensitivity of the material to stimuli. Specifically, a matched pair of polymers, one with ~5% azobenzene-containing side groups (~95% cyanobiphenyl side groups) and the other with 100% cyanobiphenyl side groups were synthesized from identical triblock pre-polymers (with polystyerene end blocks and 1,2-polybutadiene midblocks). These can be blended in various ratios to prepare a series of elastomers that are precisely matched in terms of the backbone length between physical crosslinks (because each polymer is derived from the same pre-polymer), while differing in % azobenzene side groups, allowing the effect of concentration of photoresponsive groups to be unambiguously determined.

  16. Smart polymers containing substituted coumarin side groups enable photo-induced tuning of focal length of intraocular lenses

    NASA Astrophysics Data System (ADS)

    Schraub, Martin; Hampp, Norbert

    2011-03-01

    Over the past 100 years medicine evolved continuously, which can clearly be seen in the rising average of life expectancy. But as the population becomes older and older the number of old age diseases increases. Cataract is such an old age disease and worldwide the number one reason for blindness. Implantation of IOL's is up-to-date the only possibility to restore vision. In this study we present novel polymers containing derivatized coumarins in the side chains as smart materials for IOL manufacturing. These materials enable tuning of the focal length of an already implanted IOL by 2 diopters via photo induced dimerization and cleavage of the coumarin side groups respectively. The advantages of these new polymers are increased dimerization rates while decreasing the energy dose needed for photochemical dimerization of the coumarin side groups.

  17. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    EPA Science Inventory

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  18. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    SciTech Connect

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  19. Preparation and characterization of highly cross-linked polyimide aerogels based on polyimide containing trimethoxysilane side groups.

    PubMed

    Pei, Xueliang; Zhai, Wentao; Zheng, Wenge

    2014-11-11

    In this study, highly cross-linked and completely imidized polyimide aerogels were prepared from polyimide containing trimethoxysilane side groups, which was obtained as the condensation product of polyimide containing acid chloride side groups and 3-aminopropyltrimethoxysilane. After adding water and acid catalyst, the trimethoxysilane side groups hydrolyzed and condensed one another, and a continuous increase in the complex viscosities of the polyimide solutions with time was observed. The formed polyimide gels were dried by freeze-drying from tert-butyl alcohol to obtain polyimide aerogels, which consisted of a three-dimensional network of polyimide fibers tangled together. By varying the solution concentration of the polyimide containing trimethoxysilane side groups, polyimide aerogels with different densities (ranging from 0.19 to 0.42 g/cm(3)) were obtained. The resulting polyimide aerogels had small pore diameter (ranging from 20.7 to 58.3 nm), high surface area (ranging from 310 to 344 m(2)/g), high 5% weight loss temperature in air (at about 440 °C), and an excellent mechanical property. In addition, the glass transition temperature (349 °C) of the polyimide aerogels was much higher than that (210 °C) of the corresponding linear polyimide. So, even after being heated at 300 °C for 30 min, the porous structure of the polyimide aerogels was not completely destroyed. PMID:25340747

  20. Copper-catalyzed direct alkylation of 1,3-azoles with N-tosylhydrazones bearing a ferrocenyl group: a novel method for the synthesis of ferrocenyl-based ligands.

    PubMed

    Teng, Qiang; Hu, Jianfeng; Ling, Li; Sun, Ranfeng; Dong, Junyang; Chen, Shufeng; Zhang, Hao

    2014-10-21

    Copper-catalyzed cross-coupling of ferrocenyl ketone-derived N-tosylhydrazones with benzo[d]oxazole leads to the direct C-H bond functionalization by a secondary ferrocenyl alkyl group. This direct C-H bond alkylation of azoles with N-tosylhydrazones bearing a ferrocenyl group uses inexpensive CuBr as the catalyst without any ligand. The reaction is operationally simple and conducted under mild conditions, giving the corresponding ferrocenyl-based ligands in moderate to good yields. Furthermore, they were able to act as bidentate ligands, giving rise to the corresponding palladium chelated complex 6a-6c, which were obtained by reaction of 5a-5c with [PdCl2(MeCN)2]. PMID:25127018

  1. Effect of alkyl chain length, head group and nature of the surfactant on the hydrolysis of 1,3-benzoxazine-2,4-dione and its derivatives.

    PubMed

    Al-Ayed, Abdullah S; Ali, Mohd Sajid; Al-Lohedan, Hamad A; Al-Sulaim, Adel M; Issa, Zuheir A

    2011-09-01

    The alkaline hydrolysis of carsalam (2H-1,3-benzoxazine-2,4(3H)-dione), denoted as I, and its N-substituted derivatives i.e., N-methyl-1,3-benzoxazine-2,4-dione (II) and N-benzoyl-1,3-benzoxazine-2,4-dione (III) was studied spectrophotometrically at physiological temperature. The rate of hydrolysis was found to be independent on the substrate concentration. In case of I, the reaction was fractional order with respect to [OH(-)] while for II and III, reaction obeyed the first order kinetics. Effect of cationic surfactants with varying hydrophobic chains (cetyltrimethylammonium bromide, CTAB, tetradecyltrimethylammonium bromide, TTAB and dodecyltrimethylammonium bromide, DTAB) and with different head-group (cetyl pyridinium chloride, CPC) and anionic surfactant (sodium dodecyl sulfate, SDS) was also seen on the rate of alkaline hydrolysis of the carsalam and its derivatives. Cationic surfactants first catalyzed the rate of hydrolysis at lower concentrations followed by the inhibition at higher concentrations. The length of the alkyl chain had remarkable effect on the catalytic efficiency of the surfactants. Similarly N-substitution on substrate also increased the catalysis by micelles. The anionic surfactant SDS inhibited the rate of hydrolysis at all of the concentrations studied. The catalysis by cationic micelles followed by inhibition was treated in terms of the pseudophase ion-exchange model, while for the inhibition by SDS micelles the Menger-Portnoy model was used to fit the data. The effect of salts (NaCl, NaBr and (CH(3))(4)NBr) was also seen on the hydrolysis of II and it was found that all salts inhibited the rate of reaction. The inhibition follows the trend NaCl

  2. Theory Of Alkyl Terminated Silicon Quantum Dots

    SciTech Connect

    Reboredo, F; Galli, G

    2004-08-19

    We have carried out a series of ab-initio calculations to investigate changes in the optical properties of Si quantum dots as a function of surface passivation. In particular, we have compared hydrogen passivated dots with those having alkyl groups at the surface. We find that, while on clusters with reconstructed surfaces a complete alkyl passivation is possible, steric repulsion prevents full passivation of Si dots with unreconstructed surfaces. In addition, our calculations show that steric repulsion may have a dominant effect in determining the surface structure, and eventually the stability of alkyl passivated clusters, with results dependent on the length of the carbon chain. Alkyl passivation weakly affects optical gaps of silicon quantum dots, while it substantially decreases ionization potentials and electron affinities and affect their excited state properties. On the basis of our results we propose that alkyl terminated quantum dots may be size selected taking advantage of the change in ionization potential as a function of the cluster size.

  3. Synthesis and Antioxidant Activity of Hydroxytyrosol Alkyl-Carbonate Derivatives.

    PubMed

    Fernandez-Pastor, Ignacio; Fernandez-Hernandez, Antonia; Rivas, Francisco; Martinez, Antonio; Garcia-Granados, Andres; Parra, Andres

    2016-07-22

    Three procedures have been investigated for the isolation of tyrosol (1) and hydroxytyrosol (2) from a phenolic extract obtained from the solid residue of olive milling. These three methods, which facilitated the recovery of these phenols, were chemical or enzymatic acetylation, benzylation, and carbomethoxylation, and subsequent carbonylation or acetonation reactions. Several new lipophilic alkyl-carbonate derivatives of hydroxytyrosol have been synthesized, coupling the primary hydroxy group of this phenol, through a carbonate linker, using alcohols with different chain lengths. The antioxidant properties of these lipophilic derivatives have been evaluated by different methods and compared with free hydroxytyrosol (2) and also with the well-known antioxidants BHT and α-tocopherol. Three methods were used for the determination of this antioxidant activity: FRAP and ABTS assays, to test the antioxidant power in hydrophilic media, and the Rancimat test, to evaluate the antioxidant capacity in a lipophilic matrix. These new alkyl-carbonate derivatives of hydroxytyrosol enhanced the antioxidant activity of this natural phenol, with their antioxidant properties also being higher than those of the commercial antioxidants BHT and α-tocopherol. There was no clear influence of the side-chain length on the antioxidant properties of the alkyl-carbonate derivatives of 2, although the best results were achieved mainly by the compounds with a longer chain on the primary hydroxy group of this natural phenolic substance. PMID:27337069

  4. A new derivatization reagent for LC-MS/MS screening of potential genotoxic alkylation compounds.

    PubMed

    van Wijk, A M; Niederländer, H A G; Siebum, A H G; Vervaart, M A T; de Jong, G J

    2013-02-23

    A screening method for trace analysis of potentially genotoxic alkylating compounds has been developed using butyl 1-(pyridin-4-yl) piperidine 4-carboxylate (BPPC) as a new, selective pre-column derivatization reagent for their subsequent analysis by hydrophilic interaction liquid chromatography (HILIC) hyphenated with tandem mass spectrometry (LC-MS/MS). The new derivatization reagent is a modification of 4-dimethylaminopyridine (4-DMAP) previously used for the determination of potentially genotoxic compounds. By using the new reagent the screening potential was enhanced without compromising reactivity. Derivatization at a high pH value was carried out and the reaction time at 60°C was 24h to anticipate for alkyl chlorides showing to be less reactive. The new reagent was designed to obtain reagent related fragmentation of the whole reagent as well as a side group of the reagent. Collision energies for detection of alkylating components derivatized using the new reagent are shown to be significantly more universal than with 4-DMAP. Neutral loss scanning on the fragmentation related to the build in side group remedies shortcomings in the screening for alkyl halides observed when using 4-DMAP. The new approach allows for screening of alkyl halides and alkyl sulfonates at trace levels down to 1 mg kg(-1) and target analysis at about a factor of 10 lower without a significant effect of the active pharmaceutical ingredient (API) matrix. The synthesis of the reagent, investigation of reactivity, the specificity of the fragmentation of derivatives and screening conditions in MS/MS analysis are described. PMID:23245244

  5. Temporal characteristics of polarization holographic gratings formed in a photosensitive polymeric film containing N-benzylideneaniline derivative side groups

    SciTech Connect

    Sasaki, Tomoyuki Shoho, Takashi; Noda, Kohei; Ono, Hiroshi; Kawatsuki, Nobuhiro

    2014-04-21

    A polarization holographic grating was recorded in a transparent thin film formed from polymethacrylate with N-benzylideneaniline (NBA) derivative side groups. We measured the real time diffraction properties. The data were analyzed based on a theoretical model that accounted for the distribution of optical anisotropy caused by molecular reorientation as well as for surface relief (SR) deformation caused by molecular motion. Optical anisotropy rapidly increased and then slowly decreased, with increasing recording time. This phenomenon was described based on photoisomerization and photocleavage reactions of the NBA side groups. SR deformation was also induced in the film by polarization holographic recording, without any subsequent processes. The photoinduced optical anisotropy and SR deformation were retained after the recording was turned off.

  6. Effect of donor strength of extended alkyl auxiliary groups on optoelectronic and charge transport properties of novel naphtha[2,1-b:6,5-b']difuran derivatives: simple yet effective strategy.

    PubMed

    Chaudhry, Aijaz Rasool; Ahmed, R; Irfan, Ahmad; Shaari, A; Isa, Ahmad Radzi Mat; Muhammad, Shabbir; Al-Sehemi, Abdullah G

    2015-08-01

    The present study spotlights the designing of new derivatives of 2,7-bis (4-octylphenyl) naphtho [2,1-b:6,5-b'] difuran (C8-DPNDF) by substituting the alkyl groups (methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups) at para position. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods are employed to optimize the molecular structures in ground and first excited states, respectively. Several electro-optical properties including hole/electron reorganization energies (λh/λe), electron affinities (EAs), ionization potentials (IPs), molecular electrostatic potentials (MEP), and frontier molecular orbitals (FMOs) have been evaluated. Furthermore their transfer integrals and intrinsic mobilities values have also been calculated. From this study, it is found that hole mobility of octyl containing derivative is raised to 4.69 cm(2) V(-1) s(-1). Moreover with attaching octyl group, hole transfer integral values have also been enhanced in newly designed derivatives. The balanced hole and electron reorganization energies, and improved transfer integrals lead to enhanced mobility in derivatives with octyl group, highlighting them as an efficient hole transfer material. Unlike the other electro-optical properties, the intrinsic hole mobility has increased because of transfer integral values of octyl containing derivative C8-DPNDF due to the dense and close crystal packing of C8-DPNDF. However, photostability of furan-based materials has not changed by increasing length of extended alkyl chain. Thus our present investigation highlights the importance of alkyl auxiliary groups that are often neglected/replaced with simple methyl group to save computation costs. Graphical Abstract The hole and electron reorganization energies of naphtho[2,1-b:6,5-b']difuran derivatives. PMID:26177706

  7. Are Student Groups Dysfunctional? Perspectives from Both Sides of the Classroom

    ERIC Educational Resources Information Center

    Chapman, Kenneth J.; Meuter, Matthew L.; Toy, Daniel; Wright, Lauren K.

    2010-01-01

    In today's business world, the ability to work efficiently and effectively in a team is mandatory to a business student's success. Many employers rank "ability to work with a group" as one of the most important attributes for hiring business school graduates. Although an abundance of research has investigated group processes and dynamics during…

  8. Thiophene-Diketopyrrolopyrrole-Based Quinoidal Small Molecules as Solution-Processable and Air-Stable Organic Semiconductors: Tuning of the Length and Branching Position of the Alkyl Side Chain toward a High-Performance n-Channel Organic Field-Effect Transistor.

    PubMed

    Wang, Chao; Qin, Yunke; Sun, Yuanhui; Guan, Ying-Shi; Xu, Wei; Zhu, Daoben

    2015-07-29

    A series of thiophene-diketopyrrolopyrrole-based quinoidal small molecules (TDPPQ-2-TDPPQ-5) bearing branched alkyl chains with different side-chain lengths and varied branching positions are synthesized. Field-effect transistor (FET) measurement combined with thin-film characterization is utilized to systematically probe the influence of the side-chain length and branching position on the film microstructure, molecular packing, and, hence, charge-transport property. All of these TDPPQ derivatives show air-stable n-channel transporting behavior in spin-coated FET devices, which exhibit no significant decrease in mobility even after being stored in air for 2 months. Most notably, TDPPQ-3 exhibits an outstanding n-channel semiconducting property with electron mobilities up to 0.72 cm(2) V(-1) s(-1), which is an unprecedented value for spin-coated DPP-based n-type semiconducting small molecules. A balance of high crystallinity, satisfactory thickness uniformity and continuity, and strong intermolecular interaction accounts for the superior charge-transport characteristics of TDPPQ-3 films. Our study demonstrates that tuning the length and branching position of alkyl side chains of semiconducting molecules is a powerful strategy for achieving high FET performance. PMID:26134920

  9. D-Side: A Facility and Workforce Planning Group Multi-criteria Decision Support System for Johnson Space Center

    NASA Technical Reports Server (NTRS)

    Tavana, Madjid

    2005-01-01

    "To understand and protect our home planet, to explore the universe and search for life, and to inspire the next generation of explorers" is NASA's mission. The Systems Management Office at Johnson Space Center (JSC) is searching for methods to effectively manage the Center's resources to meet NASA's mission. D-Side is a group multi-criteria decision support system (GMDSS) developed to support facility decisions at JSC. D-Side uses a series of sequential and structured processes to plot facilities in a three-dimensional (3-D) graph on the basis of each facility alignment with NASA's mission and goals, the extent to which other facilities are dependent on the facility, and the dollar value of capital investments that have been postponed at the facility relative to the facility replacement value. A similarity factor rank orders facilities based on their Euclidean distance from Ideal and Nadir points. These similarity factors are then used to allocate capital improvement resources across facilities. We also present a parallel model that can be used to support decisions concerning allocation of human resources investments across workforce units. Finally, we present results from a pilot study where 12 experienced facility managers from NASA used D-Side and the organization's current approach to rank order and allocate funds for capital improvement across 20 facilities. Users evaluated D-Side favorably in terms of ease of use, the quality of the decision-making process, decision quality, and overall value-added. Their evaluations of D-Side were significantly more favorable than their evaluations of the current approach. Keywords: NASA, Multi-Criteria Decision Making, Decision Support System, AHP, Euclidean Distance, 3-D Modeling, Facility Planning, Workforce Planning.

  10. Alkyl rearrangement processes in organozirconium complexes. Observation of internal alkyl complexes during hydrozirconation

    SciTech Connect

    Chirik, P.J.; Day, M.W.; Labinger, J.A.; Bercaw, J.E.

    1999-11-10

    Isotopically labeled alkyl zirconocene complexes of the form (CpR{sub n}){sub 2}Zr(CH{sub 2}CDR{sub 2}{prime})(X) (CpR{sub n} = alkyl-substituted cyclopentadienyl; R{prime} = H, alkyl group; X = H, D, Me) undergo isomerization of the alkyl ligand as well as exchange with free olefin in solution under ambient conditions. Increasing the substitution on the Cp ring results in slower isomerization reactions, but these steric effects are small. In contrast, changing X has a very large effect on the rate of isomerization. Pure {sigma}-bonding ligands such as methyl and hydride promote rapid isomerization, whereas {pi}-donor ligands inhibit {beta}-H elimination and hence alkyl isomerization. For ({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}Zr(R)(Cl), internal alkyl complexes have been observed for the first time. The rate of isomerization depends on the length of the alkyl group: longer alkyl chains (heptyl, hexyl) isomerize faster than shorter chains (butyl). The transient intermediate species have been identified by a combination of isotopic labeling and {sup 1}H, {sup 2}H, and {sup 13}C NMR experiments. The solid-state structure of the zirconocene cyclopentyl chloride complex, Cp{sub 2}Zr(cyclo-C{sub 5}H{sub 9})(Cl), has been determined by X-ray diffraction.

  11. Effect of side-chain carbonyl groups on the interface of vinyl polymers with water.

    PubMed

    Oda, Yukari; Horinouchi, Ayanobu; Kawaguchi, Daisuke; Matsuno, Hisao; Kanaoka, Shokyoku; Aoshima, Sadahito; Tanaka, Keiji

    2014-02-11

    The nature of the polymer-water interface in the poly(methyl 2-propenyl ether) (PMPE)-water model system is investigated by sum-frequency generation spectroscopy, which at the moment gives the best depth resolution among available techniques. PMPE, synthesized via living cationic polymerization, is structurally similar to poly(methyl methacrylate) (PMMA) except for lacking a carbonyl group. We here probe the polymer local conformation as well as the aggregation states of water at the interface. Comparing the results of our measurements to the PMMA-water system, the effect of a carbonyl group on the water structure at the interface is discussed. This knowledge should be crucial to the design and construction of highly functionalized polymer interfaces for bioapplications. PMID:24467626

  12. Sensing and transmission characteristics of a rocking filter fabricated in a side-hole fiber with zero group birefringence.

    PubMed

    Anuszkiewicz, A; Martynkien, T; Mergo, P; Makara, M; Urbanczyk, W

    2013-05-20

    We report on sensing and transmission characteristics of rocking filters fabricated in a silica side-hole fiber with group birefringence changing its sign at certain wavelength (λ(G = 0)), which corresponds to parabolic-like spectral dependence of beat length. Unusual birefringence dispersion of the side-hole fiber is induced by an elliptical germanium doped core located in a narrow glass bridge between two holes. Rocking filters fabricated in such a fiber have two resonances of the same order located on both sides of λ(G = 0). The sensitivity of both resonances has an opposite sign, which makes it possible to double the response of the rocking filter by applying the differential interrogation scheme. We demonstrate that in this way a pressure sensitivity of the rocking filter can be enlarged to 132 nm/MPa. We also show that by fabricating the rocking filter with a period close to maximum beat length a coupling between polarization modes can be obtained in a broad band reaching 240 nm. PMID:23736486

  13. Amphiphilic polyphosphazenes as membrane materials: influence of side group on radiation cross-linking.

    PubMed

    Allcock, H R; Gebura, M; Kwon, S; Neenan, T X

    1988-11-01

    The amphiphilic mixed-substituent polyphosphazenes, [NP(OCH2CF3)x (NHCH3)y)]n and [NP(OC6H5)x (NHCH3)y]n, have been prepared by the sequential replacement of chlorine in [NPCI2]n by trifluorethoxide or phenoxide and methylamine. Thin films of these species were cross-linked by exposure to gamma radiation and the semipermeability of the resultant membranes was monitored. The radiation-induced cross-linking and membrane-forming properties of these polymers were compared with those of the single substituent polymers, [NP(OCH2CF3)2]n, [NP(OC6H5)2]n, and [NP(NHCH3)2]n. The radiation-cross-linking and appeared to involve free radical reactions at the methyl groups of the methylamino substituents. The possible utility of these materials in biomedical research is discussed. PMID:3224137

  14. A simplified surfactant dosing procedure in respiratory distress syndrome: the "side-hole" randomized study. Spanish Surfactant Collaborative Group.

    PubMed

    Valls-i-Soler, A; López-Heredia, J; Fernández-Ruanova, M B; Gastiasoro, E

    1997-07-01

    The aim of this study was to compare the incidence of acute adverse events and long-term outcome of two different surfactant dosing procedures in respiratory distress syndrome (RDS). The effects of two surfactant dosing procedures on the incidence of transient hypoxia and bradycardia, gas exchange, ventilatory requirements and 28 d outcome were compared. The patients, comprising 102 infants (birthweight 600-2000 g) with RDS on mechanical ventilation with FiO2 > or = 0.4, were randomized at 2-24 h to receive 200 mg kg(-1) of Curosurf; in 56 it was given by bolus delivery, and in 55 by a simplified technique (dose given in 1 min via a catheter introduced through a side-hole in the tracheal tube adaptor. The baby's position was not changed and ventilation was not interrupted). Two additional surfactant doses (100 mg kg(-1)) were also given, by the same method, if ventilation with FiO2 > or = 0.3 was needed 12 and 24 h after the initial dose. The number of episodes of hypoxia and/or bradycardia was similar in both groups. A slight and transient increase in PaCO2 was observed in the side-hole group. The efficacy of the surfactant, based on oxygenation improvement, ventilator requirements, number of doses required and incidence of air leaks, was similar. No differences were observed in the incidence of intraventricular haemorrhage, patent ductus arteriosus, bronchopulmonary dysplasia or survival. In conclusion, a simplified surfactant dosing procedure not requiring fractional doses, ventilator disconnection, changes in the baby's position or manual bagging was found to be as effective as bolus delivery. The number of dosing-related transient episodes of hypoxia and bradycardia was not decreased by the slow, 1 min, side-hole instillation procedure. PMID:9240884

  15. Synthesis of dendrigraft poly(ϵ-caprolactone)s using side hydroxyl groups for the grafting of branch chains.

    PubMed

    Cheng, Juan; Ling, Xiujun; Zhong, Zhenlin; Zhuo, Renxi

    2011-11-15

    Dendrigraft poly(ϵ-caprolactone)s with high molecular weight and narrow polydispersity are synthesized via a convenient generation-growth approach. Copolymerization of ϵ-caprolactone (CL) and 4-(2-benzoxyethoxy)-ϵ-caprolactone (BECL) with stannous octanoate as a catalyst affords a functionalized poly(ϵ-caprolactone) (PCL) with benzyl-protected hydroxyl side groups. After removal of benzyl groups by palladium-catalyzed hydrogenolysis, the graft copolymerization of CL and BECL onto the hydroxyl-bearing linear polyester (zero-generation) affords the first-generation graft polyester. Further deprotection and graft polymerization cycles led to dendrigraft polyesters. Molecular weights are multiplied in each graft copolymerization. The second-generation dendrigraft poly(ϵ-caprolactone) has an M(w) of 236 000 g·mol(-1) and M(w) /M(n) of 1.53. PMID:21928304

  16. Understanding the effect of side groups in ionic liquids on carbon-capture properties: a combined experimental and theoretical effort

    SciTech Connect

    Yan, Fangyong; Lartey, Michael; Damodaran, Krishnan; Albenze, Erik; Thompson, Robert L.; Kim, Jihan; Harancyzk, Maciel; Nulwala, Hunaid B.; Luebke, David R.; Smit, Berend

    2013-01-01

    Ionic liquids are an emerging class of materials with applications in a variety of fields. Steady progress has been made in the creation of ionic liquids tailored to specific applications. However, the understanding of the underlying structure–property relationships has been slower to develop. As a step in the effort to alleviate this deficiency, the influence of side groups on ionic liquid properties has been studied through an integrated approach utilizing synthesis, experimental determination of properties, and simulation techniques. To achieve this goal, a classical force field in the framework of OPLS/Amber force fields has been developed to predict ionic liquid properties accurately. Cu(I)-catalyzed click chemistry was employed to synthesize triazolium-based ionic liquids with diverse side groups. Values of densities were predicted within 3% of experimental values, whereas self-diffusion coefficients were underestimated by about an order of magnitude though the trends were in excellent agreement, the activation energy calculated in simulation correlates well with experimental values. The predicted Henry coefficient for CO{sub 2} solubility reproduced the experimentally observed trends. This study highlights the importance of integrating experimental and computational approaches in property prediction and materials development, which is not only useful in the development of ionic liquids for CO{sub 2} capture but has application in many technological fields.

  17. The synthesis and imaging study of a series of novel photoactive polymers with diazoketo groups in their side chains

    NASA Astrophysics Data System (ADS)

    Liu, Lu; Zou, Yingquan; Yang, Yuchun; Huang, Yong; Liu, Qisheng; Niu, Huinan

    2009-12-01

    A kind of photoactive polymer with diazoketo groups in its side chains has been reported in SPIE and other related papers, and this photoactive polymer can be used in deep UV non-CARs (non-chemically amplified resists) system. Based on the work above, a series of novel photoactive monomers with substituents like phenyl, p-methylphenyl, p-methoxyphenyl, p-dimethylaminophenyl on the end of the molecule are designed and synthesized. By changing their substituents, the maximum-absorption wavelength of the photoactive monomers has been moved to 356nm, and it still has comparatively large absorption at 365nm (I-line). A series of photoactive polymers were obtained by polymerizing the monomer with methyl methacrylate and 2-hydroxyethyl methacrylate together. Upon irradiaton in the waveleng of 365nm, the diazoketo groups which are in the side chains of the photoactive polymers undergo the wolff rearrangment and afford ketens that react with water to provide base-soluble photoproducts. Applying this kind of photoactive polymers to non-CARs, a positive image can be obtained. This kind of photoactive polymers have great value in I-line non-CARs, TFT-LCD and IC discrete devices processing. And its anti-dry etching ability is enhanced by the introduction of the benzene ring.

  18. A dynamic and ultrafast group delay tuning mechanism in two microcavities side-coupled with a waveguide system

    SciTech Connect

    Wang, Boyun; Wang, Tao Tang, Jian; Li, Xiaoming; Zhu, Youjiang

    2014-10-07

    We theoretically propose a dynamic and ultrafast group delay tuning mechanism in two microcavities side-coupled to a waveguide system through external optical pump beams. The optical Kerr effect modulation method is applied to improve tuning rate with response time of subpicoseconds or even femtoseconds. The group delay of an all-optical analog to electromagnetically induced transparency effect can be controlled by tuning either the frequency of photonic crystal microcavities or the propagation phase of line waveguide. Group delay is controlled between 5.88 and 70.98 ps by dynamically tuning resonant frequencies of the microcavities. Alternatively, the group delay is controlled between 1.86 and 12.08 ps by dynamically tuning the propagation phase of line waveguide. All observed schemes are analyzed rigorously through finite-difference time-domain simulations and coupled-mode formalism. Results show a new direction toward microstructure integration optical pulse trapping and all-optical dynamical storage of light devices in optical communication and quantum information processing.

  19. Palladium-Catalyzed, Ring-Forming Aromatic C–H Alkylations with Unactivated Alkyl Halides

    PubMed Central

    Venning, Alexander R. O.; Bohan, Patrick T.; Alexanian, Erik J.

    2015-01-01

    A catalytic C–H alkylation using unactivated alkyl halides and a variety of arenes and heteroarenes is described. This ring-forming process is successful with a variety of unactivated primary and secondary alkyl halides, including those with β-hydrogens. In contrast to standard polar or radical cyclizations of aromatic systems, electronic activation of the substrate is not required. The mild, catalytic reaction conditions are highly functional group tolerant and facilitate access to a diverse range of synthetically and medicinally important carbocyclic and heterocyclic systems. PMID:25746442

  20. Synthesis of alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol analogues: polar side-chain modification, sulfonium and selenonium heteroatom variants, conformational analysis, and evaluation as glycosidase inhibitors.

    PubMed

    Szczepina, Monica G; Johnston, Blair D; Yuan, Yue; Svensson, Birte; Pinto, B Mario

    2004-10-01

    The syntheses of N-alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol derivatives having either a D- or an L-erythritol-3-sulfate functionalized N-substituent are reported. The alkylating agent used was a cyclic sulfate derivative, whereby selective attack of the nitrogen atom at the least hindered primary center afforded the desired ammonium salt. In aqueous solution, these salts were configurationally labile at the ammonium center. Sulfonium and/or selenonium analogues of the ammonium salts were prepared by analogous reactions. The chalcogen salts were obtained as mixtures of diastereomers, separable in some cases, differing only in the stereochemistry at the configurationally stable sulfur or selenium atoms. Proof of configuration and conformation of each compound was obtained by detailed NMR experiments. The compounds are six-membered ring analogues of salacinol, a known sulfonium-salt glucosidase inhibitor. Evaluation of the target compounds for enzyme inhibition of the glucosidase enzyme glucoamylase G2 indicated that these compounds were either inactive or, at best, only weak inhibitors of maltose hydrolysis. PMID:15453780

  1. Infrared and Raman spectra of N-acetyl- L-amino acid methylamides with aromatic side groups

    NASA Astrophysics Data System (ADS)

    Matsuura, Hiroatsu; Hasegawa, Kodo; Miyazawa, Tatsuo

    Infrared and Raman spectra of N-acetyl- L-phenylalanine methylamide, N-acetyl- L-tyrosine methylamide and N-acetyl- L-tryptophan methylamide, as model compounds of aromatic amino acid residues in proteins, were measured in the solid state and in methanol solutions. Vibrational assignments of the spectra were made by utilizing the deuteration effect and by comparison with the spectra of related compounds which include toluene, p-cresol and 3-methylindole. The amide I, III and IV bands were strong in Raman scattering, but other characteristic amide bands were ill-defined. In the Raman spectra of methanol solutions, only the bands due to the aromatic side group vibrations were markedly observed, but those due to the peptide backbone vibrations were very weak, suggesting the coexistence of various molecular conformations in solution.

  2. Molecular basis for sequence-specific DNA alkylation by CC-1065

    SciTech Connect

    Hurley, L.H.; Lee, C.S.; McGovren, J.P.; Warpehoski, M.A.; Mitchell, M.A.; Kelly, R.C.; Aristoff, P.A.

    1988-05-17

    CC-1065 is a potent antitumor antibiotic that binds covalently to N3 of adenine in the minor groove of DNA. The CC-1065 molecule is made up of three repeating pyrroloindole subunits, one of which (the left-hand one or A subunit) contains a reactive cyclopropyl function. The drug reacts with adenines in DNA in a highly sequence-specific manner, overlapping four base pairs to the 5'-side of the covalently modified base. Concomitant with CC-1065 covalent binding to DNA is an asymmetric effect on local DNA structure which extends more than one helix to turn the 5'-side of the covalent binding site. The DNA alkylation, sequence specificity, and biological potency of CC-1065 and a select group of trimeric synthetic analogues were evaluated. The results suggest that (a) noncovalent interactions between this series of compounds and DNA do not lead to the formation of complexes stable enough to be detected by footprinting methods, (b) sequence specificity and alkylation intensity can be modulated by the substituents on the nonreactive middle and right-hand segments, and (c) biological potency correlates well with ability to alkylate DNA. In addition, the extent and the sequence specificity of covalent adduct formation between linear DNA fragments and three analogues comprised of the CC-1065 alkylating subunit linked to zero (analogue A), one (analogue AB), or two (analogue ABC) nonreactive indole subunits were compared. These results provide strong experimental evidence for the importance of sequence-dependent site reactivity, rather than noncovalent minor groove interactions, in determining the alkylation specificity of some DNA-reactive molecules.

  3. Alkylating potential of oxetanes.

    PubMed

    Gómez-Bombarelli, Rafael; Palma, Bernardo Brito; Martins, Célia; Kranendonk, Michel; Rodrigues, Antonio S; Calle, Emilio; Rueff, José; Casado, Julio

    2010-07-19

    Small, highly strained heterocycles are archetypical alkylating agents (oxiranes, beta-lactones, aziridinium, and thiirinium ions). Oxetanes, which are tetragonal ethers, are higher homologues of oxiranes and reduced counterparts of beta-lactones, and would therefore be expected to be active alkylating agents. Oxetanes are widely used in the manufacture of polymers, especially in organic light-emitting diodes (OLEDs), and are present, as a substructure, in compounds such as the widely used antimitotic taxol. Whereas the results of animal tests suggest that trimethylene oxide (TMO), the parent compound, and beta,beta-dimethyloxetane (DMOX) are active carcinogens at the site of injection, no studies have explored the alkylating ability and genotoxicity of oxetanes. This work addresses the issue using a mixed methodology: a kinetic study of the alkylation reaction of 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilicity similar to that of DNA bases, by three oxetanes (TMO, DMOX, and methyloxetanemethanol), and a mutagenicity, genotoxicity, and cell viability study (Salmonella microsome test, BTC E. coli test, alkaline comet assay, and MTT assay). The results suggest either that oxetanes lack genotoxic capacity or that their mode of action is very different from that of epoxides and beta-lactones. PMID:20550097

  4. The first report of polymerization and characterization of aniline bearing chiral alkyl group on ring via covalent bond; poly[(±)-2-(sec-butyl)aniline

    NASA Astrophysics Data System (ADS)

    Modarresi-Alam, Ali Reza; Amirazizi, Homeyra Alsadat; Movahedifar, Fahimeh; Farrokhzadeh, Abdolkarim; Asli, Gholam Reza; Nahavandi, Hamed

    2015-03-01

    A chiral alkyl substituted of polyaniline derivative, poly[(±)-2-(sec-butyl)aniline] was successfully synthesized by interfacial and conventional oxidative chemical polymerization. Both distilled and dark monomers (undistilled) were used in polymerization. The polymers were characterized in details by several techniques, proton nuclear magnetic resonance (1H NMR), carbon nuclear magnetic resonance (13C NMR), high resolution mass spectroscopy (HRMS), Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis) spectroscopy, elemental analysis (CHNS) and X-ray diffraction (XRD) as well as gel-permeation chromatography (GPC) and scanning electron microscopy (SEM) images. Conductivity of polymers was also measured. Spectroscopic studies have proved the formation of polymer and confirm the pernigraniline form of polyaniline. Mass spectra of polymers synthesized were studied exactly and prove the presence of both amine and iminium nitrogen as well as counter ions of Cl-, HSO4- and SO42-. Size of polymer particles is considerably smaller by interfacial polymerization. Polymers show semi-crystalline structure in XRD analysis. More crystalline structure and conductivity gained from interfacial polymerization. Molecular weights of polymers were lower in comparison with polyaniline according to GPC results. The effect of neutral salt (LiCl) was studied on molecular weight.

  5. Preparation of a series of model poly(n-alkyl styrene)s and their viscoelasticity and glass transition temperatures

    NASA Astrophysics Data System (ADS)

    Matsushima, Satoru; Takano, Atsushi; Takahashi, Yoshiaki; Matsushita, Yushu

    Viscoelasticity and glass transition temperatures for linear polymers of many species have been investigated so far, and it is well-known that the melt viscosity for the linear polymers varies with molecular weight in essentially the same manner such as packing length theory. It is important to understand the relationship between the viscosity and the molecular structure of various kinds of linear polymers. To investigate the relationship deeply, viscoelastic measurements using linear polymer analogues which the molecular structure is systematically varied should be useful. For example, poly(n-alkyl-substituted polymers) such as poly(n-alkyl methacrylate)s are one of the good candidate. In this study, a series of poly(n-alkyl styrene)s with the different number of carbon atoms(n) in the side alkyl groups (n =1, 2, 3, 4, 6, 8, 10 and 12) were carefully synthesized by an anionic polymerization technique, and the viscoelasticity and the glass transition temperatures of the poly(n-alkyl styrene)s with high molecular weight (Mw >=4Me) and narrow molecular weight distribution (Mw/Mn <=1.1) were discussed.

  6. Electrical transport and field-effect transistors using inkjet-printed SWCNT films having different functional side groups.

    PubMed

    Gracia-Espino, Eduardo; Sala, Giovanni; Pino, Flavio; Halonen, Niina; Luomahaara, Juho; Mäklin, Jani; Tóth, Géza; Kordás, Krisztián; Jantunen, Heli; Terrones, Mauricio; Helistö, Panu; Seppä, Heikki; Ajayan, Pulickel M; Vajtai, Robert

    2010-06-22

    The electrical properties of random networks of single-wall carbon nanotubes (SWNTs) obtained by inkjet printing are studied. Water-based stable inks of functionalized SWNTs (carboxylic acid, amide, poly(ethylene glycol), and polyaminobenzene sulfonic acid) were prepared and applied to inkjet deposit microscopic patterns of nanotube films on lithographically defined silicon chips with a back-side gate arrangement. Source-drain transfer characteristics and gate-effect measurements confirm the important role of the chemical functional groups in the electrical behavior of carbon nanotube networks. Considerable nonlinear transport in conjunction with a high channel current on/off ratio of approximately 70 was observed with poly(ethylene glycol)-functionalized nanotubes. The positive temperature coefficient of channel resistance shows the nonmetallic behavior of the inkjet-printed films. Other inkjet-printed field-effect transistors using carboxyl-functionalized nanotubes as source, drain, and gate electrodes, poly(ethylene glycol)-functionalized nanotubes as the channel, and poly(ethylene glycol) as the gate dielectric were also tested and characterized. PMID:20481513

  7. The Effect of Dissolved Side-Group Polymers on Pattern Dynamics in Nematic Liquid Crystals in a Rotating Magnetic Field

    NASA Astrophysics Data System (ADS)

    Pashkovsky, E. E.; Stille, W.; Strobl, G.; Talebi, D.

    1997-05-01

    Patterns formed by inversion walls in nematic layers exposed to a rotating magnetic field were studied. Dilute solutions of a mesogenic side group polymethacrylate in a low molecular weight liquid crystal (5CB) were used in comparison with the pure solvent. As found in a previous work, in this system the intensity of backflow (fluid flow induced by director rotation) can be controlled by the polymer concentration due to a specific increase of shear viscosity coefficients. In the synchronous regime of director rotation no significant effects of backflow on the dynamics of the walls are observed. Dynamic solitons known from the synchronous regime were also found at asynchronous rotation, when soliton lattices are formed by continuous nucleation. Here comparison with theory for given values of the lattice period shows soliton currents significantly reduced by backflow. Two of the three additional pattern forming states exclusively found at asynchronous rotation were completely suppressed in solutions with sufficient polymer concentration. The third of these states is affected by backflow in the growth rate of its patterns. Numerical calculations were performed to explain behavior of the patterns in the asynchronous state. For pure 5CB a quantitative comparison with the experiment was possible.

  8. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-09-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  9. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-05-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  10. Poly(ethyleneoxide) functionalization through alkylation

    SciTech Connect

    Sivanandan, Kulandaivelu; Eitouni, Hany Basam; Li, Yan; Pratt, Russell Clayton

    2015-04-21

    A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

  11. Pressurized liquid extraction using water/isopropanol coupled with solid-phase extraction cleanup for semivolatile organic compounds, polycyclic aromatic hydrocarbons (PAH), and alkylated PAH homolog groups in sediment

    USGS Publications Warehouse

    Burkhardt, M.R.; Zaugg, S.D.; Burbank, T.L.; Olson, M.C.; Iverson, J.L.

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAH) are recognized as environmentally relevant for their potential adverse effects on human and ecosystem health. This paper describes a method to determine the distribution of PAH and alkylated homolog groups in sediment samples. Pressurized liquid extraction (PLE), coupled with solid-phase extraction (SPE) cleanup, was developed to decrease sample preparation time, to reduce solvent consumption, and to minimize background interferences for full-scan GC-MS analysis. Recoveries from spiked Ottawa sand, environmental stream sediment, and commercially available topsoil, fortified at 1.5-15 ??g per compound, averaged 94.6 ?? 7.8%, 90.7 ?? 5.8% and 92.8 ?? 12.8%, respectively. Initial method detection limits for single-component compounds ranged from 20 to 302 ??g/kg, based on 25 g samples. Results from 28 environmental sediment samples, excluding homologs, show 35 of 41 compounds (85.4%) were detected in at least one sample with concentrations ranging from 20 to 100,000 ??g/kg. The most frequently detected compound, 2,6-dimethylnaphthalene, was detected in 23 of the 28 (82%) environmental samples with a concentration ranging from 15 to 907 ??g/kg. The results from the 28 environmental sediment samples for the homolog series showed that 27 of 28 (96%) samples had at least one homolog series present at concentrations ranging from 20 to 89,000 ??g/kg. The most frequently detected homolog series, C2-alkylated naphthalene, was detected in 26 of the 28 (93%) environmental samples with a concentration ranging from 25 to 3900 ??g/kg. Results for a standard reference material using dichloromethane Soxhlet-based extraction also are compared. ?? 2005 Elsevier B.V. All rights reserved.

  12. Cracking of long-chain alkyl aromatics on USY zeolite catalysts

    SciTech Connect

    Corma, A. ); Miguel, P.J.; Orchilles, A.V. ); Koermer, G.S. )

    1992-05-01

    Long-chain alkyl aromatics are important precursors for FCC gasoline. It is well known that for short-chain alkyl aromatics like cumene the dominant cracking process is simple alkyl aryl cleavage. In contrast the authors have found that for long-chain alkyl aromatics like 1-phenylheptane, cracking over in situ USY catalysts is much more complex. Cracking in a long alkyl side chain results in a carbenium ion that isomerizes easily and gives self-alkylation of the aromatic ring. Self-alkylation produces coke precursors and heavy gasoline aromatics. Product selectivities vary with zeolite unit cell size in ways that are rationalized on the basis of decreasing acid site density and zeolite adsorption properties.

  13. Tyrosine-selective protein alkylation using pi-allylpalladium complexes.

    PubMed

    Tilley, S David; Francis, Matthew B

    2006-02-01

    A new protein modification reaction has been developed based on a palladium-catalyzed allylic alkylation of tyrosine residues. This technique employs electrophilic pi-allyl intermediates derived from allylic acetate and carbamate precursors and can be used to modify proteins in aqueous solution at room temperature. To facilitate the detection of modified proteins using SDS-PAGE analysis, a fluorescent allyl acetate was synthesized and coupled to chymotrypsinogen A and bacteriophage MS2. The tyrosine selectivity of the reaction was confirmed through trypsin digest analysis. The utility of the reaction was demonstrated by using taurine-derived carbamates as water solubilizing groups that are cleaved upon protein functionalization. This solubility switching technique was used to install hydrophobic farnesyl and C(17) chains on chymotrypsinogen A in water using little or no cosolvent. Following this, the C(17) alkylated proteins were found to associate with lipid vesicles. In addition to providing a new protein modification strategy targeting an under-utilized amino acid side chain, this method provides convenient access to synthetic lipoproteins. PMID:16433516

  14. Differential alkylation-based redox proteomics--Lessons learnt.

    PubMed

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-12-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms. PMID:26282677

  15. Differential alkylation-based redox proteomics – Lessons learnt

    PubMed Central

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-01-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms. PMID:26282677

  16. Solid-state 13C NMR study of banana liquid crystals - 3: Alkyl-tail-group packing environments of an acute-angle bent-core molecule in the hexagonal columnar and cubic phases

    NASA Astrophysics Data System (ADS)

    Kurosu, Hiromichi; Endo, Yumi; Kimura, Saori; Hashimoto, Tomoko; Harada, Motoi; Lee, Eun-Woo; Sone, Masato; Watanabe, Junji; Kang, Sungmin

    2016-02-01

    Solid-state 13C nuclear magnetic resonance (NMR) measurements were performed on the hexagonal columnar and cubic phases of an acute-angle banana-shaped molecule, N(1,7)-S30. In the hexagonal columnar phase, three peaks appear at the NMR chemical shifts assigned to the internal methylene carbons of alkyl tails, indicating that the two alkyl tails have different packing structures, and one of the tails has two different conformations within a single molecule. Combined cross-polarization/magic-angle spinning and pulse saturation transfer/magic-angle spinning measurements show that one of the alkyl chains is located inside and the other is located outside the columnar structure. In the cubic phase, pulse saturation transfer/magic-angle spinning measurement shows that only one peak appears at the NMR chemical shifts assigned to the internal methylene carbons of alkyl tails, indicating that both of the alkyl chains are located outside the cubic structure.

  17. Nuclear magnetic resonance studies of hemoproteins. IV. Hindered rotation of heme side methyl group as a probe for studying van der Waals contacts in the heme side environments of myoglobin derivatives.

    PubMed

    Morishima, I; Iizuka, T

    1975-04-29

    220 MHz roton NMR spectral evidence for restricted rotation of one methyl group in the heme side chain of ferric horse cyanomyoglobin is reported here. Temperature dependence of this methyl proton signal was computer-simulated, yielding 14,8 kcal/mol for the methyl hindered rotation. Ionic additives such as NaCl and (NH4) 2 minus SO4 caused a slackening of this restriction of methyl rotation, evidenced from collapse of methyl signal doubling by the addition of these ionic substances. This is discussed in terms of breaking of the salt bridge formed between one of the propionate COO minus group of heme and a part of the apoprotein which might lead to constraint of one of the heme side methyl groups. The peculiarity of hyperfine-shifted methyl proton signals for other myoglobin complexes such as azide and imidazole derivatives is also discussed briefly in terms of constraint of heme side methyl group buried in a hydrophobic cleft. PMID:1169971

  18. Synthesis and luminescence properties of polymeric complexes of Cu(II), Zn(II) and Al(III) with 8-hydroxyquinoline side group-containing polystyrene

    NASA Astrophysics Data System (ADS)

    Gao, Baojiao; Wei, Xiaopeng; Zhang, Yanyan

    2013-01-01

    Three kinds of metalloquinolate-containing polystyrene were prepared via a polymer reaction and a coordination reaction. 5-Chloromethyl-8-hydroxyquinoline (CHQ) was first prepared through the chloromethylation reaction of 8-hydroxyquinoline (HQ) with 1,4-bichloromethoxy-butane as chloromethylation reagent. A polymer reaction, Friedel-Crafts alkylation reaction, was carried out between polystyrene (PS) and CHQ in the presence of Lewis catalyst, and HQ was bonded onto the side chains of PS, obtaining 8-hydroxyquinoline-functionalized Polystyrene, HQ-PS. And then, by using one-pot method with two-stage procedures, the coordination reaction of HQ-PS and small molecule HQ with metal ions including Al(III), Zn(II) and Cu(II) ions, was allowed to be carried out, and three polymeric metalloquinolates, AlQ3-PS, ZnQ2-PS and CuQ2-PS, were successfully prepared, respectively. In the chemical structures of these polymeric metalloquinolates, metalloquinolates were chemically attached onto the side chains of PS. HQ-PS and three polymeric metalloquinolates were fully characterized by FTIR, 1H NMR and TGA. The luminescence properties of the three polymeric metalloquinolates were mainly investigated by UV/Vis absorption spectra and fluorescence emission spectra in solutions and in solid film states. When excited by the ray at about 365 nm, the three polymeric metalloquinolates have blue-green luminescence, and the main emission peaks in the DMF solutions are located at 490, 482 and 502 nm for AlQ3-PS, ZnQ2-PS and CuQ2-PS, respectively. As compared with their emissions in solutions, the emissions in solid film states are red-shifted to some extent, and the main emission peaks are located at 500, 488 and 510 nm for AlQ3-PS, ZnQ2-PS and CuQ2-PS, respectively. Besides, these polymeric metalloquinolates have higher thermal stability than PS as polymeric skeleton.

  19. Clinical applications of quinone-containing alkylating agents.

    PubMed

    Begleiter, A

    2000-11-01

    Quinone-containing alkylating agents are a class of chemical agents that have received considerable interest as anticancer drugs. These agents contain a quinone moiety that can be reduced and an alkylating group that can form covalent bonds with a variety of cellular components. The oxidation state of the quinone element can modulate the activity of the alkylating element, and reduction of the quinone is required for activation of the alkylating activity of many of these agents. The quinone element may also contribute to the cytotoxic activity of quinone-containing alkylating agents through the formation of reactive oxygen species during redox cycling. The natural product, mitomycin C, has been the most widely used quinone-containing alkylating agent in the clinic, but other quinone-containing alkylating agents like porfiromycin, diaziquone, carbazilquinone, triaziquone and EO9 have also been used in the clinic for the treatment of cancer. In addition, many other quinone-containing alkylating agents have been tested in preclinical studies and the development of new agents is being actively pursued. This chapter describes the current and past clinical uses of these agents in the treatment of cancer and discusses new agents that are currently in clinical trials. PMID:11056078

  20. Synthesis and characterization of chitosan alkyl urea.

    PubMed

    Wang, Jing; Jiang, Ji-Zhou; Chen, Wei; Bai, Zheng-Wu

    2016-07-10

    Chitosan is a versatile material employed for various purposes in many fields including the development of chiral stationary phases for enantioseparation. Chitosan alkyl urea is a kind of intermediate used to prepare enantioseparation materials. In order to synthesize the intermediates, in the present work, a new way to prepare chitosan alkyl urea has been established: chitosan was first reacted with methyl chloroformate yielding N-methoxyformylated chitosan, which was then converted to chitosan alkyl urea through amine-ester exchange reaction. With a large excess of methyl chloroformate and primary amine of low stereohindrance, the amino group in chitosan could be almost completely converted to ureido group. The as-prepared chitosan alkyl urea derivatives were characterized by IR, (1)H NMR, (13)C NMR,(1)H-(1)H COSY and (1)H-(13)C HSQC NMR spectra. The chemical shifts of hydrogen and carbon atoms of glucose unit were assigned. It was found that the degree of substitution was obviously lower if cyclopropyl amine, aniline, tert-butyl amine and diethyl amine were used as reactants for the amine-ester exchange reaction. The reason was explained with the aid of theoretical calculations. PMID:27106154

  1. Vapor pressures of 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids with long alkyl chains

    SciTech Connect

    Rocha, Marisa A. A. E-mail: marisa.alexandra.rocha@gmail.com; Coutinho, João A. P.; Santos, Luís M. N. B. F. E-mail: marisa.alexandra.rocha@gmail.com

    2014-10-07

    This work presents the vapor pressure at several temperatures for the 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide series, [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (N = 14, 16, 18, and 20), measured by a Knudsen effusion method combined with a quartz crystal microbalance. The thermodynamic properties of vaporization of the ionic liquids under study are analysed together with the results obtained previously for the shorter alkyl chain length [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (N = 2, 4, 6, 8, 10, and 12), in order to evaluate the effect of the alkyl side chains of the cation and to get additional insights concerning the nanostructuration of ionic liquids. The symmetry effect is explored, based on the comparison with the asymmetric imidazolium based ionic liquids, [C{sub N-1}C{sub 1}im][NTf{sub 2}]. A trend shift on the thermodynamic properties of vaporization along the alkyl side chains of the extended symmetric ionic liquids, around [C{sub 6}C{sub 6}im][NTf{sub 2}], was detected. An intensification of the odd-even effect was observed starting from [C{sub 6}C{sub 6}im][NTf{sub 2}], with higher enthalpies and entropies of vaporization for the odd numbered ionic liquids, [C{sub 7}C{sub 7}im][NTf{sub 2}] and [C{sub 9}C{sub 9}im][NTf{sub 2}]. Similar, but less pronounced, odd-even effect was found for the symmetric ionic liquids with lower alkyl side chains length, [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (with N = 4, 6, 8, 10, and 12). This effect is related with the predominant orientation of the terminal methyl group of the alkyl chain to the imidazolium ring and their influence in the cation-anion interaction. The same Critical Alkyl length at the hexyl, (C{sub 6}C{sub 1}and C{sub 6}C{sub 6}) was found for both asymmetric and symmetric series indicating that the nanostructuration of the ionic liquids is related with alkyl chain length.

  2. Fragmentation of Electrospray-Produced Deprotonated Ions of Oligodeoxyribonucleotides Containing an Alkylated or Oxidized Thymidine

    NASA Astrophysics Data System (ADS)

    Wang, Pengcheng; Williams, Renee T.; Guerrero, Candace R.; Ji, Debin; Wang, Yinsheng

    2014-07-01

    Alkylation and oxidation constitute major routes of DNA damage induced by endogenous and exogenous genotoxic agents. Understanding the biological consequences of DNA lesions often necessitates the availability of oligodeoxyribonucleotide (ODN) substrates harboring these lesions, and sensitive and robust methods for validating the identities of these ODNs. Tandem mass spectrometry is well suited for meeting these latter analytical needs. In the present study, we evaluated how the incorporation of an ethyl group to different positions (i.e., O 2, N3, and O 4) of thymine and the oxidation of its 5-methyl carbon impact collisionally activated dissociation (CAD) pathways of electrospray-produced deprotonated ions of ODNs harboring these thymine modifications. Unlike an unmodified thymine, which often manifests poor cleavage of the C3'-O3' bond, the incorporation of an alkyl group to the O 2 position and, to a much lesser extent, the O 4 position, but not the N3 position of thymine, led to facile cleavage of the C3'-O3' bond on the 3' side of the modified thymine. Similar efficient chain cleavage was observed when thymine was oxidized to 5-formyluracil or 5-carboxyluracil, but not 5-hydroxymethyluracil. Additionally, with the support of computational modeling, we revealed that proton affinity and acidity of the modified nucleobases govern the fragmentation of ODNs containing the alkylated and oxidized thymidine derivatives, respectively. These results provided important insights into the effects of thymine modifications on ODN fragmentation.

  3. Removal of the side-chain glucose groups from schizophyllan improves the thermal stability of the polycytidylic acid complexes under the physiological conditions.

    PubMed

    Koumoto, Kazuya; Karinaga, Ryouji; Mizu, Masami; Anada, Takahisa; Sakurai, Kazuo; Kunitake, Toyoki; Shinkai, Seiji

    2004-12-01

    Thermal stabilization of the complex between polycytidylic acid [poly(C)] and the modified schizophyllan (SPG) whose hydrophilic side-chain glucose groups are selectively removed utilizing mild Smith-degradation has been investigated. With the decrease in the side-chain glucose groups of schizophyllan, the complex with poly(C) can be considerably stabilized compared with unmodified SPG; for example, the T(m) value after the removal of the side-chain glucose groups from 33.3 (unmodified) to 1.0 is enhanced by 14 degrees C. In addition, the thermal stabilization effect is even operative under the physiological conditions ([NaCl] = 0.15 mol dm(-3)). This effect is exerted owing to the construction of the hydrophobic atmosphere around the complex. Although schizophyllan lost the side-chain glucose groups, it still kept the protection effect of the bound poly(C) chain against RNaseA-mediated hydrolysis as observed for unmodified schizophyllan. The assessment of the cytotoxicity for A375:human malignant melanoma, and HL60:human promyelocytic leukemia revealed that the modified schizophyllan scarcely increases the cytotoxicity. These results indicate that the present modification for schizophyllan is of great significance in a viewpoint to develop the practical gene carriers operative even under the physiological conditions. PMID:15457435

  4. Base catalysis by alkali modified zeolites. III. Alkylation with methanol

    SciTech Connect

    Hathaway, P.E.; Davis, M.E. )

    1989-10-01

    Ion exchanged CsNaX and CsNaY, cesium acetate impregnated CsNaX (CsAce/CsNaX) and CsNaY (CsAce/CsNaY), and MgO have been reacted with isopropanol at 425 C and atmospheric pressure to assess their acid/base properties at a temperature consistent with that used in the side chain alkylation of toluene with methanol. The results suggest that the ability of the catalysts tested here to promote a base mediated reaction follow the order of MgO > CsAce/CsNaY > CsAce/CsNaX {approx equal} CsNaY > CsNaX. Selectivities to acetone measured at 4.73% conversion follow this order as well, ranging from 95.7% and 93.9% for MgO and CsAce/CsNaY, respectively, to 17.6% for the CsNaX. Thus, these catalysts can be grouped into two categories: (i) catalysts which vary in acid/base properties yet possess identical topology (e.g., the zeolites) and (ii) catalysts which vary in topology yet have similar acid/base properties (e.g., MgO and CsAce/CsNaY). These catalysts were compared using the side chain alkylation of toluene, ethane, methane, and acetone with methanol. For the impregnated zeolites, similar toluene conversions were observed. No formaldehyde was observed in the product stream of the impregnated Y zeolite. Both MgO and CsAce/CsNaY had similar methanol decomposition products; i.e., no formaldehyde and high CO formation, yet unlike CsAce/CsNaY no toluene conversion was observed for MgO. No conversion of ethane or methane was observed for either impregnated zeolite at 425 C.

  5. Method of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-09-14

    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  6. Reversible and irreversible thermochromic phase transitions in single crystals of polydiacetylenes substituted with alkyl-urethanes

    NASA Astrophysics Data System (ADS)

    Koshihara, Shin-ya; Tokura, Yoshinori; Takeda, Kenji; Koda, Takao; Kobayashi, Akiko

    1990-06-01

    Reversible transitions between the two spectroscopically distinct phases (A and B phases) have been investigated for a new family of polydiacetylenes (PDAs) substituted with side groups of alkyl-urethane [-(CH2)4OCONH(CH2)n-1CH3:n =1-10]. Measurements of optical spectra as well as x-ray and calorimetric studies have revealed the first-order-like phase transitions in a series of PDAs with n=1-10 which are associated with an n-dependent thermal hysteresis ranging from 0 to 60 K in width. It has been found that the thermochromic changes become irreversible in all these PDAs once the hydrogen bond chains in the side groups are interrupted by heating beyond the polymer melting temperature.

  7. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  8. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  9. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  10. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  11. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  12. Side Effects

    MedlinePlus

    ... 2014 Select a Language: Fact Sheet 550 Side Effects WHAT ARE SIDE EFFECTS? WHO GETS SIDE EFFECTS? ... t assume that you will get every side effect that’s listed! Most people have few or only ...

  13. An efficient generation of a functionalized tertiary-alkyl radical for copper-catalyzed tertiary-alkylative Mizoroki-Heck type reaction.

    PubMed

    Nishikata, Takashi; Noda, Yushi; Fujimoto, Ryo; Sakashita, Tomomi

    2013-11-01

    α-Halocarbonyl compounds undergo β-hydrogen elimination to give conjugated olefins in the presence of a transition-metal catalyst. However, a copper/triamine catalyst system can induce the alkylative Mizoroki–Heck reaction of styrenes with tertiary-alkyl halides possessing a withdrawing group under very mild conditions. This reaction provides an efficient synthetic methodology for tertiary-alkylated styrenes. PMID:24143934

  14. Insights into genetic diversity, parentage, and group composition of Atlantic white-sided dolphins (Lagenorhynchus acutus) off the west of Ireland based on nuclear and mitochondrial genetic markers.

    PubMed

    Mirimin, Luca; Banguera-Hinestroza, Eulalia; Dillane, Eileen; Hoelzel, Alan R; Cross, Tom F; Rogan, Emer

    2011-01-01

    The analysis of stranding events and the application of molecular markers can be powerful tools to study cryptic biological aspects of delphinid species that occur mainly in open ocean habitat. In the present study, we investigated nuclear and mitochondrial genetic variability of Atlantic white-sided dolphins that stranded from 1990 to 2006 (n = 42) along the west coast of Ireland, using 8 microsatellite loci and 599 bp of the mitochondrial DNA control region. Results from both classes of markers are concordant with the hypothesis of a large random-mating population of white-sided dolphins along the west coast of Ireland. In addition, the analyses of 2 live mass stranding events (19 and 5 individuals, respectively) revealed that dolphins within each group were mainly unrelated to each other, suggesting dispersal of both sexes from the natal group (i.e., no natal phylopatry). Parentage analyses allowed the identification of mother-offspring pairs but ruled out all adult males as possible fathers. In combination with data on age of individuals, these results confirmed previous knowledge on life-history parameters, with sexually mature females ranging between 11 and 15 years of age and an interbirth interval of at least 2 years. The present study provides novel information on population and group composition of Atlantic white-sided dolphins along the west coast of Ireland, where population and social structure of the species are still poorly understood. PMID:21059883

  15. Photobehavior of the geometrical isomers of two 1,4-distyrylbenzene analogues with side groups of different electron donor/acceptor character.

    PubMed

    Ciorba, S; Galiazzo, G; Mazzucato, U; Spalletti, A

    2010-10-14

    The photobehavior of two 1,4-distyrylbenzene analogues where the central benzene ring is asymmetrically substituted with a pyrid-4-ylethenyl group at one side and thien-2-ylethenyl or a p-nitrostyryl group at the other side, has been studied in two solvents at room temperature. The four geometrical isomers (EE, ZE, EZ, and ZZ) of each compound were separated by the combined use of HPLC and spectrophotometric techniques. The radiative/reactive competition in their excited state relaxation was particularly examined: the diabatic/adiabatic contributions were estimated and a reasonable interpretation of the photoisomerization mechanism was proposed. The role of the conformational isomers was also investigated by measured and computed spectral data. Since the different electron donor/acceptor character of the side groups of these molecules can induce charge transfer phenomena that can affect the relaxation pathways of their excited states, the photobehavior was compared in inert and polar solvents to clarify the role of the intramolecular charge transfer. The latter was found to affect markedly the relaxation properties and to induce interesting fluorosolvatochromic effects, particularly in the p-nitro derivative. The participation of the triplet state in the reaction mechanism of the latter was also investigated by flash photolysis and sensitized experiments. PMID:20857985

  16. Influence of the linkage type between the polymer backbone and side groups on the surface segregation of methyl groups during film formation.

    PubMed

    Zhang, Yizhi; Fan, Hao; Wang, Yuping; Zuo, Biao; Zhang, Wei; Wang, Shunli; Wang, Xinping

    2015-12-21

    Although poly(vinyl acetate) (PVAc) differs from poly(methyl acrylate) (PMA) only in the reversed position of the ester group, a large difference in the concentration dependence of the casting solution on the corresponding surface structure of the cast films of PVAc, PMA and poly(methyl methacrylate) (PMMA) was observed. The hydrophobicity of both PMA and PMMA films increased with increasing concentration of the corresponding polymer solution, whereas cast PVAc films showed the reverse trend. The surface structure of the cast films prepared with different concentrations of the casting solution, characterized by sum frequency generation (SFG) vibrational spectra, showed that the order of the methylene groups increased while that of the acetyl methyl group decreased on the surface of cast PVAc film with increasing concentration of casting solution. However, the order of the ester methyl group increased and that of methylene groups did not change for cast PMA films with increasing concentration of casting solution. The cast PMMA film showed a reverse trend compared with the corresponding PMA film. It is apparent that well-ordered ester or acetyl methyl groups on the surface, which are oriented away from the polymer film, rather than methylene groups, play an important role in determining surface hydrophobicity, as the latter shield the OC[double bond, length as m-dash]O groups of PVAc, PMA and PMMA film surfaces from being exposed, resulting in low surface free energy. The reason for this difference is attributed to the relatively low energy for ester methyl group reorientation, an ester group structure nearer to the trans state and more regular local configuration of segments in concentrated solutions of PMA and PMMA compared to that of PVAc. PMID:26415634

  17. Ultra-bright alkylated graphene quantum dots

    NASA Astrophysics Data System (ADS)

    Feng, Lan; Tang, Xing-Yan; Zhong, Yun-Xin; Liu, Yue-Wen; Song, Xue-Huan; Deng, Shun-Liu; Xie, Su-Yuan; Yan, Jia-Wei; Zheng, Lan-Sun

    2014-10-01

    Highly efficient and stable photoluminescence (PL) are urgently desired for graphene quantum dots (GQDs) to facilitate their prospective applications as optical materials. Here, we report the facile and straightforward synthesis of alkylated graphene quantum dots (AGQDs) via the solvothermal reaction of propagatively alkylated graphene sheets (PAGenes). In contrast to most GQDs reported so far, the synthesized AGQDs process pH-independent and ultra-bright PL with a relative quantum yield of up to 65%. Structural and chemical composition characterization demonstrated that the synthesized AGQDs are nearly oxygen-defect-free with alkyl groups decorated on edges and basal plane, which may contribute to their greatly improved pH tolerance and high quantum efficiency. The photocatalytic performance of AGQDs-P25 nanocomposites was evaluated by the degradation of Rhodamine B under visible light. The photocatalytic rate is ca. 5.9 times higher than that of pure P25, indicating that AGQDs could harness the visible spectrum of sunlight for energy conversion or environmental therapy.Highly efficient and stable photoluminescence (PL) are urgently desired for graphene quantum dots (GQDs) to facilitate their prospective applications as optical materials. Here, we report the facile and straightforward synthesis of alkylated graphene quantum dots (AGQDs) via the solvothermal reaction of propagatively alkylated graphene sheets (PAGenes). In contrast to most GQDs reported so far, the synthesized AGQDs process pH-independent and ultra-bright PL with a relative quantum yield of up to 65%. Structural and chemical composition characterization demonstrated that the synthesized AGQDs are nearly oxygen-defect-free with alkyl groups decorated on edges and basal plane, which may contribute to their greatly improved pH tolerance and high quantum efficiency. The photocatalytic performance of AGQDs-P25 nanocomposites was evaluated by the degradation of Rhodamine B under visible light. The

  18. Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

    PubMed

    Johnston, Craig P; Smith, Russell T; Allmendinger, Simon; MacMillan, David W C

    2016-08-18

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox

  19. Detection of Alkylating Agents using Electrical and Mechanical Means

    NASA Astrophysics Data System (ADS)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir; Eichen, Yoav

    2011-08-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  20. PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

    DOEpatents

    Grinstead, R.R.

    1962-01-23

    A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

  1. Large birefringence and polarization holographic gratings formed in photocross-linkable polymer liquid crystals comprising bistolane mesogenic side groups

    SciTech Connect

    Emoto, Akira; Matsumoto, Taro; Shioda, Tatsutoshi; Ono, Hiroshi; Yamashita, Ayumi; Kawatsuki, Nobuhiro

    2009-10-01

    Polarization gratings with large birefringence are formed in photoreactive polymer liquid crystals with bistolane moiety and terminal cinnamic acid moiety by the use of polarized ultraviolet interference light and subsequent annealing. The polarized ultraviolet light causes the axis-selective photoreaction between the cinnamic acid groups and subsequent annealing induce the reorientation of peripheral molecules without cross-linking along the cross-linked groups. Long bistolane mesogenic moiety exhibits large birefringence in comparison with a biphenyl mesogenic moiety, the value of the induced birefringence in the bistolane mesogenic liquid crystalline (LC) polymer is strongly dependent on both the grating constant and the wavelength of the reconstruction light.

  2. MAPPING THE DARK SIDE WITH DEIMOS: GLOBULAR CLUSTERS, X-RAY GAS, AND DARK MATTER IN THE NGC 1407 GROUP

    SciTech Connect

    Romanowsky, Aaron J.; Strader, Jay; Brodie, Jean P.; Johnson, Ria; Ponman, Trevor

    2009-06-15

    NGC 1407 is the central elliptical in a nearby evolved group of galaxies apparently destined to become a galaxy cluster core. We use the kinematics of globular clusters (GCs) to probe the dynamics and mass profile of the group's center, out to a radius of 60 kpc ({approx}10 galaxy effective radii)-the most extended data set to date around an early-type galaxy. This sample consists of 172 GC line-of-sight velocities, most of them newly obtained using Keck/DEIMOS, with a few additional objects identified as dwarf-globular transition objects or as intragroup GCs. We find weak rotation for the outer parts of the GC system (v/{sigma} {approx} 0.2), with a rotational misalignment between the metal-poor and metal-rich GCs. The velocity dispersion profile declines rapidly to a radius of {approx}20 kpc, and then becomes flat or rising to {approx}60 kpc. There is evidence that the GC orbits have a tangential bias that is strongest for the metal-poor GCs-in possible contradiction to theoretical expectations. We construct cosmologically motivated galaxy+dark halo dynamical models and infer a total mass within 60 kpc of {approx}3 x 10{sup 12} M {sub sun}, which extrapolates to a virial mass of {approx}6 x 10{sup 13} M {sub sun} for a typical lambda cold dark matter ({lambda}CDM) halo-in agreement with results from kinematics of the group galaxies. We present an independent Chandra-based analysis, whose relatively high mass at {approx}20 kpc disagrees strongly with the GC-based result unless the GCs are assumed to have a peculiar orbit distribution, and we therefore discuss more generally some comparisons between X-ray and optical results. The group's B-band mass-to-light ratio of {approx}800 (uncertain by a factor of {approx}2) in Solar units is extreme even for a rich galaxy cluster, much less a poor group-placing it among the most dark matter (DM) dominated systems in the universe, and also suggesting a massive reservoir of baryons lurking in an unseen phase, in addition to

  3. Synthetic, structural, and computational investigations of N-alkyl benzo-2,1,3-selenadiazolium iodides and their supramolecular aggregates.

    PubMed

    Lee, Lucia M; Corless, Victoria B; Tran, Michael; Jenkins, Hilary; Britten, James F; Vargas-Baca, Ignacio

    2016-02-28

    Despite their versatility, the application of telluradiazoles as supramolecular building blocks is considerably constrained by their sensitivity to moisture. Albeit more robust, their selenium analogues form weaker supramolecular interactions. These, however, are enhanced when one nitrogen atom is bonded to an alkyl group. Here we investigate general methods for the synthesis of such derivatives. Methyl, iso-propyl and tert-butyl benzo-2,1,3-selenadiazolium cations were prepared by direct alkylation or cyclo-condensation of the alkyl-phenylenediamine with selenous acid. While the former reaction only proceeds with the primary and tertiary alkyl iodides, the latter is very efficient. Difficulties reported in earlier literature are attributable to the formation of adducts of benzoselenadiazole with its alkylated cations and side reactions initiated by aerobic oxidation of iodide. However, the cations themselves are resilient to oxidation and stable in acidic to neutral aqueous medium. X-ray crystallography was used in the identification and characterization of the following compounds: [C6H4N2(R)Se](+)X(-), (R = CH(CH3)2, C(CH3)3; X = I(-), I3(-)], [C6H4N2(CH3)Se](+)I(-), and [C6H4N2Se][C6H4N2(CH3)Se]2I2. Formation of SeN secondary bonding interactions (chalcogen bonds) was only observed in the last structure as anion binding to selenium is a strong competitor. The relative strengths of those forces and the structural preferences they enforce were assessed with DFT-D3 calculations supplemented by AIM analysis of the electron density. PMID:26765368

  4. New pyridinium-based fluorescent dyes: A comparison of symmetry and side-group effects on G-Quadruplex DNA binding selectivity and application in live cell imaging.

    PubMed

    Lu, Yu-Jing; Hu, Dong-Ping; Zhang, Kun; Wong, Wing-Leung; Chow, Cheuk-Fai

    2016-07-15

    A series of C1-, C2-and C3-symmetric pyridinium conjugates with different styrene-like side groups were synthesized and were utilized as G-quadruplex selective fluorescent probes. The new compounds were well-characterized. Their selectivity, sensitivity, and stability towards G-quadruplex were studied by fluorescence titration, native PAGE experiments, FRET and circular dichroism (CD) analyses. These new compounds investigated in the fluorescence assays were preferentially bound with G-quadruplex DNA compared with other type of nucleic acids and it is fascinating to realize the effects of molecular symmetry and associated side groups showing unexpectedly great influence on the fluorescent signal enhancement for the discrimination of G-quadruplexes DNA from other nucleic acids. This may correlate with the pocket symmetry and shape of the G-quadruplex DNA inherently. Among the compounds, a C2-symmetric dye (2,6-bis-((E)-2-(1H-indol-3-yl)-vinyl)-1-methylpyridin-1-ium iodide) with indolyl-groups substituted was screened out from the series giving the best selectivity and sensitivity towards G-quadruplexes DNA, particularly telo21, due to its high equilibrium binding constant (K=2.17×10(5)M(-1)). In addition, the limit of detection (LOD) of the dye to determine telo21 DNA in bioassays was found as low as 33nM. The results of the study give insight and certain crucial factors, such as molecular symmetry and the associated side groups, on developing of effective fluorescent dyes for G-quadruplex DNA applications including G-quadruplex structure stabilization, biosensing and clinical applications. The compound was also demonstrated as a very selective G-quadruplex fluorescent agent for living cell staining and imaging. PMID:26994364

  5. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  6. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  7. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  8. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  9. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  10. 4-Alkylated Silver-N-Heterocyclic Carbene (NHC) Complexes with Cytotoxic Effects in Leukemia Cells.

    PubMed

    Sandtorv, Alexander H; Leitch, Calum; Bedringaas, Siv Lise; Gjertsen, Bjørn Tore; Bjørsvik, Hans-René

    2015-09-01

    Computational chemistry has shown that backbone-alkylated imidazoles ought to be efficient ligands for transition metal catalysts with improved carbene-to-metal donation. In this work, such alkylated imidazoles were synthesized and complexed with silver(I) by means of an eight/nine-step synthetic pathway we devised to access a new class of biologically active silver complexes. The synthesis involves selective iodination of the imidazole backbone, followed by Sonogashira coupling to replace the backbone iodine. The installed alkyne moiety is then subjected to reductive hydrogenation with Pearlman's catalyst. The imidazole N1 atom is arylated by the palladium-catalyzed Buchwald N-arylation method. The imidazole N3 position was then methylated with methyl iodine, whereupon the synthesis was terminated by complexation of the imidazolium salt with silver(I) oxide. The synthetic pathway provided an overall yield of ≈20 %. The resulting complexes were tested in vitro against HL60 and MOLM-13 leukemic cells, two human-derived cell lines that model acute myeloid leukemia. The most active compounds exhibiting low IC50 values of 14 and 27 μM, against HL60 and MOLM-13 cells, respectively. The imidazole side chain was found to be essential for high cytotoxicity, as the imidazole complex bearing a C7 side chain at the 4-position was four- to sixfold more potent than the corresponding imidazole elaborated with a methyl group. PMID:26250720

  11. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    PubMed

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. PMID:26150397

  12. Radical C-H alkylation of BODIPY dyes using potassium trifluoroborates or boronic acids.

    PubMed

    Verbelen, Bram; Cunha Dias Rezende, Lucas; Boodts, Stijn; Jacobs, Jeroen; Van Meervelt, Luc; Hofkens, Johan; Dehaen, Wim

    2015-09-01

    A one-step synthetic procedure for the radical CH alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono-, di-, tri-, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid-state emissive BODIPY dyes. PMID:26215785

  13. Antibacterial activity of alkyl gallates is a combination of direct targeting of FtsZ and permeabilization of bacterial membranes

    PubMed Central

    Król, Ewa; de Sousa Borges, Anabela; da Silva, Isabel; Polaquini, Carlos R.; Regasini, Luis O.; Ferreira, Henrique; Scheffers, Dirk-Jan

    2015-01-01

    Alkyl gallates are compounds with reported antibacterial activity. One of the modes of action is binding of the alkyl gallates to the bacterial membrane and interference with membrane integrity. However, alkyl gallates also cause cell elongation and disruption of cell division in the important plant pathogen Xanthomonas citri subsp. citri, suggesting that cell division proteins may be targeted by alkyl gallates. Here, we use Bacillus subtilis and purified B. subtilis FtsZ to demonstrate that FtsZ is a direct target of alkyl gallates. Alkyl gallates disrupt the FtsZ-ring in vivo, and cause cell elongation. In vitro, alkyl gallates bind with high affinity to FtsZ, causing it to cluster and lose its capacity to polymerize. The activities of a homologous series of alkyl gallates with alkyl side chain lengths ranging from five to eight carbons (C5–C8) were compared and heptyl gallate was found to be the most potent FtsZ inhibitor. Next to the direct effect on FtsZ, alkyl gallates also target B. subtilis membrane integrity—however the observed anti-FtsZ activity is not a secondary effect of the disruption of membrane integrity. We propose that both modes of action, membrane disruption and anti-FtsZ activity, contribute to the antibacterial activity of the alkyl gallates. We propose that heptyl gallate is a promising hit for the further development of antibacterials that specifically target FtsZ. PMID:25972861

  14. Antibacterial activity of alkyl gallates is a combination of direct targeting of FtsZ and permeabilization of bacterial membranes.

    PubMed

    Król, Ewa; de Sousa Borges, Anabela; da Silva, Isabel; Polaquini, Carlos R; Regasini, Luis O; Ferreira, Henrique; Scheffers, Dirk-Jan

    2015-01-01

    Alkyl gallates are compounds with reported antibacterial activity. One of the modes of action is binding of the alkyl gallates to the bacterial membrane and interference with membrane integrity. However, alkyl gallates also cause cell elongation and disruption of cell division in the important plant pathogen Xanthomonas citri subsp. citri, suggesting that cell division proteins may be targeted by alkyl gallates. Here, we use Bacillus subtilis and purified B. subtilis FtsZ to demonstrate that FtsZ is a direct target of alkyl gallates. Alkyl gallates disrupt the FtsZ-ring in vivo, and cause cell elongation. In vitro, alkyl gallates bind with high affinity to FtsZ, causing it to cluster and lose its capacity to polymerize. The activities of a homologous series of alkyl gallates with alkyl side chain lengths ranging from five to eight carbons (C5-C8) were compared and heptyl gallate was found to be the most potent FtsZ inhibitor. Next to the direct effect on FtsZ, alkyl gallates also target B. subtilis membrane integrity-however the observed anti-FtsZ activity is not a secondary effect of the disruption of membrane integrity. We propose that both modes of action, membrane disruption and anti-FtsZ activity, contribute to the antibacterial activity of the alkyl gallates. We propose that heptyl gallate is a promising hit for the further development of antibacterials that specifically target FtsZ. PMID:25972861

  15. Ultra-bright alkylated graphene quantum dots.

    PubMed

    Feng, Lan; Tang, Xing-Yan; Zhong, Yun-Xin; Liu, Yue-Wen; Song, Xue-Huan; Deng, Shun-Liu; Xie, Su-Yuan; Yan, Jia-Wei; Zheng, Lan-Sun

    2014-11-01

    Highly efficient and stable photoluminescence (PL) are urgently desired for graphene quantum dots (GQDs) to facilitate their prospective applications as optical materials. Here, we report the facile and straightforward synthesis of alkylated graphene quantum dots (AGQDs) via the solvothermal reaction of propagatively alkylated graphene sheets (PAGenes). In contrast to most GQDs reported so far, the synthesized AGQDs process pH-independent and ultra-bright PL with a relative quantum yield of up to 65%. Structural and chemical composition characterization demonstrated that the synthesized AGQDs are nearly oxygen-defect-free with alkyl groups decorated on edges and basal plane, which may contribute to their greatly improved pH tolerance and high quantum efficiency. The photocatalytic performance of AGQDs-P25 nanocomposites was evaluated by the degradation of Rhodamine B under visible light. The photocatalytic rate is ca. 5.9 times higher than that of pure P25, indicating that AGQDs could harness the visible spectrum of sunlight for energy conversion or environmental therapy. PMID:25192187

  16. Microwave heating in peptide side chain modification via cysteine alkylation.

    PubMed

    Calce, Enrica; De Luca, Stefania

    2016-09-01

    Microwave irradiation has been successfully applied to a selective synthetic procedure for introducing molecular substituents on peptides, providing a noticeable reduction of the reaction time and also an increased crude peptide purity for some compounds. PMID:27351201

  17. Determining cysteine oxidation status using differential alkylation

    NASA Astrophysics Data System (ADS)

    Schilling, Birgit; Yoo, Chris B.; Collins, Christopher J.; Gibson, Bradford W.

    2004-08-01

    Oxidative damage to proteins plays a major role in aging and in the pathology of many degenerative diseases. Under conditions of oxidative stress, reactive oxygen and nitrogen species can modify key redox sensitive amino acid side chains leading to altered biological activities or structures of the targeted proteins. This in turn can affect signaling or regulatory control pathways as well as protein turnover and degradation efficiency in the proteasome. Cysteine residues are particularly susceptible to oxidation, primarily through reversible modifications (e.g., thiolation and nitrosylation), although irreversible oxidation can lead to products that cannot be repaired in vivo such as sulfonic acid. This report describes a strategy to determine the overall level of reversible cysteine oxidation using a stable isotope differential alkylation approach in combination with mass spectrometric analysis. This method employs 13C-labeled alkylating reagents, such as N-ethyl-[1,4-13C2]-maleimide, bromo-[1,2-13C2]-acetic acid and their non-labeled counterparts to quantitatively assess the level of cysteine oxidation at specific sites in oxidized proteins. The differential alkylation protocol was evaluated using standard peptides and proteins, and then applied to monitor and determine the level of oxidative damage induced by diamide, a mild oxidant. The formation and mass spectrometric analysis of irreversible cysteine acid modification will also be discussed as several such modifications have been identified in subunits of the mitochondrial electron transport chain complexes. This strategy will hopefully contribute to our understanding of the role that cysteine oxidation plays in such chronic diseases such as Parkinson's disease, where studies in animal and cell models have shown oxidative damage to mitochondrial Complex I to be a specific and early target.

  18. The icephobic performance of alkyl-grafted aluminum surfaces.

    PubMed

    Kulinich, S A; Honda, M; Zhu, A L; Rozhin, A G; Du, X W

    2015-02-01

    This work analyzes the anti-icing performance of flat aluminum surfaces coated with widely used alkyl-group based layers of octadecyltrimethoxysilane, fluorinated alkylsilane and stearic acid as they are subjected to repeated icing/deicing cycles. The wetting properties of the samples upon long-term immersion in water are also evaluated. The results demonstrate that smooth aluminum surfaces grafted with alkyl groups are prone to gradual degradation of their hydrophobic and icephobic properties, which is caused by interactions and reactions with both ice and liquid water. This implies that alkyl-group based monolayers on aluminum surfaces are not likely to be durable icephobic coatings unless their durability in contact with ice and/or water is significantly improved. PMID:25516115

  19. Discovery and identification of a series of alkyl decalin isomers in petroleum geological samples.

    PubMed

    Wang, Huitong; Zhang, Shuichang; Weng, Na; Zhang, Bin; Zhu, Guangyou; Liu, Lingyan

    2015-07-01

    The comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) has been used to characterize a crude oil and a source rock extract sample. During the process, a series of pairwise components between monocyclic alkanes and mono-aromatics have been discovered. After tentative assignments of decahydronaphthalene isomers, a series of alkyl decalin isomers have been synthesized and used for identification and validation of these petroleum compounds. From both the MS and chromatography information, these pairwise compounds were identified as 2-alkyl-decahydronaphthalenes and 1-alkyl-decahydronaphthalenes. The polarity of 1-alkyl-decahydronaphthalenes was stronger. Their long chain alkyl substituent groups may be due to bacterial transformation or different oil cracking events. This systematic profiling of alkyl-decahydronaphthalene isomers provides further understanding and recognition of these potential petroleum biomarkers. PMID:25945366

  20. Safety Assessment of Alkyl PEG/PPG Ethers as Used in Cosmetics.

    PubMed

    Fiume, Monice M; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2016-07-01

    The Cosmetic Ingredient Review (CIR) Expert Panel assessed the safety of 131 alkyl polyethylene glycol (PEG)/polypropylene glycol ethers as used in cosmetics, concluding that these ingredients are safe in the present practices of use and concentration described in this safety assessment when formulated to be nonirritating. Most of the alkyl PEG/PPG ethers included in this review are reported to function in cosmetics as surfactants, skin-conditioning agents, and/or emulsifying agents. The alkyl PEG/PPG ethers share very similar physiochemical properties as the alkyl PEG ethers, which were reviewed previously by the CIR Expert Panel and found safe when formulated to be nonirritating. The alkyl PEG ethers differ by the inclusion of PPG repeat units, which are used to fine-tune the surfactant properties of this group. The Panel relied heavily on data on analogous ingredients, extracted from the alkyl PEG ethers and PPG reports, when making its determination of safety. PMID:27383199

  1. Sodium ion-selective electrodes based on dibenzo-16-crown-5 compounds with pendent amide groups

    SciTech Connect

    Ohki, Akira; Maeda, Shigeru ); Lu, J.P.; Bartsch, R.A. )

    1994-05-15

    Potentiometric selectivities for alkali-metal cations of dibenzo-16-crown-5 compounds with amide-containing side arms attached to the central carbon atom of the three-carbon bridge have been determined in solvent polymeric membrane electrodes. The lariat ethers include N-alkyl- and N,N-dialkyl-sym-(R)-dibenzo-16-crown-5-oxyacetamides with R = hydrogen or an alkyl group. The presence of an alkyl group on the ring carbon which bears the amide-containing side arm markedly increases the Na[sup +]/K[sup +] selectivity of poly(vinyl chloride) matrix membrane electrodes with o-nitrophenyl octyl ether as the membrane solvent. Lariat ethers with a N,N-dipentyloxyacetamide group as the side arm and a geminal alkyl group of two or more carbon atoms exhibit high Na[sup +]K[sup +] selectivities (log K[sub Na,K][sup Pot] = [minus]2.1) with good selectivities for Na[sup +] over the other alkali-metal cations, H[sup +], NH[sub 4][sup +], and alkaline-earth-metal cations. 25 refs., 6 figs., 1 tab.

  2. Synthesis and Antioxidant Activity of Alkyl Nitroderivatives of Hydroxytyrosol.

    PubMed

    Gallardo, Elena; Palma-Valdés, Rocío; Sarriá, Beatriz; Gallardo, Irene; de la Cruz, José P; Bravo, Laura; Mateos, Raquel; Espartero, José L

    2016-01-01

    A series of alkyl nitrohydroxytyrosyl ether derivatives has been synthesized from free hydroxytyrosol (HT), the natural olive oil phenol, in order to increase the assortment of compounds with potential neuroprotective activity in Parkinson's disease. In this work, the antioxidant activity of these novel compounds has been evaluated using Ferric Reducing Antioxidant Power (FRAP), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), and Oxygen Radical Scavenging Capacity (ORAC) assays compared to that of nitrohydroxytyrosol (NO₂HT) and free HT. New compounds showed variable antioxidant activity depending on the alkyl side chain length; compounds with short chains (2-4 carbon atoms) maintained or even improved the antioxidant activity compared to NO₂HT and/or HT, whereas those with longer side chains (6-8 carbon atoms) showed lower activity than NO₂HT but higher than HT. PMID:27213306

  3. Confinement-induced order of tethered alkyl chains at the water/vapor interface.

    PubMed

    Fukuto, M; Heilmann, R K; Pershan, P S; Yu, S M; Soto, C M; Tirrell, D A

    2002-07-01

    Packing of tethered alkyl chains in Langmuir monolayers of a hairy-rod polypeptide poly[gamma-4-(n-hexadecyloxy)benzyl alpha,L-glutamate] on water has been studied by x-ray scattering measurements at room temperature. The rods lie parallel to the surface while the alkyl side chains segregate toward the vapor. Results indicate that the herringbone order of the alkyl chains is established initially by one-dimensionally confined chains between aligned rods and grows laterally with compression. PMID:12241332

  4. Alkyl Chlorides as Hydrogen Bond Acceptors

    SciTech Connect

    Nadas, Janos I; Vukovic, Sinisa; Hay, Benjamin

    2012-01-01

    To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form X-H {hor_ellipsis} Cl hydrogen bonds (X = C, N, O) of weak to moderate strength, with {Delta}E values ranging from -2.8 to -5.3 kcal/mol.

  5. Alkylation of toluene with ethanol

    SciTech Connect

    Walendziewski, J.; Trawczynski, J.

    1996-10-01

    A series of Y and ZSM-5 zeolite based catalysts was prepared. Zeolites were cation exchanged and formed with 50% of aluminum hydroxide as a binder, and the obtained catalysts were finally thermally treated. Activity tests in alkylation of toluene with ethanol were carried out in the temperature range of 325--400 C, in nitrogen or hydrogen stream, and a pressure up to 3 MPa. The feed consisted of toluene and ethanol mixed in a mole ratio 1/1 or 2/1. The obtained results showed that among the studied catalysts the highest activity in the alkylation reaction was attained by ZSM-5 zeolite based catalyst with a moderate acidity and medium silica to alumina ratio, i.e., {approximately}50. Activity and selectivity of the most active catalyst as well as conversion of the feed components were similar to those reported in other papers. The content of p-ethyltoluene in alkylation products attained ca. 60%.

  6. 3-ALKYL-1-BUTANOL ATTRACTANTS FOR FRUGIVOROUS PEST INSECTS, PATENT NO. 6.224.890

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Compositions and lures are described which provide 3-alkyl-1-butanol vapors and vapor blends of 3-alkyl-1-butanol with one or more compounds selected from the group consisting of acetic acid, ammonia, putrescine and mixtures which function as highly effective attractants for frugivorous pest flies e...

  7. Convenient synthesis of alkyl amines via the reaction of organoboranes with ammonium hydroxide

    SciTech Connect

    Kabalka, G.W.; Sastry, K.A.R.; McCollum, G.W.; Yoshioka, H.

    1981-10-09

    A process for the preparation of alkyl amines in which the reagents are generated in situ under mild and convenient reaction conditions is described. An organoborane is prepared via hydroboration, aqueous ammonium hydroxide is added, and then aqueous sodium hypochlorite is added to the mixture. Two of the alkyl groups in the trialkylborane are converted to the corresponding amines in good yield. (BLM)

  8. Synthesis of MOF having hydroxyl functional side groups and optimization of activation process for the maximization of its BET surface area

    SciTech Connect

    Kim, Jongsik; Kim, Dong Ok; Kim, Dong Wook; Sagong, Kil

    2013-01-15

    To accomplish the postsynthetic modification of MOF with organic-metal precursors (OMPs) described in our previous researches more efficiently, synthesis of MOF (HCC-2) possessing relatively larger pore size as well as higher number of hydroxyl functional side groups per its base unit than those of HCC-1 has been successfully conducted via adopting 1,4-di-(4-carboxy-2,6-dihydroxyphenyl)benzene as an organic ligand and Zn(NO{sub 3}){sub 2}{center_dot}6H{sub 2}O as a metal source, respectively. Also, optimization about the Activation process of HCC-2 was performed to maximize its BET (Brunauer-Emmett-Teller) surface area which was proved to be proportional to the number of exposed active sites on which its postsynthetic modification occurred. However, Activation process having been validated to be so effective with the acquirement of highly-purified HCC-1 (CO{sub 2} supercritical drying step followed by vacuum drying step) was less satisfactory with the case of HCC-2. This might be attributed to relatively higher hydrophilicity and bulkier molecular structure of organic ligand of HCC-2. However, it was readily settled by simple modification of above Activation process. Moreover, indispensable residues composed of both DMF and its thermally degraded derivatives which were chemically attached via coordination bond with hydroxyl functionalities even after Activation process III might enable their H{sub 2} adsorption properties to be seriously debased compared to that of IRMOF-16 having no hydroxyl functionalities. - Graphical abstract: Synthesis of new-structured MOF (HCC-2) simultaneously possessing relatively larger pore size as well as higher number of hydroxyl functional side groups per its base unit at the same time than those of HCC-1 has been performed via adopting 1,4-di-(4-carboxy-2,6-dihydroxyphenyl)benzene as an organic ligand and Zn(NO{sub 3}){sub 2}{center_dot}6H{sub 2}O as a metal source, respectively. Also, the optimization of activation process for HCC-2

  9. A biological source of oceanic alkyl nitrates

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Lewis, C. B.; Velasco, F. L.; Escobar, C.; Kellogg, D.; Velcamp, M.

    2013-12-01

    Alkyl nitrates are an important component of reactive nitrogen in the troposphere. The oceans are a source of alkyl nitrates to the atmosphere, however the source of alkyl nitrates in the oceans is unknown. It has been demonstrated that the reaction of alkyl peroxy radicals (ROO) with nitric oxide (NO) produces alkyl nitrates in the aqueous phase. We hypothesize that alkyl nitrates may be formed by organisms through the same reaction and therefore biological production could be a source of alkyl nitrates to the troposphere. This work focuses on the production of alkyl nitrates by the diatoms Chaetoceros muelleri and Thalassiosira weisfloggi. Using chemostats, we measure alkyl nitrates formed under nitrate limited conditions. We also use triggers and inhibitors of nitric oxide formation to determine if alkyl nitrate formation is affected by changes in NO production. To date, the rates of production of alkyl nitrates in our cultures, lead us to estimate a production rate on the order of femtomolar/day for C1-C3 alkyl nitrates by diatom species in the equatorial Pacific Ocean. This suggests that diatoms may contribute to the overall ocean source of alkyl nitrates; however, it is possible that other types of phytoplankton, such as cyanobacteria, that are more abundant in the open ocean, may contribute to a greater extent.

  10. Structural features of a series of S-alkylated and non-S-alkylated aminothiolate nickel(II) complexes

    NASA Astrophysics Data System (ADS)

    Chohan, B. S.

    2014-12-01

    The structural aspects of a family of S-alkylated complexes, generated by reacting iodoacetamide or iodoethanol with two mononuclear Ni(II) diaminodithiolate complexes are discussed. The S-alkylation reactions were investigated with particular attention paid to the size of the chelate ring that straps the N,N'-methylamine donors. In one complex the N-methyl groups are cis to each other and in the other they are trans. Both complexes undergo S-alkylation with two equivalents of either reagent, that coordinates through the pendant oxygen to the Ni(II), forming dications with an N2S2O2 ligand donor set. Crystal structures of [NiC12H26N4O2S2]I2 · MeOH, [NiC12H28N2O2S2]I2, and [NiC13H30N2O2S2]I2 · 1/2 MeOH, are determined by single crystal X-ray analysis. The N-methyl groups in each of the alkylated derivatives are trans to each other, suggesting that the cis configuration is highly unfavored for such complexes in octahedral conformation. Crystal packing data shows that each of the alkylated complexes interacts closely with the iodide counterions, and with solvent if present; some of these interactions include H-bonds. Only the iodoacetamide derivative shows any significant interaction with a neighboring molecule.

  11. Phosphine-alkene ligand-mediated alkyl-alkyl and alkyl-halide elimination processes from palladium(II).

    PubMed

    Tuxworth, Luke; Baiget, Lise; Phanopoulos, Andreas; Metters, Owen J; Batsanov, Andrei S; Fox, Mark A; Howard, Judith A K; Dyer, Philip W

    2012-10-28

    N-Diphenylphosphino-7-aza-benzobicyclo[2.2.1]hept-2-ene (2) behaves as a chelating phosphine-alkene ligand for Pd(0) and Pd(II), promoting direct alkyl-alkyl and indirect alkyl-halide reductive elimination reactions due to the stabilisation of the resulting bis(phosphine-alkene)Pd(0) complex. PMID:22986447

  12. Thermochromism and structural change in polydiacetylenes including carboxy and 4-carboxyphenyl groups as the intermolecular hydrogen bond linkages in the side chain.

    PubMed

    Tanioku, Chiaki; Matsukawa, Kimihiro; Matsumoto, Akikazu

    2013-02-01

    We investigated the thermochromic behavior of polydiacetylenes including the carboxy and 4-carboxyphenyl groups as the side-chain substituents adjacent to the conjugated main chain, and then, the thermal stability and the thermochromism reversibility of the polymers were related to changes in the polymer conformations monitored by IR and Raman spectroscopies and powder X-ray diffractions. The polydiacetylenes with no or a phenylene spacer between the main chain and the carboxylic acid moiety were revealed to exhibit a thermal resistance for maintaining reversible thermochromism in a high temperature range, rather than polydiacetylenes with a conventional structure with a flexible alkylene spacer. The molecular stacking structures of the diacetylenes and the corresponding polymers in the crystals were discussed based on the results of an X-ray single-crystal structure analysis as well as the powder X-ray diffraction measurements. PMID:23276165

  13. Alcohol- and water-soluble bis(tpy)quaterthiophenes with phosphonium side groups: new conjugated units for metallo-supramolecular polymers.

    PubMed

    Štenclová, P; Šichová, K; Šloufová, I; Zedník, J; Vohlídal, J; Svoboda, J

    2016-01-21

    Bis(tpy)quaterthiophenes with symmetrically distributed two and four 6-bromohexyl side groups were prepared and modified by the reaction with triethylphosphine to give the corresponding ionic species. Both ionic and non-ionic bis(tpy)quaterthiophenes (unimers) were assembled with Zn(2+) and Fe(2+) ions to conjugated metallo-supramolecular polymers (MSPs), of which the ionic ones are soluble in alcohols and those derived from tetrasubstituted unimers are soluble even in water. The differences in assembly are specified between systems with (i) ionic and non-ionic unimers, (ii) Zn(2+) and Fe(2+) ion couplers, and (iii) methanol and water solvents. A substantial decrease in the stability of Fe-MSPs and a surprisingly high red shift of the luminescence band of Zn-MSPs were observed on going from methanol to aqueous solutions. PMID:26667325

  14. Vagus nerve stimulation for treatment of partial seizures: 2. Safety, side effects, and tolerability. First International Vagus Nerve Stimulation Study Group.

    PubMed

    Ramsay, R E; Uthman, B M; Augustinsson, L E; Upton, A R; Naritoku, D; Willis, J; Treig, T; Barolat, G; Wernicke, J F

    1994-01-01

    Vagus nerve stimulation (VNS) significantly reduces the frequency of partial seizures in refractory epilepsy patients. We examined the serious adverse events, side effects, and tolerability as they relate to the surgical implant procedure and the stimulating device. We also reviewed potential drug interactions, device output complications, and impact of the therapy on overall health status. We analyzed the first 67 patients to exist the acute phase of the EO3 VNS trial comparing high (therapeutic) VNS to low (less or noneffective) VNS. Data were collected from case report forms used at each of the four visits during the 12-week baseline and at each of the four visits during the 14-week randomized phase of the trial. No significant complications were reported as a result of the implant procedure. Serious adverse events included 1 patient who experienced direct current to the vagus nerve owing to generator malfunction resulting in left vocal cord paralysis and withdrawal of the patient from the study. No clinically significant effects on vital signs, cardiac function, or gastric function were detected. Side effects associated with VNS in the high group were hoarseness (35.5%), coughing (13.9%), and throat pain (12.9%). In the low group, only hoarseness (13.9%) and throat pain (13.9%) were associated with VNS. These effects generally wrre not considered clinically significant and occurred primarily during the stimulation pulses. No patients discontinued VNS therapy during the acute phase because of side effects associated with normal stimulation. Except for the one instance of a short circuit in the system resulting in a direct current, stimulating system complications were minor, limited to programming, unscheduled stimulation, and high lead impedance. Patients, investigators, and patient companions rated patients receiving high stimulation as more "improved" than those receiving low stimulation in regards to overall health status. Antiepileptic drug (AED) plasma

  15. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  16. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  17. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  18. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  19. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  20. The effect of alkylating agents on model supported metal clusters

    SciTech Connect

    Erdem-Senatalar, A.; Blackmond, D.G.; Wender, I. . Dept. of Chemical and Petroleum Engineering); Oukaci, R. )

    1988-01-01

    Interactions between model supported metal clusters and alkylating agents were studied in an effort to understand a novel chemical trapping technique developed for identifying species adsorbed on catalyst surfaces. It was found that these interactions are more complex than had previously been suggested. Studies were completed using deuterium-labeled dimethyl sulfate (DMS), (CH{sub 3}){sub 2}SO{sub 4}, as a trapping agent to interact with the supported metal cluster ethylidyne tricobalt enneacarbonyl. Results showed that oxygenated products formed during the trapping reaction contained {minus}OCD{sub 3} groups from the DMS, indicating that the interaction was not a simple alkylation. 18 refs., 1 fig., 3 tabs.

  1. Oil compositions containing alkyl amine or alkyl mercaptan derivatives of copolymers of an alpha olefin or an alkyl vinyl ether

    SciTech Connect

    Le, H.T.

    1990-02-13

    This patent describes an oil composition. It comprises a major amount of an oil selected from a crude oil or fuel oil and a minor amount of an alkyl amine or alkyl mercaptan derivative of an alpha olefin or alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic compound copolymer having pour point depressant ;properties. The copolymer comprising the reaction product of an alpha olefin having from about 2 to about 30 carbon atoms or mixtures of alpha olefins having from about 2 to about 30 carbon atoms or an alkyl vinyl ether or mixture of alkyl vinyl ethers.

  2. Synthesis of 3-alkyl naphthalenes as novel estrogen receptor ligands

    SciTech Connect

    Fang, Jing; Akwabi-Ameyaw, Adwoa; Britton, Jonathan E.; Katamreddy, Subba R.; Navas III, Frank; Miller, Aaron B.; Williams, Shawn P.; Gray, David W.; Orband-Miller, Lisa A.; Shearin, Jean; Heyer, Dennis

    2009-06-24

    A series of estrogen receptor ligands based on a 3-alkyl naphthalene scaffold was synthesized using an intramolecular enolate-alkyne cycloaromatization as the key step. Several of these compounds bearing a C6-OH group were shown to be high affinity ligands. All compounds had similar ER{alpha} and ER{beta} binding affinity ranging from micromolar to low nanomolar.

  3. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    ERIC Educational Resources Information Center

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  4. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    PubMed Central

    Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

    2015-01-01

    An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

  5. Safety Assessment of Alkyl Ethylhexanoates as Used in Cosmetics.

    PubMed

    Fiume, Monice; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-01-01

    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) assessed the safety of 16 alkyl ethylhexanoates for use in cosmetics, concluding that these ingredients are safe in cosmetic formulations in the present practices of use and concentrations when formulated to be nonirritating. The alkyl ethylhexanoates primarily function as skin-conditioning agents in cosmetics. The highest concentration of use reported for any of the alkyl ethylhexanoates is 77.3% cetyl ethylhexanoate in rinse-off formulations used near the eye, and the highest leave-on use reported is 52% cetyl ethylhexanoate in lipstick formulations. The Panel reviewed available animal and clinical data related to these ingredients, and the similarities in structure, properties, functions, and uses of ingredients from previous CIR assessments on constituent alcohols that allowed for extrapolation of the available toxicological data to assess the safety of the entire group. PMID:26684798

  6. Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

    SciTech Connect

    Carraher, Jack M.; Ellern, Arkady; Bakac, Andreja

    2013-09-21

    Macrocyclic rhodium(II) complexes LRh(H2O)(2+) (L = L-1 = cyclam and L-2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)(2)OOH to generate the corresponding rhodium(III) alkyls L(H2O)RhR2+ (R = CH3, C2H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)(2)(H2O) CoR and (dmgBF(2))(2)(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)(2+). The new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. (C) 2013 Elsevier B.V. All rights reserved.

  7. General and modular synthesis of isomeric 5-substituted pyridin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides bearing diverse alkyl, aryl, hetaryl, amino, carbamoyl, and hydroxy groups.

    PubMed

    Štefko, Martin; Slavětínská, Lenka; Klepetářová, Blanka; Hocek, Michal

    2011-08-19

    A general modular and practical methodology for preparation of diverse 5-substituted pyridin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides was developed. Regioselective lithiation of 2,5-dibromopyridine proceeded at position 5 or 2 depending on the solvent, and the resulting bromopyridyl lithium species underwent additions to TBS-protected ribonolactone and follow-up transformations to corresponding acetylated hemiketal intermediates 7 and 10 that were diastereoselectively reduced to give either 5-bromopyridin-2-yl or 6-bromopyridin-3-yl silyl-protected C-ribonucleosides 8 or 11 in 68% and 77% overall yields as pure β-anomers. These bromopyridyl C-nucleoside intermediates were then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, aminocarbonylations, and hydroxylations to give a series of protected 1β-(5-alkyl-, 5-aryl-, 5-amino-, 5-carbamoyl-, and 5-hydroxypyridin-2-yl)-C-ribonucleosides 13a-i and β-(6-alkyl-, 6-aryl-, 6-amino-, 6-carbamoyl-, and 6-hydroxypyridin-3-yl)-C-ribonucleosides 15a-i. Deprotection of silylated nucleosides by Et(3)N·3HF, TBAF, or TFA gave a series of free C-nucleosides 14a-i and 16a-i. PMID:21739971

  8. Detection of a branched alkyl molecule in the interstellar medium: iso-propyl cyanide

    NASA Astrophysics Data System (ADS)

    Belloche, Arnaud; Garrod, Robin T.; Müller, Holger S. P.; Menten, Karl M.

    2014-09-01

    The largest noncyclic molecules detected in the interstellar medium (ISM) are organic with a straight-chain carbon backbone. We report an interstellar detection of a branched alkyl molecule, iso-propyl cyanide (i-C3H7CN), with an abundance 0.4 times that of its straight-chain structural isomer. This detection suggests that branched carbon-chain molecules may be generally abundant in the ISM. Our astrochemical model indicates that both isomers are produced within or upon dust grain ice mantles through the addition of molecular radicals, albeit via differing reaction pathways. The production of iso-propyl cyanide appears to require the addition of a functional group to a nonterminal carbon in the chain. Its detection therefore bodes well for the presence in the ISM of amino acids, for which such side-chain structure is a key characteristic.

  9. Extended 3{beta}-alkyl steranes and 3-alkyl triaromatic steroids in crude oils and rock extracts

    SciTech Connect

    Dahl, J.; Moldowan, J.M.; Summons, R.E.

    1995-09-01

    In oils and Precambian- to Miocene-age source rocks from varying depositional environments, we have conclusively identified several novel 3-alkyl sterane and triaromatic steroid series, including (1) 3{beta}-n-pentyl steranes, (2) 3{beta}-isopentyl steranes, (3) 3{beta}-n-hexyl steranes, (4) 3{beta}-n-hepatyl steranes, (5) 3,4-dimethyl steranes, (6) 3{beta}-butyl,4-methyl steranes, (7) triaromatic 3-n-pentyl steroids, and (8) triaromatic 3-isopentyl steroids. We have also tentatively identified additional homologs with 3-alkyl substituents as large as C{sub 11}. The relative abundances of these compounds vary substantially between samples, as indicated by (1) the ratio of 3{beta}-n-pentyl steranes to 3{beta}-isopentyl steranes and (2) the ratio of 3-n-pentyl triaromatic steroids to 3-isopentyl triaromatic steroids. These data suggest possible utility for these parameters as tools for oil-source rock correlations and reconstruction of depositional environments. Although no 3-alkyl steroid natural products are currently known, several lines of evidence suggest that 3{beta}-alkyl steroids result from bacterial side-chain additions to diagenetic {delta}{sup 2}-sterenes.

  10. Transition-Metal-Free Regioselective Alkylation of Pyridine N-Oxides Using 1,1-Diborylalkanes as Alkylating Reagents.

    PubMed

    Jo, Woohyun; Kim, Junghoon; Choi, Seoyoung; Cho, Seung Hwan

    2016-08-01

    Reported herein is an unprecedented base-promoted deborylative alkylation of pyridine N-oxides using 1,1-diborylalkanes as alkyl sources. The reaction proceeds efficiently for a wide range of pyridine N-oxides and 1,1-diborylalkanes with excellent regioselectivity. The utility of the developed method is demonstrated by the sequential C-H arylation and methylation of pyridine N-oxides. The reaction also can be applied for the direct introduction of a methyl group to 9-O-methylquinine N-oxide, thus it can serve as a powerful method for late-stage functionalization. PMID:27351367

  11. Molecular structures and antiproliferative activity of side-chain saturated and homologated analogs of 2-chloro-3-(n-alkylamino)-1,4-napthoquinone

    NASA Astrophysics Data System (ADS)

    Pal, Sanjima; Jadhav, Mahesh; Weyhermüller, Thomas; Patil, Yogesh; Nethaji, M.; Kasabe, Umesh; Kathawate, Laxmi; Konkimalla, V. Badireenath; Salunke-Gawali, Sunita

    2013-10-01

    Side chain homologated derivatives of 2-chloro-3-(n-alkylamino)-1,4-naphthoquinone {n-alkyl: pentyl; L-5, hexyl; L-6, heptyl; L-7 and octyl; L-8} have been synthesized and characterized by elemental analysis, FT-IR, 1H NMR, UV-visible spectroscopy and LC-MS. Compounds, L-4, {n-alkyl: butyl; L-4}, L-6 and L-8 have been characterized by single crystal X-ray diffraction studies. The single crystal X-ray structures reveal that L-4 and L-8 crystallizes in P21 space group, while L-6 in P21/c space group. Molecules of L-4 and L-8 from polymeric chains through Csbnd H⋯O and Nsbnd H⋯O close contacts. L-6 is a dimer formed by Nsbnd H⋯O interaction. Slipped π-π stacking interactions are observed between quinonoid and benzenoid rings of L-4 and L-8. Orientations of alkyl group in L-4 and L-8 is on same side of the chain and polymeric chains run opposite to one another to form zip like structure to the alkyl groups. Antiproliferative activities of L-1 to L-8{n-alkyl: methyl; L-1, ethyl; L-2, propyl; L-3 and butyl; L-4} were studied in cancer cells of colon (COLO205), brain (U87MG) and pancreas (MIAPaCa2) where L-1, L-2 and L-3 were active in MIAPaCa2 (L-1 = L-2 > L-3) and COLO205 (L-2 = L-3 > L-1) and inactive in U87MG. From antiproliferative studies with compounds L-1 to L-8 it can be concluded that homologation of 2-chloro-3-(n-alkylamino)-1,4-napthoquinone with saturated methyl groups yielded tissue specific compounds such as L-2 (for MIAPaCa2) and L-3 (for COLO205) with optimal activity.

  12. Characterizing PUF disk passive air samplers for alkyl-substituted PAHs: Measured and modelled PUF-AIR partition coefficients with COSMO-RS.

    PubMed

    Parnis, J Mark; Eng, Anita; Mackay, Donald; Harner, Tom

    2016-02-01

    Isomers of alkyl-substituted polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes are modelled with COSMO-RS theory to determine the effectiveness and accuracy of this approach for estimation of isomer-specific partition coefficients between air and polyurethane foam (PUF), i.e., KPUF-AIR. Isomer-specific equilibrium partitioning coefficients for a series of 23 unsubstituted and isomeric alkyl-substituted PAHs and dibenzothiophenes were measured at 22 °C. This data was used to determine the accuracy of estimated values using COSMO-RS, which is isomer specific, and the Global Atmospheric Passive Sampling (GAPS) template approach, which treats all alkyl-substitutions as a single species of a given side-chain carbon number. A recently developed oligomer-based model for PUF was employed, which consisted of a 1:1 condensed pair of 2,4-toluene-diisocyanide and glycerol. The COSMO-RS approach resulted in a significant reduction in the RMS error associated with simple PAHs and dibenzothiophene compared with the GAPS template approach. When used with alkylated PAHs and dibenzothiophenes grouped into carbon-number categories, the GAPS template approach gave lower RMS error (0.72) compared to the COSMO-RS result (0.87) when the latter estimates were averaged within the carbon-number-based categories. When the isomer-specific experimental results were used, the COSMO-RS approach resulted in a 21% reduction in RMS error with respect to the GAPS template approach, with a 0.57 RMS error for all alkylated PAHs and dibenzothiophenes studied. The results demonstrate that COSMO-RS theory is effective in generating isomer-specific PUF-air partition coefficients, supporting the application of PUF-based passive samplers for monitoring and research studies of polycyclic aromatic compounds (PACs) in air. PMID:26692513

  13. Neogene transpressional foreland basin development on the north side of the central alaska range, usibelli group and nenana gravel, tanana basin

    USGS Publications Warehouse

    Ridgway, K.D.; Thoms, E.E.; Layer, P.W.; Lesh, M.E.; White, J.M.; Smith, S.V.

    2007-01-01

    Neogene strata of the Tanana basin provide a long-term record of a northwardpropagating, transpressional foreland-basin system related to regional shortening of the central Alaska Range and strike-slip displacement on the Denali fault system. These strata are ???2 km thick and have been deformed and exhumed in thrust faults that form the foothills on the north side of the Alaska Range. The lower part of the sedimentary package, the Usibelli Group, consists of 800 m of mainly Miocene strata that were deposited in fluvial, lacustrine, and peat bog environments of the foredeep depozone of the foreland-basin system. Compositional data from conglomerate and sandstone, as well as recycled Upper Cretaceous palynomorphs, indicate that the Miocene foreland-basin system was supplied increasing amounts of sediment from lithologies currently exposed in thrust sheets located south of the basin. The upper part of the sedimentary package, the Nenana Gravel, consists of 1200 m of mainly Pliocene strata that were deposited in alluvial-fan and braidplain environments in the wedge-top depozone of the foreland-basin system. Compositional data from conglomerate and sandstone, as well as 40Ar/39Ar dating of detrital feldspars in sandstone and from granitic clasts in conglomerate, indicate that lithologies exposed in the central Alaska Range provided most of the detritus to the Pliocene foreland-basin system. 40Ar/39Ar dates from detrital feldspar grains also show that two main suites of plutons contributed sediment to the Nenana Gravel. Detrital feldspars with an average age of 56 Ma are interpreted to have been derived from the McKinley sequence of plutons located south of the Denali fault. Detrital feldspars with an average age of 34 Ma are interpreted to have been derived from plutons located north of the Denali fault. Plutons located south of the Denali fault provided detritus for the lower part of the Nenana Gravel, whereas plutons located north of the Denali fault began to

  14. Partitioning behavior of an acid-cleavable, 1,3-dioxolane alkyl ethoxylate, surfactant in single and binary surfactant mixtures for 2- and 3-phase microemulsion systems according to ethoxylate head group size

    SciTech Connect

    Gomez Del Rio, Javier A; Hayes, Douglas G; Urban, Volker S

    2010-01-01

    Partition coefficients for a pH-degradable 1,3-dioxolane alkyl ethoxylate surfactant, 4-CH{sub 3}O (CH{sub 2}CH{sub 2}O){sub 5.6}-CH{sub 2}, 2,2-(CH{sub 2}){sub 12}CH{sub 3}, 2-(CH{sub 2}) CH{sub 3}, 1,3-dioxolane or ''cyclic ketal'' surfactant, CK-2,13-E{sub 5.6,ave}, between isooctane- and water-rich phases of 2- and 3-phase microemulsion systems (K{sub n}) were determined as functions of the ethoxylate size, n, and temperature for the neat surfactant and its binary surfactant mixtures, to understand the partitioning of alkyl ethoxylates possessing a broad distribution of ethoxylate size and to determine conditions required for formation of 3-phase microemulsion systems at an optimal temperature where phase separation occurs rapidly, important for protein purification via proteins selective partitioning to the middle phase, driven by affinity to the second surfactant of the binary mixture. A semi-empirical thermodynamic mathematical model described the partitioning data well, provided optimal temperature values consistent with phase diagrams and theory, and demonstrated that the tail region of CK-2,13-E{sub 5.6,ave} is more polar than the hydrophobes of fatty alcohol ethoxylates. The addition of Aerosol-OT (AOT) removed the temperature sensitivity of CK-2,13-E{sub 5.6,ave}s partitioning, producing 3-phase microemulsion systems between 20 C and 40 C. Analysis of the bottom phases of the 2- and 3-phase microemulsion systems formed by CK-2,13-E{sub 5.6,ave} via small-angle neutron scattering demonstrated the presence of spherical, monodisperse oil-in-water microemulsions.

  15. Chemical reactivity and intracavitary application of alkylating sugar alcohol derivatives.

    PubMed

    Kerpel-Fronius, S; Csetényi, J; Hegedüs, L; Horváth, I P; Ringwald, G; Töttössy, B; Eckhardt, S

    1980-01-01

    Lycurium [1,4-di-(methylsulfonyloxy-ethylamino)-1,4-didesoxy-erythrioldimethylsulfonate; R-74; NSC-122402] undergoes rapid hydrolysis in aqueous solutions. The concentration of the alkylating compound(s), demonstrated by the 4-(4'-nitrobenzyl)pyridine reaction, decreases approximately by 80% in 10 min following the dissolution of the drug in saline. In patients peak plasma concentration of radioactivity after the intracavitary injection of 14C-labelled Lycurim is observed between 4 and 6 h. It is assumed, therefore, that only a negligible amount of pharmacologically active alkylating compounds reaches the circulation after intracavitary application. This conclusion is supported by clinical experience showing that intracavitary administration of the same amount of Lycurim causes much milder systemic side-effects than intravenous injection. A dose escalation study was started to determine the applicability of Lycurim in the form of high volume intraperitoneal instillation ('belly bath') for the treatment of ovarian cancer. PMID:6893858

  16. Methods of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-08-03

    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  17. Algebraic dependence of the structure factor and possible anharmonicity in a high-resolution x-ray study of a side-group polymeric liquid crystal

    NASA Astrophysics Data System (ADS)

    Nachaliel, E.; Keller, E. N.; Davidov, D.; Boeffel, C.

    1991-03-01

    We report on a high-resolution x-ray study of the smectic-A phase near the nematic-smectic-A transition of a side-group polymeric liquid crystal, polyacrylate. Except at the very near vicinity of the phase transition, the first- and the second-harmonic x-ray structure factors were found to be consistent with the harmonic theory of de Gennes and Caille. However, very close to the phase transition, the attempts to fit the two harmonics completely failed. We believe that this is evidence for the importance of anharmonic corrections near the phase transition. The fits to the experimental data yield the compressibility constant B and the splay elastic constant Ks. We found that B can be described by a power law B~tφ, where t=(Tc-T)/Tc, Tc being the phase-transition temperature. φ was found to be 0.82+/-0.08, in good agreement with theoretical predictions using exponents from the literature, but in disagreement with previous experimental results on monomeric liquid crystals. The splay elastic constant Ks has roughly the same magnitude as in monomeric liquid crystals but tends to decrease by approximately 50% upon approaching the transition from below. This temperature dependence is further evidence for the importance of anharmonicity in the system.

  18. Cytotoxicity of alkylating agents towards sensitive and resistant strains of Escherichia coli in relation to extent and mode of alkylation of cellular macromolecules and repair of alkylation lesions in deoxyribonucleic acids

    PubMed Central

    Lawley, P. D.; Brookes, P.

    1968-01-01

    1. A quantitative study was made of the relationship between survival of colony-forming ability in Escherichia coli strains B/r and Bs–1 and the extents of alkylation of cellular DNA, RNA and protein after treatment with mono- or di-functional sulphur mustards, methyl methanesulphonate or iodoacetamide. 2. The mustards and methyl methanesulphonate react with nucleic acids in the cells, in the same way as found previously from chemical studies in vitro, and with proteins. Iodoacetamide reacts only with protein, principally with the thiol groups of cysteine residues. 3. The extents of alkylation of cellular constituents required to prevent cell division vary widely according to the strain of bacteria and the nature of the alkylating agent. 4. The extents of alkylation of the sensitive and resistant strains at a given dose of alkylating agent do not differ significantly. 5. Removal of alkyl groups from DNA of cells of the resistant strains B/r and 15T− after alkylation with difunctional sulphur mustard was demonstrated; the product di(guanin-7-ylethyl) sulphide, characteristic of di- as opposed to mono-functional alkylation, was selectively removed; the time-scale of this effect suggests an enzymic rather than a chemical mechanism. 6. The sensitive strain Bs–1 removed alkyl groups from DNA in this way only at very low extents of alkylation. When sensitized to mustard action by treatment with iodoacetamide, acriflavine or caffeine, the extent of alkylation of cellular DNA corresponding to a mean lethal dose was decreased to approximately 3 molecules of di(guanin-7-ylethyl) sulphide in the genome of this strain. 7. Relatively large numbers of monofunctional alkylations per genome can be withstood by this sensitive strain. Iodoacetamide had the weakest cytotoxic action of the agents investigated; methyl methanesulphonate was significantly weaker in effect than the monofunctional sulphur mustard, which was in turn weaker than the difunctional sulphur mustard. 8

  19. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOEpatents

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  20. Introduction of a hydrogen bond between phylloquinone PhQ(A) and a threonine side-chain OH group in photosystem I.

    PubMed

    Mula, Sam; McConnell, Michael D; Ching, Amy; Zhao, Nan; Gordon, Heather L; Hastings, Gary; Redding, Kevin E; van der Est, Art

    2012-12-01

    The phylloquinone acceptor PhQ(A) in photosystem I binds to the protein through a single H-bond to the backbone nitrogen of PsaA-L722. Here, we investigate the effect of this H-bond on the electron transfer (ET) kinetics by substituting threonine for PsaA-L722. Room temperature spin-polarized transient EPR measurements show that in the PsaA-L722T mutant, the rate of PhQ(A)(-) to F(X) ET increases and the hyperfine coupling to the 2-methyl group of PhQ(A) is much larger than in the wild type. Molecular dynamics simulations and ONIOM type electronic structure calculations indicate that it is possible for the OH group of the Thr side chain to form an H-bond to the carbonyl oxygen atom, O(4) of the phylloquinone, and that this results in an increase in the 2-methyl hyperfine couplings as observed in the transient EPR data. The Arrhenius plot of the PhQ(A)(-) to F(X) ET in the PsaA-L722T mutant suggests that the increased rate is probably the result of a slight change in the electronic coupling between PhQ(A)(-) and F(X). The strong deviation from Arrhenius behavior observed at ∼200 K can be reproduced using a semiclassical model, which takes the zero-point energy of the mode coupled to the ET into account. However, since the change in slope of the Arrhenius plot occurs at the protein glass transition temperature, it is argued that it could be the result of a change in the protein relaxation dynamics at this temperature rather than quantum mechanical effects. PMID:23137346

  1. Polycyclic Aromatic Acids Are Primary Metabolites of Alkyl-PAHs-A Case Study with Nereis diversicolor.

    PubMed

    Malmquist, Linus M V; Selck, Henriette; Jørgensen, Kåre B; Christensen, Jan H

    2015-05-01

    Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl-PAHs primarily forms polycyclic aromatic acids (PAAs). We generalize this to other alkyl-PAHs, based on literature and the present study of the metabolism of 1-methylphenanthrene, 3,6-dimethylphenanthrene, and 1-, 2-, 3-, and 6-methylchrysene related to their unsubstituted parent PAHs. Also, we observed that body burdens and production of PAAs was related to the position of the methyl group, showing the same isomer specific preferences as for microbial degradation of alkyl-PAHs. We detected a high production of PAAs, and larger metabolism of alkyl-PAHs than their unsubstituted parent PAHs. We therefore propose that carboxylic acid metabolites of alkyl-PAHs have the potential of constituting a new class of contaminants in marine waters that needs attention in relation to ecological risk assessments. PMID:25827176

  2. Highly conductive side chain block copolymer anion exchange membranes.

    PubMed

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days. PMID:27216558

  3. N-Alkyl-, 1-C-Alkyl-, and 5-C-Alkyl-1,5-dideoxy-1,5-imino-(L)-ribitols as Galactosidase Inhibitors.

    PubMed

    Front, Sophie; Gallienne, Estelle; Charollais-Thoenig, Julie; Demotz, Stéphane; Martin, Olivier R

    2016-01-01

    A series of 1,5-dideoxy-1,5-imino-(l)-ribitol (DIR) derivatives carrying alkyl or functionalized alkyl groups were prepared and investigated as glycosidase inhibitors. These compounds were designed as simplified 4-epi-isofagomine (4-epi-IFG) mimics and were expected to behave as selective inhibitors of β-galactosidases. All compounds were indeed found to be highly selective for β-galactosidases versus α-glycosidases, as they generally did not inhibit coffee bean α-galactosidase or other α-glycosidases. Some compounds were also found to be inhibitors of almond β-glucosidase. The N-alkyl DIR derivatives were only modest inhibitors of bovine β-galactosidase, with IC50 values in the 30-700 μM range. Likewise, imino-L-ribitol substituted at the C1 position was found to be a weak inhibitor of this enzyme. In contrast, alkyl substitution at C5 resulted in enhanced β-galactosidase inhibitory activity by a factor of up to 1000, with at least six carbon atoms in the alkyl substituent. Remarkably, the 'pseudo-anomeric' configuration in this series does not appear to play a role. Human lysosomal β-galactosidase from leukocyte lysate was, however, poorly inhibited by all iminoribitol derivatives tested (IC50 values in the 100 μM range), while 4-epi-IFG was a good inhibitor of this enzyme. Two compounds were evaluated as pharmacological chaperones for a GM1-gangliosidosis cell line (R301Q mutation) and were found to enhance the mutant enzyme activity by factors up to 2.7-fold. PMID:26644389

  4. Leukemia after therapy with alkylating agents for childhood cancer

    SciTech Connect

    Tucker, M.A.; Meadows, A.T.; Boice, J.D. Jr.; Stovall, M.; Oberlin, O.; Stone, B.J.; Birch, J.; Voute, P.A.; Hoover, R.N.; Fraumeni, J.F. Jr.

    1987-03-01

    The risk of leukemia was evaluated in 9,170 2-or-more-year survivors of childhood cancer in the 13 institutions of the Late Effects Study Group. Secondary leukemia occurred in 22 nonreferred individuals compared to 1.52 expected, based on general population rates (relative risk (RR) = 14; 95% confidence interval (CI), 9-22). The influence of therapy for the first cancer on subsequent leukemia risk was determined by a case-control study conducted on 25 cases and 90 matched controls. Treatment with alkylating agents was associated with a significantly elevated risk of leukemia (RR = 4.8; 95% CI, 1.2-18.9). A strong dose-response relationship was also observed between leukemia risk and total dose of alkylating agents, estimated by an alkylator score. The RR of leukemia reached 23 in the highest dose category. Radiation therapy, however, did not increase risk. Although doxorubicin was also identified as a possible risk factor, the excess risk of leukemia following treatment for childhood cancer appears almost entirely due to alkylating agents.

  5. Effect of side-arm variation in dibenzo-16-crown-5 compounds on the potentiometric selectivity for sodium ion

    SciTech Connect

    Ohki, Akira; Lu, J.P.; Bartsch, R.A. )

    1994-03-01

    The influence of attaching one or two pendent groups to the central carbon of the three-carbon bridge in dibenzo-16-crown-5 upon the potentiometric response of the ionophore to Li[sup +], Na[sup +], and K[sup +] in solvent polymeric membranes has been assessed. Side-arm variation includes alkyl, OCH[sub 3], OCH[sub 2]CO[sub 2]H, OCH[sub 2]CO[sub 2]C[sub 2]H[sub 5] and OCH[sub 2]C(O)N(C[sub 2]H[sub 5])[sub 2] units. The Na[sup +]/K[sup +] selectivity of the electrodes is increased by enhanced oxygen basicity in the side arm of the ionophore. Attachment of an alkyl group to the polyether ring carbon, which bears an oxygen-containing side arm, produces a substantial increase in the Na[sup +]/K[sup +] selectivity due to preorganization of the binding site. The Na[sup +]/Li[sup +] selectivity responds to side-arm variation within the ionophore quite differently than does the Na[sup +]/K[sup +] selectivity. 28 refs., 4 figs., 2 tabs.

  6. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  7. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  8. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  9. Effects of spacer length and terminal group on the crystallization and morphology of biscarbamates: a longer spacer does not reduce the melting temperature.

    PubMed

    Khan, Mostofa Kamal; Sundararajan, Pudupadi R

    2013-05-01

    The effects of alkyl side chain and spacer lengths and the type of terminal group on the morphology and crystallization of a homologous series of biscarbamates (model compounds for polyurethanes) were investigated. Biscarbamates were synthesized with alkyl side chains of various lengths ranging from C4 to C18 and an alkyl spacer group with 12 CH2 units (C12 spacer) between the two hydrogen bonding motifs. The crystallization and morphological features are compared with the previously studied biscarbamates with a C6 spacer. As a token example, we also studied a biscarbamate molecule in which the terminal methyl group was replaced by a phenyl group. We stress four important conclusions of the study: (1) A number of studies in the literature found that the longer alkyl spacers reduced the thermal transition temperatures of the molecules, and such behavior was attributed to an increase in the flexibility of the alkyl spacer. However, the results of the present study are to the contrary. With the biscarbamates studied here, the hydrogen-bonding groups on both sides of the C12 spacer act as "anchors", and the longer spacer does not reduce the melting temperatures compared with those with the C6 spacer. (2) The melt viscosity measurements show shear-thinning behavior, which has been mostly observed with polysaccharides and hydrogen-bonded polymers. (3) Avrami analysis shows a two-stage crystallization, which is not commonly observed in organic small molecule systems. (4) The phenyl end group does not add another self-assembly code in terms of π-stacking but acts as a defect. While formation of crystals was observed for biscarbamates with short alkyl side chains with a C6 spacer, an increase in spacer length to C12 induces spherulitic morphology. Although the overall sizes of the spherulites are the same for both spacers, the rate of spherulite growth was higher and the crystallization rate was lower with the C12 spacer compared with the C6 spacer. In contrast with the

  10. Studies of structural, dynamical, and interfacial properties of 1-alkyl-3-methylimidazolium iodide ionic liquids by molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Ghatee, Mohammad Hadi; Zolghadr, Amin Reza; Moosavi, Fatemeh; Ansari, Younes

    2012-03-01

    Bulk and surface properties of the ionic liquids 1-alkyl-3-methyl-imidazolium iodides ([Cnmim]I) were simulated by classical molecular dynamics using all atom non-polarizable force field (n = 4, butyl; 6, hexyl; 8, octyl). The structure of ionic liquids were initially optimized by density functional theory and atomic charges obtained by CHELPG method. Reduction of partial atomic charges (by 20% for simulation of density and surface tension, and by 10% for viscosity) found to improve the accuracy, while a non-polarizable force field was applied. Additionally, the simulation ensembles approach the equilibrium faster when the charge reduction is applied. By these refined force field parameters, simulated surface tensions in the range of 323-393 k are quite in agreement with the experiments. Simulation of temperature dependent surface tension of [C4mim]I well beyond room temperature (up to 700 K) permits prediction of the critical temperature in agreement with that predicted from experimental surface tension data. Simulated densities in the range of 298-450 K for the three ionic liquids are within 0.8% of the experimental data. Structural properties for [C4mim]I were found to be in agreement with the results of Car-Parrinello molecular dynamics simulation we performed, which indicates a rather well-structured cation-anion interaction and occurs essentially through the imidazolium ring cation. Diffusion coefficient changes with alkyl chain length in the order of [C8mim]I > [C6mim]I > [C4mim]I for the cation and the anion. Formation of a dense domain in subsurface region is quite evident, and progressively becomes denser as the alkyl chain length increases. Bivariate orientational analysis was used to determine the average orientation of molecule in ionic liquids surface, subsurface, and bulk regions. Dynamic bisector-wise and side-wise movement of the imodazolium ring cation in the surface region can be deduced from the bivariate maps. Atom-atom density profile and

  11. Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

    PubMed

    Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan

    2016-04-14

    Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies. PMID:26982480

  12. Occupational asthma due to alkyl cyanoacrylate

    SciTech Connect

    Nakazawa, T. )

    1990-08-01

    A case of bronchial asthma induced by occupational exposure to alkyl cyanoacrylate, an adhesive, occurred in an assembly operation. Provocative exposure testing induced immediate and delayed asthmatic responses. Alkyl cyanoacrylate seemed to act as an allergen or as an irritant, resulting in the development of asthma.

  13. 2-Alkyl-4-aryl-pyrimidine fused heterocycles as selective 5-HT2A antagonists.

    PubMed

    Shireman, Brock T; Dvorak, Curt A; Rudolph, Dale A; Bonaventure, Pascal; Nepomuceno, Diane; Dvorak, Lisa; Miller, Kirsten L; Lovenberg, Timothy W; Carruthers, Nicholas I

    2008-03-15

    The synthesis and SAR for a novel series of 2-alkyl-4-aryl-tetrahydro-pyrido-pyrimidines and 2-alkyl-4-aryl-tetrahydro-pyrimido-azepines is described. Representative compounds were shown to be subtype selective 5-HT(2A) antagonists. Optimal placement of a basic nitrogen relative to the pyrimidine and the presence of a 4-fluorophenyl group in the pyrimidine 4-position was found to have a profound effect on affinity and selectivity. PMID:18282705

  14. Palladium-Catalyzed Heteroarylation and Concomitant ortho-Alkylation of Aryl Iodides.

    PubMed

    Lei, Chuanhu; Jin, Xiaojia; Zhou, Jianrong Steve

    2015-11-01

    Three-component couplings were achieved from common aryl halides, alkyl halides, and heteroarenes under palladium and norbornene co-catalysis. The reaction forges hindered aryl-heteroaryl bonds and introduces ortho-alkyl groups to aryl rings. Various heterocycles such as oxazoles, thiazoles and thiophenes underwent efficient coupling. The heteroarenes were deprotonated in situ by bases without the assistance of palladium catalysts. PMID:26358935

  15. 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.

  16. Alkylating reactivity and herbicidal activity of chloroacetamides.

    PubMed

    Jablonkai, Istvan

    2003-04-01

    The relationship between S- and N-alkylating reactivity and herbicidal activity within a series of chloroacetamides, including several commercial herbicides and newly synthesised analogues was studied. The S-alkylating reactivity of selected chloroacetamides, as well as those of atrazine and chlorfenprop-methyl, was determined by in vitro GSH conjugation at a ratio of GSH to alkylating agent of 25:1. A spectrophotometric reaction using 4-(4-nitrobenzyl)pyridine was used to characterise the N-alkylating reactivity of the chemicals. Our results indicate that a reduced level of N-alkylating reactivity correlates with an improved herbicidal efficacy at a practical rate. However, the phytoxicity of the molecules is not simply dependent on chemical reactivities, but strictly related to the molecular structure, indicating that lipophilicity, uptake, mobility and induction of detoxifying enzymes may also be decisive factors in the mode of action. PMID:12701706

  17. C-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Obora, Yasushi

    2016-04-01

    The development of practical, efficient, and atom-economical methods for the formation of carbon-carbon bonds remains a topic of considerable interest in current synthetic organic chemistry. In this review, we have summarized selected topics from the recent literature with particular emphasis on C-alkylation processes involving hydrogen transfer using alcohols as alkylation reagents. This review includes selected highlights concerning recent progress towards the modification of catalytic systems for the α-alkylation of ketones, nitriles, and esters. Furthermore, we have devoted a significant portion of this review to the methylation of ketones, alcohols, and indoles using methanol. Lastly, we have also documented recent advances in β-alkylation methods involving the dimerization of alcohols (Guerbet reaction), as well as new developments in C-alkylation methods based on sp (3) C-H activation. PMID:27573136

  18. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-01-05

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70 C and 500 C and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  19. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  20. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  1. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  2. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  3. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70.degree. C. and 500.degree. C. and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  4. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  5. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  6. Levels and pattern of alkyl nitrates, multifunctional alkyl nitrates, and halocarbons in the air over the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Fischer, Ralf G.; Kastler, Jürgen; Ballschmiter, Karlheinz

    2000-06-01

    The Albatross Campaign was a research cruise of the German research vessel RV Polarstern (cruise ANT XFV/1) in October and November 1996 across the Atlantic Ocean. The cruise started in Bremerhaven, Germany, reached the polar region at 67°N, followed the 30°W meridian longitude, crossed the equatorial region, and ended at 50°S at Punta Quilla, Argentina. A second cruise leg closer to the African continent started from Capetown, South Africa, passed the Canary Island, and ended through the English Channel at Bremerhaven, Germany, in May/June 1998. Measurements of atmospheric levels of C1-C13 alkyl mononitrates, 24 alkyl dinitrates (C3-C6), 19 hydroxy alkyl nitrates (C2-C6), and benzyl nitrate, as well as the halocarbons tetrachloroethene, hexachloroethane, and bromoform are presented in this work. The halocarbons are used to assess the origin of the air parcels analyzed. Levels and patterns of multifunctional alkyl nitrates in the marine air are described here for the first time. The air masses include polluted air from the northern Europe, as well as highly degraded air masses of the South Atlantic trade wind region that represent global baseline levels. Two independent analytical methods were used in combination to cover the whole range of organic nitrates. First, the low-volume adsorptive enrichment of organic traces on Tenax, followed by thermodesorption cold trap HRGC-ECD and thermodesorption cold trap HRGC-(EI)MSD was used. Second, high-volume adsorptive enrichment of organic traces on silica gel was applied followed by solvent desorption, NP-HPLC group separation, and HRGC-(EI)-MSD. Short-chain alkyl nitrates (C4-C6) showed mixing ratios in the range of 0.2-2.5 parts per trillion by volume (pptv), with a local minimum for the tropical regions and significantly lower ratios for the Southern Hemisphere. The mixing ratio of the sum of 36 long-chain alkyl mononitrates (C7-C13) ranged from 0.02-0.43 pptv, the mixing ratio of the sum of 23 alkyl dinitrates (C3-C

  7. Self-assembly of a series of random copolymers bearing amphiphilic side chains.

    PubMed

    Wu, Xu; Qiao, Yingjie; Yang, Hui; Wang, Jinben

    2010-09-15

    A novel series of comb-like random copolymers were prepared by polymerization of amphiphilic macromonomers, 2-(acrylamido)-octane sulfonic acid (AMC(8)S), 2-(acrylamido)-dodecane sulfonic acid (AMC(12)S), and 2-(acrylamido)-hexadecane sulfonic acid (AMC(16)S), with 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) respectively. The synthesis of the polymers with the same contents of amphiphilic units as side chains, but different chain length, enabled us to study the chain length dependence of their association in salt solution. Steady-state fluorescence measurements with pyrene as a polarity probe, quasielastic light scattering techniques (QELS) and transmission electron micrograph (TEM) were employed to investigate the associative properties of the system. The above investigations showed that all kinds of side chains begin to assemble at certain polymer concentrations and the critical aggregation concentration (CAC) decrease dramatically with the increase in the length and content of alkyl. An interesting phenomenon is that the assembly tends more favorably to occur among different molecules rather than within single molecule when the number of carbon atoms in the alkyl groups or the polymer concentration increases, leading to the formation of larger multimolecular micelle-like aggregate. The aim of the present work is to establish the fundamental preconditions of intramolecular and intermolecular association fashions for the polymers, which is useful for the exploitation of functional groups and contributes to the development of amphiphilic random polymers. PMID:20576273

  8. Binary functionalization of H:Si(111) surfaces by alkyl monolayers with different linker atoms enhances monolayer stability and packing.

    PubMed

    Arefi, Hadi H; Nolan, Michael; Fagas, Giorgos

    2016-05-14

    Alkyl monolayer modified Si forms a class of inorganic-organic hybrid materials with applications across many technologies such as thin-films, fuel/solar-cells and biosensors. Previous studies have shown that the linker atom, through which the monolayer binds to the Si substrate, and any tail group in the alkyl chain, can tune the monolayer stability and electronic properties. In this paper we study the H:Si(111) surface functionalized with binary SAMs: these are composed of alkyl chains that are linked to the surface by two different linker groups. Aiming to enhance SAM stability and increase coverage over singly functionalized Si, we examine with density functional theory simulations that incorporate vdW interactions, a range of linker groups which we denote as -X-(alkyl) with X = CH2, O(H), S(H) or NH(2) (alkyl = C6 and C12 chains). We show how the stability of the SAM can be enhanced by adsorbing alkyl chains with two different linkers, e.g. Si-[C, NH]-alkyl, through which the adsorption energy is increased compared to functionalization with the individual -X-alkyl chains. Our results show that it is possible to improve stability and optimum coverage of alkyl functionalized SAMs linked through a direct Si-C bond by incorporating alkyl chains linked to Si through a different linker group, while preserving the interface electronic structure that determines key electronic properties. This is important since any enhancement in stability and coverage to give more densely packed monolayers will result in fewer defects. We also show that the work function can be tuned within the interval of 3.65-4.94 eV (4.55 eV for bare H:Si(111)). PMID:27109872

  9. Deciphering the genomic targets of alkylating polyamide conjugates using high-throughput sequencing

    PubMed Central

    Chandran, Anandhakumar; Syed, Junetha; Taylor, Rhys D.; Kashiwazaki, Gengo; Sato, Shinsuke; Hashiya, Kaori; Bando, Toshikazu; Sugiyama, Hiroshi

    2016-01-01

    Chemically engineered small molecules targeting specific genomic sequences play an important role in drug development research. Pyrrole-imidazole polyamides (PIPs) are a group of molecules that can bind to the DNA minor-groove and can be engineered to target specific sequences. Their biological effects rely primarily on their selective DNA binding. However, the binding mechanism of PIPs at the chromatinized genome level is poorly understood. Herein, we report a method using high-throughput sequencing to identify the DNA-alkylating sites of PIP-indole-seco-CBI conjugates. High-throughput sequencing analysis of conjugate 2 showed highly similar DNA-alkylating sites on synthetic oligos (histone-free DNA) and on human genomes (chromatinized DNA context). To our knowledge, this is the first report identifying alkylation sites across genomic DNA by alkylating PIP conjugates using high-throughput sequencing. PMID:27098039

  10. Deciphering the genomic targets of alkylating polyamide conjugates using high-throughput sequencing.

    PubMed

    Chandran, Anandhakumar; Syed, Junetha; Taylor, Rhys D; Kashiwazaki, Gengo; Sato, Shinsuke; Hashiya, Kaori; Bando, Toshikazu; Sugiyama, Hiroshi

    2016-05-19

    Chemically engineered small molecules targeting specific genomic sequences play an important role in drug development research. Pyrrole-imidazole polyamides (PIPs) are a group of molecules that can bind to the DNA minor-groove and can be engineered to target specific sequences. Their biological effects rely primarily on their selective DNA binding. However, the binding mechanism of PIPs at the chromatinized genome level is poorly understood. Herein, we report a method using high-throughput sequencing to identify the DNA-alkylating sites of PIP-indole-seco-CBI conjugates. High-throughput sequencing analysis of conjugate 2: showed highly similar DNA-alkylating sites on synthetic oligos (histone-free DNA) and on human genomes (chromatinized DNA context). To our knowledge, this is the first report identifying alkylation sites across genomic DNA by alkylating PIP conjugates using high-throughput sequencing. PMID:27098039

  11. Safety Assessment of Alkyl Esters as Used in Cosmetics.

    PubMed

    Fiume, Monice M; Heldreth, Bart A; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-09-01

    The Cosmetic Ingredient Review Expert Panel (Panel) assessed the safety of 237 alkyl esters for use in cosmetics. The alkyl esters included in this assessment have a variety of reported functions in cosmetics, with skin-conditioning agent being the most common function. The Panel reviewed available animal and clinical data in making its determination of safety on these ingredients, and where there were data gaps, similarity in structure, properties, functions, and uses of these ingredients allowed for extrapolation of the available toxicological data to assess the safety of the entire group. The Panel concluded that these ingredients are safe in cosmetic formulations in the present practices of use and concentration when formulated to be nonirritating. PMID:26362120

  12. Structure–Activity Relationships for Side Chain Oxysterol Agonists of the Hedgehog Signaling Pathway

    PubMed Central

    2012-01-01

    Oxysterols (OHCs) are byproducts of cholesterol oxidation that are known to activate the Hedeghog (Hh) signaling pathway. While OHCs that incorporate hydroxyl groups throughout the scaffold are known, those that act as agonists of Hh signaling primarily contain a single hydroxyl on the alkyl side chain. We sought to further explore how side chain hydroxylation patterns affect oxysterol-mediated Hh activation, by performing a structure–activity relationship study on a series of synthetic OHCs. The most active analogue, 23(R)-OHC (35), demonstrated potent activation of Hh signaling in two Hh-dependent cell lines (EC50 values 0.54–0.65 μM). In addition, OHC 35 was approximately 3-fold selective for the Hh pathway as compared to the liver X receptor, a nuclear receptor that is also activated by endogenous OHCs. Finally, 35 induced osteogenic differentiation and osteoblast formation in cultured cells, indicating functional agonism of the Hh pathway. PMID:24900386

  13. From Both Sides.

    ERIC Educational Resources Information Center

    Glew, Frank

    1998-01-01

    Ontario Agri-Food Education's curriculum unit, "From Both Sides," applies a cooperative-learning method of conflict resolution to environmental issues. Two groups of students are assigned polar views on an issue such as pesticide use. Five steps involve preparing and presenting a position, refuting opposing positions, reversing perspectives, and…

  14. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

    PubMed Central

    Peshkov, Roman Yu; Chunyan, Wang; Tretyakov, Evgeny V; Shteingarts, Vitalij D

    2016-01-01

    Summary A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents. PMID:27559409

  15. One-pot synthesis of 4'-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling.

    PubMed

    Peshkov, Roman Yu; Panteleeva, Elena V; Chunyan, Wang; Tretyakov, Evgeny V; Shteingarts, Vitalij D

    2016-01-01

    A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents. PMID:27559409

  16. Motor fuel alkylation process utilizing low acid

    SciTech Connect

    Kocal, J.A.; Imai, T.

    1987-01-06

    A process is described for the alkylation of an isoparaffin with an olefin acting agent comprising contacting the isoparaffin with the olefin acting agent at alkylation conditions in the presence of a catalyst. The catalyst consists essentially of an anhydrous, nonalcoholic mixture of from about 5 to 15 wt. % methyl tert-butyl ether and from 85 to 95 wt. % hydrofluoric acid. The volumetric ratio of hydrofluoric acid to isoparaffin and olefin acting agent is less than 0.75.

  17. Thermally induced alkylation of diamond.

    PubMed

    Hoeb, Marco; Auernhammer, Marianne; Schoell, Sebastian J; Brandt, Martin S; Garrido, Jose A; Stutzmann, Martin; Sharp, Ian D

    2010-12-21

    We present an approach for the thermally activated formation of alkene-derived self-assembled monolayers on oxygen-terminated single and polycrystalline diamond surfaces. Chemical modification of the oxygen and hydrogen plasma-treated samples was achieved by heating in 1-octadecene. The resulting layers were characterized using X-ray photoelectron spectroscopy, thermal desorption spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and water contact angle measurements. This investigation reveals that alkenes selectively attach to the oxygen-terminated sites via covalent C-O-C bonds. The hydrophilic oxygen-terminated diamond is rendered strongly hydrophobic following this reaction. The nature of the process limits the organic layer growth to a single monolayer, and FTIR measurements reveal that such monolayers are dense and well ordered. In contrast, hydrogen-terminated diamond sites remain unaffected by this process. This method is thus complementary to the UV-initiated reaction of alkenes with diamond, which exhibits the opposite reactivity contrast. Thermal alkylation increases the range of available diamond functionalization strategies and provides a means of straightforwardly forming single organic layers in order to engineer the surface properties of diamond. PMID:21090790

  18. N-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed. PMID:27573267

  19. Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

    SciTech Connect

    Carraher, Jack M.; Ellern, Arkady; Bakac, Andreja

    2013-09-21

    We found that the macrocyclic rhodium(II) complexes LRh(H2O)2+ (L = L1 = cyclam and L2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)2OOH to generate the corresponding rhodium(III) alkyls L(H2O)RhR2+ (R = CH3, C2H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)2(H2O) CoR and (dmgBF2)2(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)2+. Moreover, the new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis.

  20. Physico-chemical properties and toxicity of alkylated polycyclic aromatic hydrocarbons.

    PubMed

    Kang, Hyun-Joong; Lee, So-Young; Kwon, Jung-Hwan

    2016-07-15

    Crude oil and refined petroleum products contain many polycyclic and heterocyclic aromatic hydrocarbons, in particular, alkylated PAHs. Although alkylated PAHs are found in significantly higher quantities than their corresponding unsubstituted PAHs, the most studies on the physico-chemical properties and toxicities of these compounds have been conducted on unsubstituted PAHs. In this study, we measured crucial physico-chemical properties (i.e., water solubility, partition coefficients between polydimethylsiloxane and water (KPDMSw), and partition coefficient between liposomes and water (Klipw)) of selected alkylated PAHs, and evaluated their toxicity using the luminescence inhibition of Aliivibrio fischeri and growth inhibition of Raphidocelis subcapitata. In general, the logarithms of these properties for alkylated PAHs showed good linear correlations with log Kow, as did those for unsubstituted PAHs. Changes in molecular symmetry on the introduction of alkyl groups on aromatic ring structure significantly altered water solubility. The inhibition of bacterial luminescence and algal growth by alkylated PAHs can be explained well by the baseline toxicity hypothesis, and good linear relationships between log Kow or log Klipw and log (1/EC50) were found. PMID:27037474

  1. A Systematic Study on the Mesomorphic Behavior of Asymmetrical 1-Alkyl-3-dodecylimidazolium Bromides

    SciTech Connect

    Yang, Mei; Mallick, Bert; Mudring, Anja-Verena

    2014-04-02

    To determine the essential parameters for mesophase formation in imidazolium-based ionic liquids (ILs), a library of 1-alkyl-3-dodecylimidazolium bromides was synthesized, abbreviated as CnC12, where 0 ≤ n ≤ 13, as the general notion is that a dodecyl side chain would guarantee the formation of an ionic liquid crystal (ILC). All salts were fully characterized by NMR spectroscopy and mass spectrometry. Their thermal properties were recorded, and mesophase formation was assessed. An odd–even effect is observed for 5 ≤ n ≤ 10 in the temperatures of melting transitions. While the majority of this series, as expected, formed mesophases, surprisingly compounds C2C12 and C6C12 could not be classified as ILCs, the latter being a room temperature IL, while C2C12 is a crystalline solid with melting point at 37 °C. The single crystal structure of compound 1-ethyl-3-dodecylimidazolium bromide (C2C12) was successfully obtained. Remarkably, the arrangement of imidazolium cores in the structure is very complicated due to multiple nonclassical hydrogen bonds between bromide anions and imidazolium head groups. In this arrangement, neighboring imidazolium rings are forced by hydrogen bonds to form a “face-to-face” conformation. This seems to be responsible for the elimination of a mesophase. To conclude, the general view of a dodecyl chain being a functional group to generate a mesophase is not entirely valid.

  2. Methods and Mechanisms for Cross-Electrophile Coupling of Csp(2) Halides with Alkyl Electrophiles.

    PubMed

    Weix, Daniel J

    2015-06-16

    Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C-H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C-C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl halides to form

  3. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    PubMed Central

    2016-01-01

    Conspectus Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C–H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C–C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl

  4. On the Other Side of the Fence: Effects of Social Categorization and Spatial Grouping on Memory and Attention for Own-Race and Other-Race Faces

    PubMed Central

    Kloth, Nadine; Shields, Susannah E.; Rhodes, Gillian

    2014-01-01

    The term “own-race bias” refers to the phenomenon that humans are typically better at recognizing faces from their own than a different race. The perceptual expertise account assumes that our face perception system has adapted to the faces we are typically exposed to, equipping it poorly for the processing of other-race faces. Sociocognitive theories assume that other-race faces are initially categorized as out-group, decreasing motivation to individuate them. Supporting sociocognitive accounts, a recent study has reported improved recognition for other-race faces when these were categorized as belonging to the participants' in-group on a second social dimension, i.e., their university affiliation. Faces were studied in groups, containing both own-race and other-race faces, half of each labeled as in-group and out-group, respectively. When study faces were spatially grouped by race, participants showed a clear own-race bias. When faces were grouped by university affiliation, recognition of other-race faces from the social in-group was indistinguishable from own-race face recognition. The present study aimed at extending this singular finding to other races of faces and participants. Forty Asian and 40 European Australian participants studied Asian and European faces for a recognition test. Faces were presented in groups, containing an equal number of own-university and other-university Asian and European faces. Between participants, faces were grouped either according to race or university affiliation. Eye tracking was used to study the distribution of spatial attention to individual faces in the display. The race of the study faces significantly affected participants' memory, with better recognition of own-race than other-race faces. However, memory was unaffected by the university affiliation of the faces and by the criterion for their spatial grouping on the display. Eye tracking revealed strong looking biases towards both own-race and own-university faces

  5. A facile and high-recovery material for rare-metals based on a water-soluble polyallylamine with side-chain thiourea groups.

    PubMed

    Nagai, Daisuke; Yoshida, Megumi; Kishi, Takuya; Morinaga, Hisatoyo; Hara, Yusuke; Mori, Masanobu; Kawakami, Satoshi; Inoue, Kenji

    2013-08-01

    We describe a facile and high-recovery material for rare metals based on a polymer combining amino groups for water solubility and thiourea groups for metal complexation. Good solubility in aqueous metal ion solutions allows for homogeneous and efficient adsorption by the polymer, and a maximum Pd(II) recovery amount (0.508 gPd gpolymer(-1)) greater than those of other polymers reported in the literature. PMID:23788410

  6. Graphene-Catalyzed Direct Friedel-Crafts Alkylation Reactions: Mechanism, Selectivity, and Synthetic Utility.

    PubMed

    Hu, Feng; Patel, Mehulkumar; Luo, Feixiang; Flach, Carol; Mendelsohn, Richard; Garfunkel, Eric; He, Huixin; Szostak, Michal

    2015-11-18

    Transition-metal-catalyzed alkylation reactions of arenes have become a central transformation in organic synthesis. Herein, we report the first general strategy for alkylation of arenes with styrenes and alcohols catalyzed by carbon-based materials, exploiting the unique property of graphenes to produce valuable diarylalkane products in high yields and excellent regioselectivity. The protocol is characterized by a wide substrate scope and excellent functional group tolerance. Notably, this process constitutes the first general application of graphenes to promote direct C-C bond formation utilizing polar functional groups anchored on the GO surface, thus opening the door for an array of functional group alkylations using benign and readily available graphene materials. Mechanistic studies suggest that the reaction proceeds via a tandem catalysis mechanism in which both of the coupling partners are activated by interaction with the GO surface. PMID:26496423

  7. Blend of alkyl phenol ethoxylates and alkyl phenol glycoxylates and their use as surfactants

    SciTech Connect

    Grolitzer, M. A.

    1985-11-12

    Nonionic surfactant compositions useful in forming stable emulsions with oil in saline solutions comprising a blend of: at least one alkyl phenol ethoxylate and at least one alkyl phenol glycoxylate. These surfactant compositions may be employed in enhanced oil recovery processes and other applications where good emulsification and high salinity tolerances are required such as textiles, leather, dairy, concrete grinding aids and drilling muds.

  8. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    SciTech Connect

    Albright, L.F.; Kranz, K.E.; Masters, K.R.

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  9. Fluoroalkyl and Alkyl Chains Have Similar Hydrophobicities in Binding to the “Hydrophobic Wall” of Carbonic Anhydrase

    SciTech Connect

    J Mecinovic; P Snyder; K Mirica; S Bai; E Mack; R Kwant; D Moustakas; A Heroux; G Whitesides

    2011-12-31

    The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H{sub 2}NSO{sub 2}C{sub 6}H{sub 4}-CONHCH{sub 2}(CX{sub 2}){sub n}CX{sub 3}, n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and

  10. From N-vinylpyrrolidone anions to modified paraffin-like oligomers via double alkylation with 1,8-dibromooctane: access to covalent networks and oligomeric amines for dye attachment

    PubMed Central

    Obels, Daniela; Lievenbrück, Melanie

    2016-01-01

    Summary The double alkylation of N-vinylpyrrolidone (N-VP) with 1,8-dibromooctane yields paraffin-like oligomeric chains bearing polymerizable vinyl moieties. These oligomers were radically crosslinked in bulk with N-VP as co-monomer yielding swellable polymer disks. The vinylic side groups of the N-VP oligomers allow thiol–ene click reactions with 2-aminoethanethiol hydrochloride to obtain reactive amino-functionalized oligomers. Further modification of the free amino groups with 1,4-difluoro-9,10-anthraquinone (DFA) yields red-colored oligomeric anthraquinone dyes. The final reaction of DFA-substituted N-VP oligomers with Jeffamine® M 600 leads to blue-colored and branched oligomers with poly(ethylene glycol) side chains. PMID:27559389

  11. From N-vinylpyrrolidone anions to modified paraffin-like oligomers via double alkylation with 1,8-dibromooctane: access to covalent networks and oligomeric amines for dye attachment.

    PubMed

    Obels, Daniela; Lievenbrück, Melanie; Ritter, Helmut

    2016-01-01

    The double alkylation of N-vinylpyrrolidone (N-VP) with 1,8-dibromooctane yields paraffin-like oligomeric chains bearing polymerizable vinyl moieties. These oligomers were radically crosslinked in bulk with N-VP as co-monomer yielding swellable polymer disks. The vinylic side groups of the N-VP oligomers allow thiol-ene click reactions with 2-aminoethanethiol hydrochloride to obtain reactive amino-functionalized oligomers. Further modification of the free amino groups with 1,4-difluoro-9,10-anthraquinone (DFA) yields red-colored oligomeric anthraquinone dyes. The final reaction of DFA-substituted N-VP oligomers with Jeffamine(®) M 600 leads to blue-colored and branched oligomers with poly(ethylene glycol) side chains. PMID:27559389

  12. Introduction of Peripheral Carboxylates to Decrease the Charge on Tm(3+) DOTAM-Alkyl Complexes: Implications for Detection Sensitivity and in Vivo Toxicity of PARACEST MRI Contrast Agents.

    PubMed

    Suchý, Mojmír; Milne, Mark; Elmehriki, Adam A H; McVicar, Nevin; Li, Alex X; Bartha, Robert; Hudson, Robert H E

    2015-08-27

    A series of structurally modified Tm(3+) DOTAM-alkyl complexes as potential PARACEST MRI contrast agents has been synthesized with the aim to decrease the overall positive charge associated with these molecules and increase their biocompatibility. Two types of structural modification have been performed, an introduction of terminal carboxylate arms to the alkyl side chains and a conjugation of one of the alkyl side chains with aspartic acid. Detailed evaluation of the magnetic resonance imaging chemical exchange contrast associated with the structurally modified contrast agents has been performed. In contrast to the acutely toxic Tm(3+) DOTAM-alkyl complexes, the structurally modified compounds were found to be tolerated well during in vivo MRI studies in mice; however, only the aspartic acid modified chelates produced an amide proton-based PARACEST signal. PMID:26214576

  13. Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

    SciTech Connect

    Qian, Wen-Jian; Park, Jung-Eun; Grant, Robert; Lai, Christopher C.; Kelley, James A.; Yaffe, Michael B.; Lee, Kyung S.; Burke, Terrence R.

    2015-07-07

    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  14. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  15. Self-organization of surfactant molecules on solid surface: an STM study of sodium alkyl sulfonates [rapid communication

    NASA Astrophysics Data System (ADS)

    Yin, Xiu-Li; Wan, Li-Jun; Yang, Zheng-Yu; Yu, Jia-Yong

    2005-02-01

    Adsorption and self-organization of sodium alkyl sulfonates (STS and SHS) on HOPG have been studied by using in situ scanning tunneling microscopy (STM). Both SHS and STS molecules adsorb on HOPG surface and form long-range well-ordered monolayers. The molecular rows and the axes of alkyl chain of the molecules cross each other at angles of 60° and 90° in the STS and SHS layers, respectively. Molecular details such as sulfonate functional group (head) and alkyl chain are clearly imaged. The neighboring molecules in different rows form a "head to head" configuration. Structural models for the molecular arrangement of the two adlayers are proposed.

  16. Imidazolinium salts as catalysts for the ring-opening alkylation of meso epoxides by alkylaluminum complexes.

    PubMed

    Zhou, H; Campbell, E J; Nguyen, S T

    2001-07-12

    [reaction: see text] Imidazolinium salts and their N-heterocyclic carbene (NHC) derivatives catalyze the alkylation of a variety of meso epoxides in the presence of triethylaluminum (yield = 70-90%), under mild conditions. Imidazolinium salts are better catalysts than their NHC derivatives but can lead to dimerization side reactions under extended reaction time. Preformed NHC.AlEt(3) complexes and Wanzlick-type olefins, which are dimers of free NHCs, are also catalysts for this reaction. PMID:11440586

  17. Catalytic Intramolecular Ketone Alkylation with Olefins by Dual Activation.

    PubMed

    Lim, Hee Nam; Dong, Guangbin

    2015-12-01

    Two complementary methods for catalytic intramolecular ketone alkylation reactions with unactivated olefins, resulting in Conia-ene-type reactions, are reported. The transformations are enabled by dual activation of both the ketone and the olefin and are atom-economical as stoichiometric oxidants or reductants are not required. Assisted by Kool's aniline catalyst, the reaction conditions can be both pH- and redox-neutral. A broad range of functional groups are thus tolerated. Whereas the rhodium catalysts are effective for the formation of five-membered rings, a ruthenium-based system that affords the six-membered ring products was also developed. PMID:26486569

  18. Synthesis and pharmacological evaluation of (nitrooxy)alkyl apovincaminates.

    PubMed

    Kawashima, Y; Ikemoto, T; Horiguchi, A; Hayashi, M; Matsumoto, K; Kawarasaki, K; Yamazaki, R; Okuyama, S; Hatayama, K

    1993-04-01

    A series of (nitrooxy)alkyl apovincaminates has been synthesized and evaluated for their effects on vertebral and femoral blood flow. These derivatives were prepared from apovincaminic acid (4). In cerebral circulation, compound 5 (0.03-1.0 mg/kg iv) caused a dose-dependent increase in cerebral blood flow (CerBF) without affecting the blood pressure. It was more potent than vinpocetine (2). The structures of 2 and 5, determined by X-ray crystallography, showed differences in the electrostatic potential image and in the conformation of the ethyl group at the 16-position. PMID:8464035

  19. Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides.

    PubMed

    Cheung, Chi Wai; Hu, Xile

    2016-01-01

    (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon-nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C-N coupling method provides general and step-economical access to aryl amines. PMID:27515391

  20. Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides

    PubMed Central

    Cheung, Chi Wai; Hu, Xile

    2016-01-01

    (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon–nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C–N coupling method provides general and step-economical access to aryl amines. PMID:27515391

  1. N-Alkyl-PEI Functional Iron Oxide Nanocluster for Efficient siRNA Delivery**

    PubMed Central

    Liu, Gang; Xie, Jin; Zhang, Fan; Wang, Zhi-Yong; Luo, Kui; Zhu, Lei; Quan, Qi-Meng; Niu, Gang; Lee, Seulki

    2013-01-01

    Small interfering RNA (siRNA) is an emerging class of therapeutics, working by regulating the expression of a specific gene involved in disease progression. Despite the promises, effective transport of siRNA with minimal side effects remains a challenge. In this study, a non-viral nanoparticle gene carrier has been developed and its efficiency for siRNA delivery and transfection has been validated at both in vitro and in vivo levels. Such a nanocarrier, abbreviated as Alkyl-PEI2k-IO, was constructed with a core of iron oxide (IO) and a shell of alkylated PEI2000 (Alkyl-PEI2k). It was found to be able to bind with siRNA, resulting in well-dispersed nanoparticles with a controlled clustering structure and narrow size distribution. Electrophoresis studies showed that the Alkyl-PEI2k-IOs could retard siRNA completely at N/P ratios above 10, protect siRNA from enzymatic degradation in serum and release complexed siRNA efficiently in the presence of polyanionic heparin. The knockdown efficiency of the siRNA loaded nanocarriers was assessed with 4T1 cells stably expressing luciferase (fluc-4T1) and further, with a fluc-4T1 xenograft model. Significant downregulation of luciferase was observed, and unlike the high molecular weight analogs, the Alkyl-PEI2k coated IOs showed a good biocompatibility. In conclusion, Alkyl-PEI2k-IOs demonstrate highly efficient delivery of siRNA and an innocuous toxic profile, making it a potential carrier for gene therapy. PMID:21861295

  2. Synthesis of prostaglandins by conjugate addition and alkylation of a directed enolate ion. 4,5-allenyl prostaglandins

    SciTech Connect

    Patterson, J.W. )

    1990-09-28

    Over the previous two decades many elegant syntheses of prostaglandins, which in more sophisticated forms, allow the stereospecific introduction of the various asymmetric carbons have been accomplished. However, among these approaches the cuprate addition/enolate alkylation of suitable cyclopentenone {sup 2} stands out because of brevity and convergence. The recent reports by Noyori{sup 3} and Corey{sup 4} and their colleagues have reduced to practice the conversion of 4-alkoxycyclopentenones to prostaglandin E{sub 2} (PGE{sub 2}) by conjugate addition of an organocopper derivative of the lower side chain followed by alkylation of the resulting carbanion with methyl 7-halohept-2-enoate. The subject of this paper is application of the Tardella tin enolate alkylation developed by Noyori to the synthesis of 4, 5-allenic prostaglandins, a pharmacologically important class of compounds. The authors results demonstrate that the tandem alkylation of an enone precursor with a cuprate reagent followed by alkylation of the corresponding tin enolate with bromide reagent is a viable synthetic method for 4,5-didehydro-PGE{sub 2}. Because the optically active forms of 1 and the vinyl iodide precursor of the PGE{sub 2} lower side chain have been employed to produce a single enantiomer of PGE{sub 2}, the extension of the methodology described here to the synthesis of single enantiomers of 4a awaits only the preparation of the separate enantiomers of allene 14.

  3. N-alkylated and O-alkylated regioisomers of 5-(hydroxyalkyl)pyrimidines: Synthesis and structural study

    NASA Astrophysics Data System (ADS)

    Meščić, Andrijana; Glavač, Danijel; Osmanović, Amar; Završnik, Davorka; Cetina, Mario; Makuc, Damjan; Plavec, Janez; Ametamey, Simon M.; Raić-Malić, Silvana

    2013-05-01

    Synthesis of novel 5-(2-hydroxyethyl) and 5-(3-hydroxypropyl) acyclic pyrimidine nucleosides is described. Introduction of penciclovir-like side chain in C-5 substituted pyrimidines occurred both at N-1 and O-2 position of pyrimidine moiety that was corroborated by correlation of signals in 2D HMBC spectra. Therefore, alkylation of 5-(acetoxyethyl)-4-methoxypyrimidin-2-one (2a) and 5-(acetoxypropyl)-4-methoxypyrimidin-2-one (2b) afforded mixture of N- and O-acyclic pyrimidine nucleosides in the ratio of 49: 45 (4a: 5a) and 41: 21 (4b: 5b). Structures of 5-(acetoxyalkyl)-4-methoxypyrimidin-2-ones, as the first examples of 4-methoxypyrimidin-2-ones, were unambiguously confirmed by single crystal X-ray diffraction analysis.

  4. Looking at Their Side of the Conflict? Effects of Single versus Multiple Perspective History Teaching on Jewish and Arab Adolescents' Attitude to Out-Group Narratives and In-Group Responsibility

    ERIC Educational Resources Information Center

    Goldberg, Tsafrir

    2014-01-01

    In the last decade, the issue of teaching the Palestinian perspective on the Jewish-Arab conflict in Israeli schools gave rise to considerable debate and competing curricula. A quasi-experimental study compared the effects of these competing approaches on learners' attitudes to out-group narratives and perceived in-group responsibility (IR).…

  5. Design and synthesis of tetrahydropyridothieno[2,3-d]pyrimidine scaffold based epidermal growth factor receptor (EGFR) kinase inhibitors: the role of side chain chirality and Michael acceptor group for maximal potency.

    PubMed

    Wu, Chia-Hsien; Coumar, Mohane Selvaraj; Chu, Chang-Ying; Lin, Wen-Hsing; Chen, Yi-Rong; Chen, Chiung-Tong; Shiao, Hui-Yi; Rafi, Shaik; Wang, Sing-Yi; Hsu, Hui; Chen, Chun-Hwa; Chang, Chun-Yu; Chang, Teng-Yuan; Lien, Tzu-Wen; Fang, Ming-Yu; Yeh, Kai-Chia; Chen, Ching-Ping; Yeh, Teng-Kuang; Hsieh, Su-Huei; Hsu, John T-A; Liao, Chun-Chen; Chao, Yu-Sheng; Hsieh, Hsing-Pang

    2010-10-28

    HTS hit 7 was modified through hybrid design strategy to introduce a chiral side chain followed by introduction of Michael acceptor group to obtain potent EGFR kinase inhibitors 11 and 19. Both 11 and 19 showed over 3 orders of magnitude enhanced HCC827 antiproliferative activity compared to HTS hit 7 and also inhibited gefitinib-resistant double mutant (DM, T790M/L858R) EGFR kinase at nanomolar concentration. Moreover, treatment with 19 shrinked tumor in nude mice xenograft model. PMID:20961149

  6. Accessibility, reactivity, and selectivity of side chains within a channel of de novo peptide assembly.

    PubMed

    Burton, Antony J; Thomas, Franziska; Agnew, Christopher; Hudson, Kieran L; Halford, Stephen E; Brady, R Leo; Woolfson, Derek N

    2013-08-28

    Ab initio design of enzymes requires precise and predictable positioning of reactive functional groups within accessible and controlled environments of de novo protein scaffolds. Here we show that multiple thiol moieties can be placed within a central channel, with approximate dimensions 6 × 42 Å, of a de novo, six-helix peptide assembly (CC-Hex). Layers of six cysteine residues are introduced at two different sites ~6 (the "L24C" mutant) and ~17 Å (L17C) from the C-terminal opening of the channel. X-ray crystal structures confirm the mutant structures as hexamers with internal free thiol, rather than disulfide-linked cysteine residues. Both mutants are hexa-alkylated upon addition of iodoacetamide, demonstrating accessibility and full reactivity of the thiol groups. Comparison of the alkylation and unfolding rates of the hexamers indicates that access is directly through the channel and not via dissociation and unfolding of the assembly. Moreover, neither mutant reacts with iodoacetic acid, demonstrating selectivity of the largely hydrophobic channel. These studies show that it is possible to engineer reactive side chains with both precision and control into a de novo scaffold to produce protein-like structures with chemoselective reactivity. PMID:23924058

  7. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  8. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  9. pKa Values for Side-Chain Carboxyl Groups of a PGB1 Variant Explain Salt and pH-Dependent Stability

    PubMed Central

    Lindman, Stina; Linse, Sara; Mulder, Frans A. A.; André, Ingemar

    2007-01-01

    Determination of pKa values of titrating residues in proteins provides a direct means of studying electrostatic coupling as well as pH-dependent stability. The B1 domain of protein G provides an excellent model system for such investigations. In this work, we analyze the observed pKa values of all carboxyl groups in a variant of PGB1 (T2Q, N8D, N37D) at low and high ionic strength as determined using 1H-13C heteronuclear NMR in a structural context. The pKa values are used to calculate the pH-dependent stability in low and high salt and to investigate electrostatic coupling in the system. The observed pKa values can explain the pH dependence of protein stability but require pKa shifts relative to model values in the unfolded state, consistent with persistent residual structure in the denatured state. In particular, we find that most of the deviations from the expected random coil values can be explained by a significantly upshifted pKa value. We show also that 13C backbone carbonyl data can be used to study electrostatic coupling in proteins and provide specific information on hydrogen bonding and electrostatic potential at nontitrating sites. PMID:17040982

  10. Controlling the reversible thermochromism of polydiacetylene/zinc oxide nanocomposites by varying alkyl chain length.

    PubMed

    Chanakul, Amornsak; Traiphol, Nisanart; Traiphol, Rakchart

    2013-01-01

    In this work, polydiacetylene (PDA)/ZnO nanocomposites are successfully fabricated by using three types of monomers with different alkyl chain length, 5,7-hexadecadiynoic acid, 10,12-tricosadiynoic acid, and 10,12-pentacosadiynoic acid. The monomers dispersed in aqueous medium spontaneously assemble onto the surface of ZnO nanoparticles, promoted by strong interfacial interactions. The PDA/ZnO nanocomposites obtained via photopolymerization process are characterized by scanning electron microscopy, laser light scattering, infrared spectroscopy, and uv/vis absorption spectroscopy. The strength of interfacial interactions and morphologies of the nanocomposites are found to vary with alkyl chain length of the monomers. The PDA/ZnO nanocomposites also exhibit rather different thermochromic behaviors compared to their pure PDA counterparts. All nanocomposites show reversible blue/purple color transition upon multiple heating/cooling cycles, while the irreversible blue/red color transition is observed in the systems of pure PDAs. The shortening of alkyl side chain in PDA/ZnO nanocomposites leads to a systematic decrease in their color-transition temperatures. Colors of the nanocomposites at elevated temperature also vary with the alkyl chain length. Our results provide a simple route for controlling the reversible thermochromism of PDA-based materials, allowing their utilization in a wider range of applications. PMID:23058980

  11. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  12. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  13. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  14. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  15. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  16. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  17. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  18. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic)....

  19. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluorocarbon alkyl ether. 721... Substances § 721.3485 Hydrofluorocarbon alkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydrofluorocarbon alkyl...

  20. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluorocarbon alkyl ether. 721... Substances § 721.3485 Hydrofluorocarbon alkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydrofluorocarbon alkyl...

  1. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  2. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  3. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  4. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  5. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  6. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl amino nitriles (generic)....

  7. 40 CFR 721.1852 - Di-alkyl borane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Di-alkyl borane (generic). 721.1852... Substances § 721.1852 Di-alkyl borane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as di-alkyl borane (PMN P-00-1087) is...

  8. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  9. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  10. 40 CFR 721.9720 - Disubstituted alkyl triazines (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Disubstituted alkyl triazines (generic... Specific Chemical Substances § 721.9720 Disubstituted alkyl triazines (generic name). (a) Chemical... as disubstituted alkyl triazines (PMNs P-85-932 and P-85-933) are subject to reporting under...

  11. 40 CFR 721.10506 - Alkylated phenols (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylated phenols (generic). 721.10506... Substances § 721.10506 Alkylated phenols (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkylated phenols (PMNs...

  12. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  13. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  14. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  15. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  16. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  17. 40 CFR 721.10506 - Alkylated phenols (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylated phenols (generic). 721.10506... Substances § 721.10506 Alkylated phenols (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkylated phenols (PMNs...

  18. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  19. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  20. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  1. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  2. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  3. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  4. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  5. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  6. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  7. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  8. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  9. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  10. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  11. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  12. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  13. Polygas spells relief from alkylation ills

    SciTech Connect

    Weismantel, G.E.

    1980-06-16

    Tight supplies and soaring prices of isobutane (for olefin alkylation), are causing renewed interest in the olefin ''polymerization'' (i.e., dimerization), route to high-octane gasoline-blending components. Modern polymerization processes, intended to supplement rather than replace alkylation offer considerable energy and capital savings, compared with alkylation-only schemes. In addition to the Institut Francais du Petrole's Dimersol ''polymerization'' tecnique which is already being used or will be used by 1981 in at least five U.S. refineries, with six more units in the planning stage, a low-cost process to ''polymerize'' excess refinery olefins, developed by International Energy Consultants Inc., is nearing commercialization. A third route to process C/sub 3//C/sub 4/ refinery streams with high conversion rates has been proposed by UOP Inc. The low motor octane number (MON) of the product gasoline (approx. 13 numbers lower than a typical alkylate), was recently confirmed in Total Petroleum Inc.'s studies, but Good Hope Refineries Inc. plans to increase its polymer gasoline MON by adding methyl tert.-butyl ether.

  14. Separate olefin processing in sulfuric acid alkylation

    SciTech Connect

    Imhoff, S.A.; Graves, D.C.

    1995-09-01

    This paper will discuss the effects of alkylating propylene, butylenes and amylenes together and suggest alternative processing schemes which will minimize the negative synergies, improve octane and/or minimize acid consumption. The first option will show the impact of segregating the propylene and amylenes. In the second option, the benefit of alkylating the individual olefins at their optimal acid strengths will be presented. Additionally, each olefin`s optimal reaction conditions will be examined. Unfortunately, many refiners may not have the existing flexibility to take advantage of separate olefin processing. First, the majority of the propylene, butylenes and amylenes must be separate upon entry to the alkylation unit. If the olefins cannot be segregated upstream, separate olefin processing will not be as beneficial. If this is the case, then the benefits of separate olefin processing will have to be weighed versus the capital and energy costs required to separate them. In addition, small units may not have sufficient numbers of Contactors and settlers to achieve adequate segregation. Later in this paper, the modifications required in the alkylation unit for separate olefin processing will be discussed.

  15. Retention behavior of alkyl-substituted polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography.

    PubMed

    Wilson, Walter B; Sander, Lane C; de Alda, Miren Lopez; Lee, Milton L; Wise, Stephen A

    2016-08-26

    Retention indices for 79 alkyl-substituted polycyclic aromatic sulfur heterocycles (PASHs) were determined by using reversed-phase liquid chromatography (LC) on a monomeric and polymeric octadecylsilane (C18) stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Based on separations of isomeric methylated polycyclic aromatic hydrocarbons on polymeric C18 phases, alkyl-substituted PASHs are expected to elute based on increasing L/B ratios. However, the correlation coefficients had a wide range of values from r=0.43 to r=0.93. Several structural features besides L/B ratios were identified to play an important role in the separation mechanism of PASHs on polymeric C18 phases. First, the location of the sulfur atom in a bay-like-region results in alkylated-PASHs being more retentive than non-bay-like-region alkylated-PASHs, and they elute later than expected based on L/B value. Second, the placement of the alkyl group in the k region of the structure resulted in a later elution than predicted by L/B. Third, highly nonplanar methyl-PASHs (i.e., 1-Me and 11-MeBbN12T) elute prior to the parent PASH (BbN12T). PMID:27477517

  16. A General Strategy for the Nickel-Catalyzed C-H Alkylation of Anilines.

    PubMed

    Ruan, Zhixiong; Lackner, Sebastian; Ackermann, Lutz

    2016-02-24

    The C-H alkylation of aniline derivatives with both primary and secondary alkyl halides was achieved with a versatile nickel catalyst of a vicinal diamine ligand. Step-economic access to functionalized 2-pyrimidyl anilines, key structural motifs in anticancer drugs, is thus provided. The C-H functionalization proceeded through facile C-H activation and SET-type C-X bond cleavage with the assistance of a monodentate directing group, which could be removed in a traceless fashion. PMID:26822673

  17. Electrophilic metal alkyl chemistry in new ligand environments. Annual report, January 1, 1992--September 15, 1992

    SciTech Connect

    Jordan, R.F.

    1992-12-31

    Methods have been worked out for efficient synthesis of various N{sub 4}{sup 2{minus}} macrocyclic ligands, neutral group 4 metal (e.g., Zr) (N{sub 4})MR{sub 2} complexes, and cationic mono-alkyl (N{sub 4})M(R){sup +} species. Intital indications are that the latter will be highly reactive in base-free form. Objective is to develop new types of electrophilic metal alkyl complexes for study of olefin polymerization and C-H activation catalysis.

  18. Synthesis and chemistry of cationic d sup 0 metal alkyl complexes

    SciTech Connect

    Jordan, R.F.

    1990-01-01

    The long term goals of this project are to design and synthesize highly unsaturated, electrophilic metal complexes and to explore their use as catalysts, reagents, and/or model systems for olefin polymerization and C-H activation chemistry. During the 1990 budget year we have focused our attention on (i) the ligand C-H activation chemistry of Cp{sub 2}Zr(CH{sub 3})(THF){sup +} and related cationic, d{sup o} Zr alkyl complexes, and (ii) the synthesis of new classes of group 4 metal alkyl complexes with non-Cp{sub 2}M ligand environments.

  19. DNA-damaging disinfection byproducts: alkylation mechanism of mutagenic mucohalic acids.

    PubMed

    Gómez-Bombarelli, Rafael; González-Pérez, Marina; Arenas-Valgañón, Jorge; Céspedes-Camacho, Isaac Fabián; Calle, Emilio; Casado, Julio

    2011-10-15

    Hydroxyhalofuranones form a group of genotoxic disinfection byproduct (DBP) of increasing interest. Among them, mucohalic acids (3,4-dihalo-5-hydroxyfuran-2(5H)-one, MXA) are known mutagens that react with nucleotides, affording etheno, oxaloetheno, and halopropenal derivatives. Mucohalic acids have also found use in organic synthesis due to their high functionalization. In this work, the alkylation kinetics of mucochloric and mucobromic acids with model nucleophiles aniline and NBP has been studied experimentally. Also, the alkylation mechanism of nucleosides by MXA has been studied in silico. The results described allow us to reach the following conclusions: (i) based on the kinetic and computational evidence obtained, a reaction mechanism was proposed, in which MXA react directly with amino groups in nucleotides, preferentially attacking the exocyclic amino groups over the endocyclic aromatic nitrogen atoms; (ii) the suggested mechanism is in agreement with both the product distribution observed experimentally and the mutational pattern of MXA; (iii) the limiting step in the alkylation reaction is addition to the carbonyl group, subsequent steps occurring rapidly; and (iv) mucoxyhalic acids, the hydrolysis products of MXA, play no role in the alkylation reaction by MXA. PMID:21910489

  20. Oligonucleoside alkyl or arylphosphonate derivatives capable of crosslinking with or cleaving nucleic acids

    DOEpatents

    Miller, P.S.; Ts'o, P.O.P.

    1999-06-15

    A composition for inactivating a target nucleic acid which comprises an oligonucleoside alkyl or arylphosphonate analogue which is complementary to the sequence of the target nucleic acid is provided. It includes a functional group which reacts with the target nucleic acid to render the target nucleic acid inactive or nonfunctional. 16 figs.

  1. Copper nanoparticle-catalyzed cross-coupling of alkyl halides with Grignard reagents.

    PubMed

    Kim, Ju Hyun; Chung, Young Keun

    2013-12-01

    A cross-coupling reaction between alkyl bromides and chlorides and various Grignard reagents was carried out in the presence of commercially available copper or copper oxide nanoparticles as a catalyst and an alkyne additive. The catalytic system shows high activity, a broad scope, and good functional group tolerance. PMID:24146018

  2. Production of poly(alkyl cyanoacrylate)nanoparticles as a coating material that changes wetting property

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Alkyl cyanoacrylates have long been used for the synthesis of colloidal nanoparticles. In the involved polymerization reaction, OH- ions derived from dissociation of water have been used as an initiator. In the current research, functional groups on the surface of proteins were utilized as an initia...

  3. Alkyl substituent effects on gas-phase acidities - The influence of hybridization.

    NASA Technical Reports Server (NTRS)

    Brauman, J. I.; Blair, L. K.

    1971-01-01

    Exploration of the effect on acidity of alkyl groups bonded to trigonal and digonal carbon. Some results on the relative acidities of toluene and p-xylene, and acetylene and substitute acetylenes, as determined by ion cyclotron resonance (icr) spectroscopy, are described. Some limitations of the CNDO/2 calculation method are discussed.

  4. Intermolecular Photocatalyzed Heck-like Coupling of Unactivated Alkyl Bromides by a Dinuclear Gold Complex.

    PubMed

    Xie, Jin; Li, Jian; Weingand, Vanessa; Rudolph, Matthias; Hashmi, A Stephen K

    2016-08-26

    A practical protocol for a photocatalyzed alkyl-Heck-like reaction of unactivated alkyl bromides and different alkenes promoted by dinuclear gold photoredox catalysis in the presence of an inorganic base is reported. Primary, secondary, and tertiary unactivated alkyl bromides with β-hydrogen can be applied. Esters, aldehydes, ketones, nitriles, alcohols, heterocycles, alkynes, alkenes, ethers, and halogen moieties are all well tolerated. In addition to 1,1-diarylalkenes, silylenolethers and enamides can also be applied, which further increases the synthetic potential of the reaction. The mild reaction conditions, broad substrate scope, and an excellent functional-group tolerance deliver an ideal tool for synthetic chemists that can even be used for challenging late-stage modifications of complex natural products. PMID:27348503

  5. Alkyl-terminated Si(111) surfaces: A high-resolution, core level photoelectron spectroscopy study

    SciTech Connect

    Terry, J.; Linford, M.R.; Wigren, C.; Cao, R.; Pianetta, P.; Chidsey, C.E.

    1999-01-01

    The bonding of alkyl monolayers to Si(111) surfaces has been studied with high-resolution core level photoelectron spectroscopy (PES). Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) Olefin insertion into the H{endash}Si bond of the H{endash}Si(111) surface, and (ii) replacement of Cl on the Cl{endash}Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, PES has revealed a C 1s component shifted to lower binding energy and a Si 2p component shifted to higher binding energy. Both components are attributed to the presence of a C{endash}Si bond at the interface. Along with photoelectron diffraction data [Appl. Phys. Lett. {bold 71}, 1056, (1997)], these data are used to show that these two synthetic methods can be used to functionalize the Si(111) surface. {copyright} {ital 1999 American Institute of Physics.}

  6. Saturation properties of 1-alkyl-3-methylimidazolium based ionic liquids.

    PubMed

    Rane, Kaustubh S; Errington, Jeffrey R

    2014-07-24

    We study the liquid-vapor saturation properties of room temperature ionic liquids (RTILs) belonging to the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) using Monte Carlo simulation. We examine the effect of temperature and cation alkyl chain length n on the saturated densities, vapor pressures, and enthalpies of vaporization. These properties are explicitly calculated for temperatures spanning from 280 to 1000 K for RTILs with n = 2, 4, 6, 8, 10, and 12. We also explore how the identity of the anion influences saturation properties. Specifically, we compare results for [C(4)mim][NTf2] with those for 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]). Simulations are completed with a recently developed realistic united-atom force field. A combination of direct grand canonical and isothermal-isobaric temperature expanded ensemble simulations are used to construct phase diagrams. Our results are compared with experimental data and Gibbs ensemble simulation data. Overall, we find good agreement between our results and those measured experimentally. We find that the vapor pressures and enthalpies of vaporization show a strong dependence on the size of the alkyl chain at low temperatures, whereas no particular trend is observed at high temperatures. Finally, we also discuss the effect of temperature on liquid phase nanodomains observed in RTILs with large hydrophobic groups. We do not observe a drastic change in liquid phase structure upon variation of the temperature, which suggests there is not a sharp phase transition between a nanostructured and homogeneous liquid, as has been suggested in earlier studies. PMID:24986360

  7. Towards understanding the mechanism of action of antibacterial N-alkyl-3-hydroxypyridinium salts: Biological activities, molecular modeling and QSAR studies.

    PubMed

    Dolezal, Rafael; Soukup, Ondrej; Malinak, David; Savedra, Ranylson M L; Marek, Jan; Dolezalova, Marie; Pasdiorova, Marketa; Salajkova, Sarka; Korabecny, Jan; Honegr, Jan; Ramalho, Teodorico C; Kuca, Kamil

    2016-10-01

    In this study, we have carried out a combined experimental and computational investigation to elucidate several bred-in-the-bone ideas standing out in rational design of novel cationic surfactants as antibacterial agents. Five 3-hydroxypyridinium salts differing in the length of N-alkyl side chain have been synthesized, analyzed by high performance liquid chromatography, tested for in vitro activity against a panel of pathogenic bacterial and fungal strains, computationally modeled in water by a SCRF B3LYP/6-311++G(d,p) method, and evaluated by a systematic QSAR analysis. Given the results of this work, the hypothesis suggesting that higher positive charge of the quaternary nitrogen should increase antimicrobial efficacy can be rejected since 3-hydroxyl group does increase the positive charge on the nitrogen but, simultaneously, it significantly derogates the antimicrobial activity by lowering the lipophilicity and by escalating the desolvation energy of the compounds in comparison with non-hydroxylated analogues. Herein, the majority of the prepared 3-hydroxylated substances showed notably lower potency than the parent pyridinium structures, although compound 8 with C12 alkyl chain proved a distinctly better antimicrobial activity in submicromolar range. Focusing on this anomaly, we have made an effort to reveal the reason of the observed activity through a molecular dynamics simulation of the interaction between the bacterial membrane and compound 8 in GROMACS software. PMID:27341309

  8. Mutagenic properties of allylic and alpha, beta-unsaturated compounds: consideration of alkylating mechanisms.

    PubMed

    Eder, E; Henschler, D; Neudecker, T

    1982-12-01

    1. Allyl and allylic compounds may exert alkylating activities by SN1, SN2 and SN2' mechanisms. This direct alkylating potential can be determined quantitatively by a modified 4-NBP (4-nitrobenzyl pyridine) test. 2. The alkylating activities in a systematically selected series of allyl and allylic compounds correlate well with the direct mutagenic potential as determined in the Ames test using Salmonella typhimurium TA 100 as tester strain. 3. The allylic structure is a prerequisite for these types of activities since structurally related molecules lacking the allylic moiety are inactive in this respect. 4. The potency of both the alkylating and mutagenic activity is determined by the strength of the leaving group: --OSO2CH3 greater than I greater than Br greater than Cl greater than--NCS. 5. Indirect mutagenicity, through metabolic activation of the olefinic bond (by addition of S9 mix to the tester medium), can be ruled out for practically all compounds, the only exception found being 2,3-dichloro-1-propene where an increase of mutagenicity is encountered after addition of S9 mix; mechanistic explanations for this exception are provided. 6. Analogous activation is demonstrated for benzyl halides, the alkylating potency of which is even higher than that of genuine allylic compounds. 7. A variety of methyl- and chlorine-substituted allyl compounds has been included in the study: both groups increase activity, either by +I (CH3) or by +M effects (Cl). 8. alpha, beta-Unsaturated carbonyl compounds, e.g. acrolein and crotonaldehyde, also display direct mutagenic activity which is due to a completely different mechanism: covalent binding to nucleophilic sites of DNA bases by Michael addition. Methyl and other alkyl substitutions decrease the mutagenic potential in this type of compound. The corresponding alcohols, also displaying mutagenic activity but to a lesser degree, are metabolically activated by ADH (alcohol dehydrogenase) of the tester strain microbes to the

  9. Dichloromethyl alkyl ethers and sulfides in the Reformatskii reaction

    SciTech Connect

    Lapkin, I.I.; Fotin, V.V.

    1986-09-10

    A study was carried out on the reaction of dichloromethyl alkyl ethers and sulfides with ..cap alpha..-brominated esters in the presence of zinc resulting in the formation of either ..cap alpha..-alkyl-..beta..-alkoxyacrylates (or ..cap alpha..-alkyl-..beta..-alkylthioacrylates) or ..cap alpha..,..cap alpha..,..cap alpha..',..cap alpha..'-tetramethyl-..beta..-alkoxyglutaric acid (or ..cap alpha..,..cap alpha..,..cap alpha..',..cap alpha..'-tetramethyl-..beta..-alkylthioglutaric acid) depending on the structure of the starting bromoester. PMR and IR spectroscopy indicates the geometry of the ..cap alpha..-alkyl-..beta..-alkoxyacrylates and ..cap alpha..-alkyl-..beta..-alkylthioacrylates.

  10. Molecular dynamics simulations of alkyl substituted nanographene crystals

    NASA Astrophysics Data System (ADS)

    Ziogos, Orestis George; Theodorou, Doros Nicolas

    2015-09-01

    Discotic polyaromatic molecules, similar to nanometric graphene flakes, constitute an interesting class of materials for organic electronic applications. Grafting flexible side chains around the periphery of such molecules enhances their processability and gives rise to diverse behaviours, such as the manifestation of liquid-crystalline character and anisotropic mechanical response. In this work, we examine by means of molecular dynamics simulations the properties of molecular crystals comprised of alkyl-substituted hexa-peri-hexabenzocoronene mesogens. Pristine and mono-substituted systems by hydrogen or iodine atoms are modelled, with variable side chain length. A general structural and mechanical robustness to peripheral substitution is reported, with the mesogens forming tightly packed molecular wires even at elevated temperature and pressure. In their discotic ordering, the molecules present relatively low translational mobility, a beneficial phenomenon for charge transport. A thermotropic dependence of the mechanical response is identified, with the systems behaving differently in their room-temperature crystalline phase and in their liquid-crystalline phase at elevated temperatures. The melting process is also examined, elucidating an initial negative expansion along a high symmetry direction and the existence of a metastable state, before falling into the final liquid-crystalline state. Dedicated to Professor Jean-Pierre Hansen, with deepest appreciation of his outstanding contributions to liquid and soft matter theory.

  11. Alkyl isocyanates as active site-directed inactivators of guinea pig liver transglutaminase.

    PubMed

    Gross, M; Whetzel, N K; Folk, J E

    1975-10-10

    Alkyl isocyanates are effective inactivators of guinea pig liver transglutaminase. Based on the specificity of the reaction the protection against inactivation by glutamine substrate, and the essential nature of calcium for the inactivation reaction, it is concluded that these reagents act as amide substrate analogs and, thus function in an active site-specific manner. Support for the contention that inactivation results from alkyl thiocarbamate ester formation through the single active site sulfhydryl group of the enzyme is (a) the loss of one free--SH group and the incorporation of 1 mol of reagent/mol of enzyme in the reaction, (b) similarity in chemical properties of the inactive enzyme derivative formed to those previously reported for another alkyl thiocarbamoylenzyme and an alkyl thiocarbamoylcysteine derivative, and (c) the finding that labeled peptides from digests of [methyl-14C]thiocarbamoyltransglutaminase and those from digests of iodoacetamide-inactivated enzyme occupy similar positions on peptide maps. Transglutaminase was found to be inactivated neither by urethan anlogs of its active ester substrates nor by urea analogs of its amide substrates. It is concluded on the basis of these findings that inactive carbamoylenzyme derivatives are formed only by direct addition of the transglutaminase active--SH group to the isocyanate C--N double bond, and not, like several serine active site enzymes, by nucleophilic displacement with urethan analogs of substrate, or by nucleophilic displacement with urea analogs of substrate. PMID:240837

  12. Biodegradation of fluorinated alkyl substances.

    PubMed

    Frömel, Tobias; Knepper, Thomas P

    2010-01-01

    The incorporation of fluorine into organic molecules entails both positive and adverse effects. Although fluorine imparts positive and unique properties such as water-and oil-repellency and chemical stability, adverse effects often pervade members of this compound class. A striking property of long perfluoroalkyl chains is their very pronounced environmental persistence. The present review is the first one designed to summarize recent accomplishments in the field of biodegradation of fluorine-containing surfactants, their metabolites, and structural analogs. The pronounced scientific and public interest in these chemicals has given impetus to undertake numerous degradation studies to assess the sources and origins of different fluorinated analog chemical known to exist in the environment. It was shown that biodegradation plays an important role in understanding how fluorinated substances reach the environment and, once they do, what their fate is. Today, PFOS and PFOA are ubiquitously detected as environmental contaminants. Their prominence as contaminants is mainly due to their extreme persistence, which is linked to their perfluoroalkyl chain length. It appears that desulfonation of a highly fluorinated surfactants can be achieved if an α-situated H atom, in relation to the sulfonate group, is present, at least under sulfur-limiting conditions. Molecules that are less heavily fluorinated can show very complex metabolic behavior, as is the case for fluorotelomer alcohols. These compounds are degraded via different but simultaneous pathways, which produce different stable metabolites, one of which is the respective perfluoroalkanoate (8:2-FTOH is transformed to PFOA). Preliminary screening tests indicate that fluorinated functional groups, such as the trifluoromethoxy group and the p-(trifluoromethyl)phenoxy group, may be useful implementations in novel, environmentally benign fluorosurfactants. More specifically, trifluoromethoxy groups constitute a substitute

  13. Star-Shaped Conjugated Molecules with Oxa- or Thiadiazole Bithiophene Side Arms.

    PubMed

    Kotwica, Kamil; Kostyuchenko, Anastasia S; Data, Przemyslaw; Marszalek, Tomasz; Skorka, Lukasz; Jaroch, Tomasz; Kacka, Sylwia; Zagorska, Malgorzata; Nowakowski, Robert; Monkman, Andrew P; Fisyuk, Alexander S; Pisula, Wojciech; Pron, Adam

    2016-08-01

    Star-shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa- or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg (opt)) as well as electrochemical (Eg (electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg (opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole-based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host-type light-emitting diodes. They also showed a strong tendency to self-organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X-ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self-assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis-NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes. PMID:27404332

  14. Synthesis of polyphosphazenes with sulfonimide side groups

    DOEpatents

    Allcock, Harry R.; Hofmann,; Michael A.; Ambler, Catherine M.; Andrew, Maher E.; Wood, Richard M.; Welna, Daniel T.

    2010-07-27

    The invention relates to sulfonimide bearing phenolic compounds and the use of those compounds to produce polyphosphazenes functionalized by one or more of those compounds alone, or in combination with cosubstituents. The invention also relates to blends of sulfonimide functionalized phosphazene polymers with other polymers, membranes formed of the functionalized polymers, and the use of those membranes in devices such as fuel cells.

  15. 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.

  16. Alkyl Chain Length and Temperature Effects on Structural Properties of Pyrrolidinium-Based Ionic Liquids: A Combined Atomistic Simulation and Small-Angle X-ray Scattering Study

    SciTech Connect

    Li, Song; Bañuelos, José Leobardo; Guo, Jianchang; Anovitz, Lawrence; Rother, Gernot; Shaw, Robert W.; Hillesheim, Patrick C.; Dai, Sheng; Baker, Gary A.; Cummings, Peter T.

    2011-12-21

    Molecular dynamics (MD) simulations of 1-alkyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([CnMPy][Tf₂N], n = 3, 4, 6, 8, 10) were conducted using an all-atom model. Radial distribution functions (RDF) were computed and structure functions were generated to compare with new X-ray scattering experimental results, reported herein. The scattering peaks in the structure functions generally shift to lower Q values with increased temperature for all the liquids in this series. However, the first sharp diffraction peak (FSDP) in the longer alkyl chain liquids displays a marked shift to higher Q values with increasing temperature. Alkyl chain-dependent ordering of the polar groups and increased tail aggregation with increasing alkyl chain length were observed in the partial pair correlation functions and the structure functions. The reasons for the observed alkyl chain-dependent phenomena and temperature effects were explored.

  17. Alkyl Chain Length and Temperature Effects on Structural Properties of Pyrrolidinium-Based Ionic Liquids: A Combined Atomistic Simulation and Small-Angle X-ray Scattering Study.

    SciTech Connect

    Li, Song; Banuelos, Jose Leo; Guo, Jianchang; Anovitz, Lawrence {Larry} M; Rother, Gernot; Shaw, Robert W; Hillesheim, Patrick C; Dai, Sheng; Baker, Gary A; Cummings, Peter T

    2011-01-01

    Molecular dynamics (MD) simulations of 1-alkyl-1-methylpyrrolidinium 12 bis(trifluoromethanesulfonyl)imide ([CnMPy][Tf2N], n = 3, 4, 6, 8, 10) were conducted 13 using an all-atom model. Radial distribution functions (RDF) were computed and structure 14 functions were generated to compare with new X-ray scattering experimental results, 15 reported herein. The scattering peaks in the structure functions generally shift to lower Q 16 values with increased temperature for all the liquids in this series. However, the first sharp 17 diffraction peak (FSDP) in the longer alkyl chain liquids displays a marked shift to higher Q 18 values with increasing temperature. Alkyl chain-dependent ordering of the polar groups and 19 increased tail aggregation with increasing alkyl chain length were observed in the partial pair 20 correlation functions and the structure functions. The reasons for the observed alkyl chain- 21 dependent phenomena and temperature effects were explored.

  18. Effects of alkyl chain length on the adsorption of an N-alkylated acridine orange cation by colloidally dispersed zirconium phosphate

    SciTech Connect

    Taniguchi, Masahiro; Yamagishi, Akihiko; Iwamoto, Toschitake )

    1990-03-22

    The adsorption of N-alkylated acridine orange derivatives (AO-C{sub n}; n = the number of carbon atoms in an alkyl group) by colloidally dispersed zirconium phosphate (ZrP) was studied by spectrophotometry and electric dichroism. An AO-C{sub n} cation was bound to ZrP by releasing a proton in the phosphate group of ZrP. The electronic spectrum of bound AO-C{sub n} showed that the dye cations formed an aggregate on the polymer. The reduced linear dichroism of a bound dye molecule, {rho}, was determined as a function of n: {rho} = 1.3-1.0 for n = 0-2, while {rho} = {minus}0.3 to {minus}0.4 for n = 3-9.

  19. ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

    DOEpatents

    Long, R.L.

    1958-09-30

    A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

  20. In pursuit of homoleptic actinide alkyl complexes.

    PubMed

    Seaman, Lani A; Walensky, Justin R; Wu, Guang; Hayton, Trevor W

    2013-04-01

    This Forum Article describes the pursuit of isolable homoleptic actinide alkyl complexes, starting with the pioneering work of Gilman during the Manhattan project. The initial reports in this area suggested that homoleptic uranium alkyls were too unstable to be isolated, but Wilkinson demonstrated that tractable uranium alkyls could be generated by purposeful "ate" complex formation, which serves to saturate the uranium coordination sphere and provide the complexes with greater kinetic stability. More recently, we reported the solid-state molecular structures of several homoleptic uranium alkyl complexes, including [Li(THF)4][U(CH2(t)Bu)5], [Li(TMEDA)]2[UMe6], [K(THF)]3[K(THF)2][U(CH2Ph)6]2, and [Li(THF)4][U(CH2SiMe3)6], by employing Wilkinson's strategy. Herein, we describe our attempts to extend this chemistry to thorium. The treatment of ThCl4(DME)2 with 5 equiv of LiCH2(t)Bu or LiCH2SiMe3 at -25 °C in THF affords [Th(CH2(t)Bu)5] (1) and [Li(DME)2][Th(CH2SiMe3)5 (2), respectively, in moderate yields. Similarly, the treatment of ThCl4(DME)2 with 6 equiv of K(CH2Ph) produces [K(THF)]2[Th(CH2Ph)6] (3), in good yield. Complexes 1-3 have been fully characterized, while the structures of 1 and 3 were confirmed by X-ray crystallography. Additionally, the electronic properties of 1 and 3 were explored by density functional theory. PMID:22716022

  1. Nickel-Catalyzed Alkylative Cross-Coupling of Anisoles with Grignard Reagents via C-O Bond Activation.

    PubMed

    Tobisu, Mamoru; Takahira, Tsuyoshi; Morioka, Toshifumi; Chatani, Naoto

    2016-06-01

    We report nickel-catalyzed cross-coupling of methoxyarenes with alkylmagnesium halides, in which a methoxy group is eliminated. A wide range of alkyl groups, including those bearing β-hydrogens, can be introduced directly at the ipso position of anisole derivatives. We demonstrate that the robustness of a methoxy group allows this alkylation protocol to be used to synthesize elaborate molecules by combining it with traditional cross-coupling reactions or oxidative transformation. The success of this method is dependent on the use of alkylmagnesium iodides, but not chlorides or bromides, which highlights the importance of the halide used in developing catalytic reactions using Grignard reagents. PMID:27193503

  2. Recognition of N-alkyl and N-aryl acetamides by N-alkyl ammonium resorcinarene chlorides.

    PubMed

    Beyeh, N Kodiah; Ala-Korpi, Altti; Cetina, Mario; Valkonen, Arto; Rissanen, Kari

    2014-11-10

    N-alkyl ammonium resorcinarene chlorides are stabilized by an intricate array of intra- and intermolecular hydrogen bonds that leads to cavitand-like structures. Depending on the upper-rim substituents, self-inclusion was observed in solution and in the solid state. The self-inclusion can be disrupted at higher temperatures, whereas in the presence of small guests the self-included dimers spontaneously reorganize to 1:1 host-guest complexes. These host compounds show an interesting ability to bind a series of N-alkyl acetamide guests through intermolecular hydrogen bonds involving the carbonyl oxygen (C=O) atoms and the amide (NH) groups of the guests, the chloride anions (Cl(-)) and ammonium (NH2(+)) cations of the hosts, and also through CH⋅⋅⋅π interactions between the hosts and guests. The self-included and host-guest complexes were studied by single-crystal X-ray diffraction, NMR titration, and mass spectrometry. PMID:25257765

  3. The Scope of Direct Alkylation of Gold Surface with Solutions of C1–C4n-Alkylstannanes

    PubMed Central

    2015-01-01

    Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms. PMID:26327466

  4. The horizontal transfer of antibiotic resistance genes is enhanced by ionic liquid with different structure of varying alkyl chain length

    PubMed Central

    Wang, Qing; Lu, Qian; Mao, Daqing; Cui, Yuxiao; Luo, Yi

    2015-01-01

    Antibiotic resistance genes (ARGs) have become a global health concern. In our previous study, an ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]) had been proven to facilitate the dissemination of ARGs in the environment. However, enhanced alkyl group chain length or the substitution of alkyl groups with the cation ring corresponded with increased antimicrobial effects. In this study, we investigated how different structures of ILs with 4, 6, and 8 C atoms in the longer alkyl chain on the imidazolium cations facilitated the dissemination of ARGs. The promotion of plasmid RP4 transfer frequency decreased with [CnMIM][BF4] increasing the alkyl chain length from 4 carbon atoms to 8 carbon atoms on the imidazolium cations, which is observed with [BMIM][BF4] (n = 4, 5.9 fold) > HMIM][BF4] (n = 6, 2.2 fold) > [OMIM][BF4] (n = 8, 1.7 fold). This illustrates that [CnMIM][BF4] with increasing the alkyl chain length exert decreasing ability in facilitating plasmid RP4 horizontal transfer, which is possibly related to IL-structure dependent toxicity. The IL-structure dependent plasmid RP4 transfer frequency was attributable to bacterial cell membrane permeability weaken with increasing alkyl chain length of [CnMIM][PF4], which was evidenced by flow cytometry. In freshwater microcosm, [CnMIm][BF4] promoted the relative abundance of the sulI and intI genes for 4.6 folds, aphA and traF for 5.2 folds higher than the untreated groups, promoting the propagation of ARGs in the aquatic environment. This is the first report that ILs with different structure of varying alkyl chain length facilitate horizontal transfer of plasmid RP4 which is widely distributed in the environment, and thus add the adverse effects of the environmental risk of ILs. PMID:26379641

  5. Highly Sensitive Thin-Film Field-Effect Transistor Sensor for Ammonia with the DPP-Bithiophene Conjugated Polymer Entailing Thermally Cleavable tert-Butoxy Groups in the Side Chains.

    PubMed

    Yang, Yang; Zhang, Guanxin; Luo, Hewei; Yao, Jingjing; Liu, Zitong; Zhang, Deqing

    2016-02-17

    The sensing and detection of ammonia have received increasing attention in recent years because of the growing emphasis on environmental and health issues. In this paper, we report a thin-film field-effect transistor (FET)-based sensor for ammonia and other amines with remarkable high sensitivity and satisfactory selectivity by employing the DPP-bithiophene conjugated polymer pDPPBu-BT in which tert-butoxycarboxyl groups are incorporated in the side chains. This polymer thin film shows p-type semiconducting property. On the basis of TGA and FT-IR analysis, tert-butoxycarboxyl groups can be transformed into the -COOH ones by eliminating gaseous isobutylene after thermal annealing of pDPPBu-BT thin film at 240 °C. The FET with the thermally treated thin film of pDPPBu-BT displays remarkably sensitive and selective response toward ammonia and volatile amines. This can be attributed to the fact that the elimination of gaseous isobutylene accompanies the formation of nanopores with the thin film, which will facilitate the diffusion and interaction of ammonia and other amines with the semiconducting layer, leading to high sensitivity and fast response for this FET sensor. This FET sensor can detect ammonia down to 10 ppb and the interferences from other volatile analytes except amines can be negligible. PMID:26883723

  6. Surface Modification of Polymers by Reaction of Alkyl Radicals.

    PubMed

    Hetemi, Dardan; Médard, Jérôme; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

    2016-01-19

    The surfaces of poly(methyl methacrylate) and polyethylene are modified either (i) by a two-step process including the thermal reaction of alkyl radicals derived from bromohexanoic acid in a mixture of 2,6-dimethylbenzene diazonium salt and neat isopentyl nitrite at 60 °C, followed by reaction with p-nitroaniline, anthraquinone, neutral red, and polyethylene glycol moieties, or (ii) by reaction of a previously anthraquinone-modified bromohexanoic acid. The modified surfaces are characterized by IR, XPS, UV, and water contact angles. A mechanism is proposed to rationalize the results. This approach is an efficient way to modify and pattern polymer surfaces with different organic groups and chemical functionalities under mild conditions. PMID:26653398

  7. Synthesis of Norbornane Bisether Antibiotics via Silver-mediated Alkylation

    PubMed Central

    Hickey, Shane M.; Ashton, Trent D.; White, Jonathan M.; Li, Jian; Nation, Roger L.; Yu, Heidi Y.; Elliott, Alysha G.; Butler, Mark S.; Huang, Johnny X.; Cooper, Matthew A.

    2015-01-01

    A small series of norbornane bisether diguanidines have been synthesized and evaluated as antibacterial agents. The key transformation—bisalkylation of norbornane diol 6—was not successful using Williamson methodology but has been accomplished using Ag2O mediated alkylation. Further functionalization to incorporate two guanidinium groups gave rise to a series of structurally rigid cationic amphiphiles; several of which (16d, 16g and 16h) exhibited antibiotic activity. For example, compound 16d was active against a broad range of bacteria including Pseudomonas aeruginosa (MIC = 8 µg/mL), Escherichia coli (MIC = 8 µg/mL) and methicillin-resistant Staphylococcus aureus (MIC = 8 µg/mL). PMID:26251697

  8. Lithium perchlorate-nitromethane-promoted alkylation of anilines with arylmethanols.

    PubMed

    Zhou, Jun; Mao, Hai-Feng; Wang, Lu; Zou, Jian-Ping; Zhang, Wei

    2011-11-01

    A new application of lithium perchlorate-nitromethane (LPNM) for the formation of aromatic C-N and C-C bonds is introduced. LPNM-promoted reactions of anilines with diarylmethanols selectively generate N-alkylated anilines or mono and double Friedel-Crafts alkylation products under different conditions by changing the reaction time, reaction temperature, and the ratio of the reactants. This method does not require the use of transition metal catalysts to prepare alkylated aniline derivatives. PMID:21547437

  9. Alkaline earth alkyl insertion chemistry of in situ generated aminoboranes.

    PubMed

    Bellham, Peter; Hill, Michael S; Kociok-Köhn, Gabriele; Liptrot, David J

    2013-01-21

    Reactions of equimolar quantities of secondary amine boranes, R(2)NH·BH(3), with the homoleptic group 2 alkyl compounds [M{CH(SiMe(3))(2)}(2)(THF)(2)] (M = Mg, Ca, Sr) provide the alkyl group 2 amido borane derivatives [M{CH(SiMe(3))(2)}{NR(2)BH(3)}(THF)](2). While the strontium derivatives of reactions with dimethylamine and pyrrolidine borane are stable and isolable compounds, the analogous magnesium and calcium compounds are found to be unstable at room temperature. Studies of the thermolysis of the alkylstrontium derivatives have allowed this instability to be rationalised as a result of β-hydride elimination, the facility of which varies with changing M(2+) charge density, to form the products of M-C insertion of H(2)B=NR(2). Subsequent to this process, alkylaminoboranes, [HB(NR(2)){CH(SiMe(3))(2)}], are observed to form through a further suggested β-hydride elimination reaction. This chemistry is also extended to the reaction of the primary amine borane (t)BuNH(2)·BH(3) with [Sr{CH(SiMe(3))(2)}(2)(THF)(2)]. In this case the crystal structure of a heteroleptic species, which may be considered as a tetrameric aggregate of two [Sr{CH(SiMe(3))(2)}{(NH(t)Bu)BH(3)}(2)] anions and two cationic [Sr{(NH(t)Bu)(BH(3))}(THF)(2)] components, has been determined. Kinetic studies of the reactions of [M{CH(SiMe(3))(2)}(2)(THF)(2)] (M = Mg, Ca, Sr) with dimethylamine borane have also been undertaken and describe a complex mechanism in which the barriers to formation of the various intermediate species are a consequence of M(2+) radius and resultant charge density as well as the steric demands of the coordinated amidoborane ligands. PMID:23070304

  10. Rotational dynamics of coumarin-153 and 4-aminophthalimide in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: effect of alkyl chain length on the rotational dynamics.

    PubMed

    Das, Sudhir Kumar; Sarkar, Moloy

    2012-01-12

    Rotational dynamics of two neutral organic solutes, coumarin-153 (C-153) and 4-aminophthalimide (AP), with only the latter having hydrogen-bond-donating ability, has been investigated in a series of 1-ethyl-3-methylimidazolium alkyl sulfate ionic liquids as a function of temperature. The ionic liquids differ only in the length of the linear alkyl side chain (alkyl = ethyl, butyl, hexyl, and octyl) on the anionic moiety. The present study has been undertaken to examine the role of alkyl side chains on the rotational dynamics of the two solutes in these ionic liquids. Analysis of the results using Stokes-Einstein-Debye hydrodynamic theory indicates that the rotational dynamics of C-153 lies between the stick and slip boundary condition in the ethyl analogue and finally reaches subslip condition as in case of the octyl substituent. The observed rotational behavior of C-153 has been explained on the basis of an increase in the size of the solvent, which offers lower friction for solute rotation. On the other hand, AP shows superstick behavior in the ethyl system and exceeds the stick limit in the octyl derivative. Superstick behavior of AP has been attributed to the specific hydrogen-bonding interaction between AP and the sulfate moiety. Proton NMR investigation confirms the hydrogen-bonding interaction between the N-H hydrogen of AP and the ionic liquid. The decrease in rotational coupling constant values for AP with increasing length of alkyl side chains has been attributed to the decrease in the solute-solvent-specific interaction with an increase in the alkyl side chain length on the sulfate moiety. PMID:22112024

  11. The effect of the cation alkyl chain length on density and diffusion in dialkylpyrrolidinium bis(mandelato)borate ionic liquids.

    PubMed

    Filippov, Andrei; Taher, Mamoun; Shah, Faiz Ullah; Glavatskih, Sergei; Antzutkin, Oleg N

    2014-12-28

    The physicochemical properties of ionic liquids are strongly affected by the selective combination of the cations and anions comprising the ionic liquid. In particular, the length of the alkyl chains of ions has a clear influence on the ionic liquid's performance. In this paper, we study the self-diffusion of ions in a series of halogen-free boron-based ionic liquids (hf-BILs) containing bis(mandelato)borate anions and dialkylpyrrolidinium cations with long alkyl chains CnH2n+1 with n from 4 to 14 within a temperature range of 293-373 K. It was found that the hf-BILs with n = 4-7 have very similar diffusion coefficients, while hf-BILs with n = 10-14 exhibit two liquid sub-phases in almost the entire temperature range studied (293-353 K). Both liquid sub-phases differ in their diffusion coefficients, while values of the slower diffusion coefficients are close to those of hf-BILs with shorter alkyl chains. To explain the particular dependence of diffusion on the alkyl chain length, we examined the densities of the hf-BILs studied here. It was shown that the dependence of the density on the number of CH2 groups in long alkyl chains of cations can be accurately described using a "mosaic type" model, where regions of long alkyl chains of cations (named 'aliphatic' regions) and the residual chemical moieties in both cations and anions (named 'ionic' regions) give additive contributions. Changes in density due to an increase in temperature and the number of CH2 groups in the long alkyl chains of cations are determined predominantly by changes in the free volume of the 'ionic' regions, while 'aliphatic' regions are already highly compressed by van der Waals forces, which results in only infinitesimal changes in their free volumes with temperature. PMID:25372279

  12. Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

    USGS Publications Warehouse

    Visscher, P.T.; Taylor, B.F.

    1993-01-01

    A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

  13. Synthesis and Cytostatic Evaluation of 4-N-Alkanoyl and 4-N-Alkyl Gemcitabine Analogues

    PubMed Central

    Pulido, Jesse; Sobczak, Adam J.; Balzarini, Jan; Wnuk, Stanislaw F.

    2014-01-01

    Couplings of gemcitabine with the functionalized carboxylic acids (C9-C13) or reactions of 4-N-tosylgemcitabine with the corresponding alkyl amines afforded 4-N-alkanoyl and 4-N-alkyl gemcitabine derivatives. The analogues with a terminal hydroxyl group on the alkyl chain were efficiently fluorinated under conditions that are compatible with protocols for 18F labeling. The 4-N-alkanoylgemcitabines showed potent cytostatic activities in the low nM range against a panel of tumor cell lines while cytotoxicity of the 4-N-alkylgemcitabines were in the low μM range. The cytotoxicity for the 4-N-alkanoylgemcitabine analogues were reduced approximately by two orders of magnitude in the 2′-deoxycytidine kinase (dCK)-deficient CEM/dCK- cell line whereas cytotoxicity of the 4-N-alkylgemcitabines were only 2-5 times lower. None of the compounds acted as efficient substrates for cytosolic dCK, and therefore, the 4-N-alkanoyl analogues need to be converted first to gemcitabine to display a significant cytostatic potential, while 4-N-alkyl derivatives attain the modest activity without “measurable” conversion to gemcitabine. PMID:24341356

  14. Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium.

    PubMed Central

    Visscher, P T; Taylor, B F

    1993-01-01

    A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters. PMID:8285707

  15. Another Side to Nuclear Education.

    ERIC Educational Resources Information Center

    Hogeboom, William L.

    1984-01-01

    Education about nuclear arms should be balanced. Most of the supplementary materials dealing with nuclear war that are available to teachers are published by anti-war groups. Basic problems with these materials are discussed and information which can be used to present the other side of the story is provided. (RM)

  16. Site-Selective Tertiary Alkyl-Fluorine Bond Formation from α-Bromoamides Using a Copper/CsF Catalyst System.

    PubMed

    Nishikata, Takashi; Ishida, Syo; Fujimoto, Ryo

    2016-08-16

    A copper-catalyzed site-selective fluorination of α-bromoamides possessing multiple reaction sites, such as primary and secondary alkyl-Br bonds, using inexpensive CsF is reported. Tertiary alkyl-F bonds, which are very difficult to synthesize, can be formed by this fluorination reaction with the aid of an amide group. Control experiments revealed that in situ generated CuF2 is a key fluorinating reagent that reacts with the tertiary alkyl radicals generated by the reaction between an α-bromocarbonyl compound and a copper(I) salt. PMID:27282558

  17. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C-O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination.

    PubMed

    Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

    2016-05-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process. PMID:27062726

  18. (L)-(Trimethylsilyl)alanine synthesis exploiting hydroxypinanone-induced diastereoselective alkylation.

    PubMed

    René, A; Vanthuyne, N; Martinez, J; Cavelier, F

    2013-08-01

    A new and efficient synthesis of (L)-(trimethylsilyl)alanine (TMSAla) with suitable protection for use in Solid Phase Peptide Synthesis (SPPS) has been accomplished starting from glycine tert-butyl ester and using hydroxypinanone as chiral inductor. The silylated side chain was introduced by alkylation of the Schiff base intermediate with iodomethyl(trimethylsilane) at -78 °C. Among the different synthetic routes that were tested including several chiral inductors and different Schiff bases, this strategy was selected and afforded (L)-TMSAla in good chemical overall yield with 98 % ee. PMID:23620077

  19. Light induced controlled release of fragrances by Norrish type II photofragmentation of alkyl phenyl ketones.

    PubMed

    Levrand, Barbara; Herrmann, Andreas

    2002-11-01

    The use of alkyl phenyl ketones as delivery systems for the controlled release of fragrances was investigated by photoirradiation of undegassed solutions with a xenon lamp as well as natural sunlight. A large variety of precursor compounds was prepared efficiently in a few reaction steps from commercially available starting materials. The Norrish type II photofragmentation was found to be the predominant reaction pathway to yield the desired perfumery alkenes and acetophenones in polar and apolar solution. Systematic GC-MS analysis of the irradiated solutions allowed identification of a series of side products that are due to the presence of oxygen. A detailed analysis of the product distribution after irradiation was carried out for a series of 4-alkoxy-1-phenylbutanone derivatives. Besides the expected acetophenones, vinyl ethers and phenylcyclobutanols, the formation of alkyl formates, alcohols and 4-oxo-4-phenylbutanoates was observed. The product distribution as influenced by solvent polarity, precursor concentration and substituent effects was investigated. The utility of alkyl phenyl ketones as precursors for the light induced controlled release of fragrances under natural daylight conditions was also demonstrated. PMID:12659532

  20. Alkyl triazole glycosides (ATGs)--a new class of bio-related surfactants.

    PubMed

    Sani, Faramarz Aliasghari; Heidelberg, Thorsten; Hashim, Rauzah; Farhanullah

    2012-09-01

    A series of glucose based surfactants varying in chain length and anomeric configuration were synthesized and investigated on their surfactant properties. The synthesis applied glycosylation of propargyl alcohol followed by cycloaddition with alkyl azides in CLICK chemistry fashion. This approach enables a homogeneous coupling of hydrophilic unprotected sugars and hydrophobic paraffin components in low molecular weight alcohols without solvent side reactions, as commonly found for APGs. The combination of alcohols as inert medium with practically quantitative coupling of the surfactant domains avoids particularly hydrophobic contaminations of the surfactant, thus providing access to pure surfactants. ATGs with chain lengths up to 12 carbons exhibit Krafft points below room temperature and no cloud points were detected. The values for the CMC of ATGs with 12 carbon alkyl chains and above were in good agreement with those of corresponding alkyl glucosides. However, lower homologues exhibited significantly smaller CMCs, and the trend of the CMC upon the chain length did not match common surfactant behavior. This deviation may be related to the triazole that links the two surfactant domains. PMID:22609603

  1. Side Effects (Management)

    MedlinePlus

    ... Cancer is Treated Side Effects Dating, Sex, and Reproduction Advanced Cancer For Children For Teens For Young ... Cancer is Treated Side Effects Dating, Sex, and Reproduction Advanced Cancer For Children For Teens For Young ...

  2. Emotional Side Effects

    MedlinePlus

    ... window. My Saved Articles » My ACS » Emotional Side Effects In this section you can learn more about ... Finding and Paying for Treatment Treatments and Side Effects Survivorship: During and After Treatment Children and Cancer ...

  3. Beneficiation of coal and metallic and non-metallic ores by froth flotation process using polyhydroxy alkyl xanthate depressants

    SciTech Connect

    Petrovich, V.

    1980-07-08

    In the concentration of metallic and non-metallic minerals by froth flotation with a high content of pyrite and the like iron sulfides, which includes the subjecting of such ores when finely ground and sized to substantially liberate particles of pyrite, to froth flotation process in the presence of any suitabl E and adeuqate collector and frother for desired metallic and non-metallic mineral for the recovery of the same, and in the presence of a polyhydroxy alkyl xanthate wetting and depressing agent for pyrite, the step of adding to a pulp of mineral slurry an amount of the order of 0.01 to 0.10 kg per metric ton of a non-collecting polyhydroxy alkyl xanthate, of which hydroxyl groups of said polyhydroxy alkyl xanthates contain from 3 to 4, and having the following general formula: HOCH/sub 2/(CHOH)mcH(CHO)OCSSK wherein M is an integer from 2 to 3; said polyhydroxy alkyl xanthates, react with pyrite and said iron sulfides of the pulp of mineral slurry to yield a water soluble or insoluble hydrophilic coating depressing the pyrite and said iron sulfides, said polyhydroxy alkyl xanthates being selected from the group consisting of potassium pentose, and potassium hexose xanthates, such as potassium arabinose xanthate, potassium xylose xanthate, potassium glucose xanthate, potassium fructose xanthate.

  4. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  5. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  6. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  7. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  8. ESCHERICHIA COLI Gene Induction by Alkylation Treatment

    PubMed Central

    Volkert, Michael R.; Nguyen, Dinh C.; Beard, K. Christopher

    1986-01-01

    Searches for alkylation-inducible (aid) genes of Escherichia coli have been conducted by screening random fusions of the Mu-dl(ApR lac) phage for fusions showing increased β-galactosidase activity after treatment with methylating agents, but not after treatments with UV-irradiation. In this report we describe gene fusions that are specifically induced by alkylation treatments. Nine new mutants are described, and their properties are compared with the five mutants described previously. The total of 14 fusion mutants map at five distinct genetic loci. They can be further subdivided on the basis of their induction by methyl methanesulfonate (MMS) and N-methyl-N'-nitro-N-nitrosoguanidine (MNNG). alkA, aidB and aidD are induced by both agents and appear to be regulated by ada. Neither aidC nor aidI is regulated by ada. Moreover, since aidC is induced only by MNNG and aidI is induced only by MMS, these two genes are likely to be individually regulated. Thus, there appear to be at least three different regulatory mechanisms controlling aid genes. PMID:3080354

  9. The photodissociation dynamics of alkyl radicals

    NASA Astrophysics Data System (ADS)

    Giegerich, Jens; Fischer, Ingo

    2015-01-01

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH3)2) and t-butyl (C(CH3)3) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH3CH2, and to those reported for t-butyl using 248 nm excitation. The translational energy (ET) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low ET part of the distribution shows an isotropic photofragment angular distribution, while the high ET part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH3-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  10. The photodissociation dynamics of alkyl radicals

    SciTech Connect

    Giegerich, Jens; Fischer, Ingo

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distribution shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  11. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic). 721.10038 Section 721.10038... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  12. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic). 721.10038 Section 721.10038... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  13. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic). 721.10038 Section 721.10038... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  14. The role of alkyl substituents in deazaadenine-based diarylethene photoswitches

    PubMed Central

    Sarter, Christopher; Heimes, Michael

    2016-01-01

    Summary Diarylethenes are an important class of reversible photoswitches and often claimed to require two alkyl substituents at the carbon atoms between which the bond is formed or broken in the electrocyclic rearrangement. Here we probe this claim by the synthesis and characterization of four pairs of deazaadenine-based diarylethene photoswitches with either one or two methyl groups at these positions. Depending on the substitution pattern, diarylethenes with one alkyl group can exhibit significant photochromism, but they generally show poor stability towards extended UV irradiation, low thermal stability, and decreased fatigue resistance. The results obtained provide an important direction for the design of new efficient DNA photoswitches for the application in bionanotechnology and synthetic biology. PMID:27340498

  15. The role of alkyl substituents in deazaadenine-based diarylethene photoswitches.

    PubMed

    Sarter, Christopher; Heimes, Michael; Jäschke, Andres

    2016-01-01

    Diarylethenes are an important class of reversible photoswitches and often claimed to require two alkyl substituents at the carbon atoms between which the bond is formed or broken in the electrocyclic rearrangement. Here we probe this claim by the synthesis and characterization of four pairs of deazaadenine-based diarylethene photoswitches with either one or two methyl groups at these positions. Depending on the substitution pattern, diarylethenes with one alkyl group can exhibit significant photochromism, but they generally show poor stability towards extended UV irradiation, low thermal stability, and decreased fatigue resistance. The results obtained provide an important direction for the design of new efficient DNA photoswitches for the application in bionanotechnology and synthetic biology. PMID:27340498

  16. Sites of Alkylation of Human Keap1 by Natural Chemoprevention Agents

    PubMed Central

    Luo, Yan; Eggler, Aimee L.; Liu, Dongting; Liu, Guowen; Mesecar, Andrew D.; van Breemen, Richard B.

    2007-01-01

    Under basal conditions, the interaction of the cytosolic protein Keap1 with the transcription factor Nrf2 results in a low level of expression of cytoprotective genes whose promoter region contains the antioxidant response element (ARE). Alkylation of one or more of the 27 cysteine sulfhydryl groups of human Keap1 is proposed to lead to Nrf2 nuclear accumulation, to upregulation of cytoprotective gene expression via the ARE, and to prevention of degenerative diseases, such as cancer. Therefore, identification of the most reactive of these cysteine residues towards specific electrophiles should help clarify this mechanism of cancer prevention, also known as chemoprevention. To address this issue, preliminary analyses of tryptic digests of Keap1 alkylated by the model electrophile 1-biotinamido-4-(4′-[maleimidoethyl-cyclohexane]-carboxamido) butane were carried out using LC-MS/MS with a cylindrical ion trap mass spectrometer and also using LC-MS/MS with a hybrid linear ion trap FT ICR mass spectrometer. Since the FT ICR instrument provided more complete peptide sequencing coverage and enabled the identification of more alkylated cysteine residues, only this instrument was used in subsequent studies of Keap1 alkylation by three electrophilic natural products that can up-regulate the ARE, xanthohumol, isoliquiritigenin and 10-shogaol. Among the various cysteine residues of Keap1, C151 was most reactive towards these three electrophiles. These in vitro results agree with evidence from in vivo experiments, and indicate that C151 is the most important site of alkylation on Keap1 by chemoprevention agents that function by activating the ARE through Nrf2. PMID:17980616

  17. 40 CFR 721.10073 - Modified alkyl acrylamide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified alkyl acrylamide (generic... Specific Chemical Substances § 721.10073 Modified alkyl acrylamide (generic). (a) Chemical substance and... acrylamide (PMN P-05-536) is subject to reporting under this section for the significant new uses...

  18. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  19. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  20. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  1. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  2. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  3. 40 CFR 721.9515 - Aminofunctional alkoxy alkyl siloxane.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aminofunctional alkoxy alkyl siloxane... Substances § 721.9515 Aminofunctional alkoxy alkyl siloxane. (a) Chemical substance and significant new uses... siloxane (PMN P-96-346) is subject to reporting under this section for the significant new uses...

  4. 40 CFR 721.9515 - Aminofunctional alkoxy alkyl siloxane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aminofunctional alkoxy alkyl siloxane... Substances § 721.9515 Aminofunctional alkoxy alkyl siloxane. (a) Chemical substance and significant new uses... siloxane (PMN P-96-346) is subject to reporting under this section for the significant new uses...

  5. 40 CFR 721.9515 - Aminofunctional alkoxy alkyl siloxane.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aminofunctional alkoxy alkyl siloxane... Substances § 721.9515 Aminofunctional alkoxy alkyl siloxane. (a) Chemical substance and significant new uses... siloxane (PMN P-96-346) is subject to reporting under this section for the significant new uses...

  6. 40 CFR 721.9515 - Aminofunctional alkoxy alkyl siloxane.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aminofunctional alkoxy alkyl siloxane... Substances § 721.9515 Aminofunctional alkoxy alkyl siloxane. (a) Chemical substance and significant new uses... siloxane (PMN P-96-346) is subject to reporting under this section for the significant new uses...

  7. 40 CFR 721.9515 - Aminofunctional alkoxy alkyl siloxane.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aminofunctional alkoxy alkyl siloxane... Substances § 721.9515 Aminofunctional alkoxy alkyl siloxane. (a) Chemical substance and significant new uses... siloxane (PMN P-96-346) is subject to reporting under this section for the significant new uses...

  8. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  9. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  10. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  11. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  12. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  13. Alkylation of refinery C5 streams to lower gasoline volatility

    SciTech Connect

    Cronkright, W.A.; Ditz, J.M.; Newsome, D.S. ); Lerner, H. ); Schorfheide, J.J. ); Libbers, D.D. )

    1994-01-01

    A pilot plant program was carried out to provide precise information about the sulfuric acid alkylation of refinery C5 streams under conditions found in commercial operation of the Exxon stirred, autorefrigerated alkylation process. The study used isobutane to alkylate the full range of pentenes in a C5 cut from an FCC unit as well as the linear olefin concentrate in the raffinate that would be obtained after processing this cut in a TAME unit. A few experiments were conducted with a mixture of C5 olefins matching the composition of the refinery feed in order to highlight the effect of impurities. The results showed that hydrocarbon impurities are a principal factor causing the high acid consumption values reported for pentene alkylation. The results also demonstrated that operating variables that affect acid consumption and alkylate quality in butene alkylation produce directionally similar effects in pentene alkylation, but of different magnitude. It is concluded that sulfur acid alkylation of pentenes produces an excellent isoparaffinic blending stock for the gasoline pool while eliminating volatile olefins and reducing gasoline RVP. Combined with the TAME process, a scheme for adding oxygen and achieving maximum RVP reduction at the same time is realized.

  14. Degradable Polymer Composites Fabricated from Starch and Alkyl Cyanoacrylate Monomer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Degradable polymer composites are fabricated from alkyl cyanoacrylate monomer and starch without special equipment. Alkyl cyanoacrylate, which is a major component of “super glue”, is a monomer that polymerizes at room temperature in the presence of initiators. During the fabrication of polymer com...

  15. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkyl pyridine. 721.8700 Section 721.8700 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl...

  16. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl ester (generic name). 721.2825 Section 721.2825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject...

  17. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl ester (generic name). 721.2825 Section 721.2825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject...

  18. 40 CFR 721.2560 - Alkylated diphenyl oxide (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated diphenyl oxide (generic name). 721.2560 Section 721.2560 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.2560 Alkylated diphenyl oxide (generic name). (a) Chemical substance and significant...

  19. 40 CFR 721.9720 - Disubstituted alkyl triazines (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Disubstituted alkyl triazines (generic name). 721.9720 Section 721.9720 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.9720 Disubstituted alkyl triazines (generic name). (a)...

  20. 40 CFR 721.2560 - Alkylated diphenyl oxide (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated diphenyl oxide (generic name). 721.2560 Section 721.2560 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.2560 Alkylated diphenyl oxide (generic name). (a) Chemical substance and significant...

  1. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl ester (generic name). 721.2825 Section 721.2825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject...

  2. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Alkyl ketene dimers. 176.120 Section 176.120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS Substances for Use Only as Components of Paper and Paperboard § 176.120 Alkyl ketene dimers....

  3. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl...

  4. 40 CFR 721.1852 - Di-alkyl borane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Di-alkyl borane (generic). 721.1852 Section 721.1852 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1852 Di-alkyl borane...

  5. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  6. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  7. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS Substances for Use Only as Components of Paper and Paperboard § 176.120 Alkyl ketene dimers. Alkyl ketene dimers may be safely used as a component of articles intended for use in producing, manufacturing,...

  8. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS Substances for Use Only as Components of Paper and Paperboard § 176.120 Alkyl ketene dimers. Alkyl ketene dimers may be safely used as a component of articles intended for use in producing, manufacturing,...

  9. 1-vinyl-4-alkyl-1,2,4-triazolium salts

    SciTech Connect

    Ermakova, T.G.; Chipanina, N.N.; Gritza, A.I.; Kuznetsova, N.P.; Lopyrev, V.A.; Tatarova, L.A.

    1985-04-01

    Quaternary salts based on 1-vinyl-1,2,4-triazole have been synthesized. Alkyl iodides and bromides and dimethyl sulfate served as the quaternizing agent. Polymeric quaternary salts of 1-vinyl-1,2,4-triazole have been obtained by alkylation of its polymer.

  10. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  11. 40 CFR 721.10430 - Tetra alkyl ammonium salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Tetra alkyl ammonium salt (generic... Specific Chemical Substances § 721.10430 Tetra alkyl ammonium salt (generic). (a) Chemical substance and... ammonium salt (PMN P-97-823) is subject to reporting under this section for the significant new...

  12. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  13. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  14. 40 CFR 721.10430 - Tetra alkyl ammonium salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Tetra alkyl ammonium salt (generic... Specific Chemical Substances § 721.10430 Tetra alkyl ammonium salt (generic). (a) Chemical substance and... ammonium salt (PMN P-97-823) is subject to reporting under this section for the significant new...

  15. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  16. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  17. Microwave-assisted synthesis of alkyl cellulose in aqueous medium

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Alkyl celluloses are commercial products that are made typically in an alcohol medium over the course of several hours. In this work an alternative, simplified synthesis of alkyl cellulose is reported, using microwave irradiation and aqueous alkaline medium. No alcohol is needed during the reaction....

  18. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  19. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  20. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  1. Copper-catalyzed trifluoromethylselenolation of aryl and alkyl halides: the silver effect in transmetalation.

    PubMed

    Chen, Chaohuang; Hou, Chuanqi; Wang, Yuguang; Hor, T S Andy; Weng, Zhiqiang

    2014-01-17

    A catalytic trifluoromethylselenolation of aryl and alkyl halides by a Cu(I) catalyst has been developed. A key intermediate, [(phen)Cu(SeCF3)]2 (5) was successfully isolated and characterized by X-ray diffraction. The important role of silver in the transmetalation process during the catalytic cycle was elucidated. A wide range of trifluoromethylselanes have been prepared from readily available starting materials from a method that tolerates various important functional groups. PMID:24372349

  2. Stereospecific Ni-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with Alkyl Halides

    PubMed Central

    2015-01-01

    A general method for the alkenylation of alkyl electrophiles using nearly stoichiometric amounts of the air- and moisture-stable potassium organotrifluoroborates has been developed. Various functional groups were tolerated on both the nucleophilic and electrophilic partner. Reactions of highly substituted E- and Z-alkenyltrifluoroborates, as well as vinyl- and propenyltrifluoroborates, were successful, and no loss of stereochemistry or regiochemistry was observed. PMID:24666316

  3. Structure-activity relationships of C1 and C6 side chains of zaragozic acid A derivatives.

    PubMed

    Ponpipom, M M; Girotra, N N; Bugianesi, R L; Roberts, C D; Berger, G D; Burk, R M; Marquis, R W; Parsons, W H; Bartizal, K F; Bergstom, J D

    1994-11-11

    Systematic modification of the C6 acyl side chain of zaragozic acid A, a potent squalene synthase inhibitor, was undertaken to improve its biological activity. Simplification of the C6 side chain to the octanoyl ester has deleterious effects; increasing the linear chain length improves the in vitro activity up to the tetradecanoyl ester. An omega-phenoxy group is a better activity enhancer than an omega-phenyl group. A number of C6 carbamates, ethers, and carbonates were prepared and found to have similar activity profiles as the C6 esters. In the preparation of C6 ethers, C4 and C4,6 bisethers were also isolated; their relative activity is: C6 > C4 > C4,6. These C6 long-chain derivatives are subnanomolar squalene synthase inhibitors; they are, however, only weakly active in inhibiting hepatic cholesterol synthesis in mice. The C6 short-chain derivatives are much less active in vitro, but they all have improved oral activity in mice. Modification of the C1 alkyl side chain of the n-butanoyl analogue (ED50 4.5 mg/kg) did not improve the po activity further. A number of these C6 long-chain derivatives are also potent antifungal agents in vitro. PMID:7966163

  4. The carbon functional group budget of a peatland

    NASA Astrophysics Data System (ADS)

    Moody, Catherine; Worrall, Fred; Clay, Gareth; Apperley, David

    2016-04-01

    Organic matter samples were taken from each organic matter reservoir and fluvial flux found in a peatland and analysed by elemental analysis for carbon, hydrogen, nitrogen and oxygen content, and by 13C solid state nuclear magnetic resonance (NMR) for functional group composition. The samples analysed were: aboveground, belowground, heather, mosses and sedges, litter layer, four different depths from a peat core, and monthly samples of fluvial particulate and dissolved organic matter. All organic matter samples were taken from a 100% peat catchment within Moor House National Nature Reserve in the North Pennines, UK. The proportion of carbon atoms from each of the eight carbon functional groups (C-alkyl, N-alkyl/methoxyl C, O-alkyl, O2-alkyl/acetal C, aromatic/unsaturated C, phenolic C, aldehyde/ketone C and amide/carboxyl C) from each type of organic matter were combined with an existing carbon budget from the same site, to give a functional group carbon budget. The budget results show that the ecosystem is accumulating N-alkyl/methoxyl C, O-alkyl, O2-alkyl/acetal C and phenolic C groups, but losing C-alkyl, aromatic/unsaturated C, amide/carboxyl C and aldehyde/ketone C. Comparing the functional group compositions between the sampled organic matter pools shows that DOM arises from two distinct sources; from the peat itself and from a vegetation source.

  5. Side Effects of Hormone Therapy

    MedlinePlus

    ... Men Living with Prostate Cancer Side Effects of Hormone Therapy Side Effects Urinary Dysfunction Bowel Dysfunction Erectile Dysfunction Loss of Fertility Side Effects of Hormone Therapy Side Effects of Chemotherapy Side Effects: When ...

  6. Ni-Catalyzed C-C Couplings Using Alkyl Electrophiles.

    PubMed

    Iwasaki, Takanori; Kambe, Nobuaki

    2016-10-01

    Much effort has been devoted to developing new methods using Ni catalysts for the cross-coupling reaction of alkyl electrophiles with organometallic reagents, and significant achievements in this area have emerged during the past two decades. Nickel catalysts have enabled the coupling reaction of not only primary alkyl electrophiles, but also sterically hindered secondary and tertiary alkyl electrophiles possessing β-hydrogens with various organometallic reagents to construct carbon skeletons. In addition, Ni catalysts opened a new era of asymmetric cross-coupling reaction using alkyl halides. Recent progress in nickel-catalyzed cross-coupling reaction of alkyl electrophiles with sp(3)-, sp(2)-, and sp-hybridized organometallic reagents including asymmetric variants as well as mechanistic insights of nickel catalysis are reviewed in this chapter. PMID:27580894

  7. Abuse potential and dopaminergic effect of alkyl nitrites.

    PubMed

    Jeon, Seo Young; Kim, Yun Ji; Kim, Young-Hoon; Shin, Jisoon; Yun, Jaesuk; Han, Kyoungmoon; Park, Hye-Kyung; Kim, Hyung Soo; Cha, Hye Jin

    2016-08-26

    The abuse of alkyl nitrites is common among adolescents and young adults worldwide. However, the information regarding the effects of alkyl nitrites on the central nervous system and the associated psychological abuse potential is scarce. The abuse potential of 3 representative alkyl nitrites - isobutyl nitrite, isoamyl nitrite, and butyl nitrite - was evaluated in mice using conditioned place preference tests with an unbiased method. The dopamine levels released by synaptosomes extracted from the striatal region were measured using high performance liquid chromatography. Mice treated with the test substances (50mg/kg, i.p.) exhibited a significantly increased drug-paired place preference. Moreover, greater levels of dopamine were released by striatal region synaptosomes in response to isobutyl nitrite treatment in mice. Thus, our findings suggest that alkyl nitrites could lead to psychological dependence and dopaminergic effects. Furthermore, these results provide scientific evidence to support the regulation of alkyl nitrites as psychoactive substances in the future. PMID:27369324

  8. Alkyl substitution effects on the intercalation of carcinogenic hydrocarbon and hydrocarbon metabolites into DNA

    SciTech Connect

    LeBreton, P.R.

    1986-05-01

    A large number of carcinogenic hydrocarbons and hydrocarbon metabolites intercalate into DNA with binding constants in terms of PO/sub 4//sup -/ concentration which lie in the range 10/sup 3/-10/sup 4/ M/sup -1/. These binding constants are similar to those associated with base stacking and hydrogen bonding interactions that occur naturally in DNA. Previous studies show that different metabolites derived from the same parent hydrocarbon exhibit different binding properties. In recent studies the authors have examined the effects of alkyl substitution on hydrocarbon binding to calf thymus DNA. Such groups can enhance or inhibit carcinogenic activity. Studies of 1-alkyl BP/sup +/ derivatives and of their 7,8-dihydrodiols indicate that the alkyl groups ethyl, isopropyl and t-butyl inhibit intercalation. Methyl groups can either inhibit or enhance intercalation into DNA. The binding constants of DMBA and BA are nearly the same. However, DMA, which is a ..pi.. electron model compound of the bay region diol epoxide of DMBA, binds 6.7 times better than anthracene. Similarly, highly carcinogenic 5-methylchyrsene binds to DNA 3.9 times better than chrysene. /sup +/Abbreviations: BP, benzo(a)pyrene; DMBA, 7,12-dimethylbenz(a)anthracene; BA, benz(a)anthracene DMA, 9,10-dimethylanthracene.

  9. An efficient copper-catalyzed cross-coupling reaction of alkyl-triflates with alkyl-Grignard reagents

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A highly efficient method for the formation of C-C covalent bonds by cross-coupling reaction between alkyl-triflates and alkyl-Grignard reagents catalyzed by copper catalyst, Li2CuCl4, is described. The reaction works with most primary triflates in diethyl ether at low temperature within 0.5-3 h an...

  10. Amplification of surface-initiated ring-opening metathesis polymerization of 5-(perfluoro-n-alkyl)norbornenes by macroinitiation.

    PubMed

    Escobar, Carlos A; Harl, Robert R; Maxwell, Kathryn E; Mahfuz, Nur N; Rogers, Bridget R; Jennings, G Kane

    2013-10-01

    This article reports the enhanced rate of the surface-initiated polymerization (SIP) of 5-(perfluoro-n-alkyl)norbornenes (NBFn) by combining two SIP techniques, namely surface-initiated atom-transfer polymerization (SI-ATRP) to grow a macroinitiator and surface-initiated ring-opening metathesis polymerization (SI-ROMP) to produce the final coating. This polymerization approach promotes the rapid growth of dense partially fluorinated coatings that are highly hydrophobic and oleophobic and yield thicknesses from 4-12 μm. Specifically, the growth rate and the limiting thickness of pNBFn with different side chain lengths (n = 4, 6, 8, and 10) at various monomer concentrations and temperatures are evaluated through two approaches: growing the polymer from an initiator-terminated monolayer (control) or from a modified poly(2-hydroxyethyl methacrylate) (PHEMA) macroinitiator. X-ray photoelectron spectroscopy (XPS) analysis shows that 38% of the hydroxyl termini in the macroinitiator react with a norbornenyl diacid chloride (NBDAC) molecule, and 7% of such anchored norbornenyl groups react with a catalyst molecule. The kinetic data have been modeled to determine the propagation velocity and the termination rate constant. The PHEMA macroinitiator provides thicker films and faster growth as compared to the monolayer, achieving a 12 μm thick coating of pNBF8 in 15 min. Increasing the monomer side chain length, n, from 4 to 10 improves the growth rate and the limiting polymer thickness. Performing the polymerization process at higher temperature increases the growth rate and the limiting thickness as evidenced by an increase in the film growth rate constant. Arrhenius plots show that the reactions involved in the macroinitiation process exhibit lower activation energies than those formed from a monolayer. Electrochemical impedance spectroscopy reveals that the films exhibit resistance against ion transport in excess of 1 × 10(10) Ω·cm(2). PMID:24024903

  11. Control over the Self-Assembly Modes of Pt(II) Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks.

    PubMed

    Allampally, Naveen Kumar; Mayoral, María José; Chansai, Sarayute; Lagunas, María Cristina; Hardacre, Christopher; Stepanenko, Vladimir; Albuquerque, Rodrigo Q; Fernández, Gustavo

    2016-06-01

    We report the self-assembly of a new family of hydrophobic, bis(pyridyl) Pt(II) complexes featuring an extended oligophenyleneethynylene-derived π-surface appended with six long (dodecyloxy (2)) or short (methoxy (3)) side groups. Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt⋅⋅⋅Pt ≈14 Å) in both nonpolar solvents and the solid state. Dispersion-corrected PM6 calculations suggest that this organization is driven by cooperative π-π, C-H⋅⋅⋅Cl and π-Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt⋅⋅⋅Pt ≈4.4 Å) stabilized by multiple π-π and C-H⋅⋅⋅Cl contacts are obtained in the crystalline state for 3 lacking long side chains, as shown by X-ray analysis and PM6 calculations. Our results reveal not only the key role of alkyl chain length in controlling self-assembly modes but also show the relevance of Pt-bound chlorine ligands as new supramolecular synthons. PMID:27113990

  12. Incorporation of Acid-Labile Masking Groups for the Traceless Synthesis of C-Terminal Peptide α-Ketoacids.

    PubMed

    Thuaud, Frédéric; Rohrbacher, Florian; Zwicky, André; Bode, Jeffrey W

    2016-08-01

    An optimized protocol for the masking of α-ketoacids with acid-labile cyclic acetal protecting groups is reported. Unlike prior approaches, these new conditions allow the synthesis of protected α-ketoacids bearing aromatic, hindered alkyl, and protected polar side chains. Attachment to a Wang-type linker and solid support provides a resin that delivers fully unprotected C-terminal peptide α-ketoacids upon resin cleavage. These peptides are the key starting materials for chemical protein synthesis using the α-ketoacid-hydroxylamine ligation. PMID:27439001

  13. Pd and Mo Catalyzed Asymmetric Allylic Alkylation

    PubMed Central

    Trost, Barry M.

    2012-01-01

    The ability to control the alkylation of organic substrates becomes ever more powerful by using metal catalysts. Among the major benefits of metal catalysis is the possibility to perform such processes asymmetrically using only catalytic amounts of the chiral inducing agent which is a ligand to the metal of the catalyst. A unique aspect of asymmetric metal catalyzed processes is the fact that many mechanisms exist for stereoinduction. Furthermore, using the same catalyst system, many types of bonds including but not limited to C-C, C-N, C-O, C-S, C-P, and C-H can be formed asymmetrically. An overview of this process using palladium and molybdenum based metals being developed in my laboratories and how they influence strategy in synthesizing bioactive molecular targets is presented. PMID:22736934

  14. Models for cytochrome P450 prosthetic heme alkylation. Reaction of diazoacetophenone with (tetraphenylporphyrinato)iron(II) chloride

    SciTech Connect

    Komives, E.A.; Tew, D.; Olmstead, M.M.; Ortiz de Montellano, P.R.

    1988-09-07

    The reaction of diazoacetophenone with (tetraphenylporphyrinato)iron(II) yields (N-(2-phenyl-2-oxoethyl)tetraphenylporphyrinato)iron(II) chloride. The structure of this product has been established by spectroscopic methods and by x-ray crystallography. The crystal structure shows that the first carbon of the N-alkyl group is 2.94 /angstrom/ from the iron atom and that the oxygen of the N-alkyl group points away from the iron. No evidence is seen for the Fe-C-N product expected from insertion of the diazo carbon into the metalloporphyrin iron-nitrogen bond or for intermediates in which the oxygen of the N-(2-phenyl-2-oxoethyl) group is coordinated to the iron. These results suggest it is unlikely that carbene-insertion or oxygen-coordinated intermediates will be detected during the N-alkylation of cytochrome P450 by diazo ketones. The results also rationalize the failure to detect iron-chelated enol species during N-alkylation of the prosthetic group of cytochrome P450 by catalytically activated phenylacetylene. 43 references, 5 figures, 4 tables.

  15. Auxiliary-assisted palladium-catalyzed arylation and alkylation of sp2 and sp3 carbon-hydrogen bonds.

    PubMed

    Shabashov, Dmitry; Daugulis, Olafs

    2010-03-24

    We have developed a method for auxiliary-directed, palladium-catalyzed beta-arylation and alkylation of sp(3) and sp(2) C-H bonds in carboxylic acid derivatives. The method employs a carboxylic acid 2-methylthioaniline- or 8-aminoquinoline amide substrate, aryl or alkyl iodide coupling partner, palladium acetate catalyst, and an inorganic base. By employing 2-methylthioaniline auxiliary, selective monoarylation of primary sp(3) C-H bonds can be achieved. If arylation of secondary sp(3) C-H bonds is desired, 8-aminoquinoline auxiliary may be used. For alkylation of sp(3) and sp(2) C-H bonds, 8-aminoquinoline auxiliary affords the best results. Some functional group tolerance is observed and amino- and hydroxy-acid derivatives can be functionalized. Preliminary mechanistic studies have been performed. A palladacycle intermediate has been isolated, characterized by X-ray crystallography, and its reactions have been studied. PMID:20175511

  16. Microwave assisted N-alkylation of amine functionalized crystal-like mesoporous phenylene-silica.

    PubMed

    Lourenço, Mirtha A O; Siegel, Renée; Mafra, Luís; Ferreira, Paula

    2013-04-28

    N-alkylation reaction of amine functionalized phenylene moieties in crystal-like mesoporous silica is successfully achieved with about 87% of conversion in two reaction cycles. A potassium iodide catalyzed method commonly used for the selective N-monoalkylation of aniline is adapted and optimized to the N-monoalkylation reactions of the amine functionalized periodic mesoporous phenylene-silica (NH2-PMO) under microwave irradiation with preservation of the ordered mesostructure and of the crystal-like molecular scale periodicity of the material. This functionalization opens an avenue for the preparation of new materials with different amino-alkyl groups specially designed for a desired application, namely on the adsorption or catalytic fields. PMID:23508286

  17. Alkylation of Staurosporine to Derive a Kinase Probe for Fluorescence Applications.

    PubMed

    Disney, Alexander J M; Kellam, Barrie; Dekker, Lodewijk V

    2016-05-01

    The natural product staurosporine is a high-affinity inhibitor of nearly all mammalian protein kinases. The labelling of staurosporine has proven effective as a means of generating protein kinase research tools. Most tools have been generated by acylation of the 4'-methylamine of the sugar moiety of staurosporine. Herein we describe the alkylation of this group as a first step to generate a fluorescently labelled staurosporine. Following alkylation, a polyethylene glycol linker was installed, allowing subsequent attachment of fluorescein. We report that this fluorescein-staurosporine conjugate binds to cAMP-dependent protein kinase in the nanomolar range. Furthermore, its binding can be antagonised with unmodified staurosporine as well as ATP, indicating it targets the ATP binding site in a similar fashion to native staurosporine. This reagent has potential application as a screening tool for protein kinases of interest. PMID:27008372

  18. Alkylation of Staurosporine to Derive a Kinase Probe for Fluorescence Applications

    PubMed Central

    Disney, Alexander J. M.; Kellam, Barrie

    2016-01-01

    Abstract The natural product staurosporine is a high‐affinity inhibitor of nearly all mammalian protein kinases. The labelling of staurosporine has proven effective as a means of generating protein kinase research tools. Most tools have been generated by acylation of the 4′‐methylamine of the sugar moiety of staurosporine. Herein we describe the alkylation of this group as a first step to generate a fluorescently labelled staurosporine. Following alkylation, a polyethylene glycol linker was installed, allowing subsequent attachment of fluorescein. We report that this fluorescein–staurosporine conjugate binds to cAMP‐dependent protein kinase in the nanomolar range. Furthermore, its binding can be antagonised with unmodified staurosporine as well as ATP, indicating it targets the ATP binding site in a similar fashion to native staurosporine. This reagent has potential application as a screening tool for protein kinases of interest. PMID:27008372

  19. Swelling behavior of O-alkylated APCS coals as examined by the EPR spin probe method

    SciTech Connect

    Ding, Ruisong; Tucker, D.; Kispert, L.D.

    1995-12-31

    Known O-alkylation procedures have been used to derivatize the carboxyl and hydroxyl groups in the APCS coals Lewiston-Stockton, Wyodak-Anderson, Beulah-Zap, Illinois {number_sign}6, Upper Freeport, and Pittsburgh {number_sign}8. In general the resulting decrease in hydrogen bonding reduced the cyclical variation in nitroxide spin probe retention observed for nonalkylated coals when small amounts (<1%) of pyridine are present in the toluene swelling solvent. An increase in spin probe retention by the O-alkylated coals relative to the underivatized coals indicates a more open arrangement in the coal due to a decrease in attractive forces, confirming that microporosity increases with increasing rank.

  20. Luminescence nanothermometry with alkyl-capped silicon nanoparticles dispersed in nonpolar liquids

    PubMed Central

    2014-01-01

    Silicon nanoparticles (Si NPs) with a diameter size ranging from 4 to 8 nm were successfully fabricated. They exhibit a visible photoluminescence (PL) due to the quantum confinement effect. Chemical functionalization of these Si NPs with alkyl groups allowed to homogeneously disperse them in nonpolar liquids (NPLs). In comparison to most of literature results for Si NPs, an important PL peak position variation with temperature (almost 1 meV/K) was obtained from 303 to 390 K. The influence of the liquid viscosity on the peak positions is also presented. These variations are discussed considering energy transfer between nanoparticles. The high PL thermal sensitivity of the alkyl-capped Si NPs paves the way for their future application as nanothermometers. PMID:24565261

  1. Electrophilic Metal Alkyl Chemistry in New Ligand Environments

    SciTech Connect

    Jordan, Richard F.

    2013-06-30

    The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH2=CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (α-diimine)PdMe{sup +} species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (α-diimine)PdMe{sup +} catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe{sup +} species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

  2. U. S. refiners must increase alkylation capacity to meet demand

    SciTech Connect

    Rhodes, A.

    1994-08-22

    Alkylation is one of the most important refinery processes for producing conventional gasoline. And alkylate will continue to be a preferred blending stock in the reformulated-gasoline era. US alkylation units are operating at more than 90% of capacity, and additional capacity will be required to meet projected demand in 1998 and beyond. This capacity will come primarily through debottlenecking existing units, but new capacity will be required in the U.S., particularly after the year 2000. This paper briefly discusses industry trends, supply and demand, and solid acid catalyst technology.

  3. Covalent binding to glutathione of the DNA-alkylating antitumor agent, S23906-1.

    PubMed

    David-Cordonnier, Marie-Hélène; Laine, William; Joubert, Alexandra; Tardy, Christelle; Goossens, Jean-François; Kouach, Mostafa; Briand, Gilbert; Thi Mai, Huong Doan; Michel, Sylvie; Tillequin, Francois; Koch, Michel; Leonce, Stéphane; Pierre, Alain; Bailly, Christian

    2003-07-01

    The benzoacronycine derivative, S23906-1, was characterized recently as a novel potent antitumor agent through alkylation of the N2 position of guanines in DNA. We show here that its reactivity towards DNA can be modulated by glutathione (GSH). The formation of covalent adducts between GSH and S23906-1 was evidenced by EI-MS, and the use of different GSH derivatives, amino acids and dipeptides revealed that the cysteine thiol group is absolutely required for complex formation because glutathione disulfide (GSSG) and other S-blocked derivatives failed to react covalently with S23906-1. Gel shift assays and fluorescence measurements indicated that the binding of S23906-1 to DNA and to GSH are mutually exclusive. Binding of S23906-1 to an excess of GSH prevents DNA alkylation. Additional EI-MS measurements performed with the mixed diester, S28053-1, showed that the acetate leaving group at the C1 position is the main reactive site in the drug: a reaction scheme common to GSH and guanines is presented. At the cellular level, the presence of GSH slightly reduces the cytotoxic potential of S23906-1 towards KB-3-1 epidermoid carcinoma cells. The GSH-induced threefold reduction of the cytotoxicity of S23906-1 is attributed to the reduced formation of lethal drug-DNA covalent complexes in cells. Treatment of the cells with buthionine sulfoximine, an inhibitor of GSH biosynthesis, facilitates the formation of drug-DNA adducts and promotes the cytotoxic activity. This study identifies GSH as a reactant for the antitumor drug, S23906-1, and illustrates a pathway by which GSH may modulate the cellular sensitivity to this DNA alkylating agent. The results presented here, using GSH as a biological nucleophile, fully support our initial hypothesis that DNA alkylation is the major mechanism of action of the promising anticancer drug S23906-1. PMID:12823555

  4. Peptide nanotube aligning side chains onto one side.

    PubMed

    Tabata, Yuki; Mitani, Shota; Kimura, Shunsaku

    2016-06-01

    A novel pseudo cyclic penta-β-peptide composed of a β-naphthylalanine, two β-alanines, and a sequence of ethylenediamine-succinic acid (CP5ES) is synthesized and investigated on peptide nanotube (PNT) formation. When the PNT is formed with the maximum number of intermolecular hydrogen bonds between the cyclic peptides, the sequence enables the alignment of the side chains, naphthyl groups, on one side of the PNT. Microscopic and spectroscopic observations of CP5ES crystals reveal that CP5ES forms rod- or needle-shaped molecular assemblies showing exciton coupling of the Cotton effect and predominant monomer emission, which are different from a reference cyclic tri-β-peptide composed of a β-naphthylalanine and two β-alanines. Insertion of a sequence of ethylenediamine-succinic acid into β-amino acids in the cyclic skeleton is therefore suggested to be effective to make the side chains aligning on one side of the PNT. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd. PMID:27282135

  5. 3-O-Alkyl-2,3-dehydrosilibinins: Two synthetic approaches and in vitro effects toward prostate cancer cells.

    PubMed

    Zhang, Sheng; Vue, Bao; Huang, Michael; Zhang, Xiaojie; Lee, Timmy; Chen, Guanglin; Zhang, Qiang; Zheng, Shilong; Wang, Guangdi; Chen, Qiao-Hong

    2016-07-15

    Eight 3-O-alkyl-2,3-dehydrosilibinins have been synthesized from commercially available silibinin through two synthetic approaches. A one-pot reaction, starting with aerobic oxidation of silibinin followed by direct alkylation of the phenolic hydroxyl group in the subsequent 2,3-dehydrosilibinin, furnishes the desired derivatives in 11-16% yields. The three-step procedure employing benzyl ether to protect 7-OH in silibinin generates the desired derivatives in 30-46% overall yields. The antiproliferative activity of the 2,3-dehydrosilibinin derivatives against both androgen-sensitive and androgen-insensitive prostate cancer cells have been assessed using a WST-1 cell proliferation assay. All derivatives exhibited greater antiproliferative potency than silibinin, with 2,3-dehydrosilibinins each possessing a three- to five-carbon linear alkyl group to 3-OH (IC50 values in a range of 1.71-3.06μM against PC-3 and LNCaP cells) as the optimal derivatives. The optimal potency was reached with three- to five-carbon alkyl groups. Our findings suggest that 3-O-propyl-2,3-dehydrosilibinin effectively inhibits the growth of PC-3 prostate cancer cells by arresting cell cycle in the G0/G1 phase, but not by activating PC-3 cell apoptosis. PMID:27261177

  6. Synthesis and Antifungal Activity of Natural Product-Based 6-Alkyl-2,3,4,5-tetrahydropyridines

    PubMed Central

    Dai, Liyan; Jacob, Melissa R.; Khan, Shabana I.; Khan, Ikhlas A.; Clark, Alice M.; Li, Xing-Cong

    2011-01-01

    Seven 6-alkyl-2,3,4,5-tetrahydropyridines (5a–5g) that mimic the natural piperideines that were recently identified in the fire ant venom have been synthesized. Compounds 5c–5g with the C-6 alkyl chain lengths from C14 to C18 showed varying degrees of antifungal activities, with 5e (6-hexadecyl-2,3,4,5-tetrahydropyridine) and 5f (6-heptadecyl-2,3,4,5-tetrahydropyridine) being the most active. Compound 5e exhibited minimum fungicidal concentrations (MFCs) of 3.8, 15.0, 7.5, and 7.5 μg/mL against Cryptococcus neoformans, Candida albicans, Candida glabrata, and Candida krusei, respectively. The antifungal activities of these compounds appear to be associated with the C-6 side chain length. This study represents the first effort to evaluate antifungal activities of synthetic analogs of the newly identified fire ant venom alkaloids. PMID:21905650

  7. Triethylaluminum- or triethylborane-induced free radical reaction of alkyl iodides and alpha,beta-unsaturated compounds.

    PubMed

    Liu, Jing-Yuan; Jang, Yoeng-Jiunn; Lin, Wen-Wei; Liu, Ju-Tsung; Yao, Ching-Fa

    2003-05-16

    A series of alpha,beta-unsaturated compounds, 1a-c, 9, 13, and 17, were used as reactants in free radical conjugate addition reactions with different radicals generated from alkyl iodides such as 3, 4, or 5 in the presence of triethylborane-oxygen in air or via the use of triethylaluminum-benzoyl peroxide as a free radical initiator. When the reactions were carried out using triethylborane-air, the products, in most cases, were clean and were easily purified. However, higher yields of the 1,4-adducts and less side reactions occurred when less reactive substrates were used as Michael acceptors in reactions with triethylaluminum-benzoyl peroxide and alkyl iodide under similar conditions. A mechanism for this is proposed in Scheme 1. PMID:12737587

  8. Radical-based alkylation of guanine derivatives in aqueous medium.

    PubMed

    Chatgilialoglu, Chryssostomos; Caminal, Clara; Mulazzani, Quinto G

    2011-05-01

    The radical-based alkylation of 8-bromoguanosine (1a) and 8-bromo-2'-deoxyguanosine (1b) at the C8 position has been investigated in aqueous solutions. Alkyl radicals were generated by scavenging of the primary species of γ-radiolysis by the alcohol substrate. These reactions result in the efficient formation of intermolecular C-C bonds in aqueous media, by using the reactivity of α-hydroxyalkyl radicals derived from alcohols with 1a and 1b. A mechanism for the formation of C8 guanine alkylated adducts has been proposed, based on the quantification of radiation chemical yields for the disappearance of starting material and the formation of all products. Two α-hydroxyalkyl radicals are needed to form an alkylated guanine, the first one adding to C8 followed by ejection of Br(-) with formation of guanyl adduct and the second one acting as reducing agent of the guanyl adduct. PMID:21431230

  9. Perfluorinated Alkyl Compounds: Challenges To Develop Robust And Reliable Methods

    EPA Science Inventory

    An increasing number of studies have been conducted to investigate the environmental distribution of perfluorinated alkyl compounds (PFCs), some of which are known to be toxic in laboratory studies. Despite growing public concerns, environmental monitoring data are still limited...

  10. Synthetic Method for Oligonucleotide Block by Using Alkyl-Chain-Soluble Support.

    PubMed

    Matsuno, Yuki; Shoji, Takao; Kim, Shokaku; Chiba, Kazuhiro

    2016-02-19

    A straightforward method for the synthesis of oligonucleotide blocks using a Cbz-type alkyl-chain-soluble support (Z-ACSS) attached to the 3'-OH group of 3'-terminal nucleosides was developed. The Z-ACSS allowed for the preparation of fully protected deoxyribo- and ribo-oligonucleotides without chromatographic purification and released dimer- to tetramer-size oligonucleotide blocks via hydrogenation using a Pd/C catalyst without significant loss or migration of protective groups such as 5'-end 4,4'-dimethoxtrityl, 2-cyanoethyl on internucleotide bonds, or 2'-TBS. PMID:26845521

  11. Decreased protective efficacy of reduced and alkylated human immune serum globulin in experimental infection with Haemophilus influenzae type b.

    PubMed Central

    Schreiber, J R; Barrus, V A; Siber, G R

    1985-01-01

    Conventionally prepared immune serum globulin frequently produces severe side effects when administered intravenously. A modified preparation in which 4 to 5 interchain disulfide bonds have been reduced and alkylated has been made for intravenous use. However, reduction and alkylation may affect Fc-mediated functions of immunoglobulin G, particularly its ability to fix complement by the classical pathway. To determine whether reduction and alkylation alters the protective activity of immune serum globulin in vivo we compared it with two less harshly prepared globulins (pH 4 treated or ultrafiltered) in an infant rat model of Haemophilus influenzae b infection. Antibody binding to the capsular and noncapsular components of H. influenzae b and in vitro bactericidal activity were similar in the globulin preparations. Infant rats were treated with various doses of globulins adjusted to provide identical concentrations of anticapsular antibodies as measured by the Farr radioactive antigen binding assay. At high doses of anticapsular antibody (greater than 1,500 ng per pup), all preparations protected well. At marginal doses (750 ng per pup), however, rats given reduced and alkylated globulin had a significantly greater incidence of bacteremia (P less than 0.05), meningitis (P less than 0.01), and death (P less than 0.05) and a higher magnitude of bacteremia (P less than 0.02) than rats who received pH4-treated or ultrafiltered globulins. These differences were not due to differences in anticapsular antibody concentrations achieved in the serum. The 50% protective serum concentrations of anticapsular antibody in this model were 200 to 300 ng/ml for reduced and alkylated globulin and 100 to 200 ng/ml for acid-treated globulin. Absorption of the globulins with purified H. influenzae b capsule reduced in vitro bactericidal activity and rat protective activity. However, the magnitude of bacteremia was lower in rats receiving absorbed pH 4-treated globulin than in those

  12. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    PubMed Central

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  13. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents.

    PubMed

    Shrestha, Bijay; Giri, Ramesh

    2015-01-01

    We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N',N'-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  14. Alkyl and phenolic glycosides from Saussurea stella.

    PubMed

    Wang, Tian-Min; Wang, Ru-Feng; Chen, Hu-Biao; Shang, Ming-Ying; Cai, Shao-Qing

    2013-07-01

    One alkyl glycoside, saussurostelloside A (1), two phenolic glycosides, saussurostellosides B1 (2) and B2 (3), and 27 known compounds, including eleven flavonoids, seven phenolics, six lignans, one neolignan, one phenethyl glucoside and one fatty acid, were isolated from an ethanol extract of Saussurea stella (Asteraceae). Their structures were elucidated by NMR, MS, UV, and IR spectroscopic analysis. Of the known compounds, (+)-medioresinol-di-O-β-D-glucoside (7), picraquassioside C (10), and diosmetin-3'-O-β-D-glucoside (27) were isolated from the Asteraceae family for the first time, while (+)-pinoresinol-di-O-β-D-glucoside (6), di-O-methylcrenatin (11), protocatechuic acid (14), 1,5-di-O-caffeoylquinic acid (17), formononetin (28), and phenethyl glucoside (29) were isolated from the Saussurea genus for the first time. The anti-inflammatory activities of three new compounds (1-3), five lignans ((-)-arctiin (4), (+)-pinoresinol-4-O-β-D-glucoside (5), (+)-pinoresinol-di-O-β-D-glucoside (6), (+)-medioresinol-di-O-β-D-glucoside (7) and (+)-syringaresinol-4-O-β-D-glucoside (8)), one neolignan (picraquassioside C (10)), and one phenolic glycoside (di-O-methylcrenatin (11)) were evaluated by testing their inhibition of the release of β-glucuronidase from PAF-stimulated neutrophils. Only compound 5 showed moderate inhibition of the release of β-glucuronidase, with an inhibition ratio of 39.1%. PMID:23567860

  15. Significant Improvement of Semiconducting Performance of the Diketopyrrolopyrrole-Quaterthiophene Conjugated Polymer through Side-Chain Engineering via Hydrogen-Bonding.

    PubMed

    Yao, Jingjing; Yu, Chenmin; Liu, Zitong; Luo, Hewei; Yang, Yang; Zhang, Guanxin; Zhang, Deqing

    2016-01-13

    Three diketopyrrolopyrrole (DPP)-quaterthiophene conjugated polymers, pDPP4T-1, pDPP4T-2, and pDPP4T-3, in which the molar ratios of the urea-containing alkyl chains vs branching alkyl chains are 1:30, 1:20, and 1:10, respectively, were prepared and investigated. In comparison with pDPP4T without urea groups in the alkyl side chains and pDPP4T-A, pDPP4T-B, and pDPP4T-C containing both linear and branched alkyl chains, thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 exhibit higher hole mobilities; thin-film mobility increases in the order pDPP4T-1 < pDPP4T-2 < pDPP4T-3, and hole mobility of a thin film of pDPP4T-3 can reach 13.1 cm(2) V(-1) s(-1) after thermal annealing at just 100 °C. The incorporation of urea groups in the alkyl side chains also has an interesting effect on the photovoltaic performances of DPP-quaterthiophene conjugated polymers after blending with PC71BM. Blended thin films of pDPP4T-1:PC71BM, pDPP4T-2:PC71BM, and pDPP4T-3:PC71BM exhibit higher power conversion efficiencies (PCEs) than pDPP4T:PC71BM, pDPP4T-A:PC71BM, pDPP4T-B:PC71BM, and pDPP4T-C:PC71BM. The PCE of pDPP4T-1:PC71BM reaches 6.8%. Thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 and corresponding thin films with PC71BM were characterized with AFM, GIXRD, and STEM. The results reveal that the lamellar packing order of the alkyl chains is obviously enhanced for thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3; after thermal annealing, slight inter-chain π-π stacking emerges for pDPP4T-2 and pDPP4T-3. Blends of pDPP4T-1, pDPP4T-2, and pDPP4T-3 with PC71BM show a more pronounced micro-phase separation. These observations suggest that the presence of urea groups may further facilitate the assemblies of these conjugated polymers into nanofibers and ordered aggregation of PC71BM. PMID:26669732

  16. Two Droplets Burning Side by Side

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Fiber-Supported Droplet Combustion (FSDC) experiment team got more than twice as many burns have been completed as were originally scheduled for STS-95. This image was taken July 12, 1997, MET:10/08:13 (approximate). As shown here, scientists were able to burn two droplets side by side, more closely mimicking behavior of burning fuel in an engine. This shows ignition of a single drop that subsequently burned while a fan blew through the chamber, giving the scientists data on burning with convection, but no buoyancy -- an important distinction when you're trying to solve a problem by breaking it into parts. FSDC-2 studied fundamental phenomena related to liquid fuel droplet combustion in air. Pure fuels and mixtures of fuels were burned as isolated single and dual droplets with and without forced air convection. The FSDC guest investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (1.1 MB, 11-second MPEG, screen 320 x 240 pixels; downlinked video, higher quality not available) A still JPG composite of this movie is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300176.html.

  17. HPLC and TLC characterisation of ecdysteroid alkyl ethers.

    PubMed

    Lapenna, Silvia; Dinan, Laurence

    2009-10-01

    Semi-synthetic ecdysteroid alkyl ethers have increased potential over natural ecdysteroids as actuators of ligand-inducible gene-expression systems based on the ecdysteroid receptor for in vivo applications. However, a scalable synthesis of these compounds has yet to be developed. We report a set of reversed-phase (RP; C(18) and C(6)) and normal-phase (NP; diol) HPLC systems which can be used to analyse and separate ecdysteroid ethers with single or multiple O-methyl substitutions at the 2alpha-, 3beta-, 14alpha-, 22- and 25-positions. The elution order of methyl ether analogues of the prototypical ecdysteroid 20-hydroxyecdysone (20E) was 3-methyl<2-methyl<14-methyl<25-methyl<22-methyl with both C(18)- and C(6)-RP-HPLC, when eluted with methanol/water mixtures. Further, the elution order of 20E 22-O-alkyl ethers was methylalkyl ethers can also be adequately resolved by NP-HPLC and silica HPTLC. On the latter, detection of ecdysteroid O-alkyl ethers with the p-anisaldehyde/sulphuric acid reagent distinguishes 22-O-alkyl ethers from non-22-O-alkyl ether analogues by the colour of the resulting spot. PMID:19648067

  18. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    SciTech Connect

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  19. Alcohols as alkylating agents in heteroarene C–H functionalization

    PubMed Central

    Jin, Jian; MacMillan, David W. C.

    2015-01-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ‘spin-center shift’ (SCS)2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. Considering traditional radical-based alkylation methods require the use of stoichiometric oxidants, elevated temperatures, or peroxides3–7, the development of a mild protocol using simple and abundant alkylating agents would have significant utility in the synthesis of diversely functionalized pharmacophores. In this manuscript, we describe the successful execution of this idea via the development of a dual catalytic alkylation of heteroarenes using alcohols as mild alkylating reagents. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer (HAT) catalysis. The utility of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

  20. Salvage of failed protein targets by reductive alkylation.

    PubMed

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins. PMID:24590719

  1. Alcohols as alkylating agents in heteroarene C-H functionalization

    NASA Astrophysics Data System (ADS)

    Jin, Jian; MacMillan, David W. C.

    2015-09-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  2. Alcohols as alkylating agents in heteroarene C-H functionalization.

    PubMed

    Jin, Jian; MacMillan, David W C

    2015-09-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

  3. Pseudo-hydroxide extraction in the separation of sodium hydroxide from aqueous solutions using alkyl phenols

    SciTech Connect

    Kang, Hyun Ah; Moyer, Bruce A

    2006-01-01

    Pseudo-hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1-octanol at 25 degrees C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4-tert-octylphenol. 3,5-di-tertbutylphenol. 2,4-di-tert-butylphenol. 2,6-di-tert-butyl-4-methylphenol. A good correlation with phenol pK(a) was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol - OH group. The effective partition ratios (P-eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1-octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation-exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for a. Ion-pair extraction to give Na+OH- ion pairs and corresponding free ions in 1-octanol the phase and b. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic-phase Na(+)A(-) ion pairs and corresponding free organic-phase ions.

  4. Diarmed (adamantyl/alkyl) surfactants from nitrilotriacetic acid.

    PubMed

    Trillo, Juan V; Vázquez Tato, José; Jover, Aida; de Frutos, Santiago; Soto, Victor H; Galantini, Luciano; Meijide, Francisco

    2014-11-01

    The compounds presented here constitute a clear example of molecular biomimetics as their design is inspired on the structure and properties of natural phospholipids. Thus novel double-armed surfactants have been obtained in which nitrilotriacetic acid plays the role of glycerol in phospholipids. The hydrophobic arms are linked to the head group through amide bonds (which is also the case of sphingomyelin): (R1NHCOCH2)(R2NHCOCH2)NCH2CO2H (R1 being CH3(CH2)11, CH3(CH2)17, CH3(CH2)7CHCH(CH2)8, and adamantyl, and R2=adamantyl). The dependence of the surface tension with concentration shows the typical profile of surfactants since a breaking point, which corresponds to the critical aggregation concentration (cac), is observed in all cases. The cac of these diarmed derivatives are about 1-3 orders of magnitude lower than those of classical monoalkyl derivatives used as reference compounds. In contrast to conventional surfactants, reversed trends in cac values and molecular areas at the solution-air interface have been observed. This anomalous behavior is tied to the structure of the surfactants and suggests that long and flexible alkyl chains should self-coil previous to the aggregation or adsorption phenomena. Above cac all compounds form large aggregates, globular in shape, which tend to associate forming giant aggregates. PMID:25465758

  5. Side Effects of Chemotherapy

    MedlinePlus

    ... reactions to the different drugs. The doctors, nurses, and pharmacists will describe what to look out for in ... will be monitored very closely by doctors, nurses, and pharmacists to make sure that all side effects are ...

  6. Proteinase from germinating bean cotyledons. Evidence for involvement of a thiol group in catalysis.

    PubMed

    Csoma, C; Polgár, L

    1984-09-15

    To degrade storage proteins germinating seeds synthesize proteinases de novo that can be inhibited by thiol-blocking reagents [Baumgartner & Chrispeels (1977) Eur. J. Biochem. 77, 223-233]. We have elaborated a procedure for isolation of such a proteinase from the cotyledons of Phaseolus vulgaris. The purification procedure involved fractionation of the cotyledon homogenate with acetone and with (NH4)2SO4 and successive chromatographies on DEAE-cellulose, activated thiol-Sepharose Sepharose and Sephacryl S-200. The purified enzyme has an Mr of 23,400, proved to be highly specific for the asparagine side chain and blocking of its thiol group resulted in loss of the catalytic activity. The chemical properties of the thiol group of the bean enzyme were investigated by acylation with t-butyloxycarbonyl-L-asparagine p-nitro-phenyl ester and by alkylations with iodoacetamide and iodoacetate. Deviations from normal pH-rate profile were observed, which indicated that the thiol group is not a simple functional group, but constitutes a part of an interactive system at the active site. The pKa value for acylation and the magnitude of the rate constant for alkylation with iodoacetate revealed that the bean proteinase possesses some properties not shared by papain and the other cysteine proteinases studied to date. PMID:6385962

  7. Molecular dynamics study of the effect of alkyl chain length on melting points of [CnMIM][PF6] ionic liquids

    SciTech Connect

    Zhang, Y; Maginn, EJ

    2014-01-01

    Based on molecular dynamics simulations, the melting points T-m of a series of 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids [CnMIM][PF6] with n = 2, 4, 10, 12, and 14 were studied using the free energy-based pseudosupercritical path (PSCP) method. The experimental trend that the Tm decreases with increasing alkyl chain length for ILs with short alkyl chains and increases for the ones with long alkyl chains was correctly captured. Further analysis revealed that the different trends are the results of the balance between fusion enthalpy and fusion entropy. For the ILs with short alkyl chains (ethyl and butyl groups), fusion entropy plays the dominant role so that [C4MIM][PF6], which has a larger fusion entropy due to its higher liquid phase entropy has the lower melting temperature. As for the ILs with long alkyl chains, due to the enhanced van der Waals interactions brought about by the long non-polar alkyl chains, enthalpy becomes the deciding factor and the melting points increase when the alkyl chain goes from C10 to C14. While the melting points for [C2MIM][PF6] and [C4MIM][PF6] were quantitatively predicted and the trends for the long chain ILs were captured correctly, the absolute melting points for [C10MIM][PF6], [C12MIM][PF6] and [C14MIM][PF6] were systematically overestimated in the simulations. Three possible reasons for the overestimation were studied but all ruled out. Further simulation or experimental studies are needed to explain the difference.

  8. Palladium-Catalyzed Dearomative Allylic Alkylation of Indoles with Alkynes To Synthesize Indolenines with C3-Quarternary Centers.

    PubMed

    Gao, Shang; Wu, Zijun; Fang, Xinxin; Lin, Aijun; Yao, Hequan

    2016-08-01

    A palladium-catalyzed dearomative allylic alkylation of indoles with alkynes to construct indolenines with C3-quarternary centers was reported. The in situ formed arylallene intermediate omitted the need to install leaving groups on the allylic compounds and employ extra oxidants to oxidize the allylic C-H bonds. The reaction exhibited good functional group tolerance and high atom economy. Moreover, the reaction was further expanded to synthesize pyrroloindolines and furanoindolines. PMID:27442021

  9. Alkylation of C60. Reaction between C60 anions and tert-butyl chloride and mass spectrometry analysis

    NASA Astrophysics Data System (ADS)

    Bourcier, S.; Chaurand, P.; Ciot, C.; Della-Negra, S.; Fabre, C.; Greugny, V.; Marx, L.; Rassat, A.; Rousseau, A.

    1996-11-01

    Alkylation of C60 in tetrahydrofuran with tert-butyl chloride and lithium gives a variety of products. Adducts of general formula C60Hn(t-Bu)qOx(thf)y (where t-Bu is the tert-butyl group and thf the tetrahydrofuryl group (C4H7O)) have been detected by mass spectrometry, with n <= 8, q + y <= 18 and x = 0, 1, 2 depending on experimental conditions. IR and NMR spectra of products confirm these assignments.

  10. [Psychoanalysis and Side Effect].

    PubMed

    Shirahase, Joichiro

    2015-01-01

    A study of psychoanalysis from the perspective of side effects reveals that its history was a succession of measures to deal with its own side effects. This, however, does not merely suggest that, as a treatment method, psychoanalysis is incomplete and weak: rather, its history is a record of the growth and development of psychoanalysis that discovered therapeutic significance from phenomena that were initially regarded as side effects, made use of these discoveries, and elaborated them as a treatment method. The approach of research seen during the course of these developments is linked to the basic therapeutic approach of psychoanalysis. A therapist therefore does not draw conclusions about a patient's words and behaviors from a single aspect, but continues to make efforts to actively discover a variety of meanings and values from them, and to make the patient's life richer and more productive. This therapeutic approach is undoubtedly one of the unique aspects of psychoanalysis. I discuss the issue of psychoanalysis and side effects with the aim of clarifying this unique characteristic of psychoanalysis. The phenomenon called resistance inevitably emerges during the process of psychoanalytic treatment. Resistance can not only obstruct the progress of therapy; it also carries the risk of causing a variety of disadvantages to the patient. It can therefore be seen as an adverse effect. However, if we re-examine this phenomenon from the perspective of transference, we find that resistance is in fact a crucial tool in psychoanalysis, and included in its main effect, rather than a side effect. From the perspective of minimizing the character of resistance as a side effect and maximizing its character as a main effect, I have reviewed logical organization, dynamic evaluation, the structuring of treatment, the therapist's attitudes, and the training of therapists. I conclude by stating that psychoanalysis has aspects that do not match the perspective known as a side

  11. Side pocket mandrel

    SciTech Connect

    Crawford, D.W.; Crawford, M.S.; Crawford, W.B.

    1987-12-29

    A side pocket mandrel is described comprising: a tubular body section having a hollow interior that defines a main bore to one side thereof and another bore to the other side thereof; and a short-length seating section welded to one end of the body section. The seating section has a main bore formed to one side thereof aligned with the main bore in the body section, and a valve seating bore formed on the other side thereof generally aligned with the other bore. The seating bore has a polish section adjacent its outer end. The outer end opening through an exterior end surface of the mandrel. The seating bore has a recessed section adjacent the polish section. That provides an inwardly facing stop shoulder at one end thereof and a latch shoulder at the other end thereof facing the stop shoulder; and a tubular member welded to the seating section in axial alignment with the main bores. The axis of the polish section of the seating bore is inclined toward the axes of the main bores at a small angle.

  12. Structure-activity studies on organoselenium alkylating agents.

    PubMed

    Kang, S I; Spears, C P

    1990-01-01

    A variety of organoselenium alkylating agents were synthesized, using 2-hydroxyethyl and 3-hydroxypropyl selenocyanate intermediates, and studied to determine their chemical reactivities with 4-(4-nitrobenzyl)pyridine (NBP) and cytotoxicities against CCRF-CEM, L1210/0, and L1210/L-PAM cells. The comparison between the 2-chloroethyl sulfides and selenides 1-4 revealed the markedly enhanced nucleophilicity of selenium (Se) over sulfur (S) by two or more orders of magnitude. This finding indicates that a major consideration in the design of antitumor alkylating organoselenides is the reactivity of selenium. A Taft plot of the experimental first-order rate constant, knbp, and sigma* in a series of 2-chloroethylseleno compounds gave a slope of -1.73 (rho*), with the exception of 2-chloroethyl 2-nitrophenyl selenide (10). The anomalous behavior of 10 is explained in terms of the ortho-nitro stabilization effect directly interacting with the selenium atom of ethyleneselenonium ion to form a 5-membered cyclic intermediate. In the same series, a 5000-fold difference in alkylating reactivity offered only a sixfold variation in cytotoxicity against CCRF-CEM cells. Increasing the alkylating chain length from ethlene to propylene units markedly reduced alkylating reactivities. In the CH3Se(CH2)n Cl series, 16 (n = 3) was 1.5 X 10(5) times slower than 2 (n = 2) in NBP alkylation, revealing that 3-chloro-n-propyl selenides are not chemically reactive enough to be biological alkylating agents despite the presence of the highly nucleophilic selenium atom. Replacement of chloride with mesylate in 3-substituted propyl selenides, such as 17 and 20, restored desirable reactivities and cytotoxicities. PMID:2313578

  13. The binding of analogs of porphyrins and chlorins with elongated side chains to albumin.

    PubMed

    Ben Dror, Shimshon; Bronshtein, Irena; Weitman, Hana; Smith, Kevin M; O'Neal, William G; Jacobi, Peter A; Ehrenberg, Benjamin

    2009-09-01

    In previous studies, we demonstrated that elongation of side chains of several sensitizers endowed them with higher affinity for artificial and natural membranes and caused their deeper localization in membranes. In the present study, we employed eight hematoporphyrin and protoporphyrin analogs and four groups containing three chlorin analogs each, all synthesized with variable numbers of methylenes in their alkyl carboxylic chains. We show that these tetrapyrroles' affinity for bovine serum albumin (BSA) and their localization in the binding site are also modulated by chain lengths. The binding constants of the hematoporphyrins and protoporphyrins to BSA increased as the number of methylenes was increased. The binding of the chlorins depended on the substitution at the meso position opposite to the chains. The quenching of the sensitizers' florescence by external iodide ions decreased as the side chains became longer, indicating to deeper insertion of the molecules into the BSA binding pocket. To corroborate this conclusion, we studied the efficiency of photodamage caused to tryptophan in BSA upon illumination of the bound sensitizers. The efficiency was found to depend on the side-chain lengths of the photosensitizer. We conclude that the protein site that hosts these sensitizers accommodates different analogs at positions that differ slightly from each other. These differences are manifested in the ease of access of iodide from the external aqueous phase, and in the proximity of the photosensitizers to the tryptophan. In the course of this study, we developed the kinetic equations that have to be employed when the sensitizer itself is being destroyed. PMID:19330323

  14. 3. VIEW NORTH, SOUTHWEST FRONT, SOUTHEAST SIDE Front and side ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. VIEW NORTH, SOUTHWEST FRONT, SOUTHEAST SIDE Front and side elevation. Note gasoline sign post added. Flush store window not altered, 1900 clapboard siding and panelling remaining. - 510 Central Avenue (Commercial Building), Ridgely, Caroline County, MD

  15. Surface active molecules: preparation and properties of long chain n-acyl-l-alpha-amino-omega-guanidine alkyl acid derivatives.

    PubMed

    Infante, R; Dominguez, J G; Erra, P; Julia, R; Prats, M

    1984-12-01

    Synopsis A new route for the synthesis of long chain N(alpha)-acyl-l-alpha-amino-omega-guamdine alkyl acid derivatives, with cationic or amphoteric character has been established. The general formula of these compounds is shown below. A physico-chemical and antimicrobial study of these products as a function of the alkyl ester or sodium salt (R), the straight chain length of the fatty acid residue (x) and the number of carbons between the omega-guanidine and omega-carboxyl group (n) has been investigated. The water solubility, surface tension, critical micelle concentration (c.m.c.) and minimum inhibitory concentration (MIC) against Gram-positive and Gram-negative bacteria (including Pseudomonas) has been determined. Dicyclohexylcarbodiimide has been used to condense fatty acids and alpha-amino-omega-guanidine alkyl acids. In these conditions protection of the omega-guanidine group is not necessary. The main characteristic of this synthetic procedure is the use of very mild experimental conditions (temperature, pH) to form the amide linkage which leads to pure optical compounds in high yield in the absence of electrolytes. The results show that some structural modifications, particularly the protection of the carboxyl group, promote variations of the surfactant and antimicrobial properties. Only those molecules with the blocked carboxyl group (cationic molecules, where R = Me, Et or Pr) showed a good surfactant and antimicrobial activity. When the carboxyl group was unprotected (amphoteric molecules, where R = Na(+)) the resulting compounds were inactive. PMID:19467126

  16. Nonprescription ibuprofen: side effect profile.

    PubMed

    Furey, S A; Waksman, J A; Dash, B H

    1992-01-01

    Single doses of nonprescription analgesics are commonly used to treat self-diagnosed conditions. To evaluate the safety of single doses of nonprescription-strength ibuprofen, we examined reported side effects from 15 double-blind, randomized, controlled trials we conducted of the drug to treat various common painful conditions (e.g., headache, sore throat). All studies included placebo and another nonprescription analgesic, acetaminophen. A total of 878 subjects received ibuprofen 200 or 400 mg, 849 acetaminophen 650 or 1000 mg, and 852 placebo. The overall frequency of side effects was comparable: ibuprofen 2.4%, acetaminophen 3.2%, and placebo 2.1%. The frequency of central nervous system symptoms was 0.8%, 2.1%, and 0.9%, respectively. Upper gastro-intestinal upset ranged from 0.8-0.9% of subjects in all groups. We conclude that single doses of nonprescription ibuprofen are well tolerated and demonstrate a side effect profile indistinguishable from that of acetaminophen and placebo. PMID:1437701

  17. Iron-copper cooperative catalysis in the reactions of alkyl Grignard reagents: exchange reaction with alkenes and carbometalation of alkynes.

    PubMed

    Shirakawa, Eiji; Ikeda, Daiji; Masui, Seiji; Yoshida, Masatoshi; Hayashi, Tamio

    2012-01-11

    Iron-copper cooperative catalysis is shown to be effective for an alkene-Grignard exchange reaction and alkylmagnesiation of alkynes. The Grignard exchange between terminal alkenes (RCH═CH(2)) and cyclopentylmagnesium bromide was catalyzed by FeCl(3) (2.5 mol %) and CuBr (5 mol %) in combination with PBu(3) (10 mol %) to give RCH(2)CH(2)MgBr in high yields. 1-Alkyl Grignard reagents add to alkynes in the presence of a catalyst system consisting of Fe(acac)(3), CuBr, PBu(3), and N,N,N',N'-tetramethylethylenediamine to give β-alkylvinyl Grignard reagents. The exchange reaction and carbometalation take place on iron, whereas copper assists with the exchange of organic groups between organoiron and organomagnesium species through transmetalation with these species. Sequential reactions consisting of the alkene-Grignard exchange and the alkylmagnesiation of alkynes were successfully conducted by adding an alkyne to a mixture of the first reaction. Isomerization of Grignard reagents from 2-alkyl to 1-alkyl catalyzed by Fe-Cu also is applicable as the first 1-alkyl Grignard formation step. PMID:22128888

  18. Alkyl polycyclic aromatic hydrocarbons emissions in diesel/biodiesel exhaust

    NASA Astrophysics Data System (ADS)

    Casal, Carina S.; Arbilla, Graciela; Corrêa, Sergio M.

    2014-10-01

    Polycyclic aromatic hydrocarbons (PAHs) are widely studied in environmental matrices, such as air, water, soil and sediment, because of their toxicity, mutagenicity and carcinogenicity. Because of these properties, the environmental agencies of developed countries have listed sixteen PAHs as priority pollutants. Few countries have limits for these compounds for ambient air, but they only limit emissions from stationary and mobile sources and occupational areas. There are several studies to specifically address the 16 priority PAHs and very little for the alkyl PAHs. These compounds are more abundant, more persistent and frequently more toxic than the non-alkylated PAHs, and the toxicity increases with the number of alkyl substitutions on the aromatic ring. In this study, a method was developed for the analysis of PAHs and alkyl PAHs by using a GC-MS and large injection volume injection coupled with program temperature vaporisation, which allows for limits of detection below 1.0 ng μL-1. Several variables were tested, such as the injection volume, injection velocity, injector initial temperature, duration of the solvent split and others. This method was evaluated in samples from particulate matter from the emissions of engines employing standard diesel, commercial diesel and biodiesel B20. Samples were collected on a dynamometer bench for a diesel engine cycle and the results ranged from 0.5 to 96.9 ng mL-1, indicating that diesel/biodiesel makes a significant contribution to the formation of PAHs and alkyl PAHs.

  19. Formulation of solid lipid nanoparticles (SLN): the value of different alkyl polyglucoside surfactants.

    PubMed

    Keck, Cornelia M; Kovačević, Andjelka; Müller, Rainer H; Savić, Snežana; Vuleta, Gordana; Milić, Jela

    2014-10-20

    Alkyl polyglycosides (APGs) represent a group of nonionic tensides with excellent skin compatibility. Thus they seem to be excellent stabilizers for lipid nanoparticles for dermal application. To investigate this, different APGs were selected to evaluate their influence on the formation and characteristics of solid lipid nanoparticles (SLN). Contact angle analysis of the aqueous solutions/dispersions of the APGs on cetyl palmitate films revealed good wettability for all APG surfactants. Cetyl palmitate based SLN were prepared by hot high pressure homogenization and subjected to particle size, charge and inner structure analysis. 1% of each APG was sufficient to obtain SLN with a mean size between 150 nm and 175 nm and a narrow size distribution. The zeta potential in water was ∼ -50 mV; the values in the original medium were distinctly lower, but still sufficient high to provide good physical stability. Physical stability at different temperatures (5°C, 25°C and 40°C) was confirmed by a constant particle size over an observation period of 90 days in all dispersions. In comparison to SLN stabilized with classical surfactants, e.g., Polysorbate, APG stabilized SLN possess a smaller size, improved physical stability and contain less surfactant. Therefore, the use of APGs for the stabilization of lipid nanoparticles is superior in comparison to classical stabilizers. Further, the results indicate that the length of the alkyl chain of the APG influences the diminution efficacy, the final particle size and the crystallinity of the particles. APGs with short alkyl chain led to a faster reduction in size during high pressure homogenization, to a smaller particle size of the SLN and to a lower recrystallization index, i.e., to a lower crystallinity of the SLN. The crystallinity of the SLN increased with an increase in the alkyl chain length of APGs. Therefore, by using the tested APGs differing in the alkyl chain length, not only small sized and physically stable but

  20. When alcohol is the answer: Trapping, identifying and quantifying simple alkylating species in aqueous environments.

    PubMed

    Penketh, Philip G; Shyam, Krishnamurthy; Baumann, Raymond P; Zhu, Rui; Ishiguro, Kimiko; Sartorelli, Alan C; Ratner, Elena S

    2016-09-01

    Alkylating agents are a significant class of environmental carcinogens as well as commonly used anticancer therapeutics. Traditional alkylating activity assays have utilized the colorimetric reagent 4-(4-nitrobenzyl)pyridine (4NBP). However, 4NBP based assays have a relatively low sensitivity towards harder, more oxophilic alkylating species and are not well suited for the identification of the trapped alkyl moiety due to adduct instability. Herein we describe a method using water as the trapping agent which permits the trapping of simple alkylating electrophiles with a comparatively wide range of softness/hardness and permits the identification of donated simple alkyl moieties. PMID:27188264

  1. Alkyl substituent effect on density, viscosity and chemical behavior of 1-alkyl-3-methylimidazolium chloride.

    PubMed

    Olmo, Lourdes del; Lage-Estebanez, Isabel; López, Rafael; García de la Vega, José M

    2014-09-01

    Molecular structure of the conformers of 1-C n -3-methylimidazolium chloride (n = 1 to 4) ionic liquids has been explored and the relationships with density and viscosity have been studied using COSMO related methodologies. Effects of the number of conformers, ionic character, anion-cation relative positions and the alkyl chain length of the cation on predictions of properties have been analyzed. The quality of the predictions has been tested by comparing with experimental results. Moreover, COSMO polarization charge densities, σ-profiles and σ-potentials of the conformers have been analyzed. Predictions on the chemical behavior based on the values of these properties in the conformers have been used to elucidate the affinity for electrophilic and nucleophilic reagents of ionic liquids. PMID:25149437

  2. Drugs derived from cannabinoids. 4. Effect of alkyl substitution in sulfur and carbocyclic analogs.

    PubMed

    Razdan, R K; Handrick, G R; Dalzell, H C; Howes, J F; Winn, M; Plotnikoff, N P; Dodge, P W; Dren, A T

    1976-04-01

    Various CNS-active cannabinoids in which the alicyclic ring was thiopheno, cyclopenteno, or cyclohexeno with the alkyl substituent in various positions (structural types 1-6) were synthesized by procedures described previously. These compounds were compared in selected pharmacological tests in mice, rats, dogs, and cats. The results suggested that methyl substitution in the close proximity of the phenolic hydroxyl group strongly influenced the activity of some cannabinoids, particularly of those which had a planar five-membered alicyclic ring rather than a six-membered ring. PMID:944269

  3. Selective and Serial Suzuki-Miyaura Reactions of Polychlorinated Aromatics with Alkyl Pinacol Boronic Esters.

    PubMed

    Laulhé, Sébastien; Blackburn, J Miles; Roizen, Jennifer L

    2016-09-01

    Among cross-coupling reactions, the Suzuki-Miyaura transformation stands out because of its practical advantages, including the commercial availability and low toxicity of the required reagents, mild reaction conditions, and functional group compatibility. Nevertheless, few conditions can be used to cross-couple alkyl boronic acids or esters with aryl halides, especially 2-pyridyl halides. Herein, we describe two novel Suzuki-Miyaura protocols that enable selective conversion of polychlorinated aromatics, with a focus on reactions to convert 2,6-dichloropyridines to 2-chloro-6-alkylpyridines or 2-aryl-6-alkylpyridines. PMID:27537216

  4. Enantioselective synthesis of dialkylated N-heterocycles by palladium-catalyzed allylic alkylation.

    PubMed

    Numajiri, Yoshitaka; Jiménez-Osés, Gonzalo; Wang, Bo; Houk, K N; Stoltz, Brian M

    2015-03-01

    The enantioselective synthesis of α-disubstituted N-heterocyclic carbonyl compounds has been accomplished using palladium-catalyzed allylic alkylation. These catalytic conditions enable access to various heterocycles, such as morpholinone, thiomorpholinone, oxazolidin-4-one, 1,2-oxazepan-3-one, 1,3-oxazinan-4-one, and structurally related lactams, all bearing fully substituted α-positions. Broad functional group tolerance was explored at the α-position in the morpholinone series. We demonstrate the utility of this method by performing various transformations on our useful products to readily access a number of enantioenriched compounds. PMID:25714704

  5. Molecular structures of thimerosal (Merthiolate) and other arylthiolate mercury alkyl compounds.

    PubMed

    Melnick, Jonathan G; Yurkerwich, Kevin; Buccella, Daniela; Sattler, Wesley; Parkin, Gerard

    2008-07-21

    The molecular structure of sodium ethylmercury thiosalicylate (also known as thimerosal and Merthiolate) and related arylthiolate mercury alkyl compounds, namely PhSHgMe and PhSHgEt, have been determined by single crystal X-ray diffraction. (1)H NMR spectroscopic studies indicate that the appearance of the (199)Hg mercury satellites of the ethyl group of thimerosal is highly dependent on the magnetic field and the viscosity of the solvent as a consequence of relaxation due to chemical shift anisotropy. PMID:18533648

  6. Access to Cyclic Amino Boronates via Rhodium-Catalyzed Functionalization of Alkyl MIDA Boronates.

    PubMed

    St Denis, Jeffrey D; Lee, C Frank; Yudin, Andrei K

    2015-12-01

    Herein, we describe the rhodium-catalyzed C-H amination reaction of 1,2-boryl sulfamate esters derived from amphoteric α-boryl aldehydes. Depending on the substitution pattern of the boryl sulfamate ester, a diverse range of five- or six-membered ring heterocycles are accessible using this transformation. The highly chemoselective nature of the C-H functionalization reaction preserves the alkyl boronate functional group, which enables the synthesis of B-C-N and B-C-C-N motifs that are present in a number of hydrolase inhibitors. PMID:26588176

  7. Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N-Heterocyclic Carbene-Copper Complex.

    PubMed

    Gholap, Sandeep Suryabhan; Takimoto, Masanori; Hou, Zhaomin

    2016-06-13

    The alkylative carboxylation of allenamide catalyzed by an N-heterocyclic carbene (NHC)-copper(I) complex [(IPr)CuCl] with CO2 and dialkylzinc reagents was investigated. The reaction of allenamides with dialkylzinc reagents (1.5 equiv) and CO2 (1 atm.) proceeded smoothly in the presence of a catalytic quantity of [(IPr)CuCl] to afford (Z)-α,β-dehydro-β-amino acid esters in good yields. The reaction is regioselective, with the alkyl group introduced onto the less hindered γ-carbon, and the carboxyl group introduced onto the β-carbon atom of the allenamides. The first step of the reaction was alkylative zincation of the allenamides to give an alkenylzinc intermediate followed by nucleophilic addition to CO2 . A variety of cyclic and acyclic allenamides were found to be applicable to this transformation. Dialkylzinc reagents bearing β-hydrogen atoms, such as Et2 Zn or Bu2 Zn, also gave the corresponding alkylative carboxylation products without β-hydride elimination. The present methodology provides an easy route to alkyl-substituted α,β-dehydro-β-amino acid ester derivatives under mild reaction conditions with high regio- and stereoselectivtiy. PMID:27167688

  8. Safety Assessment of Alkyl PEG Sulfosuccinates as Used in Cosmetics.

    PubMed

    Johnson, Wilbur; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-09-01

    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) reviewed the safety of alkyl polyethylene glycol (PEG) sulfosuccinates, which function in cosmetics mostly as surfactants/cleansing agents. Although these ingredients may cause ocular and skin irritation, dermal penetration is unlikely because of the substantial polarity and molecular size of these ingredients. The Panel considered the negative oral carcinogenicity and reproductive and developmental toxicity data on chemically related laureths (PEG lauryl ethers) and negative repeated dose toxicity and skin sensitization data on disodium laureth sulfosuccinate supported the safety of these alkyl PEG sulfosuccinates in cosmetic products, but. The CIR Expert Panel concluded that the alkyl PEG sulfosuccinates are safe in the present practices of use and concentration when formulated to be nonirritating. PMID:26362121

  9. Alkylation of imidazole under ultrasound irradiation over alkaline carbons

    NASA Astrophysics Data System (ADS)

    Costarrosa, L.; Calvino-Casilda, V.; Ferrera-Escudero, S.; Durán-Valle, C. J.; Martín-Aranda, R. M.

    2006-06-01

    N-Alkyl-imidazole has been synthesized by sonochemical irradiation of imidazole and 1-bromobutane using alkaline-promoted carbons (exchanged with the binary combinations of Na, K and Cs). The catalysts were characterized by X-ray photoelectron spectroscopy, thermal analysis and N 2 adsorption isotherms. Under the experimental conditions, N-alkyl-imidazoles can be prepared with a high activity and selectivity. It is observed that imidazole conversion increases in parallel with increasing the basicity of the catalyst. The influence of the alkaline promoter, the reaction temperature, and the amount of catalyst on the catalytic activity has been studied. For comparison, the alkylation of imidazole has also been performed in a batch reactor system under thermal activation.

  10. Mass-analyzed threshold ionization spectroscopy of p-methylphenol and p-ethylphenol cations and the alkyl substitution effect

    NASA Astrophysics Data System (ADS)

    Lin, Jung Lee; Li, Changyong; Tzeng, Wen Bih

    2004-06-01

    The mass-analyzed threshold ionization (MATI) spectra of p-methylphenol and p-ethylphenol have been recorded by ionizing via various vibronic levels. The adiabatic ionization energies (IEs) of p-methylphenol and p-ethylphenol are determined to be 65918±5 and 65628±5 cm-1, which are less than that of phenol by 2707 and 2997 cm-1, respectively. This redshift indicates that the interaction between the alkyl group and the ring of alkylphenols in the cationic D0 state is greater than that in the neutral S0 state. Moreover, a longer alkyl group gives rise to a greater redshift in the IE. Analysis of the MATI spectra shows that most of the active modes are related to the in-plane ring vibrations of these two cations. However, the length of the alkyl group has an insignificant effect on the frequency of the observed ring vibrations. No band with frequency less than 350 cm-1 is observed for the p-methylphenol cation. In contrast, many low-frequency bands resulting from the characteristic motions (e.g., the C-C2H5 torsion and C-C2H5 and C-OH bending vibrations) appear in the MATI spectra of p-ethylphenol. The present results show that the ethyl group enhances the substituent-sensitive and many large-amplitude vibrations of the cation.

  11. Impact of the Crystalline Packing Structures on Charge Transport and Recombination via Alkyl Chain Tunability of DPP-Based Small Molecules in Bulk Heterojunction Solar Cells.

    PubMed

    Song, Chang Eun; Kim, Yu Jin; Suranagi, Sanjaykumar R; Kini, Gururaj P; Park, Sangheon; Lee, Sang Kyu; Shin, Won Suk; Moon, Sang-Jin; Kang, In-Nam; Park, Chan Eon; Lee, Jong-Cheol

    2016-05-25

    A series of small compound materials based on benzodithiophene (BDT) and diketopyrrolopyrrole (DPP) with three different alkyl side chains were synthesized and used for organic photovoltaics. These small compounds had different alkyl branches (i.e., 2-ethylhexyl (EH), 2-butyloctyl (BO), and 2-hexyldecyl (HD)) attached to DPP units. Thin films made of these compounds were characterized and their solar cell parameters were measured in order to systematically analyze influences of the different side chains of compounds on the film microstructure, molecular packing, and hence, charge-transport and recombination properties. The relatively shorter side chains in the small molecules enabled more ordered packing structures with higher crystallinities, which resulted in higher carrier mobilities and less recombination factors; the small molecule with the EH branches exhibited the best semiconducting properties with a power conversion efficiency of up to 5.54% in solar cell devices. Our study suggested that tuning the alkyl chain length of semiconducting molecules is a powerful strategy for achieving high performance of organic photovoltaics. PMID:27156705

  12. 4. VIEW EAST, SOUTHWEST FRONT, NORTHWEST SIDE Side elevation. Note ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    4. VIEW EAST, SOUTHWEST FRONT, NORTHWEST SIDE Side elevation. Note the ground floor windows which were added. Siding is vinyl, but the burned area exposes asbestos siding added when the rear and upper areas were converted to living spaces. - 510 Central Avenue (Commercial Building), Ridgely, Caroline County, MD

  13. Impact of Alkyl Spacer Length on Aggregation Pathways in Kinetically Controlled Supramolecular Polymerization.

    PubMed

    Ogi, Soichiro; Stepanenko, Vladimir; Thein, Johannes; Würthner, Frank

    2016-01-20

    We have investigated the kinetic and thermodynamic supramolecular polymerizations of a series of amide-functionalized perylene bisimide (PBI) organogelator molecules bearing alkyl spacers of varied lengths (ethylene to pentylene chains, PBI-1-C2 to PBI-1-C5) between the amide and PBI imide groups. These amide-functionalized PBIs form one-dimensional fibrous nanostructures as the thermodynamically favored states in solvents of low polarity. Our in-depth studies revealed, however, that the kinetic behavior of their supramolecular polymerization is dependent on the spacer length. Propylene- and pentylene-tethered PBIs follow a similar polymerization process as previously observed for the ethylene-tethered PBI. Thus, the monomers of these PBIs are kinetically trapped in conformationally restricted states through intramolecular hydrogen bonding between the amide and imide groups. In contrast, the intramolecularly hydrogen-bonded monomers of butylene-tethered PBI spontaneously self-assemble into nanoparticles, which constitute an off-pathway aggregate state with regard to the thermodynamically stable fibrous supramolecular polymers obtained. Thus, for this class of π-conjugated system, an unprecedented off-pathway aggregate with high kinetic stability could be realized for the first time by introducing an alkyl linker of optimum length (C4 chain) between the amide and imide groups. Our current system with an energy landscape of two competing nucleated aggregation pathways is applicable to the kinetic control over the supramolecular polymerization by the seeding approach. PMID:26699283

  14. Effect of alkyl functionalization on charging of colloidal silica in apolar media.

    PubMed

    Poovarodom, Saran; Poovarodom, Sathin; Berg, John C

    2010-11-15

    The present work examines the effect of alkyl-silane treatment on the charging of colloids in apolar solvent using two otherwise identical 250 nm diameter, spherical silica particles, one with untreated surface and the other treated with hexadecyltrimethoxysilane (C16), dispersed in an apolar isoparaffin solvent (Isopar-L) containing one of three oil-soluble surfactants: Aerosol-OT, OLOA 11,000, and zirconyl 2-ethyl hexanoate. The electrophoretic mobility of each dispersion was determined using phase angle light scattering (PALS). It was found that at sufficiently high surfactant concentration, i.e., where micelles begin to form in the bulk, the particle surfaces could be electrically charged. All three surfactants studied imparted a negative surface charge to the untreated silica particles. In all cases, the C16-treated particles were also found to be negatively charged but had a much higher magnitude of mobility than the untreated silica. Although the increase in magnitude of mobility as a result of the alkyl functionalization was surprising, it could be attributed to the increase in the number of surface hydroxyl groups arising from the hydrolysis of unbound methoxy groups of the silane molecules. The added hydroxyl groups provided additional potential acid-base interaction sites, resulting in higher particle mobility. It was also found that further increases in surfactant concentration lowered the particle mobility, attributed to the increasing concentration of electrically charged micelles, which may partially neutralize the surface charge or compress the electrical double layer. PMID:20728088

  15. Synthesis and chemistry of cationic d sup 0 metal alkyl complexes

    SciTech Connect

    Jordan, R.F.

    1991-01-01

    The objective of this project is to develop new types of electrophilic metal alkyl complexes for catalytic C-H activation and olefin polymerization chemistry, and associated fundamental mechanistic studies. We have focused our efforts on four classes of early metal alkyl complexes: (1) cationic group 4 Cp{sub 2}M(R){sup +} complexes (1) which are active species in Cp{sub 2}MX{sub 2}-based Ziegler-Natta olefin polymerization catalyst systems and which catalyze productive C-H activation reactions of heterocycles, (2) neutral (dicarbollide)(Cp*)M(R) complexes (2) which are structurally are electronically very similar to 1, (3) half-sandwich complexes CpM(R){sub 2}(L){sub n}{sup +} which are highly coordinatively and electronically unsaturated, and (4) new group 5 (dicarbollide)(Cp)MR{sub 2} and (dicarbollide){sub 2} MR complexes which are more unsaturated than group 5 Cp{sub 2}M systems due to incorporation of the dicarbollide ligand.

  16. Enantioselective Synthesis of α-Quaternary Mannich Adducts by Palladium-Catalyzed Allylic Alkylation: Total Synthesis of (+)-Sibirinine

    PubMed Central

    2016-01-01

    A catalytic enantioselective method for the synthesis of α-quaternary Mannich-type products is reported. The two-step sequence of (1) Mannich reaction followed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effect access asymmetric Mannich-type products of “thermodynamic” enolates of substrates possessing additional enolizable positions and acidic protons. Palladium-catalyzed decarboxylative allylic alkylation enables the enantioselective synthesis of five-, six-, and seven-membered ketone, lactam, and other heterocyclic systems. The mild reaction conditions are notable given the acidic free N–H groups and high functional group tolerance in each of the substrates. The utility of this method is highlighted in the first total synthesis of (+)-sibirinine. PMID:25578104

  17. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    SciTech Connect

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  18. Direct β-Alkylation of Aldehydes via Photoredox Organocatalysis

    PubMed Central

    2015-01-01

    Direct β-alkylation of saturated aldehydes has been accomplished by synergistically combining photoredox catalysis and organocatalysis. Photon-induced enamine oxidation provides an activated β-enaminyl radical intermediate, which readily combines with a wide range of Michael acceptors to produce β-alkyl aldehydes in a highly efficient manner. Furthermore, this redox-neutral, atom-economical C–H functionalization protocol can be achieved both inter- and intramolecularly. Mechanistic studies by various spectroscopic methods suggest that a reductive quenching pathway is operable. PMID:24754456

  19. Alkyl phospholipid antihypertensive agents in method of lowering blood pressure

    DOEpatents

    Snyder, Fred L.; Blank, Merle L.; Muirhead, Ernest E.; Leach, deceased, Byron E.; Byers, Lawrence W.

    1988-01-01

    The composition of this invention is 1-O-alkyl-2-acetoyl-sn-glycero-3-phosphocholine, having the ionic structural formula; ##STR1## wherein R is saturated alkyl having 9-21 carbon atoms, or salts or hydrates of the composition. Preferably R has 13-19 carbon atoms and most preferably R has 15 carbon atoms. The composition of this invention is useful for reducing hypertension in warm-blooded animals, including humans, when administered either orally or by injection or innoculation, e.g., intravenous injection. The composition can be prepared from naturally occurring lipids or synthetically from commercially available material.

  20. Study of Class I and Class III Polyhydroxyalkanoate (PHA) Synthases with Substrates Containing a Modified Side Chain.

    PubMed

    Jia, Kaimin; Cao, Ruikai; Hua, Duy H; Li, Ping

    2016-04-11

    Polyhydroxyalkanoates (PHAs) are carbon and energy storage polymers produced by a variety of microbial organisms under nutrient-limited conditions. They have been considered as an environmentally friendly alternative to oil-based plastics due to their renewability, versatility, and biodegradability. PHA synthase (PhaC) plays a central role in PHA biosynthesis, in which its activity and substrate specificity are major factors in determining the productivity and properties of the produced polymers. However, the effects of modifying the substrate side chain are not well understood because of the difficulty to accessing the desired analogues. In this report, a series of 3-(R)-hydroxyacyl coenzyme A (HACoA) analogues were synthesized and tested with class I synthases from Chromobacterium sp. USM2 (PhaCCs and A479S-PhaCCs) and Caulobacter crescentus (PhaCCc) as well as class III synthase from Allochromatium vinosum (PhaECAv). It was found that, while different PHA synthases displayed distinct preference with regard to the length of the alkyl side chains, they could withstand moderate side chain modifications such as terminal unsaturated bonds and the azide group. Specifically, the specific activity of PhaCCs toward propynyl analogue (HHxyCoA) was only 5-fold less than that toward the classical substrate HBCoA. The catalytic efficiency (kcat/Km) of PhaECAv toward azide analogue (HABCoA) was determined to be 2.86 × 10(5) M(-1) s(-1), which was 6.2% of the value of HBCoA (4.62 × 10(6) M(-1) s(-1)) measured in the presence of bovine serum albumin (BSA). These side chain modifications may be employed to introduce new material functions to PHAs as well as to study PHA biogenesis via click-chemistry, in which the latter remains unknown and is important for metabolic engineering to produce PHAs economically. PMID:26974339