Direct Aldehyde C-H Arylation and Alkylation via the Combination of Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis.

PubMed

Zhang, Xiaheng; MacMillan, David W C

2017-08-23

A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety of commercially available aldehydes, along with aryl or alkyl bromides, into the corresponding ketones in excellent yield. This C-H abstraction coupling technology has been successfully applied to the expedient synthesis of the medicinal agent haloperidol.

Metal-Free-Visible Light C-H Alkylation of Heteroaromatics via Hypervalent Iodine-Promoted Decarboxylation.

PubMed

Genovino, Julien; Lian, Yajing; Zhang, Yuan; Hope, Taylor O; Juneau, Antoine; Gagné, Yohann; Ingle, Gajendra; Frenette, Mathieu

2018-05-16

A metal-free photoredox C-H alkylation of heteroaromatics from readily available carboxylic acids using an organic photocatalyst and hypervalent iodine reagents under blue LED light is reported. The developed methodology tolerates a broad range of functional groups and can be applied to the late-stage functionalization of drugs and drug-like molecules. The reaction mechanism was investigated with control experiments and photophysical experiments as well as DFT calculations.

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

NASA Astrophysics Data System (ADS)

Athokpam, Bijyalaxmi; Ramesh, Sai G.

2018-04-01

We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the Hβ and Hα reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the Hα abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

Direct observation of unimolecular decay of CH 3 CH 2 CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantlymore » to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 10(7) s(-1), which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s(-1) at 298 K.« less

Base-Controlled Completely Selective Linear or Branched Rhodium(I)-Catalyzed C-H ortho-Alkylation of Azines without Preactivation.

PubMed

Tran, Gaël; Hesp, Kevin D; Mascitti, Vincent; Ellman, Jonathan A

2017-05-15

A [Rh I ]/bisphosphine/base catalytic system for the ortho-selective C-H alkylation of azines by acrylates and acrylamides is reported. This catalytic system features an unprecedented complete linear or branched selectivity that is solely dependent on the catalytic base that is used. Complete branched selectivity is even achieved for ethyl methacrylate, which enables the introduction of a quaternary carbon center. Excellent functional group compatibility is demonstrated for both linear and branched alkylations. The operational simplicity and broad scope of this transformation allow for rapid access to functionalized azines of direct pharmaceutical and agrochemical relevance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of OH stretching mode of CH3OH chemisorbed on Ni3+ and Ni4+ by infrared photodissociation spectroscopy.

PubMed

Hirabayashi, Shinichi; Okawa, Ryuji; Ichihashi, Masahiko; Kondow, Tamotsu; Kawazoe, Yoshiyuki

2007-08-09

Structures of nickel cluster ions adsorbed with methanol, Ni3+ (CH3OH)m (m = 1-3) and Ni4+ (CH3OH)m (m = 1-4) were investigated by using infrared photodissociation (IR-PD) spectroscopy based on a tandem-type mass spectrometer, where they were produced by passing Ni3,4+ through methanol vapor under a multiple collision condition. The IR-PD spectra were measured in the wavenumber region between 3100 and 3900 cm-1. In each IR-PD spectrum, a single peak was observed at a wavenumber lower by approximately 40 cm-1 than that of the OH stretching vibration of a free methanol molecule and was assigned to the OH stretching vibrations of the methanol molecules in Ni3,4+ (CH3OH)m. The photodissociation was analyzed by assuming that Ni3,4+ (CH3OH)m dissociate unimolecularly after the photon energy absorbed by them is statistically distributed among the accessible modes of Ni3,4+ (CH3OH)m. In comparison with the calculations performed by the density functional theory, it is concluded that (1) the oxygen atom of each methanol molecule is bound to one of the nickel atoms in Ni3,4+ (defined as molecular chemisorption), (2) the methanol molecules in Ni3,4+ (CH3OH)m do not form any hydrogen bonds, and (3) the cross section for demethanation [CH4 detachment from Nin+ (CH3OH)] is related to the electron density distribution inside the methanol molecule.

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons in the 3 μm region: role of hydrogenation and alkylation

NASA Astrophysics Data System (ADS)

Maltseva, Elena; Mackie, Cameron J.; Candian, Alessandra; Petrignani, Annemieke; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2018-03-01

Aim. We aim to elucidate the spectral changes in the 3 μm region that result from chemical changes in the molecular periphery of polycyclic aromatic hydrocarbons (PAHs) with extra hydrogens (H-PAHs) and methyl groups (Me-PAHs). Methods: Advanced laser spectroscopic techniques combined with mass spectrometry were applied on supersonically cooled 1,2,3,4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 1,2,3,6,7,8-hexahydropyrene, 9-methylanthracene, and 9,10-dimethylanthracene, allowing us to record mass-selective and conformationally selective absorption spectra of the aromatic, aliphatic, and alkyl CH-stretches in the 3.175 - 3.636 µm region with laser-limited resolution. We compared the experimental absorption spectra with standard harmonic calculations and with second-order vibrational perturbation theory anharmonic calculations that use the SPECTRO program for treating resonances. Results: We show that anharmonicity plays an important if not dominant role, affecting not only aromatic, but also aliphatic and alkyl CH-stretch vibrations. The experimental high-resolution data lead to the conclusion that the variation in Me- and H-PAHs composition might well account for the observed variations in the 3 μm emission spectra of carbon-rich and star-forming regions. Our laboratory studies also suggest that heavily hydrogenated PAHs form a significant fraction of the carriers of IR emission in regions in which an anomalously strong 3 μm plateau is observed.

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.

Alcohols as alkylating agents in heteroarene C-H functionalization.

PubMed

Jin, Jian; MacMillan, David W C

2015-09-03

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.

Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH{sub 3}CH{sub 2}CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice–Ramsperger–Kassel–Marcus calculations of the microcanonical unimolecular decay rate for CH{sub 3}CH{sub 2}CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronicmore » structure calculations, contributes significantly to the decay rate. Infrared transitions of CH{sub 3}CH{sub 2}CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH{sub 3}CH{sub 2}CHOO of ca. 10{sup 7} s{sup −1}, which are slower than those obtained for syn-CH{sub 3}CHOO or (CH{sub 3}){sub 2}COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH{sub 3}CH{sub 2}CHOO under atmospheric conditions, giving a rate of 279 s{sup −1} at 298 K.« less

HeI photoelectron spectroscopic studies on the electronic structure of alkyl nitrosamines

NASA Astrophysics Data System (ADS)

Jiang, Peng; Qian, Ximei; Li, Chunhui; Qiao, Chunhua; Wang, Dianxun

1997-10-01

HeI photoelectron spectroscopic (PES) studies on the electronic structure of alkyl nitrosamines R 2N 2O (R = CH 3-, CH 3CH 2-, and CH 3CH 2CH 2-) are reported. The assignment of the PES bands for this series of compounds has been made with the aid of the band shapes, the band intensity and ab initio SCF MO calculations based on the 631 ∗ G basis sets. Both PES experiment and the ab initio SCF MO calculations show that the detoxification ability of nitrosamine with longer alkyl chain is stronger.

Mechanistic Insight into Ketone α-Alkylation with Unactivated Olefins via C-H Activation Promoted by Metal-Organic Cooperative Catalysis (MOCC): Enriching the MOCC Chemistry.

PubMed

Dang, Yanfeng; Qu, Shuanglin; Tao, Yuan; Deng, Xi; Wang, Zhi-Xiang

2015-05-20

Metal-organic cooperative catalysis (MOCC) has been successfully applied for hydroacylation of olefins with aldehydes via directed C(sp(2))-H functionalization. Most recently, it was reported that an elaborated MOCC system, containing Rh(I) catalyst and 7-azaindoline (L1) cocatalyst, could even catalyze ketone α-alkylation with unactivated olefins via C(sp(3))-H activation. Herein we present a density functional theory study to understand the mechanism of the challenging ketone α-alkylation. The transformation uses IMesRh(I)Cl(L1)(CH2═CH2) as an active catalyst and proceeds via sequential seven steps, including ketone condensation with L1, giving enamine 1b; 1b coordination to Rh(I) active catalyst, generating Rh(I)-1b intermediate; C(sp(2))-H oxidative addition, leading to a Rh(III)-H hydride; olefin migratory insertion into Rh(III)-H bond; reductive elimination, generating Rh(I)-1c(alkylated 1b) intermediate; decoordination of 1c, liberating 1c and regenerating Rh(I) active catalyst; and hydrolysis of 1c, furnishing the final α-alkylation product 1d and regenerating L1. Among the seven steps, reductive elimination is the rate-determining step. The C-H bond preactivation via agostic interaction is crucial for the bond activation. The mechanism rationalizes the experimental puzzles: why only L1 among several candidates performed perfectly, whereas others failed, and why Wilkinson's catalyst commonly used in MOCC systems performed poorly. Based on the established mechanism and stimulated by other relevant experimental reactions, we attempted to enrich MOCC chemistry computationally, exemplifying how to develop new organic catalysts and proposing L7 to be an alternative for L1 and demonstrating the great potential of expanding the hitherto exclusive use of Rh(I)/Rh(III) manifold to Co(0)/Co(II) redox cycling in developing MOCC systems.

Torsion-rotation structure and quasi-symmetric-rotor behaviour for the CH3SH asymmetric CH3-bending and C-H stretching bands of E parentage

NASA Astrophysics Data System (ADS)

Lees, R. M.; Xu, Li-Hong; Guislain, B. G.; Reid, E. M.; Twagirayezu, S.; Perry, D. S.; Dawadi, M. B.; Thapaliya, B. P.; Billinghurst, B. E.

2018-01-01

High-resolution Fourier transform spectra of the asymmetric methyl-bending and methyl-stretching bands of CH3SH have been recorded employing synchrotron radiation at the FIR beamline of the Canadian Light Source. Analysis of the torsion-rotation structure and relative intensities has revealed the novel feature that for both bend and stretch the in-plane and out-of-plane modes behave much like a Coriolis-coupled l-doublet pair originating from degenerate E modes of a symmetric top. As the axial angular momentum K increases, the energies of the coupled "l = ±1" modes diverge linearly, with effective Coriolis ζ constants typical for symmetric tops. For the methyl-stretching states, separated at K = 0 by only about 1 cm-1, the assigned sub-bands follow a symmetric top Δ(K - l) = 0 selection rule, with only ΔK = -1 transitions observed to the upper l = -1 in-plane A‧ component and only ΔK = +1 transitions to the lower l = +1 out-of-plane A″ component. The K = 0 separation of the CH3-bending states is larger at 9.1 cm-1 with the l-ordering reversed. Here, both ΔK = +1 and ΔK = -1 transitions are seen for each l-component but with a large difference in relative intensity. Term values for the excited state levels have been fitted to J(J + 1) power-series expansions to obtain substate origins. These have then been fitted to a Fourier model to characterize the torsion-K-rotation energy patterns. For both pairs of vibrational states, the torsional energies display the customary oscillatory behaviour as a function of K and have inverted torsional splittings relative to the ground state. The spectra show numerous perturbations, indicating local resonances with the underlying bath of high torsional levels and vibrational combination and overtone states. The overall structure of the two pairs of bands represents a new regime in which the vibrational energy separations, torsional splittings and shifts due to molecular asymmetry are all of the same order, creating a

Communication: Direct comparison between theory and experiment for correlated angular and product-state distributions of the ground-state and stretching-excited O(3P) + CH4 reactions

NASA Astrophysics Data System (ADS)

Czakó, Gábor

2014-06-01

Motivated by a recent experiment [H. Pan and K. Liu, J. Chem. Phys. 140, 191101 (2014)], we report a quasiclassical trajectory study of the O(3P) + CH4(vk = 0, 1) → OH + CH3 [k = 1 and 3] reactions on an ab initio potential energy surface. The computed angular distributions and cross sections correlated to the OH(v = 0, 1) + CH3(v = 0) coincident product states can be directly compared to experiment for O + CH4(v3 = 0, 1). Both theory and experiment show that the ground-state reaction is backward scattered, whereas the angular distributions shift toward sideways and forward directions upon antisymmetric stretching (v3) excitation of the reactant. Theory predicts similar behavior for the O + CH4(v1 = 1) reaction. The simulations show that stretching excitation enhances the reaction up to about 15 kcal/mol collision energy, whereas the O + CH4(vk = 1) reactions produce smaller cross sections for OH(v = 1) + CH3(v = 0) than those of O + CH4(v = 0) → OH(v = 0) + CH3(v = 0). The former finding agrees with experiment and the latter awaits for confirmation. The computed cold OH rotational distributions of O + CH4(v = 0) are in good agreement with experiment.

Communication: direct comparison between theory and experiment for correlated angular and product-state distributions of the ground-state and stretching-excited O((3)P) + CH4 reactions.

PubMed

Czakó, Gábor

2014-06-21

Motivated by a recent experiment [H. Pan and K. Liu, J. Chem. Phys. 140, 191101 (2014)], we report a quasiclassical trajectory study of the O((3)P) + CH4(vk = 0, 1) → OH + CH3 [k = 1 and 3] reactions on an ab initio potential energy surface. The computed angular distributions and cross sections correlated to the OH(v = 0, 1) + CH3(v = 0) coincident product states can be directly compared to experiment for O + CH4(v3 = 0, 1). Both theory and experiment show that the ground-state reaction is backward scattered, whereas the angular distributions shift toward sideways and forward directions upon antisymmetric stretching (v3) excitation of the reactant. Theory predicts similar behavior for the O + CH4(v1 = 1) reaction. The simulations show that stretching excitation enhances the reaction up to about 15 kcal/mol collision energy, whereas the O + CH4(vk = 1) reactions produce smaller cross sections for OH(v = 1) + CH3(v = 0) than those of O + CH4(v = 0) → OH(v = 0) + CH3(v = 0). The former finding agrees with experiment and the latter awaits for confirmation. The computed cold OH rotational distributions of O + CH4(v = 0) are in good agreement with experiment.

The photodissociation dynamics of alkyl radicals

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

Giegerich, Jens; Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de

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 distributionmore » 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.« less

Infrared spectroscopy of dense clouds in the C-H stretch region - Methanol and 'diamonds'

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Sandford, S. A.; Tielens, A. G. G. M.; Herbst, T. M.

1992-01-01

The paper presents high spectral resolution studies in the 3100-2600/cm range of the protostars NGC 7538 IRS9, W33A, W3 IRS 5, and S140 IRS 1. Well-resolved absorption bands at about 2825/cm and 2880/cm were found superposed on the LF wing of the strong O-H stretch feature. The 2880/cm band, previously detected toward W33A, is also in the spectrum of NGC 7538 IRS 9. The relative strength of these two bands varies, showing that they are associated with two different carriers. The new band at about 2880/cm falls near the position of C-H stretching vibrations in tertiary carbon atoms. The strength of this feature, in combination with the lack of strong features associated with primary and secondary carbon atoms, suggests that the carrier of the new feature has a diamondlike structure. This new feature is tentatively attributed to interstellar 'diamonds'. The detection of this band in the spectra of all four dense molecular clouds suggests that the carrier is ubiquitous in dense clouds.

Fourier transform synchrotron spectroscopy of torsional and CO-stretching bands of CH 3 17 OH

NASA Astrophysics Data System (ADS)

Moruzzi, G.; Murphy, R. J.; Vos, J.; Lees, R. M.; Predoi-Cross, A.; Billinghurst, B. E.

2011-07-01

The Fourier transform spectrum of the CH 317OH isotopologue of methanol has been recorded in the 65-1200 cm -1 spectral region at a resolution of 0.00096 cm -1 using synchrotron source radiation at the Canadian Light Source. Here we present an extension to higher torsional states of our investigation of the torsion-rotation transitions within the small-amplitude vibrational ground state, now including assignments of more than 16 500 lines involving quantum numbers in the ranges v t ⩽ 3, J ⩽ 30 and | K| ⩽ 12, as well as a study of the strong CO-stretching band centered at 1020 cm -1. Energy term values have been determined for assigned ground and CO-stretching levels by use of the Ritz program, and have been fitted to series expansions in powers of J( J + 1) to determine substate origins and effective B values. Several Fermi anharmonic and Coriolis level-crossing resonances coupling the CO stretch with high torsional ground-state levels have been identified and characterized. The study is motivated by astrophysical applications, with a principal aim being the compilation of an extensive set of energy term values to permit prediction of astronomically observable sub-millimetre transitions to within an uncertainty of a few MHz.

High-resolution Fourier transform synchrotron spectroscopy of the C-S stretching band of methyl mercaptan, CH332SH

NASA Astrophysics Data System (ADS)

Lees, R. M.; Xu, Li-Hong; Billinghurst, B. E.

2016-01-01

The C-S stretching fundamental band of 12CH332SH, the principal isotopologue of methyl mercaptan, has been investigated by Fourier transform infrared spectroscopy on the Far-Infrared beamline at the Canadian Light Source synchrotron. The band is centered around 710 cm-1 and shows well-resolved a-type parallel structure. Most of the A and E spectral sub-bands have been assigned up to K = 12 for the vt = 0 torsional state and K = 9 for the vt = 1 state, along with a smaller variety of sub-bands for vt = 2. C-S stretching energy term values have been determined employing known ground-state energies, and have been fitted to series expansions in powers of J(J + 1) to determine the substate origins. The origins have in turn been fitted to a Fourier model to characterize the oscillatory torsional energy structure of the C-S stretching state. The amplitude of oscillation of the vt = 0 torsional curves is significantly larger for the C-S stretch state compared to the ground state. A strategy devised to relate this amplitude to an effective torsional barrier height indicates a decrease of about 7% in the effective V3 for the C-S stretch. The vibrational frequency determined for the stretching fundamental from the Fourier fit is 710.3 cm-1. The C-S stretching manifold is crossed by excited vt = 4 torsional levels of the ground state, and strong torsion-vibrational resonant coupling is observed via perturbations in the spectrum together with forbidden sub-bands induced by mixing and intensity borrowing.

Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups: Intensity Scaling for the C-H Stretching Modes and Astrophysical Implications

NASA Astrophysics Data System (ADS)

Yang, X. J.; Li, Aigen; Glaser, R.; Zhong, J. X.

2017-03-01

The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μ {{m}} ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs may have an aliphatic component, as revealed by the detection in many UIE sources of the aliphatic C-H stretching feature at 3.4 μ {{m}}. The ratio of the observed intensity of the 3.4 μ {{m}} feature to that of the 3.3 μ {{m}} aromatic C-H feature allows one to estimate the aliphatic fraction of the UIE carriers. This requires knowledge of the intrinsic oscillator strengths of the 3.3 μ {{m}} aromatic C-H stretch ({A}3.3) and the 3.4 μ {{m}} aliphatic C-H stretch ({A}3.4). Lacking experimental data on {A}3.3 and {A}3.4 for the UIE candidate materials, one often has to rely on quantum-chemical computations. Although the second-order Møller-Plesset (MP2) perturbation theory with a large basis set is more accurate than the B3LYP density functional theory, MP2 is computationally very demanding and impractical for large molecules. Based on methylated PAHs, we show here that, by scaling the band strengths computed at an inexpensive level (e.g., B3LYP/6-31G*), we are able to obtain band strengths as accurate as those computed at far more expensive levels (e.g., MP2/6-311+G(3df,3pd)). We calculate the model spectra of methylated PAHs and their cations excited by starlight of different spectral shapes and intensities. We find that {({I}3.4/{I}3.3)}{mod}, the ratio of the model intensity of the 3.4 μ {{m}} feature to that of the 3.3 μ {{m}} feature, is insensitive to the spectral shape and intensity of the exciting starlight. We derive a straightforward relation for determining the aliphatic fraction of the UIE carriers (I.e., the ratio of the number of C atoms in aliphatic units {N}{{C},{ali}} to that in aromatic rings {N}{{C},{aro}}) from the observed band ratios {({I}3.4/{I}3.3)}{obs}: {N

One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

PubMed

Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

2015-05-19

The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

Identifying the first folded alkylbenzene via ultraviolet, infrared, and Raman spectroscopy of pentylbenzene through decylbenzene

DOE PAGES

Hewett, Daniel M.; Bocklitz, Sebastian; Tabor, Daniel P.; ...

2017-05-23

The conformational preferences of pentyl- through decylbenzene are studied under jet-cooled conditions in the gas phase. Laser-induced fluorescence excitation spectra, fluorescence-dip infrared spectra in the alkyl CH stretch region, and Raman spectra are combined to provide assignments for the observed conformers. Density functional theory calculations at the B3LYP-D3BJ/def2TZVP level of theory provide relative energies and normal mode vibrations that serve as inputs for an anharmonic local mode theory introduced in earlier work on alkylbenzenes with n = 2–4. This model explicitly includes anharmonic mixing of the CH stretch modes with the overtones of scissors/bend modes of the CH 2 andmore » CH 3 groups in the alkyl chain, and is used to assign and interpret the single-conformation IR spectra. In octylbenzene, a pair of LIF transitions shifted -92 and -78 cm -1 from the all-trans electronic origin have unique alkyl CH stretch transitions that are fit by the local model to a g1g3g4 conformation in which the alkyl chain folds back over the aromatic ring π cloud. Its calculated energy is only 1.0 kJ mol -1 above the all-trans global minimum. This fold is at an alkyl chain length less than half that of the pure alkanes (n = 18), consistent with a smaller energy cost for the g1 dihedral and the increased dispersive interaction of the chain with the π cloud. Local site frequencies for the entire set of conformers from the local mode model show ‘edge effects’ that raise the site frequencies of CH 2(1) and CH 2(2) due to the phenyl ring and CH 2(n - 1) due to the methyl group. The g1g3g4 conformer also shows local sites shifted up in frequency at CH 2(3) and CH 2(6) due to interaction with the π cloud.« less

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

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

Herrmann, W.A.; Felixberger, J.K.; Anwander, R.

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 tetrahedralmore » 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.« less

Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

PubMed

Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

2010-05-17

Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

High resolution spectroscopy of jet cooled phenyl radical: The ν1 and ν2 a1 symmetry C-H stretching modes

NASA Astrophysics Data System (ADS)

Chang, Chih-Hsuan; Nesbitt, David J.

2016-07-01

A series of CH stretch modes in phenyl radical (C6H5) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (˜60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a1 symmetry, ν1 and ν2, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν1 and ν2 band origins are determined to be 3073.968 50(8) cm-1 and 3062.264 80(7) cm-1, respectively, which both agree within 5 cm-1 with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm-1 blue shift between gas phase and Ar matrix values for ν1 and ν2. This differs substantially from the much smaller red shift (Δν ≈ - 1 cm-1) reported for the ν19 mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (Trot ≈ 11 K) conditions.

Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices.

PubMed

Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

2012-03-28

Irradiation at 239 ± 20 nm of a p-H(2) matrix containing methoxysulfinyl chloride, CH(3)OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν(1), CH(2) antisymmetric stretching), 2999.5 (ν(2), CH(3) antisymmetric stretching), 2950.4 (ν(3), CH(3) symmetric stretching), 1465.2 (ν(4), CH(2) scissoring), 1452.0 (ν(5), CH(3) deformation), 1417.8 (ν(6), CH(3) umbrella), 1165.2 (ν(7), CH(3) wagging), 1152.1 (ν(8), S=O stretching mixed with CH(3) rocking), 1147.8 (ν(9), S=O stretching mixed with CH(3) wagging), 989.7 (ν(10), C-O stretching), and 714.5 cm(-1) (ν(11), S-O stretching) modes of syn-CH(3)OSO. When CD(3)OS(O)Cl in a p-H(2) matrix was used, lines at 2275.9 (ν(1)), 2251.9 (ν(2)), 2083.3 (ν(3)), 1070.3 (ν(4)), 1056.0 (ν(5)), 1085.5 (ν(6)), 1159.7 (ν(7)), 920.1 (ν(8)), 889.0 (ν(9)), 976.9 (ν(10)), and 688.9 (ν(11)) cm(-1) appeared and are assigned to syn-CD(3)OSO; the mode numbers correspond to those used for syn-CH(3)OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86∕aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH(3)OSO near 2991, 2956, 1152, and 994 cm(-1) to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD(3)OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H(2) such that the Cl atom, produced via UV photodissociation of CH(3)OS(O)Cl in situ, might escape from the original cage to yield isolated CH(3)OSO radicals.

Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization.

PubMed

Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof

2008-09-24

High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For

Photodissociation dynamics of the simplest alkyl peroxy radicals, CH 3OO and C 2H 5OO, at 248 nm

DOE PAGES

Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.

2018-01-28

The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH 3OO) and ethyl peroxy C 2H 5OO , are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH3OO- or C2H5OO- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH3OO exhibits repulsive O loss resulting in the formation of O(1D) + CH3O with high translational energy release. Minor two-body channels leadingmore » to OH + CH2O and CH3O + O(3P) formation are also detected. In addition, small amounts of H + O(3P) + CH2O are observed and attributed to O loss followed by CH3O dissociation. C2H5OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(1D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O2 + C2H5 and HO2 + C2H4 are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C2H5OO dissociation yields a three-body product channel, CH3 + O(3P) + CH2O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C2H5O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociatio n and ground state two-body dissociation but no O(1D) production.« less

Photodissociation dynamics of the simplest alkyl peroxy radicals, CH 3OO and C 2H 5OO, at 248 nm

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

Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.

The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH 3OO) and ethyl peroxy C 2H 5OO , are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH3OO- or C2H5OO- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH3OO exhibits repulsive O loss resulting in the formation of O(1D) + CH3O with high translational energy release. Minor two-body channels leadingmore » to OH + CH2O and CH3O + O(3P) formation are also detected. In addition, small amounts of H + O(3P) + CH2O are observed and attributed to O loss followed by CH3O dissociation. C2H5OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(1D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O2 + C2H5 and HO2 + C2H4 are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C2H5OO dissociation yields a three-body product channel, CH3 + O(3P) + CH2O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C2H5O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociatio n and ground state two-body dissociation but no O(1D) production.« less

Coupled-cluster sum-frequency generation nonlinear susceptibilities of methyl (CH3) and methylene (CH2) groups.

PubMed

Tetsassi Feugmo, Conrard Giresse; Liégeois, Vincent; Champagne, Benoît

2017-11-15

The first vibrational sum frequency generation (SFG) spectra based on molecular properties calculated at the coupled cluster singles and doubles (CCSD) level of approximation have been simulated for interfacial model alkyl chains, providing benchmark data for comparisons with approximate methods, including density functional theory (DFT). The approach proceeds in three steps. In the first two steps, the molecular spectral properties are determined: the vibrational normal modes and frequencies and then the derivatives of the dipole moment and of the polarizability with respect to the normal coordinates. These derivatives are evaluated with a numerical differentiation approach, of which the accuracy was monitored using Romberg's procedure. Then, in the last step, a three-layer model is employed to evaluate the macroscopic second-order nonlinear optical responses and thereby the simulated SFG spectra of the alkyl interface. Results emphasize the following facts: (i) the dipole and polarizability derivatives calculated at the DFT level with the B3LYP exchange-correlation functional can differ, with respect to CCSD, by as much as ±10 to 20% and ±20 to 50% for the CH 3 and CH 2 vibrations, respectively; (ii) these differences are enhanced when considering the SFG intensities as well as their variations as a function of the experimental configuration (ppp versus ssp) and as a function of the tilt and rotation angles, defining the orientation of the alkyl chain at the interface; (iii) these differences originate from both the vibrational normal coordinates and the Cartesian derivatives of the dipole moment and polarizability; (iv) freezing the successive fragments of the alkyl chain strongly modifies the SFG spectrum and enables highlighting the delocalization effects between the terminal CH 3 group and its neighboring CH 2 units; and finally (v) going from the free chain to the free methyl model, and further to C 3v constraints on leads to large variations of two ratios

Raman bandshape analysis on CH and CSC stretching modes of dimethyl sulfoxide in liquid binary mixture: comparative study with quantum-chemical calculations.

PubMed

Upadhyay, Ganesh; Gomti Devi, Th

2014-12-10

The interacting nature of dimethyl sulfoxide (DMSO) in binary mixtures has been carried out on CH and CSC stretching modes of vibration using chloroform (CLF), chloroform-d (CLFd), acetonitrile (ACN) and acetonitrile-d3 (ACNd) solvents. Peak frequencies of both the stretching modes show blue shift with the increase in solvent concentration. Variation of Raman bandwidth with the solvent concentration was discussed using different mechanisms. Ab initio calculation for geometry optimization and vibrational wavenumber calculation have been performed on monomer and dimer structures of DMSO to explain the experimentally observed Raman spectra. Theoretically calculated values are found in good agreement with the experimental results. Vibrational and reorientational relaxation times have been studied corresponding to solvent concentrations to elucidate the interacting mechanisms of binary mixtures. Copyright © 2014 Elsevier B.V. All rights reserved.

Sub-Doppler infrared spectroscopy of CH2OH radical in a slit supersonic jet: Vibration-rotation-tunneling dynamics in the symmetric CH stretch manifold

PubMed Central

Schuder, Michael D.; Wang, Fang; Chang, Chih-Hsuan; Nesbitt, David J.

2017-01-01

The sub-Doppler CH-symmetric stretch (ν3) infrared absorption spectrum of a hydroxymethyl (CH2OH) radical is observed and analyzed with the radical formed in a slit-jet supersonic discharge expansion (Trot = 18 K) via Cl atom mediated H atom abstraction from methanol. The high sensitivity of the spectrometer and reduced spectral congestion associated with the cooled expansion enable first infrared spectroscopic observation of hydroxymethyl transitions from both ± symmetry tunneling states resulting from large amplitude COH torsional motion. Nuclear spin statistics due to exchange of the two methyl H-atoms aid in unambiguous rovibrational assignment of two A-type Ka = 0 ← 0 and Ka = 1 ← 1 bands out of each ± tunneling state, with additional spectral information obtained from spin-rotation splittings in P, Q, and R branch Ka = 1 ← 1 transitions that become resolved at low N. A high level ab initio potential surface (CCSD(T)-f12b/cc-pvnzf12 (n = 2,3)/CBS) is calculated in the large amplitude COH torsional and CH2 wag coordinates, which in the adiabatic approximation and with zero point correction predicts ground state tunneling splittings in good qualitative agreement with experiment. Of particular astrochemical interest, a combined fit of the present infrared ground state combination differences with recently reported millimeter-wave frequencies permits the determination of improved accuracy rotational constants for the ground vibrational state, which will facilitate ongoing millimeter/microwave searches for a hydroxymethyl radical in the interstellar medium. PMID:28527463

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.

Infrared absorption of CH3OSO detected with time-resolved Fourier-transform spectroscopy.

PubMed

Chen, Jin-Dah; Lee, Yuan-Pern

2011-03-07

A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to detect temporally resolved infrared absorption spectra of CH(3)OSO produced upon irradiation of a flowing gaseous mixture of CH(3)OS(O)Cl in N(2) or CO(2) at 248 nm. Two intense transient features with origins near 1152 and 994 cm(-1) are assigned to syn-CH(3)OSO; the former is attributed to overlapping bands at 1154 ± 3 and 1151 ± 3 cm(-1), assigned to the S=O stretching mixed with CH(3) rocking (ν(8)) and the S=O stretching mixed with CH(3) wagging (ν(9)) modes, respectively, and the latter to the C-O stretching (ν(10)) mode at 994 ± 6 cm(-1). Two weak bands at 2991 ± 6 and 2956 ± 3 cm(-1) are assigned as the CH(3) antisymmetric stretching (ν(2)) and symmetric stretching (ν(3)) modes, respectively. Observed vibrational transition wavenumbers agree satisfactorily with those predicted with quantum-chemical calculations at level B3P86∕aug-cc-pVTZ. Based on rotational parameters predicted at that level, the simulated rotational contours of these bands agree satisfactorily with experimental results. The simulation indicates that the S=O stretching mode of anti-CH(3)OSO near 1164 cm(-1) likely makes a small contribution to the observed band near 1152 cm(-1). A simple kinetic model of self-reaction is employed to account for the decay of CH(3)OSO and yields a second-order rate coefficient k=(4 ± 2)×10(-10) cm(3)molecule(-1)s(-1). © 2011 American Institute of Physics.

Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes

NASA Astrophysics Data System (ADS)

Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

2016-06-01

We have demonstrated large enhancements of CH bond acidities in alcohol, ether, and amine cations through infrared predissociation spectroscopy based on the vacuum ultraviolet photoionization detection. In this study, we investigate for the cationic alkanes (pentane, hexane, and heptane) with different alkyl chain lengths. The σ electrons are ejected in the ionization of alkanes, while nonbonding electrons are ejected in ionization of alcohols, ethers, and amines. Nevertheless, the acidity enhancements of CH in these cationic alkanes have also been demonstrated by infrared spectroscopy. The correlations of their CH bond acidities with the alkyl chain lengths as well as the mechanisms of their acidity enhancements will be discussed by comparison of infrared spectra and theoretical calculations.

Theoretical verification and extension of the McKean relationship between bond lengths and stretching frequencies

NASA Astrophysics Data System (ADS)

Larsson, J. A.; Cremer, D.

1999-08-01

Vibrational spectra contain explicit information on the electronic structure and the bonding situation of a molecule, which can be obtained by transforming the vibrational normal modes of a molecule into appropriate internal coordinate modes, which are localized in a fragment of the molecule and which are associated to that internal coordinate that describes the molecular fragment in question. It is shown that the adiabatic internal modes derived recently (Int. J. Quant. Chem., 67 (1998) 1) are the theoretical counterparts of McKean's isolated CH stretching modes (Chem. Soc. Rev., 7 (1978) 399). Adiabatic CH stretching frequencies obtained from experimental vibrational spectra can be used to determine CH bond lengths with high accuracy. Contrary to the concept of isolated stretching frequencies a generalization to any bond of a molecule is possible as is demonstrated for the CC stretching frequencies. While normal mode frequencies do not provide a basis to determine CC bond lengths and CC bond strengths, this is possible with the help of the adiabatic CC stretching frequencies. Measured vibrational spectra are used to describe different types of CC bonds in a quantitative way. For CH bonds, it is also shown that adiabatic stretching frequency leads to the definition of an ideal dissociation energy, which contrary to the experimentally determined dissociation energy is a direct measure of the bond strength. The difference between measured and ideal dissociation energies gives information on stabilization or destabilization of the radicals formed in a dissociation process.

On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

PubMed

Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

2007-01-08

Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

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

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

DOE PAGES

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.; ...

2017-09-27

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in μ-η(2) :η(1) :η(1) hapticities and their high catalytic activity for isoprene 1,4-cis-polymerization.

PubMed

Zhang, Guangchao; Wei, Yun; Guo, Liping; Zhu, Xiancui; Wang, Shaowu; Zhou, Shuangliu; Mu, Xiaolong

2015-02-02

Two series of new dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in novel μ-η(2) :η(1) :η(1) hapticities are synthesized and characterized. Treatment of [RE(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of 3-(tBuN=CH)C8 H5 NH (L1 ) in THF gives the dinuclear rare-earth metal alkyl complexes trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH(CH2 SiMe3 )}Ind)RE(thf)(CH2 SiMe3 )]2 (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L1 is deprotonated by the metal alkyl species and the imino C=N group is transferred to the amido group by alkyl CH2 SiMe3 insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ-η(2) :η(1) :η(1) bonding modes, forming the dinuclear rare-earth metal alkyl complexes. When L1 is reduced to 3-(tBuNHCH2 )C8 H5 NH (L2 ), the reaction of [Yb(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of L2 in THF, interestingly, generated the trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (major) and cis-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (minor) complexes. The catalytic activities of these dinuclear rare-earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio- and stereoselectivities for isoprene 1,4-cis-polymerization. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CH stretching overtone spectra of trimethyl amine and dimethyl sulfide

NASA Astrophysics Data System (ADS)

Billinghurst, Brant E.; Gough, Kathleen M.; Low, Geoffrey R.; Kjaergaard, Henrik G.

2004-01-01

Trimethyl amine (TMA) exhibits the largest known difference in CH bond lengths within a methyl group, due to what is known as the lone pair trans effect. Dimethyl sulfide also exhibits this effect, but to a far lesser extent, making it ideal for comparison to TMA. In this paper, the first through fourth overtone spectra of N(CH3)3, N(CD3)3, N(CD2H)(CD3)2, N(CH3)(CD3)2, N(CD3)(CH3)2 and S(CH3)2 are reported and all major bands are assigned. The intensities of the observed bands are compared to intensities predicted by the harmonically coupled anharmonic oscillator local mode model. Good correlation is found between the experimental intensities and those predicted with the local mode model and HF/6-311++G(2d,2p) calculated dipole moment functions. An increase in the ability to resolve peaks as methyl groups are deuterated suggests that the lone pair mediates increased coupling between methyl groups.

Solubilization of cyclohexane in aqueous solutions of sodium. cap alpha. -alkyl alkanoates

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

Sagitani, H.; Suzuki, T.; Nagai, M.

1982-01-01

The effect of branched alkyl chain length and the position of the COONa group on the solubilizing power of n-alkane sodium carboxylates was studied. The lipophilic property and the amount of solubilized cyclohexane increased with the branched chain length of branched soaps, and with the change of the position of the -COONa group from 3 to 7 in the alkyl chain of pentadecane -3, -5, and -7 sodium carboxylates. Alpha-branched soaps having proper branched alkyl chains were better solubilizers for cyclohexane than straight chain compounds. The amount of cyclohexane solublized by C/sub 10/ H/sub 21/ CH(C/sub 6/H/sub 13/) COONa wasmore » about three times greater than the amount solubilized by C/sub 17/ H/sub 35/ COONa. There was a marked increase in the solubilization of cyclohexane replacing ..cap alpha..-branched fatty acid soaps with optimum amount of cosurfactants such as C/sub 8/H/sub 17/ (OCH/sub 2/CH/sub 2/)/sub 2/OH. Namely, solubilization increased markedly at the optimum hydrophile-lipophile balance of mixed surfactant. 21 references.« less

Conformational explosion: Understanding the complexity of short chain para-dialkylbenzene potential energy surfaces

NASA Astrophysics Data System (ADS)

Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.

2018-05-01

The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S1 ← S0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an "egg carton" shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experimental techniques in conjunction with computational methods, subsets of origin transitions in the LIF excitation spectrum can be classified into different conformational families. Two conformations are resolved in para-diethylbenzene, seven in para-dipropylbenzene, and about nineteen in para-dibutylbenzene. These chains are largely independent of each other as there are no new single-chain conformations induced by the presence of a second chain. A cursory LIF excitation scan of para-dioctylbenzene shows a broad congested spectrum at frequencies consistent with interactions of alkyl chains with the phenyl π cloud.

Conformational explosion: Understanding the complexity of short chain para-dialkylbenzene potential energy surfaces.

PubMed

Mishra, Piyush; Hewett, Daniel M; Zwier, Timothy S

2018-05-14

The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S 1 ← S 0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an "egg carton" shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experimental techniques in conjunction with computational methods, subsets of origin transitions in the LIF excitation spectrum can be classified into different conformational families. Two conformations are resolved in para-diethylbenzene, seven in para-dipropylbenzene, and about nineteen in para-dibutylbenzene. These chains are largely independent of each other as there are no new single-chain conformations induced by the presence of a second chain. A cursory LIF excitation scan of para-dioctylbenzene shows a broad congested spectrum at frequencies consistent with interactions of alkyl chains with the phenyl π cloud.

Vibrational overtone spectra of metallocenes: effect of the coordinating metal on the CH bond lengths

NASA Astrophysics Data System (ADS)

Billinghurst, Brant E.; Gough, Kathleen M.

2003-03-01

The first through third overtone spectra of ferrocene, ruthenocene, nickelocene, cobaltocene, dicyclopentadienyl magnesium and sodium cyclopentadienyl are examined with particular attention to the CH stretching of the cyclopentadienyl. Using semi-empirical correlations between CH bond length and CH stretching frequencies in each overtone region, we have determined that the type of metal atom within a metallocene complex has little effect on the CH bond length in the cyclopentadienyl. The only exception is cobaltocene where there is evidence that the Jahn-Teller effect results in several different CH bond lengths. Evidence that bis(cyclopentadienyl) magnesium is not ionic has been observed.

Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

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

Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis

Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH{sub 2} + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH{sub 2}) considered are acetamide (CH{sub 3}CONH{sub 2}), propionamide (CH{sub 3}CH{sub 2}CONH{sub 2}), and butyramide (CH{sub 3}CH{sub 2}CH{sub 2}CONH{sub 2}); the electrolytes (LiX) are lithium perchlorate (LiClO{sub 4}), lithium bromide (LiBr), and lithium nitrate (LiNO{sub 3}). Differential scanning calorimetric measurements reveal glass transition temperatures (T{sub g}) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady statemore » fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T{sub g}s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH{sub 3}CONH{sub 2} + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence

Cooperatively enhanced ionic hydrogen bonds in Cl-(CH3OH)(1-3)Ar clusters.

PubMed

Beck, Jordan P; Lisy, James M

2010-09-23

Infrared predissociation (IRPD) spectra of Cl−(CH3OH)1-3Ar and Cl-(CH3OD)1-3Ar were obtained in the OH and CH stretching regions. The use of methanol-d1 was necessary to distinguish between CH stretches and hydrogen-bonded OH features. The spectra of Cl-(CH3OH)2-3Ar show intense features at frequencies lower than the CH stretches, indicating structures with very strong hydrogen bonds. These strong hydrogen bonds arise from structures in which a Cl-···methanol ionic hydrogen bond is cooperatively enhanced by the presence of a second shell and, in the case of Cl-(CH3OH)3Ar, a third shell methanol. The strongest hydrogen bond is observed in the Cl-(CH3OH)3Ar spectrum at 2733 cm-1, shifted a remarkable -948 cm-1 from the neutral, gas-phase methanol value. Harmonic, ab initio frequency calculations are not adequate in describing these strong hydrogen bonds. Therefore, we describe a simple computational approach to better approximate the hydrogen bond frequencies. Overall, the results of this study indicate that high-energy isomers are very efficiently trapped using our experimental method of introducing Cl- into neutral, cold methanol-argon clusters.

Unimolecular reactivity of organotrifluoroborate anions, RBF3- , and their alkali metal cluster ions, M(RBF3 )2- (M = Na, K; R = CH3 , CH3 CH2 , CH3 (CH2 )3 , CH3 (CH2 )5 , c-C3 H5 , C6 H5 , C6 H5 CH2 , CH2 CHCH2 , CH2 CH, C6 H5 CO).

PubMed

Bathie, Fiona L B; Bowen, Chris J; Hutton, Craig A; O'Hair, Richard A J

2018-07-15

Potassium organotrifluoroborates (RBF 3 K) are important reagents used in organic synthesis. Although mass spectrometry is commonly used to confirm their molecular formulae, the gas-phase fragmentation reactions of organotrifluoroborates and their alkali metal cluster ions have not been previously reported. Negative-ion mode electrospray ionization (ESI) together with collision-induced dissociation (CID) using a triple quadrupole mass spectrometer were used to examine the fragmentation pathways for RBF 3 - (where R = CH 3 , CH 3 CH 2 , CH 3 (CH 2 ) 3 , CH 3 (CH 2 ) 5 , c-C 3 H 5 , C 6 H 5 , C 6 H 5 CH 2 , CH 2 CHCH 2 , CH 2 CH, C 6 H 5 CO) and M(RBF 3 ) 2 - (M = Na, K), while density functional theory (DFT) calculations at the M06/def2-TZVP level were used to examine the structures and energies associated with fragmentation reactions for R = Me and Ph. Upon CID, preferentially elimination of HF occurs for RBF 3 - ions for systems where R = an alkyl anion, whereas R - formation is favoured when R = a stabilized anion. At higher collision energies loss of F - and additional HF losses are sometimes observed. Upon CID of M(RBF 3 ) 2 - , formation of RBF 3 - is the preferred pathway with some fluoride transfer observed only when M = Na. The DFT-calculated relative thermochemistry for competing fragmentation pathways is consistent with the experiments. The main fragmentation pathways of RBF 3 - are HF elimination and/or R - loss. This contrasts with the fragmentation reactions of other organometallate anions, where reductive elimination, beta hydride transfer and bond homolysis are often observed. The presence of fluoride transfer upon CID of Na(RBF 3 ) 2 - but not K(RBF 3 ) 2 - is in agreement with the known fluoride affinities of Na + and K + and can be rationalized by Pearson's HSAB theory. Copyright © 2018 John Wiley & Sons, Ltd.

Hydrophile-lipophile balance of alkyl ethoxylated surfactants as a function of intermolecular energies.

PubMed

Urbina-Villalba, G; Rogel, E; Márquez, M L; Reif, I

1994-06-01

The semiempirical MNDO method has been used in order to examine the variation of the molecular properties of hydrocarbons CnH2n + 2 (with 1 < or = n < or = 19) and ethylene oxide chains CH3(CH2CH2O)mCH3 (with 1 < or = m < or = 19) as a function of their molecular length. Least-square fits of those properties have been calculated, along with two mathematical relations between the hydrophile-lipophile balance of alkyl-phenol ethoxylated surfactants and (1) the ratio of molecular lengths between their lipophilic and hydrophilic branches; (2) the intermolecular energies between the molecules of surfactant, water and hexane.

The First Laboratory Detection of Vibration-rotation Transitions of 12CH+ and 13CH+ and Improved Measurement of Their Rotational Transition Frequencies

NASA Astrophysics Data System (ADS)

Doménech, José L.; Jusko, Pavol; Schlemmer, Stephan; Asvany, Oskar

2018-04-01

C–H stretches of the fundamental ions CH+ and 13CH+, which have long been searched for, have been observed for the first time in the laboratory. The state-dependent attachment of He atoms to these ions at cryogenic temperatures has been exploited to obtain high-resolution rovibrational data. In addition, the lowest rotational transitions of CH+, 13CH+ and CD+ have been revisited and their rest frequency values have improved substantially.

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

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

Hull, Emily A.; West, Aaron C.; Pestovsky, Oleg

2015-01-22

In this paper, transition metal complexes (NH 3) 5CoX2 + (X = CH 3, Cl) and L(H 2O)MX 2+, where M = Rh or Co, X = CH 3, NO, or Cl, and L is a macrocyclic N 4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH 3) 5CoCH 3 2+ and L(H 2O)M IIIX 2+ (X = CH 3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the othermore » hand, when X = halide or NO 2, visible light photolysis leads to dissociation of X – and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO 2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH 3) 5CoCH 3 2+ and L 1(H 2O)CoCH 3 2+.« less

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation.

PubMed

Hull, Emily A; West, Aaron C; Pestovsky, Oleg; Kristian, Kathleen E; Ellern, Arkady; Dunne, James F; Carraher, Jack M; Bakac, Andreja; Windus, Theresa L

2015-02-28

Transition metal complexes (NH3)5CoX(2+) (X = CH3, Cl) and L(H2O)MX(2+), where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH3(2+) and L(H2O)M(III)X(2+) (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X(-) and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M-X bonding orbitals and/or metal d orbitals to M-X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d-d bands in the visible, so that homolytic cleavage of the M-X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH3(2+) and L(1)(H2O)CoCH3(2+).

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

NASA Technical Reports Server (NTRS)

Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

2011-01-01

Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

Tuning the Energy Gap of SiCH3 Nanomaterials Under Elastic Strain

NASA Astrophysics Data System (ADS)

Ma, Shengqian; Li, Feng; Geng, Jiguo; Zhu, Mei; Li, Suyan; Han, Juguang

2018-05-01

SiCH3 nanomaterials have been studied using the density functional theory. When the nanosheets and nanoribbons (armchair and zigzag) are introduced, their energy gap is modulated under elastic strain and width. The results show that the band gap of SiCH3 nanomaterials can be easily tuned using elastic strains and widths. Surprisingly, the band gap can be modulated along two directions, namely, compressing and stretching. The band gap decreases when increasing stretching strain or decreasing compressing strain. In addition, the band gap decreases when increasing the nanoribbon width. For energy gap engineering, the band gap can be tuned by strains and widths. Therefore, the SiCH3 nanomaterials play important roles in potential applications for strain sensors, electronics, and optical electronics.

Single-shot time stretch stimulated Raman spectroscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Saltarelli, Francesco; Kumar, Vikas; Viola, Daniele; Crisafi, Francesco; Preda, Fabrizio; Cerullo, Giulio; Polli, Dario

2017-02-01

Stimulated Raman scattering spectroscopy is a powerful technique for label-free molecular identification, but its broadband implementation is technically challenging. We introduce and experimentally demonstrate a novel approach based on photonic time stretch. The broadband femtosecond Stokes pulse, after interacting with the sample, is stretched by a telecom fiber to 15ns, mapping its spectrum in time. The signal is sampled through a fast analog-to-digital converter, providing single-shot spectra at 80-kHz rate. We demonstrate 10^-5 sensitivity over 500 cm-1 in the C-H region. Our results pave the way to high-speed broadband vibrational imaging for materials science and biophotonics.

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

The rate of charge tunneling is insensitive to polar terminal groups in self-assembled monolayers in Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn junctions.

PubMed

Yoon, Hyo Jae; Bowers, Carleen M; Baghbanzadeh, Mostafa; Whitesides, George M

2014-01-08

This paper describes a physical-organic study of the effect of uncharged, polar, functional groups on the rate of charge transport by tunneling across self-assembled monolayer (SAM)-based large-area junctions of the form Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn. Here Ag(TS) is a template-stripped silver substrate, -M- and -T are "middle" and "terminal" functional groups, and EGaIn is eutectic gallium-indium alloy. Twelve uncharged polar groups (-T = CN, CO2CH3, CF3, OCH3, N(CH3)2, CON(CH3)2, SCH3, SO2CH3, Br, P(O)(OEt)2, NHCOCH3, OSi(OCH3)3), having permanent dipole moments in the range 0.5 < μ < 4.5, were incorporated into the SAM. A comparison of the electrical characteristics of these junctions with those of junctions formed from n-alkanethiolates led to the conclusion that the rates of charge tunneling are insensitive to the replacement of terminal alkyl groups with the terminal polar groups in this set. The current densities measured in this work suggest that the tunneling decay parameter and injection current for SAMs terminated in nonpolar n-alkyl groups, and polar groups selected from common polar organic groups, are statistically indistinguishable.

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

PubMed

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

Vibrational autoionization of state-selective jet-cooled methanethiol (CH 3SH) investigated with infrared + vacuum-ultraviolet photoionization

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

Xie, Min; Shen, Zhitao; Pratt, S. T.

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH 3SH + to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3SH) on exciting CH 3SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν 3, SH stretching mode) and 2948 cm -1 (ν 2, CHmore » 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2) states of CH 3SH +. When IR light at 3014 cm -1 (overlapped ν 1/ν 9, CH 3 antisymmetric stretching and CH 2 antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν 1 and ν 9) of CH 3SH + were observed. When IR light at 2867 cm -1 (2ν 10, overtone of CH 3 deformation mode) and 2892 cm -1 (2ν 4, overtone of CH 2 scissoring mode) was employed, both Δν = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3SH + (ν 4 + = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH 3SH is a p-like lone pair orbital on the S atom. Finally, the quantum yields for autoionization of various vibrational excited states are discussed. Values of ν 1 = 3035, ν 2 = 2884, ν 3 = 2514, and ν 9 = 2936 cm -1 for CH 3SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3SH + at 3026, 2879, 2502, and 2933 cm -1.« less

Vibrational autoionization of state-selective jet-cooled methanethiol (CH 3SH) investigated with infrared + vacuum-ultraviolet photoionization

DOE PAGES

Xie, Min; Shen, Zhitao; Pratt, S. T.; ...

2017-10-24

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH 3SH + to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3SH) on exciting CH 3SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν 3, SH stretching mode) and 2948 cm -1 (ν 2, CHmore » 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2) states of CH 3SH +. When IR light at 3014 cm -1 (overlapped ν 1/ν 9, CH 3 antisymmetric stretching and CH 2 antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν 1 and ν 9) of CH 3SH + were observed. When IR light at 2867 cm -1 (2ν 10, overtone of CH 3 deformation mode) and 2892 cm -1 (2ν 4, overtone of CH 2 scissoring mode) was employed, both Δν = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3SH + (ν 4 + = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH 3SH is a p-like lone pair orbital on the S atom. Finally, the quantum yields for autoionization of various vibrational excited states are discussed. Values of ν 1 = 3035, ν 2 = 2884, ν 3 = 2514, and ν 9 = 2936 cm -1 for CH 3SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3SH + at 3026, 2879, 2502, and 2933 cm -1.« less

High-resolution spectroscopy of the C-N stretching band of methylamine

NASA Astrophysics Data System (ADS)

Lees, Ronald M.; Sun, Zhen-Dong; Billinghurst, B. E.

2011-09-01

The C-N stretching infrared fundamental of CH3NH2 has been investigated by high-resolution laser sideband and Fourier transform synchrotron spectroscopy to explore the energy level structure and to look for possible interactions with high-lying torsional levels of the ground state and other vibrational modes. The spectrum is complicated by two coupled large-amplitude motions in the molecule, the CH3 torsion and the NH2 inversion, which lead to rich spectral structure with a wide range of energy level splittings and relative line intensities. Numerous sub-bands have been assigned for K values ranging up to 12 for the stronger a inversion species for the vt = 0 torsional state, along with many of the weaker sub-bands of the s species. The C-N stretching sub-state origins have been determined by fitting the upper-state term values to J(J + 1) power-series expansions. For comparison with the ground-state behaviour, both ground and C-N stretch origins have been fitted to a phenomenological Fourier series model that produces an interesting pattern with the differing periodicities of the torsional and inversion energies. The amplitude of the torsional energy oscillation increases substantially for the C-N stretch, while the amplitude of the inversion energy oscillation is relatively unchanged. Independent inertial scale factors ρ were fitted for the torsion and the inversion and differ significantly in the upper state. The C-N stretching vibrational energy is determined to be 1044.817 cm-1, while the effective upper state B-value is 0.7318 cm-1. Several anharmonic resonances with vt = 4 ground-state levels have been observed and partially characterized. A variety of J-localized level-crossing resonances have also been seen, five of which display forbidden transitions arising from intensity borrowing that allow determination of the interaction coupling constants.

Interfacial assignment of branched-alkyl benzene sulfonates: A molecular simulation

NASA Astrophysics Data System (ADS)

Liu, Zi-Yu; Wei, Ning; Wang, Ce; Zhou, He; Zhang, Lei; Liao, Qi; Zhang, Lu

2015-11-01

A molecular dynamics simulation was conducted to analyze orientations of sodium branched-alkyl benzene sulfonates molecules at nonane/water interface, which is helpful to design optimal surfactant structures to achieve ultralow interfacial tension (IFT). Through the two dimensional density profiles, monolayer collapses are found when surfactant concentration continues to increase. Thus the precise scope of monolayer is certain and orientation can be analyzed. Based on the simulated results, we verdict the interfacial assignment of branched-alkyl benzene sulfonates at the oil-water interface, and discuss the effect of hydrophobic tail structure on surfactant assignment. Bigger hydrophobic size can slow the change rate of surfactant occupied area as steric hindrance, and surfactant meta hydrophobic tails have a stronger tendency to stretch to the oil phase below the collapsed concentration. Furthermore, an interfacial model with reference to collapse, increasing steric hindrance and charge repulsive force between interfacial surfactant molecules, responsible for effecting of surfactant concentration and structure has been supposed.

Functionalization of carbon dioxide and carbon disulfide using a stable uranium(III) alkyl complex.

PubMed

Matson, Ellen M; Forrest, William P; Fanwick, Phillip E; Bart, Suzanne C

2011-04-06

A rare uranium(III) alkyl complex, Tp*(2)U(CH(2)Ph) (2) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate), was synthesized by salt metathesis from Tp*(2)UI (1) and KCH(2)Ph and fully characterized using (1)H NMR, infrared, and electronic absorption spectroscopies as well as X-ray crystallography. This complex has a uranium-carbon distance of 2.57(2) Å, which is comparable to other uranium alkyls reported. Treating this compound with either carbon dioxide or carbon disulfide results in insertion into the uranium-carbon bond to generate Tp*(2)U(κ(2)-O(2)CCH(2)Ph) (3) and Tp*(2)U(SC(S)CH(2)Ph) (4), respectively. These species, characterized spectroscopically and by X-ray crystallography, feature new carboxylate and dithiocarboxylate ligands. Analysis by electronic absorption spectroscopy supports the trivalent oxidation state of the uranium center in both of these derivatives. Addition of trimethylsilylhalides (Me(3)SiX; X = Cl, I) to 3 results in the release of the free silyl ester, Me(3)SiOC(O)CH(2)Ph, forming the initial uranium monohalide species, Tp*(2)UX, which can then be used over multiple cycles for the functionalization of carbon dioxide. © 2011 American Chemical Society

Density functional theory with van der waals corrections study of the adsorption of alkyl, alkylthiol, alkoxyl, and amino-alkyl chains on the H:Si(111) surface.

PubMed

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

2014-11-11

Surface modification of silicon with organic monolayers tethered to the surface by different linkers is an important process in realizing future miniaturized electronic and sensor devices. Understanding the roles played by the nature of the linking group and the chain length on the adsorption structures and stabilities of these assemblies is vital to advance this technology. This paper presents a density functional theory (DFT) study of the hydrogen passivated Si(111) surface modified with alkyl chains of the general formula H:Si-(CH2)n-CH2 and H:Si-X-(CH2)n-CH3, where X = NH, O, S and n = (0, 1, 3, 5, 7, 9, 11), at half coverage. For (X)-hexane and (X)-dodecane functionalization, we also examined various coverages up to full monolayer grafting in order to validate the result of half covered surface and the linker effect on the coverage. We find that it is necessary to take into account the van der Waals interaction between the alkyl chains. The strongest binding is for the oxygen linker, followed by S, N, and C, irrespective of chain length. The result revealed that the sequence of the stability is independent of coverage; however, linkers other than carbon can shift the optimum coverage considerably and allow further packing density. For all linkers apart from sulfur, structural properties, in particular, surface-linker-chain angles, saturate to a single value once n > 3. For sulfur, we identify three regimes, namely, n = 0-3, n = 5-7, and n = 9-11, each with its own characteristic adsorption structures. Where possible, our computational results are shown to be consistent with the available experimental data and show how the fundamental structural properties of modified Si surfaces can be controlled by the choice of linking group and chain length.

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

PubMed

Hsieh, Wen-Pin; Chien, Yu-Hsiang

2015-02-23

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Secondary Alkyl Chlorides**

PubMed Central

Lu, Zhe; Fu, Gregory C.

2010-01-01

The first method for achieving alkyl–alkyl Suzuki reactions of unactivated secondary alkyl chlorides has been developed. Carbon–carbon bond formation occurs under mild conditions (at room temperature) with the aid of commercially available catalyst components. This method has proved to be versatile: without modification, it can be applied to Suzuki reactions of secondary and primary alkyl bromides and iodides, as well as primary alkyl chlorides. Mechanistic investigations suggest that oxidative addition is not the turnover-limiting step of the catalytic cycle for unactivated secondary alkyl iodides and bromides, whereas it may be (partially) for chlorides. PMID:20715038

Presence of global and local α-relaxations in an alkyl phosphate glass former

NASA Astrophysics Data System (ADS)

Wu, Tao; Jin, Xiao; Saini, Manoj K.; Liu, Ying Dan; Ngai, K. L.; Wang, Li-Min

2017-10-01

The dynamics of a molecular glass former, tributyl phosphate (TBP), with an alkyl phosphate structure (three alkyl branches emanating from a polar core of PO4) is studied in the supercooled regime by dielectric and thermal (or enthalpic) relaxations. The dielectric fragility index md and the stretching exponent βd of the Kohlrausch-Williams-Watts correlation function are determined. Analyses of the enthalpic relaxation data by the Tool-Narayanaswamy-Moynihan-Hodge formalism yield the enthalpic fragility index mH and stretching exponent βH. The large difference between the dielectric md and the enthalpic mH, as well as between βd and βH, is a remarkable finding. The differences are interpreted by the formation of molecular self-assemblies. The interpretation is supported by the quite comparable fragility determined by viscosity and the enthalpic relaxation. The Kirkwood factor calculated at low temperatures is also consistent with the interpretation. The results suggest that the enthalpic relaxation involving the motions of all parts of TBP is global, while the dielectric relaxation detects the local rotation, which might originate from the rotation of the dipole moment of the core. The presence of two structural α-relaxations, one global and one local, with a large difference in dynamics is revealed for the first time in a molecular glass former.

Alkyl group substitution by oxime-bound palladium(II) (the Shaw reaction): Alkly group selectivity and deuterium isotope effects

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

Wells, A.P.; Kitching, W.

1992-08-01

This report provides information regarding the selectivity of alkyl groups and the nature of the transition state for C-H palladation by oxime-bound palladium(II) (the Shaw reaction). The kinetic deuterium isotope effects are also presented. 21 refs.

Interpreting CARS images of tissue within the C-H-stretching region

NASA Astrophysics Data System (ADS)

Dietzek, Benjamin; Meyer, Tobias; Medyukhina, Anna; Bergner, Norbert; Krafft, Christoph; Romeike, Bernd F. M.; Reichart, Rupert; Kalff, Rolf; Schmitt, Michael; Popp, Jürgen

2014-03-01

Single band coherent anti-Stokes Raman scattering (CARS) microscopy within the CH-stretching region is applied to detect individual cells and nuclei of human brain tissue and brain tumors - an information which allows for histopathologic grading of the tissue. The CARS image contrast within the C-H-stretching region correlated to the tissue composition. Based on the specific application example of identifying nuclei within (coherent) Raman images of neurotissue sections, we shall derive general design parameters for lasers optimally suited to serve in a clinical environment and discuss the potential of recently developed methods to analyze spectrally resolved CARS images and image segmentation algorithms.

Storage capacity and vibration frequencies of guest molecules in CH4 and CO2 hydrates by first-principles calculations.

PubMed

Cao, Xiaoxiao; Su, Yan; Liu, Yuan; Zhao, Jijun; Liu, Changling

2014-01-09

Using first-principle calculations at B97-D/6-311++G(2d,2p) level, we systematically explore the gas capacity of five standard water cavities (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) in clathrate hydrate and study the inclusion complexes to infer general trends in vibrational frequencies of guest molecules as a function of cage size and number of guest molecules. In addition, the Raman spectra of hydrates from CO2/CH4 gases are simulated. From our calculations, the maximum cage occupancy of the five considered cages (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) is one, one, two, three, and seven for both CH4 and CO2 guest molecules, respectively. Meanwhile, the optimum cage occupancy are one, one, one, two, and four for CO2 molecules and one, one, two, three, and five for CH4 molecules, respectively. Both the C-H stretching frequency of CH4 and the C-O stretching frequency of CO2 gradually decrease as size of the water cages increases. Meanwhile, the C-H stretching frequency gradually increases as the amount of CH4 molecules in the water cavity (e.g., 5(12)6(8)) increases.

Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization.

PubMed

Lyubov, Dmitry M; Cherkasov, Anton V; Fukin, Georgy K; Ketkov, Sergey Yu; Shavyrin, Andrey S; Trifonov, Alexander A

2014-10-14

The reaction of Ap(9Me)Lu(CH2SiMe3)2(thf) (Ap(9Me) = (2,4,6-trimethylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) with two molar equivalents of PhSiH3 affords a trinuclear alkyl-hydrido cluster [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2]. The analogous reactions with Ap(9Me)Ln(CH2SiMe3)2(thf) (Ln = Y, Yb) are more complex and result in the formation of mixtures of two types of trinuclear alkyl-hydrido complexes [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiH2Ph)(thf)2] differing in the alkyl group. The DFT calculations of [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] (Ap* = (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) confirm localization of the HOMO on the Ap*-Y(1A)-CH2SiMe3 fragment, thus explaining its enhanced reactivity. Analysis of the electron density distribution reveals the Y-H and H-H bonding interactions in the (Y)3(μ(2)-H)3(μ(3)-H)2 moiety. The NMR studies of diamagnetic complexes [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] demonstrated that the trinuclear cores are retained in the solution and revealed exchange between μ(3)- and μ(2)-bridging hydrido ligands. Complexes [(Ap*Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2], the cationic yttrium hydrido cluster [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(thf)3](+)[B(C6F5)4](-) as well as [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] proved to be active in catalysis of ethylene polymerization under mild conditions.

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 sulfates...

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 sulfates...

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 sulfates...

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 sulfates...

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 sulfates...

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 reporting...

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 reporting...

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 reporting...

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 reporting...

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 reporting...

New investigation of the ν3 C-H stretching region of 12CH4 through the analysis of high temperature infrared emission spectra

NASA Astrophysics Data System (ADS)

Amyay, Badr; Gardez, Aline; Georges, Robert; Biennier, Ludovic; Vander Auwera, Jean; Richard, Cyril; Boudon, Vincent

2018-04-01

The ν3 C-H stretching region of methane was reinvestigated in this work using high temperature (620-1715 K) emission spectra recorded in Rennes at Doppler limited resolution. This work follows our recent global analysis of the Dyad system Δn = ±1 (1000-1500 cm-1), with n being the polyad number [B. Amyay et al., J. Chem. Phys. 144, 24312 (2016)]. Thanks to the high temperature, new assignments of vibration-rotation methane line positions have been achieved successfully in the Pentad system and some associated hot bands (Δn = ±2) observed in the spectral region 2600-3300 cm-1. In particular, rotational assignments in the cold band [Pentad-ground state (GS)] and in the first related hot band (Octad-Dyad) were extended up to J = 30 and 27, respectively. In addition, 1525 new transitions belonging to the Tetradecad-Pentad hot band system were assigned for the first time, up to J = 20. The effective global model used to deal with the new assignments was developed to the 6th order for the first three polyads (Monad, Dyad, and Pentad), and to the 5th order for both the Octad and the Tetradecad. 1306 effective parameters were fitted with a dimensionless standard deviation σ = 2.64. The root mean square deviations dRMS obtained are 4.18 × 10-3 cm-1 for the Pentad-GS cold band, 2.48 × 10-3 cm-1 for the Octad-Dyad, and 1.43 × 10-3 cm-1 for the Tetradecad-Pentad hot bands.

Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

PubMed

Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

2018-03-12

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

Intramolecular interactions in polymethylenic chains with polar end groups: The spectroscopic signature

NASA Astrophysics Data System (ADS)

Milani, Alberto; Castiglioni, Chiara; Brambilla, Luigi; Zerbi, Giuseppe

2012-02-01

We present a computational study based on DFT simulations of the infrared spectra of several short alkyl chains carrying polar end groups. The work aims to provide guidelines for the detection of marker bands signalling the occurrence of specific intramolecular interactions between the polar head and CH2 groups at different distances. In particular, the CH stretching region is investigated and new features assigned to normal modes localized on the CH2 groups nearest to the electron-withdrawing atom are identified. The study has been extended also to the rationalization of the experimental IR features shown by a 1-Chloroeicosane (C20H41Cl) sample.

[Alkylating agents].

PubMed

Pourquier, Philippe

2011-11-01

With the approval of mechlorethamine by the FDA in 1949 for the treatment of hematologic malignancies, alkylating agents are the oldest class of anticancer agents. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in specific indications and sometimes represent the unique option for the treatment of refractory diseases. Here, we are reviewing the major classes of alkylating agents and their mechanism of action, with a particular emphasis for the new generations of alkylating agents. As for most of the chemotherapeutic agents used in the clinic, these compounds are derived from natural sources. With a complex but original mechanism of action, they represent new interesting alternatives for the clinicians, especially for tumors that are resistant to conventional DNA damaging agents. We also briefly describe the different strategies that have been or are currently developed to potentiate the use of classical alkylating agents, especially the inhibition of pathways that are involved in the repair of DNA lesions induced by these agents. In this line, the development of PARP inhibitors is a striking example of the recent regain of interest towards the "old" alkylating agents.

Conformational Study of Dibenzyl Ether

NASA Astrophysics Data System (ADS)

Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Hewett, Daniel M.; Zwier, Timothy S.

2017-06-01

Understanding the initial stages of polycyclic aromatic hydrocarbon (PAH) aggregation, the onset of soot formation, is an important goal on the pathway to cleaner combustion processes. PAHs with short alkyl chains, present in fuel-rich combustion environments, can undergo reactions that will chemically link aromatic rings together. One such example of a linked diaryl compound is dibenzyl ether, C_{6}H_{5}-CH_{2}-O-CH_{2}-C_{6}H_{5}. The -CH_{2}-O-CH_{2}- linkage has a length and flexibility well-suited to forming a π-stacked conformation between the two phenyl rings. In this talk, we will explore the single-conformation spectroscopy of dibenzyl ether under jet-cooled conditions in the gas phase. Laser-induced fluorescence, chirped pulse Fourier transform microwave (8-18 GHz region), and single-conformation infrared spectroscopy in the alkyl CH stretch region were all carried out on the molecule, thereby interrogating its full array of electronic, vibrational and rotational degrees of freedom. This work is the first step in a broader study to determine the extent of π-stacking in linked aryl compounds as a function of linkage and PAH size.

Computing energy levels of CH4, CHD3, CH3D, and CH3F with a direct product basis and coordinates based on the methyl subsystem.

PubMed

Zhao, Zhiqiang; Chen, Jun; Zhang, Zhaojun; Zhang, Dong H; Wang, Xiao-Gang; Carrington, Tucker; Gatti, Fabien

2018-02-21

Quantum mechanical calculations of ro-vibrational energies of CH 4 , CHD 3 , CH 3 D, and CH 3 F were made with two different numerical approaches. Both use polyspherical coordinates. The computed energy levels agree, confirming the accuracy of the methods. In the first approach, for all the molecules, the coordinates are defined using three Radau vectors for the CH 3 subsystem and a Jacobi vector between the remaining atom and the centre of mass of CH 3 . Euler angles specifying the orientation of a frame attached to CH 3 with respect to a frame attached to the Jacobi vector are used as vibrational coordinates. A direct product potential-optimized discrete variable vibrational basis is used to build a Hamiltonian matrix. Ro-vibrational energies are computed using a re-started Arnoldi eigensolver. In the second approach, the coordinates are the spherical coordinates associated with four Radau vectors or three Radau vectors and a Jacobi vector, and the frame is an Eckart frame. Vibrational basis functions are products of contracted stretch and bend functions, and eigenvalues are computed with the Lanczos algorithm. For CH 4 , CHD 3 , and CH 3 D, we report the first J > 0 energy levels computed on the Wang-Carrington potential energy surface [X.-G. Wang and T. Carrington, J. Chem. Phys. 141(15), 154106 (2014)]. For CH 3 F, the potential energy surface of Zhao et al. [J. Chem. Phys. 144, 204302 (2016)] was used. All the results are in good agreement with experimental data.

Computing energy levels of CH4, CHD3, CH3D, and CH3F with a direct product basis and coordinates based on the methyl subsystem

NASA Astrophysics Data System (ADS)

Zhao, Zhiqiang; Chen, Jun; Zhang, Zhaojun; Zhang, Dong H.; Wang, Xiao-Gang; Carrington, Tucker; Gatti, Fabien

2018-02-01

Quantum mechanical calculations of ro-vibrational energies of CH4, CHD3, CH3D, and CH3F were made with two different numerical approaches. Both use polyspherical coordinates. The computed energy levels agree, confirming the accuracy of the methods. In the first approach, for all the molecules, the coordinates are defined using three Radau vectors for the CH3 subsystem and a Jacobi vector between the remaining atom and the centre of mass of CH3. Euler angles specifying the orientation of a frame attached to CH3 with respect to a frame attached to the Jacobi vector are used as vibrational coordinates. A direct product potential-optimized discrete variable vibrational basis is used to build a Hamiltonian matrix. Ro-vibrational energies are computed using a re-started Arnoldi eigensolver. In the second approach, the coordinates are the spherical coordinates associated with four Radau vectors or three Radau vectors and a Jacobi vector, and the frame is an Eckart frame. Vibrational basis functions are products of contracted stretch and bend functions, and eigenvalues are computed with the Lanczos algorithm. For CH4, CHD3, and CH3D, we report the first J > 0 energy levels computed on the Wang-Carrington potential energy surface [X.-G. Wang and T. Carrington, J. Chem. Phys. 141(15), 154106 (2014)]. For CH3F, the potential energy surface of Zhao et al. [J. Chem. Phys. 144, 204302 (2016)] was used. All the results are in good agreement with experimental data.

Stretch marks

MedlinePlus

Stretch marks can appear when there is rapid stretching of the skin. The marks appear as parallel ... often disappear after the cause of the skin stretching is gone. Avoiding rapid weight gain helps reduce ...

Rh-Catalyzed Intermolecular Reactions of α-Alkyl-α-Diazo Carbonyl Compounds with Selectivity over β-Hydride Migration.

PubMed

DeAngelis, Andrew; Panish, Robert; Fox, Joseph M

2016-01-19

Rh-carbenes derived from α-diazocarbonyl compounds have found broad utility across a remarkable range of reactivity, including cyclopropanation, cyclopropenation, C-H insertions, heteroatom-hydrogen insertions, and ylide forming reactions. However, in contrast to α-aryl or α-vinyl-α-diazocarbonyl compounds, the utility of α-alkyl-α-diazocarbonyl compounds had been moderated by the propensity of such compounds to undergo intramolecular β-hydride migration to give alkene products. Especially challenging had been intermolecular reactions involving α-alkyl-α-diazocarbonyl compounds. This Account discusses the historical context and prior limitations of Rh-catalyzed reactions involving α-alkyl-α-diazocarbonyl compounds. Early studies demonstrated that ligand and temperature effects could influence chemoselectivity over β-hydride migration. However, effects were modest and conflicting conclusions had been drawn about the influence of sterically demanding ligands on β-hydride migration. More recent advances have led to a more detailed understanding of the reaction conditions that can promote intermolecular reactivity in preference to β-hydride migration. In particular, the use of bulky carboxylate ligands and low reaction temperatures have been key to enabling intermolecular cyclopropenation, cyclopropanation, carbonyl ylide formation/dipolar cycloaddition, indole C-H functionalization, and intramolecular bicyclobutanation with high chemoselectivity over β-hydride migration. Cyclic α-diazocarbonyl compounds have been shown to be particularly resilient toward β-hydride migration and are the first class of compounds that can engage in intermolecular reactivity in the presence of tertiary β-hydrogens. DFT calculations were used to propose that for cyclic α-diazocarbonyl compounds, ring constraints relieve steric interaction for intermolecular reactions and thereby accelerate the rate of intermolecular reactivity relative to intramolecular �

Experimental verification of the cluster model of CH3F-(ortho-H2)n in solid para-H2 by using mid-infrared pump-probe laser spectroscopy

NASA Astrophysics Data System (ADS)

Miyamoto, Yuki; Mizoguchi, Asao; Kanamori, Hideto

2017-03-01

The bleaching process in the C-F stretching mode (ν3 band) of CH3F-(ortho-H2)n [n = 0 and 1] clusters in solid para-H2 was monitored using pump and probe laser spectroscopy on the C-H stretching mode (ν1 and 2ν5 bands). From an analysis of the depleted spectral profiles, the transition frequency and linewidth of each cluster were directly determined. The results agree with the values previously derived from a deconvolution analysis of the broadened ν1/2ν5 spectrum observed by FTIR spectroscopy. The complementary increase and decrease between the n = 0 and 1 components were also verified through monitoring the ν1 and 2ν5 bands, which suggests a closed system among the CH3F-(ortho-H2)n clusters. These observations provide experimental verification of the CH3F-(ortho-H2)n cluster model. On the other hand, a trial to observe the bleaching process by pumping the C-H stretching mode was not successful. This result may be important for understanding the dynamics of vibrational relaxation processes in CH3F-(ortho-H2)n in solid para-H2.

Experimental verification of the cluster model of CH3F-(ortho-H2)n in solid para-H2 by using mid-infrared pump-probe laser spectroscopy.

PubMed

Miyamoto, Yuki; Mizoguchi, Asao; Kanamori, Hideto

2017-03-21

The bleaching process in the C-F stretching mode (ν 3 band) of CH 3 F-(ortho-H 2 ) n [n = 0 and 1] clusters in solid para-H 2 was monitored using pump and probe laser spectroscopy on the C-H stretching mode (ν 1 and 2ν 5 bands). From an analysis of the depleted spectral profiles, the transition frequency and linewidth of each cluster were directly determined. The results agree with the values previously derived from a deconvolution analysis of the broadened ν 1 /2ν 5 spectrum observed by FTIR spectroscopy. The complementary increase and decrease between the n = 0 and 1 components were also verified through monitoring the ν 1 and 2ν 5 bands, which suggests a closed system among the CH 3 F-(ortho-H 2 ) n clusters. These observations provide experimental verification of the CH 3 F-(ortho-H 2 ) n cluster model. On the other hand, a trial to observe the bleaching process by pumping the C-H stretching mode was not successful. This result may be important for understanding the dynamics of vibrational relaxation processes in CH 3 F-(ortho-H 2 ) n in solid para-H 2 .

Theoretical DFT, vibrational and NMR studies of benzimidazole and alkyl derivatives

NASA Astrophysics Data System (ADS)

Infante-Castillo, Ricardo; Rivera-Montalvo, Luis A.; Hernández-Rivera, Samuel P.

2008-04-01

Benzimidazoles are heterocyclic compounds that have awaked great interest during the last few years because of their proven biological activity as antiviral, antimicrobial, and antitumoral agents. For this reason, the development of a systematic FT-IR, FT-Raman and NMR study of 1-substituted compounds in 2-methylbenzimidazole constitutes a significant tool in understanding the molecular dynamics and the structural parameters that govern their behavior. Two new 1-alkyl-2-methylbenzimidazoles compounds were synthesized from reaction of 2-methylbenzimidazole with primary and secondary alkyl halides using a strong base as a catalyst. These compounds were purified and characterized by elemental analysis and different spectroscopic methods. The comparative analysis of vibrational modes of benzimidazole and its alkyl derivatives show that regions of absorption are very similar in all of them. However, changes are produced at low frequencies specifically in the C-H out of plane deformations, ring breathing and ring skeletal vibrations. The ring out-of plane bending modes shift by 10-15 cm -1 in some cases as results of alkyl substitution. The theoretical calculated spectra, using Density Functional Theory (DFT) approximation, and experimental results were consistent with each other. The GIAO method was used to calculate absolute shieldings, which agree consistently with those measured by 1H and 13C NMR. The consistency and efficiency of the GIAO 13C and 1H NMR calculations were thoroughly checked by the analysis of statistical parameters concerning computed and experimental 13C and 1H NMR chemical shift values of the studied compounds.

Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study

NASA Astrophysics Data System (ADS)

Kamarchik, E.; Rodrigo, C.; Bowman, J. M.; Reisler, H.; Krylov, A. I.

2012-02-01

The dissociation of the hydroxymethyl radical, CH2OH, and its isotopolog, CD2OH, following the excitation of high OH stretch overtones is studied by quasi-classical molecular dynamics calculations using a global potential energy surface (PES) fitted to ab initio calculations. The PES includes CH2OH and CH3O minima, dissociation products, and all relevant barriers. Its analysis shows that the transition states for OH bond fission and isomerization are both very close in energy to the excited vibrational levels reached in recent experiments and involve significant geometry changes relative to the CH2OH equilibrium structure. The energies of key stationary points are refined using high-level electronic structure calculations. Vibrational energies and wavefunctions are computed by coupled anharmonic vibrational calculations. They show that high OH-stretch overtones are mixed with other modes. Consequently, trajectory calculations carried out at energies about ˜3000 cm-1 above the barriers reveal that despite initial excitation of the OH stretch, the direct OH bond fission is relatively slow (10 ps) and a considerable fraction of the radicals undergoes isomerization to the methoxy radical. The computed dissociation energies are: D0(CH2OH → CH2O + H) = 10 188 cm-1, D0(CD2OH → CD2O + H) = 10 167 cm-1, D0(CD2OH → CHDO + D) = 10 787 cm-1. All are in excellent agreement with the experimental results. For CH2OH, the barriers for the direct OH bond fission and isomerization are: 14 205 and 13 839 cm-1, respectively.

Enantioselective remote meta-C-H arylation and alkylation via a chiral transient mediator.

PubMed

Shi, Hang; Herron, Alastair N; Shao, Ying; Shao, Qian; Yu, Jin-Quan

2018-06-18

Enantioselective carbon-hydrogen (C-H) activation reactions by asymmetric metallation could provide new routes for the construction of chiral molecules 1,2 . However, current methods are typically limited to the formation of five- or six-membered metallacycles, thereby preventing the asymmetric functionalization of C-H bonds at positions remote to existing functional groups. Here we report enantioselective remote C-H activation using a catalytic amount of a chiral norbornene as a transient mediator, which relays initial ortho-C-H activation to the meta position. This was used in the enantioselective meta-C-H arylation of benzylamines, as well as the arylation and alkylation of homobenzylamines. The enantioselectivities obtained using the chiral transient mediator are comparable across different classes of substrates containing either neutral σ-donor or anionic coordinating groups. This relay strategy could provide an alternative means to remote chiral induction, one of the most challenging problems in asymmetric catalysis 3,4 .

Stretching & Flexibility: An Interactive Encyclopedia of Stretching. [CD-ROM].

ERIC Educational Resources Information Center

2002

This CD-ROM offers 140 different stretches in full-motion video sequences. It focuses on the proper techniques for overall physical fitness, injury prevention and rehabilitation, and 23 different sports (e.g., golf, running, soccer, skiing, climbing, football, and baseball). Topics include stretching for sports; stretching awareness and education…

Preparation and use of tetra-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents

DOEpatents

Miller, Rebecca L.; Pinkerton, Anthony B.; Abney, Kent D.; Kinkead, Scott A.

1997-01-01

Preparation and use of tetra-C-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents. Tetra-C-alkyl derivatives of cobalt dicarbollide, Co(C.sub.2 R.sub.2 B.sub.9 H.sub.9).sub.2.sup.- (CoB.sub.2 R.sub.4.sup.- ; R=CH.sub.3 and C.sub.6 H.sub.13) are demonstrated to be significant cesium and strontium extractants from acidic and alkaline solutions into non-toxic organic solvent systems. Extractions using mesitylene and diethylbenzene are compared to those with nitrobenzene as the organic phase. CoB.sub.2 -hexyl.sub.4.sup.- in diethylbenzene shows improved selectivity (10.sup.4) for Cs over Na in acidic solution. In dilute alkaline solution, CoB.sub.2 -hexyl.sub.4.sup.- extracts Cs less efficiently, but more effectively removes Sr from higher base concentrations. A general synthesis of tetra-C-alkyl cobalt dicarbollides is described.

Preparation and use of tetra-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents

DOEpatents

Miller, R.L.; Pinkerton, A.B.; Abney, K.D.; Kinkead, S.A.

1997-02-11

Preparation and use of tetra-C-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents. Tetra-C-alkyl derivatives of cobalt dicarbollide, Co(C{sub 2}R{sub 2}B{sub 9}H{sub 9}){sub 2}{sup {minus}}(CoB{sub 2}R{sub 4}{sup {minus}}; R=CH{sub 3} and C{sub 6}H{sub 13}) are demonstrated to be significant cesium and strontium extractants from acidic and alkaline solutions into non-toxic organic solvent systems. Extractions using mesitylene and diethylbenzene are compared to those with nitrobenzene as the organic phase. CoB{sub 2}-hexyl{sub 4}{sup {minus}} in diethylbenzene shows improved selectivity (10{sup 4}) for Cs over Na in acidic solution. In dilute alkaline solution, CoB{sub 2}-hexyl{sub 4}{sup {minus}} extracts Cs less efficiently, but more effectively removes Sr from higher base concentrations. A general synthesis of tetra-C-alkyl cobalt dicarbollides is described. 6 figs.

Quantum-state-resolved reactivity of overtone excited CH 4 on Ni(111): Comparing experiment and theory

DOE PAGES

Hundt, P. Morten; van Reijzen, Maarten E.; Beck, Rainer D.; ...

2017-02-07

Quantum state resolved reactivity measurements probe the role of vibrational symmetry on the vibrational activation of the dissociative chemisorption of CH 4 on Ni(111). IR-IR double resonance excitation in a molecular beam was used to prepare CH 4 in three different vibrational symmetry components A 1, E, and F 2 of the 2ν 32 antisymmetric stretch overtone vibration as well as in the ν1+ν3 symmetric plus antisymmetric C-H stretch combination band of F 2 symmetry. We measured the quantum state specific dissociation probability S 0 (sticking coefficient) for each of the four vibrational states by detecting chemisorbed carbon on Ni(111)more » as the product of CH 4 dissociation by Auger electron spectroscopy. We also observe strong mode specificity, where S 0 for the most reactive state ν 1+ν 3 is an order of magnitude higher than for the least reactive, more energetic 2ν 3-E state. Our first principles quantum scattering calculations show that as molecules in the ν1 state approach the surface, the vibrational amplitude becomes localized on the reacting C-H bond, making them very reactive. We found that this behavior results from the weakening of the reacting C-H bond as the molecule approaches the surface, decoupling its motion from the three non-reacting C-H stretches. Similarly, we find that overtone normal mode states with more ν 1 character are more reactive: S 0(2ν 1) > S 0(ν 1+ν 3) > S 0(2ν 3). The 2ν 3 eigenstates excited in the experiment can be written as linear combinations of these normal mode states. The highly reactive 2ν 1 and ν 1+ν 3 normal modes, being of A 1 and F 2 symmetry, can contribute to the 2ν 3-A 1 and 2ν 3-F 2 eigenstates, respectively, boosting their reactivity over the E component, which contains no ν 1 character due to symmetry.« less

The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

PubMed Central

Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

2012-01-01

If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association. PMID:22937173

New thermochemical parameter for describing solvent effects on IR stretching vibration frequencies. Communication 2. Assessment of cooperativity effects.

PubMed

Solomonov, Boris N; Varfolomeev, Mikhail A; Novikov, Vladimir B; Klimovitskii, Alexander E

2006-05-15

Solvent effects on O-H stretching vibration frequency of methanol in hydrogen bond complexes with different bases, CH3OH...B, have been investigated by FTIR spectroscopy. Using chloroform as a solvent results in strengthening of CH3OH...B hydrogen bonding due to cooperativity between CH3OH...B and Cl3CH...CH3OH bonds. A method is proposed for quantifying the hydrogen bond cooperativity effect. The determined cooperativity factors take into account all specific interactions of the solute in proton-donor solvents. In addition, a method of estimation of cooperativity factors Ab and AOX in system (CH3OH)2...B is proposed. It is demonstrated that in such systems, the cooperativity factor of the OH...B bond decreases and that of the OH...O bond increases with increasing the acceptor strength of the base B. The obtained results are in a good agreement with the data obtained previously from matrix-isolation FTIR spectroscopy.

N-alkyl functionalised expanded ring N-heterocyclic carbene complexes of rhodium(I) and iridium(I): structural investigations and preliminary catalytic evaluation.

PubMed

Dunsford, Jay J; Tromp, Dorette S; Cavell, Kingsley J; Elsevier, Cornelis J; Kariuki, Benson M

2013-05-28

A series of new N-alkyl functionalised 6- and 7-membered expanded ring N-heterocyclic carbene (NHC) pro-ligands 3-6 and their corresponding complexes of rhodium(I) and iridium(I), [M(NHC)(COD)Cl] 7-14 and [M(NHC)(CO)2Cl] 15-22 are described. The complexes have been characterised by (1)H and (13)C{(1)H} NMR, mass spectrometry, IR and X-ray diffraction. It is noted from X-ray diffraction studies that the N-alkyl substituents are found to orientate themselves away from the metal centre due to unfavourable steric interactions resulting in low percent buried volume (%V(bur)) values in the solid state. The heterocycle ring size is also found to dictate the spatial orientation of the N-alkyl substituents in the neopentyl functionalised derivatives 10 and 14. The 7-membered derivative 14 allows for a conformational 'twist' of the heterocycle ring with the N-alkyl substituents adopting a mutually trans configuration with respect to each other, while the more rigid 6-membered system 10 does not allow for this conformational 'twist' and consequently the N-alkyl substituents adopt a mutually cis configuration. The σ-donor function of this new class of expanded ring NHC ligand has also been probed by measured IR stretching frequencies of the [M(NHC)(CO)2Cl] complexes 15-22. A preliminary catalytic survey of the hydrogenation of functionalised alkenes with molecular hydrogen under mild conditions has also been undertaken with complex , affording an insight into the application of large ring NHC ancillary ligands bearing N-alkyl substituents in hydrogenation transformations.

Infrared absorption of methanethiol clusters (CH3SH)n, n = 2-5, recorded with a time-of-flight mass spectrometer using IR depletion and VUV ionization

NASA Astrophysics Data System (ADS)

Fu, Lung; Han, Hui-Ling; Lee, Yuan-Pern

2012-12-01

We investigated IR spectra in the CH- and SH-stretching regions of size-selected methanethiol clusters, (CH3SH)n with n = 2-5, in a pulsed supersonic jet using infrared (IR)-vacuum ultraviolet (VUV) ionization. VUV emission at 132.50 nm served as the source of ionization in a time-of-flight mass spectrometer. Clusters were dissociated with light from a tunable IR laser before ionization. The variations in intensity of methanethiol cluster ions (CH3SH)n+ were monitored as the IR laser light was tuned across the range 2470-3100 cm-1. In the SH-stretching region, the spectrum of (CH3SH)2 shows a weak band near 2601 cm-1, red-shifted only 7 cm-1 from that of the monomer. In contrast, all spectra of (CH3SH)n, n = 3-5, show a broad band near 2567 cm-1 with much greater intensity. In the CH-stretching region, absorption bands of (CH3SH)2 are located near 2865, 2890, 2944, and 3010 cm-1, red-shifted by 3-5 cm-1 from those of CH3SH. These red shifts increase slightly for larger clusters and bands near 2856, 2884, 2938, and 3005 cm-1 were observed for (CH3SH)5. These spectral results indicate that the S-H...S hydrogen bond plays an important role in clusters with n = 3-5, but not in (CH3SH)2, in agreement with theoretical predictions. The absence of a band near 2608 cm-1 that corresponds to absorption of the non-hydrogen-bonded SH moiety and the large width of observed feature near 2567 cm-1 indicate that the dominant stable structures of (CH3SH)n, n = 3-5, have a cyclic hydrogen-bonded framework.

Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

NASA Astrophysics Data System (ADS)

Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

2017-06-01

The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

Intramolecular vibrational redistribution of CH 2I 2 dissolved in supercritical Xe

NASA Astrophysics Data System (ADS)

Sekiguchi, K.; Shimojima, A.; Kajimoto, O.

2003-03-01

Intramolecular vibrational energy redistribution (IVR) of CH 2I 2 in supercritical Xe has been studied. The first overtone of the C-H stretching mode was excited with a near infrared laser pulse and the transient UV absorption near 390 nm was monitored. Signals showed a rise and decay profile, which gave the IVR and VET (intermolecular vibrational energy transfer) rates, respectively. Solvent density dependence of each rate was obtained by tuning the pressure at a constant temperature. The IVR rate in supercritical Xe increased with increasing solvent density and asymptotically reached a limiting value. This result suggests that the IVR process of CH 2I 2 in condensed phase is a solvent-assisted process.

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.

Stereoconvergent Amine-Directed Alkyl–Alkyl Suzuki Reactions of Unactivated Secondary Alkyl Chlorides

PubMed Central

Lu, Zhe; Wilsily, Ashraf; Fu, Gregory C.

2011-01-01

A new family of stereoconvergent cross-couplings of unactivated secondary alkyl electrophiles has been developed, specifically, arylamine-directed alkyl–alkyl Suzuki reactions. This represents the first such investigation to be focused on the use of alkyl chlorides as substrates. Structure-enantioselectivity studies are consistent with the nitrogen, not the aromatic ring, serving as the primary site of coordination of the arylamine to the catalyst. The rate law for this asymmetric cross-coupling is compatible with transmetalation being the turnover-limiting step of the catalytic cycle. PMID:21553917

Stretch Marks

MedlinePlus

... stretch marks. This isn't true with regular tanning or tanning beds , though: Stretch marks are less likely to ... up looking more obvious. Plus, the sun and tanning beds do more harm than good when it ...

Stretch Garment Dermatitis

PubMed Central

Mihan, Richard; Ayres, Samuel

1968-01-01

A disease of the skin, not hitherto described, is caused by pressure or tension on the skin from the wearing of tight-fitting stretch garments such as “stretch bras,” “stretch girdles” and “stretch socks.” The condition is not due to chemical sensitization of fabrics, dyes or other additives but is of mechanical origin. The eruption may assume various clinical forms and may be characterized by a nondescript erythematous and eczematous appearance or may consist of an exaggeration, in the areas covered by the stretch garment, of already existing dermatosis such as lichen planus, psoriasis, acne vulgaris, discoid lupus erythematosus or atopic dermatitis. ImagesFigure 1.Figure 2.Figure 3.Figure 4.Figure 5. PMID:5639939

Alkylation of enolates: An electrophilicity perspective

NASA Astrophysics Data System (ADS)

Elango, M.; Parthasarathi, R.; Subramanian, V.; Chattaraj, P. K.

Enolates are ambient nucleophiles, and alkylation can occur either at a carbon or at an oxygen site. It is known that the ratio of C/O alkylation depends significantly on various factors, including the type of enolate, alkylating agent, site of alkylation, and solvent environment. Analysis of regioselectivity and solvent effects on alkylation of lithium enolates is investigated using various reactivity descriptors, including generalized philicity. These results point out the reliability of both global and local reactivity descriptors in providing significant information about site selectivity and chemical reactivity of lithium enolates.

Structural isomers of polyfluorinated di- and tri-alkylated phosphate ester surfactants present in industrial blends and in microwave popcorn bags.

PubMed

Trier, Xenia; Nielsen, Nikoline Juul; Christensen, Jan H

2011-09-01

In this study, we provide strategies for detecting and quantifying the structural isomers of polyfluorinated di- and tri-alkyl surfactants (PFAS) by mass spectrometry (MS). We specifically investigate polyfluorinated dialkylated phosphate ester surfactants (x:2/y:2 diPAPS, (F(CF(2))( x )CH(2)CH(2)O-P(O)(O)(-)-OCH(2)CH(2)(CF(2))( y )F)) and their thioether analogues (x:2/y:2 S-diPAPS, F(CF(2))( x )CH(2)CH(2)SCH(2)-C[CH(2)O)(2)P(O)(O)(-)]-CH(2)SCH(2)CH(2)(CF(2))( y )F), which are used for industrial applications, such as oil- and water-repellent coatings on paper and board. DiPAPS have been found in human blood and are metabolised to the persistent perfluoroalkyl carboxylic acids (PFCA) in rats. A microwave popcorn bag extract was analysed by ultrahigh-pressure liquid chromatography coupled to a negative electrospray ionisation-quadrupole time-of-flight MS. The extract contained S-diPAPS, diPAPS and trialkylated (triPAPS) impurities. TriPAPS were also present in industrial and synthetic diPAPS standards, and were verified with an 8:2/8:2/8:2 triPAPS standard. The eight elemental compositions (m/z's) of diPAPS in the extract represent 19 precursor ion structures, and the six S-diPAPS m/z's represent at least 13 structures. The diPAPS had [M-H](-) precursor ions of m/z 789, 889,…1,489 and the S-diPAPS of m/z 921, 1,021,…1,421, corresponding to fluorinated chains from C(6-18). Each m/z appeared as one to three chromatographic peaks of structural isomers, where, e.g. m/z 1,189 was present as 10:2/10:2, 8:2/12:2 and 6:2/14:2 diPAPS. The isomers formed different products ions, thus only half of the m/z 1,189 diPAPS concentration was measured with one precursor ion > product ion transition. In general, knowledge about structural isomers of poly-alkylated PFAS is needed for the estimation of types and amounts of perfluorinated degradation products, such as PFCA from diPAPS.

Chemoselective phototransformation of C-H bonds on a polymer surface through a photoinduced cerium recycling redox reaction.

PubMed

Huang, Zhenhua; Wu, Zhengfang; Yang, Peng; Yang, Wantai

2014-09-01

It is generally accepted that Ce(4+) is unable to directly oxidize unreactive alkyl C-H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl(3)/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce(3+) was first photooxidized to form Ce(4+) in the presence of H(+), and the in situ formed Ce(4+) then performs an oxidation reaction on the C-H bonds of the polymer surface to form surface-carbon radicals for radical graft polymerization reactions and functional-group transformations, while reducing to Ce(3+) and releasing H(+) in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bonds on polymer surfaces into small-molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer-surface modification. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thioimidazolium Ionic Liquids as Tunable Alkylating Agents.

PubMed

Guterman, Ryan; Miao, Han; Antonietti, Markus

2018-01-19

Alkylating ionic liquids based on the thioimidazolium structure combine the conventional properties of ionic liquids, including low melting point and nonvolatility, with the alkylating function. Alkyl transfer occurs exclusively from the S-alkyl position, thus allowing for easy derivatization of the structure without compromising specificity. We apply this feature to tune the electrophilicty of the cation to profoundly affect the reactivity of these alkylating ionic liquids, with a caffeine-derived compound possessing the highest reactivity. Anion choice was found to affect reaction rates, with iodide anions assisting in the alkylation reaction through a "shuttling" process. The ability to tune the properties of the alkylating agent using the toolbox of ionic liquid chemistry highlights the modular nature of these compounds as a platform for alkylating agent design and integration in to future systems.

Palladium-Catalyzed Allylic C-H Bond Functionalization of Olefins

NASA Astrophysics Data System (ADS)

Liu, Guosheng; Wu, Yichen

Transition metal-mediated carbon-hydrogen bond cleavage and functionalization is a mechanistically interesting and synthetically attractive process. One of the important cases is the removal of a allylic hydrogen from an olefin by a PdII salt to yield a π-allylpalladium complex, followed by nucleophilic attack to efficient produce allylic derivatives. In contrast to the well-known allylic acetoxylation of cyclohexene, the reaction of open-chain olefins is fairly poor until recent several years. Some palladium catalytic systems have been reported to achieve allylic C-H functionalization, including acetoxylation, amination and alkylation of terminal alkenes. In the most of cases, ligand is crucial to the success of the transformation. This review surveys the recent development of palladium-catalyzed allylic C-H functionalziation of alkenes. These results promise a significant increase in the scope of olefin transformation.

Get up and Stretch

ERIC Educational Resources Information Center

Crupi, Jeffrey

2004-01-01

Daily stretching has many benefits for one's body. It can relieve stress and tension, it increases flexibility and it can help prevent injuries. There are many stretching exercises that a teacher can do with his or her students to help promote daily stretching routines. In this article, the author presents several stretching exercises and some…

Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

PubMed

Chen, Yuehua; Wang, Huiyong; Wang, Jianji

2014-05-01

Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

Cluster size resolving analysis of CH3F-(ortho-H2)n in solid para-hydrogen using FTIR absorption spectroscopy at 3 μm region.

PubMed

Miyamoto, Yuki; Momose, Takamasa; Kanamori, Hideto

2012-11-21

Infrared absorption spectra of methyl fluoride with ortho-hydrogen (ortho-H(2)) clusters in a solid para-hydrogen (para-H(2)) crystal at 3.6 K were studied in the C-H stretching fundamental region (~3000 cm(-1)) using an FTIR spectrometer. As shown previously, the ν(3) C-F stretching fundamental band of CH(3)F-(ortho-H(2))(n) (n = 0, 1, 2, ...) clusters at 1040 cm(-1) shows a series of n discrete absorption lines, which correspond to different-sized clusters. We observed three unresolved broad peaks in the C-H stretching region and applied this cluster model to them assuming the same intensity distribution function as the ν(3) band. A fitting analysis successfully gave us the linewidth and lineshift of the components in each vibrational band. It was found that the separately determined linewidth, matrix shift of the band origin, and cluster shift are dependent on the vibrational mode. From the transition intensities of the monomer component derived from the fitting analysis, we discuss the mixing ratio of the vibrational modes due to Fermi resonance.

A DFT-Elucidated Comparison of the Solution-Phase and SAM Electrochemical Properties of Short-Chain Mercaptoalkylferrocenes: Synthetic and Spectroscopic Aspects, and the Structure of Fc-CH2CH2-S-S-CH2CH2-Fc.

PubMed

Lewtak, Jan P; Landman, Marilé; Fernández, Israel; Swarts, Jannie C

2016-03-07

Facile synthetic procedures to synthesize a series of difficult-to-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(η(5)-C5H5)(η(5)-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group P1̅. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH(+) involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS(•), with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S-(CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group ΔE = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. (1)H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, ΔE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-thioether, Fc(CH2)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)

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

Guo, Han; Jackson, Bret

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH 4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v 3 and 2v 3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v 1 symmetric stretch of CH 4 is more effective at promoting the dissociative chemisorption of CH 4 than exciting the 1v 3 antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v 3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)

DOE PAGES

Guo, Han; Jackson, Bret

2016-05-13

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH 4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v 3 and 2v 3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v 1 symmetric stretch of CH 4 is more effective at promoting the dissociative chemisorption of CH 4 than exciting the 1v 3 antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v 3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Dynamic stretching and golf swing performance.

PubMed

Moran, K A; McGrath, T; Marshall, B M; Wallace, E S

2009-02-01

The aim of the present study was to examine the effect of dynamic stretching, static stretching and no stretching, as part of a general warm-up, on golf swing performance with a five-iron. Measures of performance were taken 0 min, 5 min, 15 min and 30 min after stretching. Dynamic stretching produced significantly greater club head speeds than both static stretching (Delta=1.9m.s (-1); p=0.000) and no stretching (Delta=1.7 m.s (-1); p=0.000), and greater ball speeds than both static stretching (Delta=3.5m.s (-1); p=0.003) and no stretching (Delta=3.3m.s (-1); p=0.001). Dynamic stretching produced significantly straighter swing-paths than both static stretching (Delta=-0.61 degrees , p=0.000) and no stretching (Delta=-0.72 degrees , p=0.01). Dynamic stretching also produced more central impact points than the static stretch (Delta=0.7 cm, p=0.001). For the club face angle, there was no effect of either stretch or time. For all of the variables measured, there was no significant difference between the static stretch and no stretch conditions. All of the results were unaffected by the time of measurement after stretching. The results indicate that dynamic stretching should be used as part of a general warm-up in golf.

Stretching Safely and Effectively

MedlinePlus

... shown that stretching immediately before an event weakens hamstring strength. Instead of static stretching, try performing a " ... If you play soccer, for instance, stretch your hamstrings as you're more vulnerable to hamstring strains. ...

The Relation Between Stretching Typology and Stretching Duration: The Effects on Range of Motion.

PubMed

Thomas, Ewan; Bianco, Antonino; Paoli, Antonio; Palma, Antonio

2018-04-01

Different stretching strategies and protocols are widely used to improve flexibility or maintain health, acting on the muscle tendon-unit, in order to improve the range of motion (ROM) of the joints. This review aims to evaluate the current body of literature in order to understand the relation between stretching typology and ROM, and secondly to evaluate if a relation exists between stretching volume (either as a single training session, weekly training and weekly frequency) and ROM, after long-term stretching. Twenty-three articles were considered eligible and included in the quantitative synthesis. All stretching typologies showed ROM improvements over a long-term period, however the static protocols showed significant gains (p<0.05) when compared to the ballistic or PNF protocols. Time spent stretching per week seems fundamental to elicit range of movement improvements when stretches are applied for at least or more than 5 min, whereas the time spent stretching within a single session does not seem to have significant effects for ROM gains. Weekly frequency is positively associated to ROM. Evaluated data indicates that performing stretching at least 5 days a week for at least 5 min per week using static stretching may be beneficial to promote ROM improvements. © Georg Thieme Verlag KG Stuttgart · New York.

Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

PubMed

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

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.

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.; Song, Y.

2007-01-01

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (??1) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH4-H2O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 ??C, and pressures up to 37 MPa. The results show that the CH4 ??1 band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH4-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell. ?? 2007 Elsevier Ltd. All rights reserved.

CONTRIBUTION OF INSPIRATORY FLOW TO ACTIVATION OF EGFR, RAS, MAPK, ATF-2 AND C-JUN DURING LUNG STRETCH

EPA Science Inventory

Contribution of Inspiratory Flow to Activation of EGFR, Ras, MAPK, ATF-2 and c-Jun during Lung Stretch

R. Silbajoris 1, Z. Li 2, J. M. Samet 1 and Y. C. Huang 1. 1 NHEERL, ORD, US EPA, RTP, NC and 2 CEMALB, UNC-CH, Chapel Hill, NC .

Mechanical ventilation with larg...

Molecular design of sequence specific DNA alkylating agents.

PubMed

Minoshima, Masafumi; Bando, Toshikazu; Shinohara, Ken-ichi; Sugiyama, Hiroshi

2009-01-01

Sequence-specific DNA alkylating agents have great interest for novel approach to cancer chemotherapy. We designed the conjugates between pyrrole (Py)-imidazole (Im) polyamides and DNA alkylating chlorambucil moiety possessing at different positions. The sequence-specific DNA alkylation by conjugates was investigated by using high-resolution denaturing polyacrylamide gel electrophoresis (PAGE). The results showed that polyamide chlorambucil conjugates alkylate DNA at flanking adenines in recognition sequences of Py-Im polyamides, however, the reactivities and alkylation sites were influenced by the positions of conjugation. In addition, we synthesized conjugate between Py-Im polyamide and another alkylating agent, 1-(chloromethyl)-5-hydroxy-1,2-dihydro-3H-benz[e]indole (seco-CBI). DNA alkylation reactivies by both alkylating polyamides were almost comparable. In contrast, cytotoxicities against cell lines differed greatly. These comparative studies would promote development of appropriate sequence-specific DNA alkylating polyamides against specific cancer cells.

Spectroscopy of the low-frequency vibrational modes of CH3+ isotopologues

NASA Astrophysics Data System (ADS)

Asvany, Oskar; Thorwirth, Sven; Redlich, Britta; Schlemmer, Stephan

2018-05-01

The low-frequency stretching and bending vibrations of the isotopologues CH2D+,CD2H+ and CD3+ have been recorded at low temperature and low resolution. For this, a cryogenic 22-pole trapping machine coupled to an IR beamline of the FELIX free electron laser facility has been used. To record the overview spectra, the laser induced reactions CDm Hn+ + H2 → hν CDm-1 Hn+1+ +HD have been applied for these species. As this scheme is not applicable to CH3+, the latter has been tagged with He and subsequently dissociated by the IR beam. For the resulting CH3+ -He spectrum, broad features are observed below 1000 cm-1 possibly related to vibrational motions involving the He atom. The extracted vibrational band positions for all species are compared to results from high-level quantum-chemical calculations.

Stretch-Oriented Polyimide Films

NASA Technical Reports Server (NTRS)

Hinkley, Jeffrey A.; Klinedinst, D.; Feuz, L.

2000-01-01

Two thermoplastic polyimides - one amorphous, the other crystallizable -- were subjected to isothermal stretching just above their glass transition temperatures. Room-temperature strengths in the stretch direction were greatly improved and, moduli increased up to 3.6-fold. Optimum stretching conditions were determined.

Mass spectral analysis of long chain alkyl aromatic compounds synthesized from alpha-olefin alkylation

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

Cheng, M.T.; Hudson, J.D.

1994-12-31

Long chain alkyl aromatic compounds are important petrochemicals with many applications. They are generally synthesized by alkylating the corresponding aromatic nucleus. In this report, the authors will describe the mass spectral fragmentation of alkylphenols and alkylsalicylates.

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

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

Guo, Han; Jackson, Bret, E-mail: jackson@chem.umass.edu

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

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 this...

Stereocontrolled Alkylative Construction of Quaternary Carbon Centers

PubMed Central

Kummer, David A.; Chain, William J.; Morales, Marvin R.; Quiroga, Olga; Myers, Andrew G.

2009-01-01

Protocols for the stereodefined formation of α,α-disubstituted enolates of pseudoephedrine amides are presented followed by the implementation of these in diastereoselective alkylation reactions. Direct alkylation of α,α-disubstituted pseudoephedrine amide substrates is demonstrated to be both efficient and diastereoselective across a range of substrates, as exemplified by alkylation of the diastereomeric pseudoephedrine α-methylbutyramides, where both substrates are found to undergo stereospecific replacement of the α-C-H bond with α-C-alkyl, with retention of stereochemistry. This is shown to arise by sequential stereospecific enolization and alkylation reactions, with the alkyl halide attacking a common π-face of the E- and Z-enolates, proposed to be that opposite the pseudoephedrine alkoxide side-chain. Pseudoephedrine α-phenylbutyramides are found to undergo highly stereoselective but not stereospecific α-alkylation reactions, which evidence suggests is due to facile enolate isomerization. Also, we show that α, α-disubstituted pseudoephedrine amide enolates can be generated in a highly stereocontrolled fashion by conjugate addition of an alkyllithium reagent to the s-cis-conformer of an α-alkyl-α,β-unsaturated pseudoephedrine amide, providing α,α-disubstituted enolate substrates that undergo alkylation in the same sense as those formed by direct deprotonation. Methods are presented to transform the α-quaternary pseudoephedrine amide products into optically active carboxylic acids, ketones, primary alcohols, and aldehydes. PMID:18788739

Molecular structure, supramolecular organization and thermotropic phase behavior of N-acylglycine alkyl esters with matched acyl and alkyl chains.

PubMed

Reddy, S Thirupathi; Swamy, Musti J

2017-11-01

N-Acylglycines (NAGs), the endogenous single-tailed lipids present in rat brain and other mammalian tissues, play significant roles in cell physiology and exhibit interesting pharmacological properties. In the present study, a homologous series of N-acylglycine alkyl esters (NAGEs) with matched chains were synthesized and characterized. Results of differential scanning calorimetric studies revealed that all NAGEs exhibit a single sharp phase transition and that the transition enthalpy and entropy show a linear dependence on the N-acyl and ester alkyl chain length. The structure of N-myristoylglycine myristyl ester (NMGME), solved by single-crystal X-ray diffraction, showed that the molecule adopts a linear geometry and revealed that the structure of N-myristoyl glycyl moiety in NMGME is identical to that in N-myristoylglycine. The molecules are packed in layers with the polar functional groups of the ester and amide functionalities located at the center of the layer. The crystal packing is stabilized by NH⋯O hydrogen bonds between the amide CO and NH groups of adjacent molecules as well as by CH⋯O hydrogen bonds between the amide carbonyl and the methylene CH adjacent to the ester carbonyl of neighboring molecules as well as between ester carbonyl and methylene group of the glycine moiety of adjacent molecules. Powder X-ray diffraction studies showed a linear dependence of the d-spacings on the acyl chain length, suggesting that all NAGEs adopt a structure similar to the packing exhibited in the crystal lattice of NMGME. Copyright © 2017 Elsevier B.V. All rights reserved.

Raman spectroscopic characterization of CH4 density over a wide range of temperature and pressure

USGS Publications Warehouse

Shang, Linbo; Chou, I-Ming; Burruss, Robert; Hu, Ruizhong; Bi, Xianwu

2014-01-01

The positions of the CH4 Raman ν1 symmetric stretching bands were measured in a wide range of temperature (from −180 °C to 350 °C) and density (up to 0.45 g/cm3) using high-pressure optical cell and fused silica capillary capsule. The results show that the Raman band shift is a function of both methane density and temperature; the band shifts to lower wavenumbers as the density increases and the temperature decreases. An equation representing the observed relationship among the CH4 ν1 band position, temperature, and density can be used to calculate the density in natural or synthetic CH4-bearing inclusions.

Influence of the stretch wrapping process on the mechanical behavior of a stretch film

NASA Astrophysics Data System (ADS)

Klein, Daniel; Stommel, Markus; Zimmer, Johannes

2018-05-01

Lightweight construction is an ongoing task in packaging development. Consequently, the stability of packages during transport is gaining importance. This study contributes to the optimization of lightweight packaging concepts regarding their stability. A very widespread packaging concept is the distribution of goods on a pallet whereas a Polyethylene (PE) stretch film stabilizes the lightweight structure during the shipment. Usually, a stretch wrapping machine applies this stretch film to the pallet. The objective of this study is to support packaging development with a method that predicts the result of the wrapping process, based on the mechanical characterization of the stretch film. This result is not only defined by the amount of stretch film, its spatial distribution on the pallet and its internal stresses that result in a containment force. More accurate, this contribution also considers the influence of the deformation history of the stretch film during the wrapping process. By focusing on similarities of stretch wrappers rather than on differences, the influence of generalized process parameters on stretch film mechanics and thereby on pallet stability can be determined experimentally. For a practical use, the predictive method is accumulated in an analytic model of the wrapping process that can be verified experimentally. This paves the way for experimental and numerical approaches regarding the optimization of pallet stability.

Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.

PubMed

Ratani, Tanvi S; Bachman, Shoshana; Fu, Gregory C; Peters, Jonas C

2015-11-04

We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2](-) may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.

Stretch-induced contraction in pulmonary arteries.

PubMed

Kulik, T J; Evans, J N; Gamble, W J

1988-12-01

Stretch stimulates contraction of systemic blood vessels, but the response has not been described in pulmonary vessels. To determine whether pulmonary arteries contract when stretched, isolated cylindrical segments of pulmonary arteries were suspended between two parallel wires, stretched, and the active force was generated in response to stretch measured. Eighty-nine percent of segments from small (in situ diameter less than 1,000 microns) feline pulmonary arteries contracted when stretched, and in 65% of these the magnitude of stretch was related to the magnitude of contraction. Large (in situ diameter greater than or equal to 1,000 microns) feline pulmonary arteries did not contract with stretch. Multiple, rapidly repeated stretches resulted in a diminution of active force development. Stretch-induced contraction required external Ca2+ and was abolished by diltiazem (10 microns), but it was not affected by phenoxybenzamine, phentolamine, diethylcarbamazine, or mechanical removal of endothelium. Indomethacin blunted but did not abolish stretch-induced contraction, an effect that may have been nonspecific. This study suggests that stretch can act, probably directly, on smooth muscle in small feline pulmonary arteries to elicit contraction and that it may be a determinant of pulmonary vascular tone. In addition, feline pulmonary arteries are suitable for the in vitro study of stretch-induced contraction.

Short Durations of Static Stretching when Combined with Dynamic Stretching do not Impair Repeated Sprints and Agility

PubMed Central

Wong, Del P.; Chaouachi, Anis; Lau, Patrick W.C.; Behm, David G.

2011-01-01

This study aimed to compare the effect of different static stretching durations followed by dynamic stretching on repeated sprint ability (RSA) and change of direction (COD). Twenty-five participants performed the RSA and COD tests in a randomized order. After a 5 min aerobic warm up, participants performed one of the three static stretching protocols of 30 s, 60 s or 90 s total duration (3 stretches x 10 s, 20 s or 30 s). Three dynamic stretching exercises of 30 s duration were then performed (90 s total). Sit-and-reach flexibility tests were conducted before the aerobic warm up, after the combined static and dynamic stretching, and post- RSA/COD test. The duration of static stretching had a positive effect on flexibility with 36.3% and 85.6% greater sit-and-reach scores with the 60 s and 90 s static stretching conditions respectively than with the 30 s condition (p ≤ 0.001). However there were no significant differences in RSA and COD performance between the 3 stretching conditions. The lack of change in RSA and COD might be attributed to a counterbalancing of static and dynamic stretching effects. Furthermore, the short duration (≤ 90 s) static stretching may not have provided sufficient stimulus to elicit performance impairments. Key points The duration of combined static and dynamic stretching had a positive effect on flexibility with 36.3% and 85.6% greater sit and reach scores with the 60 s and 90 s static stretching conditions respectively than with the 30 s condition (p ≤ 0.001). No significant differences in RSA and COD between the 3 stretching conditions. The lack of change in RSA and COD might be attributed to a counterbalancing of static and dynamic stretching effects. The short duration (≤ 90 s) static stretching may not have provided sufficient stimulus to elicit performance impairments. PMID:24149890

Short Durations of Static Stretching when Combined with Dynamic Stretching do not Impair Repeated Sprints and Agility.

PubMed

Wong, Del P; Chaouachi, Anis; Lau, Patrick W C; Behm, David G

2011-01-01

This study aimed to compare the effect of different static stretching durations followed by dynamic stretching on repeated sprint ability (RSA) and change of direction (COD). Twenty-five participants performed the RSA and COD tests in a randomized order. After a 5 min aerobic warm up, participants performed one of the three static stretching protocols of 30 s, 60 s or 90 s total duration (3 stretches x 10 s, 20 s or 30 s). Three dynamic stretching exercises of 30 s duration were then performed (90 s total). Sit-and-reach flexibility tests were conducted before the aerobic warm up, after the combined static and dynamic stretching, and post- RSA/COD test. The duration of static stretching had a positive effect on flexibility with 36.3% and 85.6% greater sit-and-reach scores with the 60 s and 90 s static stretching conditions respectively than with the 30 s condition (p ≤ 0.001). However there were no significant differences in RSA and COD performance between the 3 stretching conditions. The lack of change in RSA and COD might be attributed to a counterbalancing of static and dynamic stretching effects. Furthermore, the short duration (≤ 90 s) static stretching may not have provided sufficient stimulus to elicit performance impairments. Key pointsThe duration of combined static and dynamic stretching had a positive effect on flexibility with 36.3% and 85.6% greater sit and reach scores with the 60 s and 90 s static stretching conditions respectively than with the 30 s condition (p ≤ 0.001).No significant differences in RSA and COD between the 3 stretching conditions.The lack of change in RSA and COD might be attributed to a counterbalancing of static and dynamic stretching effects.The short duration (≤ 90 s) static stretching may not have provided sufficient stimulus to elicit performance impairments.

Mild Palladium Catalyzed ortho C-H Bond Functionalizations of Aniline Derivatives.

PubMed

Tischler, Ms Orsolya; Tóth, Mr Balázs; Novák, Zoltán

2017-02-01

This account collects the developments and transformations which avoid the utilization of harsh reaction conditions in the field of palladium catalyzed, ortho-directed C-H activation of aniline derivatives from the first attempts to up-to-date results, including the results of our research laboratory. The discussed functionalizations performed under mild conditions include acylation, olefination, arylation, alkylation, alkoxylation reactions. Beside the optimization studies and the synthetic applications mechanistic investigations are also presented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

Lewis, Jared; Bergman, Robert; Ellman, Jonathan

2008-02-04

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

Direct production of OH radicals upon CH overtone activation of (CH{sub 3}){sub 2}COO Criegee intermediates

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

Liu, Fang; Beames, Joseph M.; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2014-12-21

Ozonolysis of alkenes, a principle non-photolytic source of atmospheric OH radicals, proceeds through unimolecular decay of energized carbonyl oxide intermediates, known as Criegee intermediates. In this work, cold dimethyl-substituted Criegee intermediates are vibrationally activated in the CH stretch overtone region to drive the 1,4 hydrogen transfer reaction that leads to OH radical products. IR excitation of (CH{sub 3}){sub 2}COO reveals the vibrational states with sufficient oscillator strength, coupling to the reaction coordinate, and energy to surmount the effective barrier (≤ 16.0 kcal mol{sup −1}) to reaction. Insight on the dissociation dynamics is gleaned from homogeneous broadening of the spectral features,more » indicative of rapid intramolecular vibrational energy redistribution and/or reaction, as well as the quantum state distribution of the OH X{sup 2}Π (v = 0) products. The experimental results are compared with complementary electronic structure calculations, which provide the IR absorption spectrum and geometric changes along the intrinsic reaction coordinate. Additional theoretical analysis reveals the vibrational modes and couplings that permit (CH{sub 3}){sub 2}COO to access to the transition state region for reaction. The experimental and theoretical results are compared with an analogous recent study of the IR activation of syn-CH{sub 3}CHOO and its unimolecular decay to OH products [F. Liu, J. M. Beames, A. S. Petit, A. B. McCoy, and M. I. Lester, Science 345, 1596 (2014)].« less

Palladium-Catalyzed Borylation of Primary Alkyl Bromides

PubMed Central

Joshi-Pangu, Amruta; Ma, Xinghua; Diane, Mohamed; Iqbal, Sidra; Kribs, Robert J.; Huang, Richard; Wang, Chao-Yuan

2012-01-01

A mild Pd-catalyzed process for the borylation of alkyl bromides has been developed using bis(pinacolato)diboron as a boron source. This process accommodates the use of a wide range of functional groups on the alkyl bromide substrate. Primary bromides react with complete selectivity in the presence of a secondary bromide. The generality of this approach is demonstrated by its extension to the use of alkyl iodides and alkyl tosylates, as well as borylation reactions employing bis(neopentyl glycolato)diboron as the boron source. PMID:22774861

CH stretching vibration of N-methylformamide as a sensitive probe of its complexation: infrared matrix isolation and computational study.

PubMed

Sałdyka, M; Mielke, Z; Mierzwicki, K; Coussan, S; Roubin, P

2011-08-21

The complexes between trans-N-methylformamide (t-NMF) and Ar, N(2), CO, H(2)O have been studied by infrared matrix isolation spectroscopy and/or ab initio calculations. The infrared spectra of NMF/Ne, NMF/Ar and NMF/N(2)(CO,H(2)O)/Ar matrices have been measured and the effect of the complexation on the perturbation of t-NMF frequencies was analyzed. The geometries of the complexes formed between t-NMF and Ar, N(2), CO and H(2)O were optimized in two steps at the MP2/6-311++G(2d,2p) level of theory. The four structures, found for every system at this level, were reoptimized on the CP-corrected potential energy surface; both normal and CP corrected harmonic frequencies and intensities were calculated. For every optimized structure the interaction energy was partitioned according to the SAPT scheme and the topological distribution of the charge density (AIM theory) was performed. The analysis of the experimental and theoretical results indicates that the t-NMF-N(2) and CO complexes present in the matrices are stabilized by very weak N-H···N and N-H···C hydrogen bonds in which the N-H group of t-NMF serves as a proton donor. In turn, the t-NMF-H(2)O complex present in the matrix is stabilized by O-H···O(C) hydrogen bonding in which the carbonyl group of t-NMF acts as a proton acceptor. Both, the theoretical and experimental results indicate that involvement of the NH group of t-NMF in formation of very weak hydrogen bonds with the N(2) or CO molecules leads to a clearly noticeable red shift of the CH stretching wavenumber whereas engagement of the CO group as a proton acceptor triggers a blue shift of this wavenumber.

Aryl sulfonate based anticancer alkylating agents.

PubMed

Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

2018-05-01

This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

DOEpatents

Ginosar, Daniel M [Idaho Falls, ID; Petkovic, Lucia [Idaho Falls, ID

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.

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.

An Effective-Hamiltonian Approach to CH5+, Using Ideas from Atomic Spectroscopy

NASA Astrophysics Data System (ADS)

Hougen, Jon T.

2016-06-01

In this talk we present the first steps in the design of an effective Hamiltonian for the vibration-rotation energy levels of CH5+. Such a Hamiltonian would allow calculation of energy level patterns anywhere along the path travelled by a hypothetical CH5+ (or CD5+) molecule as it passes through various coupling cases, and might thus provide some hints for assigning the observed high-resolution spectra. The steps discussed here, which have not yet addressed computational problems, focus on mapping the vibration-rotation problem in CH5+ onto the five-electron problem in the boron atom, using ideas and mathematical machinery from Condon and Shortley's book on atomic spectroscopy. The mapping ideas are divided into: (i) a mapping of particles, (ii) a mapping of coordinates (i.e., mathematical degrees of freedom), and (iii) a mapping of quantum mechanical interaction terms. The various coupling cases along the path correspond conceptually to: (i) the analog of a free-rotor limit, where the H atoms see the central C atom but do not see each other, (ii) the low-barrier and high-barrier tunneling regimes, and (iii) the rigid-molecule limit, where the H atoms remain locked in some fixed molecular geometry. Since the mappings considered here often involve significant changes in mathematics, a number of interesting qualitative changes occur in the basic ideas when passing from B to CH5+, particularly in discussions of: (i) antisymmetrization and symmetrization ideas, (ii) n,l,ml,ms or n,l,j,mj quantum numbers, and (iii) Russell-Saunders computations and energy level patterns. Some of the mappings from B to CH5+ to be discussed are as follows. Particles: the atomic nucleus is replaced by the C atom, the electrons are replaced by protons, and the empty space between particles is replaced by an "electron soup." Coordinates: the radial coordinates of the electrons map onto the five local C-H stretching modes, the angular coordinates of the electrons map onto three rotational

Hamstring Stiffness Returns More Rapidly After Static Stretching Than Range of Motion, Stretch Tolerance, and Isometric Peak Torque.

PubMed

Hatano, Genki; Suzuki, Shigeyuki; Matsuo, Shingo; Kataura, Satoshi; Yokoi, Kazuaki; Fukaya, Taizan; Fujiwara, Mitsuhiro; Asai, Yuji; Iwata, Masahiro

2017-12-18

Hamstring injuries are common, and lack of hamstring flexibility may predispose to injury. Static stretching increases range of motion (ROM) but also results in reduced muscle strength after stretching. The effects of stretching on the hamstring muscles and the duration of these effects remain unclear. To determine the effects of static stretching on the hamstrings and the duration of these effects. Randomized crossover study. University laboratory. Twenty-four healthy volunteers. We measured the torque-angle relationship (ROM, passive torque (PT) at the onset of pain, and passive stiffness) and isometric muscle force using an isokinetic dynamometer. After a 60-minute rest, the ROM of the dynamometer was set at maximum tolerable intensity; this position was maintained for 300 seconds while static passive torque (SPT) was measured continuously. We remeasured the torque-angle relationship and isometric muscle force after rest periods of 10, 20, and 30 minutes. Change in SPT during stretching; changes in ROM, PT at the onset of pain, passive stiffness, and isometric muscle force before stretching compared with 10, 20, and 30 minutes after stretching. SPT decreased significantly during stretching. Passive stiffness decreased significantly 10 and 20 minutes after stretching, but there was no significant pre- vs. post-stretching difference after 30 minutes. PT at the onset of pain and ROM increased significantly after stretching at all rest intervals, while isometric muscle force decreased significantly after all rest intervals. The effect of static stretching on passive stiffness of the hamstrings was not maintained as long as the changes in ROM, stretch tolerance, and isometric muscle force. Therefore, frequent stretching is necessary to improve the viscoelasticity of the muscle-tendon unit. Muscle force was decreased for 30 minutes after stretching; this should be considered prior to activities requiring maximal muscle strength.

Cooperativity of hydrogen-bonded networks in 7-azaindole(CH3OH)n (n=2,3) clusters evidenced by IR-UV ion-dip spectroscopy and natural bond orbital analysis.

PubMed

Sakota, Kenji; Kageura, Yutaka; Sekiya, Hiroshi

2008-08-07

IR-UV ion-dip spectra of the 7-azaindole (7AI)(CH(3)OH)(n) (n=1-3) clusters have been measured in the hydrogen-bonded NH and OH stretching regions to investigate the stable structures of 7AI(CH(3)OH)(n) (n=1-3) in the S(0) state and the cooperativity of the H-bonding interactions in the H-bonded networks. The comparison of the IR-UV ion-dip spectra with IR spectra obtained by quantum chemistry calculations shows that 7AI(CH(3)OH)(n) (n=1-3) have cyclic H-bonded structures, where the NH group and the heteroaromatic N atom of 7AI act as the proton donor and proton acceptor, respectively. The H-bonded OH stretch fundamental of 7AI(CH(3)OH)(2) is remarkably redshifted from the corresponding fundamental of (CH(3)OH)(2) by 286 cm(-1), which is an experimental manifestation of the cooperativity in H-bonding interaction. Similarly, two localized OH fundamentals of 7AI(CH(3)OH)(3) also exhibit large redshifts. The cooperativity of 7AI(CH(3)OH)(n) (n=2,3) is successfully explained by the donor-acceptor electron delocalization interactions between the lone-pair orbital in the proton acceptor and the antibonding orbital in the proton donor in natural bond orbital (NBO) analyses.

Fourier transform spectroscopy of the CO-stretching band of O-18 methanol

NASA Astrophysics Data System (ADS)

Lees, R. M.; Murphy, Reba-Jean; Moruzzi, Giovanni; Predoi-Cross, Adriana; Xu, Li-Hong; Appadoo, D. R. T.; Billinghurst, B.; Goulding, R. R. J.; Zhao, Saibei

2009-07-01

The high-resolution Fourier transform spectrum of the ν8 CO-stretching band of CH 318OH between 900 and 1100 cm -1 has been recorded at the Canadian Light Source (CLS) synchrotron facility in Saskatoon, and the majority of the torsion-rotation structure has been analyzed. For the ν t = 0 torsional ground state, subbands have been identified for K values from 0 to 11 for A and E torsional symmetries up to J values typically well over 30. For ν t = 1, A and E subbands have been assigned up to K = 7, and several ν t = 2 subbands have also been identified. Upper-state term values determined from the assigned transitions using the Ritz program have been fitted to J( J + 1) power-series expansions to obtain substate origins and sets of state-specific parameters giving a compact representation of the substate J-dependence. The ν t = 0 subband origins have been fitted to effective molecular constants for the excited CO-stretching state and a torsional barrier of 377.49(32) cm -1 is found, representing a 0.89% increase over the ground-state value. The vibrational energy for the CO-stretch state was found to be 1007.49(7) cm -1. A number of subband-wide and J-localized perturbations have been seen in the spectrum, arising both from anharmonic and Coriolis interactions, and several of the interacting states have been identified.

Infrared Spectroscopy of NaCl(CH3OH)n Complexes in Helium Nanodroplets.

PubMed

Sadoon, Ahmed M; Sarma, Gautam; Cunningham, Ethan M; Tandy, Jon; Hanson-Heine, Magnus W D; Besley, Nicholas A; Yang, Shengfu; Ellis, Andrew M

2016-10-10

Infrared (IR) spectra of complexes between NaCl and methanol have been recorded for the first time. These complexes were formed in liquid helium nanodroplets by consecutive pick-up of NaCl and CH 3 OH molecules. For the smallest NaCl(CH 3 OH) n , complexes where n = 1-3, the IR data suggest that the lowest-energy isomer is the primary product in each case. The predominant contribution to the binding comes from ionic hydrogen bonds between the OH in each methanol molecule and the chloride ion in the NaCl, as established by the large red shift of the OH stretching bands compared with the isolated CH 3 OH molecule. For n ≥ 4, there is a dramatic shift from discrete vibrational bands to very broad absorption envelopes, suggesting a profound change in the structural landscape and, in particular, access to multiple low-energy isomers.

Protein lysine-Nζ alkylation and O-phosphorylation mediated by DTT-generated reactive oxygen species

PubMed Central

Kumar, Nigam; Ippel, Hans; Weber, Christian; Hackeng, Tilman; Mayo, Kevin H

2013-01-01

Reactive oxygen species (ROS) play crucial roles in physiology and pathology. In this report, we use NMR spectroscopy and mass spectrometry (MS) to demonstrate that proteins (galectin-1, ubiquitin, RNase, cytochrome c, myoglobin, and lysozyme) under reducing conditions with dithiothreitol (DTT) become alkylated at lysine-Nζ groups and O-phosphorylated at serine and threonine residues. These adduction reactions only occur in the presence of monophosphate, potassium, trace metals Fe/Cu, and oxygen, and are promoted by reactive oxygen species (ROS) generated via DTT oxidation. Superoxide mediates the chemistry, because superoxide dismutase inhibits the reaction, and hydroxyl and phosphoryl radicals are also likely involved. While lysine alkylation accounts for most of the adduction, low levels of phosphorylation are also observed at some serine and threonine residues, as determined by western blotting and MS fingerprinting. The adducted alkyl group is found to be a fragment of DTT that forms a Schiff base at lysine Nζ groups. Although its exact chemical structure remains unknown, the DTT fragment includes a SH group and a –CHOH–CH2– group. Chemical adduction appears to be promoted in the context of a well-folded protein, because some adducted sites in the proteins studied are considerably more reactive than others and the reaction occurs to a lesser extent with shorter, unfolded peptides and not at all with small organic molecules. A structural signature involving clusters of positively charged and other polar groups appears to facilitate the reaction. Overall, our findings demonstrate a novel reaction for DTT-mediated ROS chemistry with proteins. PMID:23315912

Sorbate-nitrite interactions: acetonitrile oxide as an alkylating agent.

PubMed

Pérez-Prior, M Teresa; Gómez-Bombarelli, Rafael; González-Pérez, Marina; Manso, José A; García-Santos, M Pilar; Calle, Emilio; Casado, Julio

2009-07-01

Because chemical species with DNA-damaging and mutagenic activity are formed in sorbate-nitrite mixtures and because sorbic acid sometimes coexists with nitrite occurring naturally or incorporated as a food additive, the study of sorbate-nitrite interactions is important. Here, the alkylating potential of the products resulting from such interactions was investigated. Drawn were the following conclusions: (i) Acetonitrile oxide (ACNO) is the compound responsible for the alkylating capacity of sorbate-nitrite mixtures; (ii) ACNO alkylates 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilic characteristics similar to those of DNA bases, forming an adduct (AD; epsilon = 1.4 x 10(4) M(-1) cm(-1); lambda = 519 nm); (iii) the NBP alkylation reaction complies with the rate equation, r = d[AD]/dt = k(alk)(ACNO)[ACNO][NBP]-k(hyd)(AD)[AD], k(alk)(ACNO) being the NBP alkylation rate constant for ACNO and k(hyd)(AD) the rate constant for the adduct hydrolysis reaction; (iv) the small fraction of ACNO forming the adduct with NBP, as well as the small magnitude of the quotient (k(alk) (ACNO)/k(hyd)(ACNO)) as compared with those reported for other alkylating agents, such as some lactones and N-alkyl-N-nitrosoureas, reveals the ACNO effective alkylating capacity to be less significant; (v) the low value of the NBP-ACNO adduct life (defined as the total amount of adduct present along the progression of the NBP alkylation per unit of alkylating agent concentration) points to the high instability of this adduct; and (vi) the obtained results are in accordance with the low carcinogenicity of ACNO.

Conformational Explosion: Understanding the Complexity of the Para-Dialkylbenzene Potential Energy Surfaces

NASA Astrophysics Data System (ADS)

Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.

2017-06-01

This talk focuses on the single-conformation spectroscopy of small-chain para-dialkylbenzenes. This work builds on previous studies from our group on long-chain n-alkylbenzenes that identified the first folded structure in octylbenzene. The dialkylbenzenes are representative of a class of molecules that are common components of coal and aviation fuel and are known to be present in vehicle exhaust. We bring the molecules para-diethylbenzene, para-dipropylbenzene and para-dibutylbenzene into the gas phase and cool the molecules in a supersonic expansion. The jet-cooled molecules are then interrogated using laser-induced fluorescence excitation, fluorescence dip IR spectroscopy (FDIRS) and dispersed fluorescence. The LIF spectra in the S_{0}-S_{1} origin region show dramatic increases in the number of resolved transitions with increasing length of alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an 'egg carton' shape to the potential energy surface. We use a combination of electronic frequency shift and alkyl CH stretch infrared spectra to generate a consistent set of conformational assignments.

High-Pressure Balloon-Assisted Stretching of the Coracohumeral Ligament to Determine the Optimal Stretching Positions: A Cadaveric Study.

PubMed

Baek, Sora; Lee, Kyu Jin; Kim, Keewon; Han, Seung-Ho; Lee, U-Young; Lee, Kun-Jai; Chung, Sun Gun

2016-10-01

The coracohumeral ligament (CHL) is a thick capsular structure and markedly thickened when affected by adhesive capsulitis. Therapeutic stretching is the most commonly applied treatment for adhesive capsulitis, but optimal stretching postures for maximal therapeutic effects on the CHL have not been fully investigated. To investigate the most effective stretching direction for the CHL by measuring the stretching intensity in 5 different directions and to determine whether the stretching intervention resulted in loosening of the ligament by comparing the changes of CHL tightness before and after stretching. Biomechanical cadaver study. Academic institution cadaver laboratory. Nine fresh frozen cadaveric shoulders. A high-pressure balloon catheter inserted under the CHL and intraballoon pressure was measured, to evaluate CHL tightness without ligament damage as well as to augment and monitor stretching intensity. To find the optimal stretching direction, the glenohumeral joint was stretched from the neutral position into 5 directions sequentially under pressure-monitoring: flexion, extension [EX], external rotation [ER], EX+ER, and EX+ER+adduction [AD] directions. CHL tightness was determined by a surrogate parameter, the additional pressure created by the overlying CHL. The pressure increase (ΔP str ) by a specific directional stretch was considered as the stretching intensity. ΔP str by the 5 directions were mean (standard deviation) values of 0.03 ± 0.07 atm, 0.87 ± 1.31 atm, 1.13 ± 1.36 atm, 1.49 ± 1.32 atm, and 2.10 ± 1.70 atm, respectively, revealing the highest ΔP str by the EX+ER+AD stretch (P < .05). The balloon pressure by the overlying CHL was decreased from 0.45 ± 0.35 atm to 0.18 ± 0.14 atm (P = .012) before and after the stretching manipulation. EX+ER+AD of the glenohumeral joint resulted in the greatest increase in balloon pressure, implying that it could be the most effective stretching direction. A series of stretching manipulations

Prophylactic stretching does not reduce cramp susceptibility.

PubMed

Miller, Kevin C; Harsen, James D; Long, Blaine C

2018-03-01

Some clinicians advocate stretching to prevent muscle cramps. It is unknown whether static or proprioceptive neuromuscular facilitation (PNF) stretching increases cramp threshold frequency (TF c ), a quantitative measure of cramp susceptibility. Fifteen individuals completed this randomized, counterbalanced, cross-over study. We measured passive hallux range of motion (ROM) and then performed 3 minutes of either static stretching, PNF stretching (hold-relax-with agonist contraction), or no stretching. ROM was reassessed and TF c was measured. PNF stretching increased hallux extension (pre-PNF 81 ± 11°, post-PNF 90 ± 10°; P < 0.05) but not hallux flexion (pre-PNF 40 ± 7°, post-PNF 40 ± 7°; P > 0.05). Static stretching increased hallux extension (pre-static 80 ± 11°, post-static 88 ± 9°; P < 0.05) but not hallux flexion (pre-static 38 ± 9°, post-static 39 ± 8°; P > 0.05). No ROM changes occurred with no stretching (P > 0.05). TF c was unaffected by stretching (no stretching 18 ± 7 Hz, PNF 16 ± 4 Hz, static 16 ± 5 Hz; P = 0.37). Static and PNF stretching increased hallux extension, but neither increased TF c . Acute stretching may not prevent muscle cramping. Muscle Nerve 57: 473-477, 2018. © 2017 Wiley Periodicals, Inc.

The formation of quasi-alicyclic rings in alkyl-aromatic compounds

NASA Astrophysics Data System (ADS)

Straka, Pavel; Buryan, Petr; Bičáková, Olga

2018-02-01

The alkyl side chains of n-alkyl phenols, n-alkyl benzenes and n-alkyl naphthalenes are cyclised, as demonstrated by GC measurements, FTIR spectroscopy and molecular mechanics calculations. Cyclisation occurs due to the intramolecular interaction between an aromatic ring (-δ) and a hydrogen of the terminal methyl group (+δ) of an alkyl chain. In fact, conventional molecules are not aliphatic-aromatic, but quasi-alicyclic-aromatic. With the aromatic molecules formed with a quasi-alicyclic ring, the effect of van der Waals attractive forces increases not only intramolecularly but also intermolecularly. This effect is strong in molecules with propyl and higher alkyl substituents. The increase of intermolecular van der Waals attractive forces results in bi-linearity in the GC retention time of the compounds in question, observed in the dependence of the logarithm of the relative retention time on the number of carbons in a molecule in both polar and nonpolar stationary phases with both capillary and packed columns. The role of van der Waals forces has been demonstrated using the potential energies of covalent and noncovalent interactions for 2-n-alkyl phenols, n-alkyl benzenes and 1-n-alkyl- and 2-n-alkyl naphthalenes.

Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

PubMed

Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

2017-07-06

The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of Tributylstannyl Anioniods with Alkyl Bromides.

DTIC Science & Technology

1981-09-28

g (12 mmol) of cesium tert-butoxide was added to the reaction vessel before the addition of n-butyllithium. Alkylation of Tributylstannyl Anionoids...Dry reaction vessels were purged with argon. The desired alkyl halide (1.0 mmol unless noted) and any desired additive were added to the reaction ...OFFICE OF NAVAL RESEARCH Contract N00014-79-C-0584 Task No. NR 053-714 TECHNICAL REPORT No. 2 Reactions of Tributylstannyl Anionoids with Alkyl

Alkylation Damage by Lipid Electrophiles Targets Functional Protein Systems*

PubMed Central

Codreanu, Simona G.; Ullery, Jody C.; Zhu, Jing; Tallman, Keri A.; Beavers, William N.; Porter, Ned A.; Marnett, Lawrence J.; Zhang, Bing; Liebler, Daniel C.

2014-01-01

Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions. PMID:24429493

Alkylating agents for Waldenstrom's macroglobulinaemia.

PubMed

Yang, Kun; Tan, Jianlong; Wu, Taixiang

2009-01-21

Waldenstrom's macroglobulinaemia (WM) is an uncommon B-cell lymphoproliferative disorder characterized by bone marrow infiltration and production of monoclonal immunoglobulin. Uncertainty remains if alkylating agents, such as chlorambucil, melphalan or cyclophosphamide, are an effective form of management. To assess the effects and safety of the alkylating agents on Waldenstrom's macroglobulinaemia (WM). We searched the Cochrane Central Register of Controlled Trials (Issue 1, 2008), MEDLINE (1966 to 2008), EMBASE (1980 to 2008), the Chinese Biomedical Base (1982 to 2008) and reference lists of articles.We also handsearched relevant conference proceedings from 1990 to 2008. Randomised controlled trials (RCTs) comparing alkylating agents given concomitantly with radiotherapy, splenectomy, plasmapheresis, stem-cell transplantation in patients with a confirmed diagnosis of WM. Two authors independently assessed trial quality and extracted data. We contacted study authors for additional information. We collected adverse effects information from the trials. One trial involving 92 participants with pretreated/relapsed WM compared the effect of fludarabine versus the combination of cyclophosphamide (the alkylating agent), doxorubicin and prednisone (CAP). Compared to CAP, the Hazard ratio (HR) for deaths of treatment with fludarabine was estimated to be 1.04, with a standard error of 0.30 (95% CI 0.58 to 1.48) and it indicated that the mean difference of median survival time was -4.00 months, and 16.00 months for response duration. The relative risks (RR) of response rate was 2.80 (95% CI 1.10 to 7.12). There were no statistically difference in overall survival rate and median survival months, while on the basis of response rate and response duration, fludarabine seemed to be superior to CAP for pretreated/relapsed patients with macroglobulinaemia. Although alkylating agents have been used for decades they have never actually been tested in a proper randomised trial. This

Chemical Forms of Selenium in the Metal-Resistant Bacterium Ralstonia metallidurans CH34 Exposed to Selenite and Selenate

PubMed Central

Sarret, Géraldine; Avoscan, Laure; Carrière, Marie; Collins, Richard; Geoffroy, Nicolas; Carrot, Francine; Covès, Jacques; Gouget, Barbara

2005-01-01

Ralstonia metallidurans CH34, a soil bacterium resistant to a variety of metals, is known to reduce selenite to intracellular granules of elemental selenium (Se0). We have studied the kinetics of selenite (SeIV) and selenate (SeVI) accumulation and used X-ray absorption spectroscopy to identify the accumulated form of selenate, as well as possible chemical intermediates during the transformation of these two oxyanions. When introduced during the lag phase, the presence of selenite increased the duration of this phase, as previously observed. Selenite introduction was followed by a period of slow uptake, during which the bacteria contained Se0 and alkyl selenide in equivalent proportions. This suggests that two reactions with similar kinetics take place: an assimilatory pathway leading to alkyl selenide and a slow detoxification pathway leading to Se0. Subsequently, selenite uptake strongly increased (up to 340 mg Se per g of proteins) and Se0 was the predominant transformation product, suggesting an activation of selenite transport and reduction systems after several hours of contact. Exposure to selenate did not induce an increase in the lag phase duration, and the bacteria accumulated approximately 25-fold less Se than when exposed to selenite. SeIV was detected as a transient species in the first 12 h after selenate introduction, Se0 also occurred as a minor species, and the major accumulated form was alkyl selenide. Thus, in the present experimental conditions, selenate mostly follows an assimilatory pathway and the reduction pathway is not activated upon selenate exposure. These results show that R. metallidurans CH34 may be suitable for the remediation of selenite-, but not selenate-, contaminated environments. PMID:15870319

Stretching: Does It Help?

ERIC Educational Resources Information Center

Vardiman, Phillip; Carrand, David; Gallagher, Philip M.

2010-01-01

Stretching prior to activity is universally accepted as an important way to improve performance and help prevent injury. Likewise, limited flexibility has been shown to decrease functional ability and predispose a person to injuries. Although this is commonly accepted, appropriate stretching for children and adolescents involved with sports and…

Status of stretched-membrane heliostats

NASA Astrophysics Data System (ADS)

Alpert, D. J.; Houser, R. M.; Heckes, A. A.

1990-01-01

Since the early 1980s, Sandia National Laboratories has been developing stretched-membrane heliostats for solar central receiver power plants. They differ from conventional glass-mirror heliostats in that the optical surface is a stretched membrane -- a thin metal foil stretched over both sides of a large diameter ring. The reflective surface is provided by either a silvered-acrylic film or thin glass mirrors attached to the front membrane. Heliostats with single 14 m diameter (150 sq meter) stretched-membrane reflectors have been designed. Because of their simplicity and light weight, stretched-membrane heliostats are expected to cost up to one-third less than conventional glass-mirror designs. Two generations of 50 sq meter prototype stretched-membrane mirror modules have been built and evaluated at Sandia's Central Receiver Test Facility in Albuquerque, NM. They demonstrated that the optical performance of membrane heliostats rivals that of glass-mirror heliostats. The durability of the silvered-acrylic reflective film has improved so that a lifetime of at least 5 years is likely; methods of replacing the film in the field are being investigated. Sandia recently initiated the final phase of development: the design of fully integrated, market-ready heliostats. Field tests of these heliostats are planned to begin in FY90.

STRETCHING IMPACTS INFLAMMATION RESOLUTION IN CONNECTIVE TISSUE

PubMed Central

Berrueta, Lisbeth; Muskaj, Igla; Olenich, Sara; Butler, Taylor; Badger, Gary J.; Colas, Romain A.; Spite, Matthew; Serhan, Charles N.; Langevin, Helene M.

2016-01-01

Acute inflammation is accompanied from its outset by the release of specialized pro-resolving mediators (SPMs), including resolvins, that orchestrate the resolution of local inflammation. We showed earlier that, in rats with subcutaneous inflammation of the back induced by carrageenan, stretching for 10 minutes twice daily reduced inflammation and improved pain, two weeks after carrageenan injection. In this study, we hypothesized that stretching of connective tissue activates local pro-resolving mechanisms within the tissue in the acute phase of inflammation. In rats injected with carrageenan and randomized to stretch vs. no stretch for 48 hours, stretching reduced inflammatory lesion thickness and neutrophil count, and increased resolvin (RvD1) concentrations within lesions. Furthermore, subcutaneous resolvin injection mimicked the effect of stretching. In ex vivo experiments, stretching of connective tissue reduced the migration of neutrophils and increased tissue RvD1 concentration. These results demonstrate a direct mechanical impact of stretching on inflammation-regulation mechanisms within connective tissue. PMID:26588184

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.

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 to...

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 to...

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) are...

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) are...

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 to...

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 to...

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) are...

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) are...

A Triatomic Silicon(0) Cluster Stabilized by a Cyclic Alkyl(amino) Carbene.

PubMed

Mondal, Kartik Chandra; Roy, Sudipta; Dittrich, Birger; Andrada, Diego M; Frenking, Gernot; Roesky, Herbert W

2016-02-24

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl4 (cAAC=cyclic alkyl(amino) carbene :C(CMe2)2 (CH2)N(2,6-iPr2C6H3) with potassium graphite produces stable (cAAC)3Si3, a carbene-stabilized triatomic silicon(0) molecule. The Si-Si bond lengths in (cAAC)3Si3 are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si-Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)3Si3 possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymerization of Conducting Polymers Confined to Free Surfaces: A comparison of the Langmuir-Blodgett Polymerization of 3-Alkyl Pyrroles and 2- Alkyl Anilines

DTIC Science & Technology

1992-05-19

Confined to Free Surfaces: A Comparison of the Langmuir-Blodgett Polymerization of 3- Alkyl Pyrroles and 2- Alkyl Anilines Submitted for Publication in...Surfaces: A Comparison of the Langmuir Blodgett Polymerizations of 3- alkyl pyrroles and 2- alkyl anilines R. S. Duran and H.C. Zhou Dept. of Chemistry...polymerization reactions in more detail and compare them. To do this, the polymerization reactions were run under two conditions. In the first case

21 CFR 176.120 - Alkyl ketene dimers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... section. (a) The alkyl ketene dimers are manufactured by the dehydrohalogenation of the acyl halides derived from the fatty acids of animal or vegetable fats and oils. (b) The alkyl ketene dimers are used as...

Methane to methanol conversion induced by thorium oxide through the CH3Th(O)H intermediate in solid argon.

PubMed

Gong, Yu; Andrews, Lester; Jackson, Virgil E; Dixon, David A

2012-10-15

Reactions of ThO molecules and CH(4) have been investigated in solid argon near 4 K. The CH(3)Th(O)H molecule is produced when the sample is exposed to UV irradiation. Identification of this new intermediate is substantiated by observation of the Th═O and Th-H stretching vibrational modes with isotopic substitution via matrix infrared spectroscopy, and the assignments are supported by electronic structure frequency calculations. Methanol absorptions increase together with formation of the CH(3)Th(O)H molecule, suggesting a methane to methanol conversion induced by thorium oxide proceeding through the CH(3)Th(O)H intermediate. The formation of CH(3)Th(O)H from ThO + CH(4) is exothermic (ΔH(rxn) = -11 kcal/mol) with an energy barrier of 30 kcal/mol at the CCSD(T)//B3LYP level. Decomposition of this intermediate to form methanol involves spin crossing, and the overall reaction from the intermediate is endothermic by 127 kcal/mol. There is no activation energy for the reaction of thorium atoms with methanol to give CH(3)Th(O)H, as observed in separate experiments with Th and CH(3)OH.

Immediate Effects of Proprioceptive Neuromuscular Facilitation Stretching Programs Compared With Passive Stretching Programs for Hamstring Flexibility: A Critically Appraised Topic.

PubMed

Hill, Kristian J; Robinson, Kendall P; Cuchna, Jennifer W; Hoch, Matthew C

2017-11-01

Clinical Scenario: Increasing hamstring flexibility through clinical stretching interventions may be an effective means to prevent hamstring injuries. However the most effective method to increase hamstring flexibility has yet to be determined. For a healthy individual, are proprioceptive neuromuscular facilitation (PNF) stretching programs more effective in immediately improving hamstring flexibility when compared with static stretching programs? Summary of Key Findings: A thorough literature search returned 195 possible studies; 5 studies met the inclusion criteria and were included. Current evidence supports the use of PNF stretching or static stretching programs for increasing hamstring flexibility. However, neither program demonstrated superior effectiveness when examining immediate increases in hamstring flexibility. Clinical Bottom Line: There were consistent findings from multiple low-quality studies that indicate there is no difference in the immediate improvements in hamstring flexibility when comparing PNF stretching programs to static stretching programs in physically active adults. Strength of Recommendation: Grade B evidence exists that PNF and static stretching programs equally increase hamstring flexibility immediately following the stretching program.

A Concentration-Dependent Insulin Immobilization Behavior of Alkyl-Modified Silica Vesicles: The Impact of Alkyl Chain Length.

PubMed

Zhang, Jun; Zhang, Long; Lei, Chang; Huang, Xiaodan; Yang, Yannan; Yu, Chengzhong

2018-05-01

The insulin immobilization behaviors of silica vesicles (SV) before and after modification with hydrophobic alkyl -C 8 and -C 18 groups have been studied and correlated to the grafted alkyl chain length. In order to minimize the influence from the other structural parameters, monolayered -C 8 or -C 18 groups are grafted onto SV with controlled density. The insulin immobilization capacity of SV is dependent on the initial insulin concentrations (IIC). At high IIC (2.6-3.0 mg/mL), the trend of insulin immobilization capacity of SV is SV-OH > SV-C 8 > SV-C 18 , which is determined mainly by the surface area of SV. At medium IIC (0.6-1.9 mg/mL), the trend changes to SV-C 8 ≥ SV-C 18 > SV-OH as both the surface area and alkyl chain length contribute to the insulin immobilization. At an extremely low IIC, the hydrophobic-hydrophobic interaction between the alkyl group and insulin molecules plays the most significant role. Consequently, SV-C 18 with longer alkyl groups and the highest hydrophobicity show the best insulin enrichment performance compared to SV-C 8 and SV-OH, as evidenced by an insulin detection limit of 0.001 ng/mL in phosphate buffered saline (PBS) and 0.05 ng/mL in artficial urine determined by mass spectrometry (MS).

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,...

Stretch Band Exercise Program

ERIC Educational Resources Information Center

Skirka, Nicholas; Hume, Donald

2007-01-01

This article discusses how to use stretch bands for improving total body fitness and quality of life. A stretch band exercise program offers a versatile and inexpensive option to motivate participants to exercise. The authors suggest practical exercises that can be used in physical education to improve or maintain muscular strength and endurance,…

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 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 the...

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 the...

Effect of polyoxyethylene n-alkyl ethers on carrier-mediated transport of lanthanide ions through cellulose triacetate membranes

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

Sugiura, Masaaki

1992-02-01

Fluxes of 14 kinds of lanthanides across cellulose triacetate membranes were determined by using mixtures of o-nitrophenyl n-octyl ether and a series of polyoxythylene n-alkyl ethers (POE ethers) as plasticizers, and hinokitiol as carrier. Effects of alkyl and polyoxyethylene (POE) chains of POE ether on the flux were demonstrated. The transport of the lanthanides was coupled to a flow of hydrogen ions. The POE ethers used (C{sub n}H{sub 2n+1}(OCH{sub 2}CH{sub 2}){sub x}OH, referred to as C{sub n}E{sub x}) were C{sub 10}E{sub 3}, C{sub 12}E{sub 3}, C{sub 14}E{sub 3}, C{sub 16}E{sub 3}, C{sub 12}E{sub 2}, C{sub 12}E{sub 4}, C{sub 12}E{sub 6}more » and C{sub 12}E{sub 8}, In all cases, high fluxes were observed for the lanthanides from samarium to lutetium. On the contrary, the fluxes for lanthanum to neodymium were extremely low. In experiments testing the effect of the alkyl chain, the order of the POE ethers in the lanthanide flux for samarium to lutetium was C{sub 12}E{sub 3} > C{sub 10}E{sub 3} > C{sub 14}E{sub 3} >C{sub 16}E{sub 3}. In experiments testing the effect of the POE chain, the flux decreased with an increase in the chain length.« less

Time-resolved photoelectron imaging of iodide-nitromethane (I-·CH3NO2) photodissociation dynamics.

PubMed

Kunin, Alice; Li, Wei-Li; Neumark, Daniel M

2016-12-07

Femtosecond time-resolved photoelectron spectroscopy is used to probe the decay channels of iodide-nitromethane (I - ·CH 3 NO 2 ) binary clusters photoexcited at 3.56 eV, near the vertical detachment energy (VDE) of the cluster. The production of I - is observed, and its photoelectron signal exhibits a mono-exponential rise time of 21 ± 1 ps. Previous work has shown that excitation near the VDE of the I - ·CH 3 NO 2 complex transfers an electron from iodide to form a dipole-bound state of CH 3 NO 2 - that rapidly converts to a valence bound (VB) anion. The long appearance time for the I - fragment suggests that the VB anion decays by back transfer of the excess electron to iodide, reforming the I - ·CH 3 NO 2 anion and resulting in evaporation of iodide. Comparison of the measured lifetime to that predicted by RRKM theory suggests that the dissociation rate is limited by intramolecular vibrational energy redistribution in the re-formed anion between the high frequency CH 3 NO 2 vibrational modes and the much lower frequency intermolecular I - ·CH 3 NO 2 stretch and bends, the predominant modes involved in cluster dissociation to form I - . Evidence for a weak channel identified as HI + CH 2 NO 2 - is also observed.

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

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

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 triaromaticmore » 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.« less

Surface modification and antimicrobial properties of cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Bespalova, Yulia A.

Surface modification of cellulose nanocrystals (CNC) was performed by acetylation and subsequent reaction with various tertiary amines with different lengths of alkyl groups. Chloroacetic anhydride (95%) was used for acetylation. The acetylation of CNC was confirmed using IR spectroscopy. The bands associated with C=0 stretching (1740 cm-1) and C-Cl stretching (793 cm -1) was present in the acetylated CNC but they were absent in the neat CNC. It has been suggested that the primary hydroxyl groups of CNC are substituted by chloro acetyl groups during acetylation reaction. Subsequent reaction of chloro acetylated CNC with N, N - Dimethyl ethylamine, N, N - Dimethyl hexylamine, N, N - Dimethyl dodecylamine, N, N - Dimethyl hexadecylamine and N, N - Dimethyl decylamine formed quaternary ammonium salts. These quaternary ammonium salts were characterized by FTIR and solid state13C NMR spectroscopy. FTIR spectra of five types of quaternary ammonium salts of CNC are similar and they showed infrared bands at 2905 -1 and 2850 cm-1, attributed to symmetrical and unsymmetrical C-H stretching vibration. The absence of C-Cl band at 793 cm-1 proves that quaternary salt formation was successful. The 13C NMR spectrum of quaternary ammonium modified CNC with N, N - Dimethyl dodecylamine shows several additional resonances ranging from 14.5 ppm to 58.0 ppm when compared to 13C NMR spectrum of pure CNC. This evidence proves that long alkyl chains have been added to the pure CNC. The disc diffusion method confirmed that quaternary ammonium modified CNCs with a chain longer than ten carbons are effective antimicrobial agents against Staphylococcus aureus and E. coli bacteria. Pure CNC and quaternary ammonium modified CNCs with an alkyl chain length of ten or less were not able to inhibit bacteria growth.

Rhodium(III)-Catalyzed ortho-Alkylation of Phenoxy Substrates with Diazo Compounds via C-H Activation: A Case of Decarboxylative Pyrimidine/Pyridine Migratory Cyclization Rather than Removal of Pyrimidine/Pyridine Directing Group.

PubMed

Ravi, Manjula; Allu, Srinivasarao; Swamy, K C Kumara

2017-03-03

An efficient Rh(III)-catalyzed ortho-alkylation of phenoxy substrates with diazo compounds has been achieved for the first time using pyrimidine or pyridine as the directing group. Furthermore, bis-alkylation has also been achieved using para-substituted phenoxypyrimidine and 3 mol equiv of the diazo ester. The ortho-alkylated derivatives of phenoxy products possessing the ester functionality undergo decarboxylative pyrimidine/pyridine migratory cyclization (rather than deprotection of pyrimidine/pyridine group) using 20% NaOEt in EtOH affording a novel class of 3-(pyrimidin-2(1H)-ylidene)benzofuran-2(3H)-ones and 6-methyl-3-(pyridin-2(1H)-ylidene)benzofuran-2(3H)-one. The ortho-alkylated phenoxypyridine possessing ester functionality also undergoes decarboxylative pyridine migratory cyclization using MeOTf/NaOMe in toluene providing 6-methyl-3-(1-methylpyridin-2(1H)-ylidene)benzofuran-2(3H)-one.

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.

Isomeric Detergent Comparison for Membrane Protein Stability: Importance of Inter-Alkyl-Chain Distance and Alkyl Chain Length

PubMed Central

Cho, Kyung Ho; Hariharan, Parameswaran; Mortensen, Jonas S.; Du, Yang; Nielsen, Anne K.; Byrne, Bernadette; Kobilka, Brian K.; Loland, Claus J.; Guan, Lan

2017-01-01

Membrane proteins encapsulated by detergent micelles are widely used for structural study. Because of their amphipathic property, detergents have the ability to maintain protein solubility and stability in an aqueous medium. However, conventional detergents have serious limitations in their scope and utility, particularly for eukaryotic membrane proteins and membrane protein complexes. Thus, a number of new agents have been devised; some have made significant contributions to membrane protein structural studies. However, few detergent design principles are available. In this study, we prepared meta and ortho isomers of the previously reported para-substituted xylene-linked maltoside amphiphiles (XMAs), along with alkyl chain-length variation. The isomeric XMAs were assessed with three membrane proteins, and the meta isomer with a C12 alkyl chain was most effective at maintaining solubility/stability of the membrane proteins. We propose that interplay between the hydrophile–lipophile balance (HLB) and alkyl chain length is of central importance for high detergent efficacy. In addition, differences in inter-alkyl-chain distance between the isomers influence the ability of the detergents to stabilise membrane proteins. PMID:27981750

Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

PubMed

Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

2017-12-18

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkyl group effects on CO insertion into coordinatively unsaturated early-transition-metal alkyls. Preparations and the first structural characterizations of tantalum enolate-O and tantalum. eta. sup 2 -acyl complexes

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

Meyer, T.Y.; Garner, L.R.; Baenziger, N.C.

1990-10-03

Low-pressure carbonylation of the mono(peralkylcyclopentadienyl)tantalum(V) alkyls ({eta}-C{sub 5}Me{sub 4}R)TaR{prime}Cl{sub 3} (R = Me, Et; R{prime} = CH{sub 2}C{sub 6}H{sub 4}-p-Me, CH{sub 2}CMe{sub 3}) yields either the O-bound enolate or the {eta}{sup 2}-acyl as shown by ir/NMR spectroscopy and x-ray diffractometry. The p-tolyl enolate ({eta}-C{sub 5}Me{sub 5})Ta(OCH{double bond}CHC{sub 6}H{sub 4}-p-Me)Cl{sub 3}, derived directly from carbonylation of the tantalum 4-methylbenzyl precursor, is shown to possess a cis configuration in solution and in the solid state. Key structural features from a single-crystal x-ray diffraction study of the tetrahydrofuran-ligated enolate complex are reported. The mechanism of formation of the enolate from carbonylation of themore » 4-methylbenzyl complex is discussed. The previously reported acyl ({eta}-C{sub 5}Me{sub 4}R)Ta(C(O)CH{sub 2}CMe{sub 3})Cl{sub 3} has been reexamined and found to possess a symmetric, strongly distorted {eta}{sup 2}-acyl coordination by solution {sup 1}H NMR spectroscopy and solid-state x-ray diffractometry. The molecular structures of ({eta}-C{sub 5}Me{sub 5})Ta(OCH{double bond}CHC{sub 6}H{sub 4}-p-Me)Cl{sub 3} and ({eta}-C{sub 5}Me{sub 5})Ta(C(O)CH{sub 2}CMe{sub 3})Cl{sub 3}, which are reported here, are the first structural determinations of a tantalum enolate and of a tantalum {eta}{sup 2}-acyl. 41 refs., 2 figs., 8 tabs.« less

Endovascular rescue method for undesirably stretched coil.

PubMed

Cho, Jae Hoon

2014-10-01

Undesirable detachment or stretching of coils within the parent artery during aneurysm embolization can be related with thrombus formation, which can be caused occlusion of parent artery or embolic event(s). To escape from this situation, several rescue methods have been reported. A case with undesirably stretched coil in which another rescue method was used, is presented. When the stretched coil is still located in the coil delivery microcatheter, the stretched coil can be removed safely using a snare and a handmade monorail microcatheter. After a snare is lodged in the handmade monorail microcatheter, the snare is introduced over the coil delivery micorcatheter and located in the distal part of the stretched coil. After then, the handmade monorail microcatheter captures the stretched coil and the snare as one unit. This technique using a handmade monorail microcatheter and a snare can be a good rescue modality for the undesirably stretched coil, still remained within the coil delivery microcatheter.

Endovascular Rescue Method for Undesirably Stretched Coil

PubMed Central

2014-01-01

Undesirable detachment or stretching of coils within the parent artery during aneurysm embolization can be related with thrombus formation, which can be caused occlusion of parent artery or embolic event(s). To escape from this situation, several rescue methods have been reported. A case with undesirably stretched coil in which another rescue method was used, is presented. When the stretched coil is still located in the coil delivery microcatheter, the stretched coil can be removed safely using a snare and a handmade monorail microcatheter. After a snare is lodged in the handmade monorail microcatheter, the snare is introduced over the coil delivery micorcatheter and located in the distal part of the stretched coil. After then, the handmade monorail microcatheter captures the stretched coil and the snare as one unit. This technique using a handmade monorail microcatheter and a snare can be a good rescue modality for the undesirably stretched coil, still remained within the coil delivery microcatheter. PMID:25371791

A randomized controlled trial for the effect of passive stretching on measures of hamstring extensibility, passive stiffness, strength, and stretch tolerance.

PubMed

Marshall, Paul W M; Cashman, Anthony; Cheema, Birinder S

2011-11-01

To measure hamstring extensibility, stiffness, stretch tolerance, and strength following a 4-week passive stretching program. Randomized controlled trial. Twenty-two healthy participants were randomly assigned to either a 4-week stretching program consisting of 4 hamstring and hip stretches performed 5 times per week, or a non-stretching control group. Hamstring extensibility and stiffness were measured before and after training using the instrumented straight leg raise test (iSLR). Stretch tolerance was measured as the pain intensity (visual analog scale; VAS) elicited during the maximal stretch. Hamstring strength was measured using isokinetic dynamometry at 30 and 120° s(-1). Hamstring extensibility increased by 20.9% in the intervention group following 4 weeks of training (p<0.001; d=0.86). Passive stiffness was reduced by 31% in the intervention group (p<0.05; d=-0.89). Stretch tolerance VAS scores were not different between groups at either time point, and no changes were observed following training. There were no changes in hamstring concentric strength measured at 30 and 120° s(-1). Passive stretching increases hamstring extensibility and decreases passive stiffness, with no change in stretch tolerance defined by pain intensity during the stretch. Compared to previous research, the volume of stretching was higher in this study. The volume of prescribed stretching is important for eliciting the strong clinical effect observed in this study. Copyright © 2011 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

PubMed Central

Fang, Wei-Jie; Yakovleva, Tatyana; Aldrich, Jane V.

2014-01-01

Peptide C-terminal N-alkyl amides have gained more attention over the past decade due to their biological properties, including improved pharmacokinetic and pharmacodynamic profiles. However, the synthesis of this type of peptide on solid phase by current available methods can be challenging. Here we report a convenient method to synthesize peptide C-terminal N-alkyl amides using the well-known Fukuyama N-alkylation reaction on a standard resin commonly used for the synthesis of peptide C-terminal primary amides, the PAL-PEG-PS (Peptide Amide Linker-polyethylene glycol-polystyrene) resin. The alkylation and oNBS deprotection were conducted under basic conditions and were therefore compatible with this acid labile resin. The alkylation reaction was very efficient on this resin with a number of different alkyl iodides or bromides, and the synthesis of model enkephalin N-alkyl amide analogs using this method gave consistently high yields and purities, demonstrating the applicability of this methodology. The synthesis of N-alkyl amides was more difficult on a Rink amide resin, especially the coupling of the first amino acid to the N-alkyl amine, resulting in lower yields for loading the first amino acid onto the resin. This method can be widely applied in the synthesis of peptide N-alkyl amides. PMID:22252422

Synthesis, characterization, and relative stabilities of self-assembled monolayers on gold generated from bidentate n-alkyl xanthic acids.

PubMed

Moore, H Justin; Colorado, Ramon; Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

2013-08-27

A series of self-assembled monolayers (SAMs) on gold were generated by the adsorption of n-alkyl xanthic acids (NAXAs) having the general formula CH3(CH2)nOCS2H (n = 12-15). The structural features of these SAMs were characterized by optical ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). This series of xanthate SAMs were compared to SAMs generated from the corresponding n-alkanethiols and aliphatic dithiocarboxylic acids (ADTCAs). The collected data indicate that the NAXAs generate densely packed and well-ordered monolayers. The contact angles of hexadecane on the xanthate monolayers exhibited a large "odd-even" effect similar to that produced by the ADTCA SAMs. The relative stability of these bidentate xanthate SAMs was evaluated by monitoring the changes in ellipsometric thicknesses and wettability as a function of time under various conditions. The results demonstrate that SAMs formed from NAXAs are much less stable than analogous n-alkanethiolate and ADTCA SAMs.

40 CFR 721.10677 - Alkyl phosphonate (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10677 Alkyl phosphonate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl phosphonate (PMN P-12-584...

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.

Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions: relevance of their surface active properties and of the type of emulsifier.

PubMed

González, María J; Medina, Isabel; Maldonado, Olivia S; Lucas, Ricardo; Morales, Juan C

2015-09-15

The antioxidant activity of gallic acid and a series of alkyl gallates (C4-C18) and glycosylated alkyl gallates (C4-C18) on fish oil-in-water emulsions was studied. Three types of emulsifiers, lecithin, Tween-20 and sodium dodecyl sulphate (SDS) were tested. A nonlinear behavior of the antioxidant activity of alkyl gallates when increasing alkyl chain length was observed for emulsions prepared with lecithin. Medium-size alkyl gallates (C6-C12) were the best antioxidants. In contrast, for emulsions prepared with Tween-20, the antioxidants seem to follow the polar paradox. Glucosyl alkyl gallates were shown previously to be better surfactants than alkyl gallates. Nevertheless, they exhibited a worse antioxidant capacity than their corresponding alkyl gallates, in emulsions prepared with lecithin or Tween-20, indicating the greater relevance of having three OH groups at the polar head in comparison with having improved surfactant properties but just a di-ortho phenolic structure in the antioxidant. Copyright © 2015 Elsevier Ltd. All rights reserved.

Anisotropic instability of a stretching film

NASA Astrophysics Data System (ADS)

Xu, Bingrui; Li, Minhao; Deng, Daosheng

2017-11-01

Instability of a thin liquid film, such as dewetting arising from Van der Waals force, has been well studied, and is typically characterized by formation of many droplets. Interestingly, a thin liquid film subjected to an applied stretching during a process of thermal drawing is evolved into an array of filaments, i.e., continuity is preserved along the direction of stretching while breakup occurs exclusively in the plane of cross section. Here, to understand this anisotropic instability, we build a physical model by considering both Van der Waals force and the effect of stretching. By using the linear instability analysis method and then performing a numerical calculation, we find that the growth rate of perturbations at the cross section is larger than that along the direction of stretching, resulting in the anisotropic instability of the stretching film. These results may provide theoretical guidance to achieve more diverse structures for nanotechnology.

Manipulation of sensory input can improve stretching outcomes.

PubMed

Capobianco, Robyn A; Almuklass, Awad M; Enoka, Roger M

2018-02-01

The primary purpose of our study was to assess the influence of modulating sensory input with either transcutaneous electrical nerve stimulation (TENS) or self-massage with therapy balls on the maximal range of motion (ROM) about the ankle joint when stretching the calf muscles. We also investigated the influence of these two conditions on the force capacity and force control of plantar flexor muscles. Twenty healthy adults (25 ± 3 yr) performed three sessions of ankle plantar flexor stretching (three stretches of 30 s each): stretching alone (SS), stretching with concurrent TENS (TENS), and stretching after self-massage using therapy balls (SM). TENS was applied for 60 s prior to and during each stretch, and SM was performed for 60 s prior to each of the three stretches. Maximal voluntary contraction (MVC) torque and force steadiness at 20% MVC were recorded before and at 15 min after the final stretch. Ankle dorsiflexion ROM was assessed before, after, and at 5, 10, and 15 min after the last stretch. The increase in ROM was greater after SM (24%) than after SS (13%) and TENS (9%; p < .001). Maximal discomfort level (0-10 VAS) during stretching was similar for all conditions. MVC torque increased after SM only (p < .001, Cohen's D = 1.5): SM, 16%; SS, -1%; TENS, -3%. Force steadiness did not change. The sensory fibres that contribute to stretch tolerance were engaged by self-massage but not by TENS, resulting in greater increases in flexibility and MVC torque after self-massage.

Hydraulic fracture during epithelial stretching

NASA Astrophysics Data System (ADS)

Casares, Laura; Vincent, Romaric; Zalvidea, Dobryna; Campillo, Noelia; Navajas, Daniel; Arroyo, Marino; Trepat, Xavier

2015-03-01

The origin of fracture in epithelial cell sheets subject to stretch is commonly attributed to excess tension in the cells’ cytoskeleton, in the plasma membrane, or in cell-cell contacts. Here, we demonstrate that for a variety of synthetic and physiological hydrogel substrates the formation of epithelial cracks is caused by tissue stretching independently of epithelial tension. We show that the origin of the cracks is hydraulic; they result from a transient pressure build-up in the substrate during stretch and compression manoeuvres. After pressure equilibration, cracks heal readily through actomyosin-dependent mechanisms. The observed phenomenology is captured by the theory of poroelasticity, which predicts the size and healing dynamics of epithelial cracks as a function of the stiffness, geometry and composition of the hydrogel substrate. Our findings demonstrate that epithelial integrity is determined in a tension-independent manner by the coupling between tissue stretching and matrix hydraulics.

Hydraulic fracture during epithelial stretching

PubMed Central

Casares, Laura; Vincent, Romaric; Zalvidea, Dobryna; Campillo, Noelia; Navajas, Daniel; Arroyo, Marino; Trepat, Xavier

2015-01-01

The origin of fracture in epithelial cell sheets subject to stretch is commonly attributed to excess tension in the cells’ cytoskeleton, in the plasma membrane, or in cell-cell contacts. Here we demonstrate that for a variety of synthetic and physiological hydrogel substrates the formation of epithelial cracks is caused by tissue stretching independently of epithelial tension. We show that the origin of the cracks is hydraulic; they result from a transient pressure build-up in the substrate during stretch and compression maneuvers. After pressure equilibration cracks heal readily through actomyosin-dependent mechanisms. The observed phenomenology is captured by the theory of poroelasticity, which predicts the size and healing dynamics of epithelial cracks as a function of the stiffness, geometry and composition of the hydrogel substrate. Our findings demonstrate that epithelial integrity is determined in a tension-independent manner by the coupling between tissue stretching and matrix hydraulics. PMID:25664452

Effect of the C-2 hydroxyl group on the mesomorphism of alkyl glycosides: synthesis and thermotropic behavior of alkyl 2-deoxy-D-arabino-hexopyranosides.

PubMed

Singh, Madan Kumar; Jayaraman, Narayanaswamy; Rao, D S Shankar; Prasad, S Krishna

2008-10-01

A homologous series of alkyl 2-deoxy-alpha-d-arabino-hexopyranosides and alkyl 2-deoxy-beta-d-arabino-hexopyranosides were synthesized, upon glycosylation of 1-alkanols (from C8 to C18 alkanols) with ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-d-arabino-hexopyranoside, followed by a deprotection. The thermotropic behavior of these new types of alkyl glycosides was investigated. It was observed that the beta-anomers of these alkyl glycosides, bearing nonyl to tetradecyl alkyl chain are mesomorphic, exhibiting monotropic smectic A phase. In contrast, the alpha-anomers are all non-mesomorphic. An effort to identify the liquid crystalline behavior of binary mixtures of the alpha- and beta-anomers was undertaken and it was found that mixtures containing equimolar amounts of the anomers exhibited mesomorphic behavior. A fine balance of the hydrophilic and hydrophobic components within the molecule is also found to be important for the alkyl 2-deoxy glycosides to form the mesophase.

Direct N-alkylation of unprotected amino acids with alcohols

PubMed Central

Yan, Tao; Feringa, Ben L.; Barta, Katalin

2017-01-01

N-alkyl amino acids find widespread application as highly valuable, renewable building blocks. However, traditional synthesis methodologies to obtain these suffer from serious limitations, providing a major challenge to develop sustainable alternatives. We report the first powerful catalytic strategy for the direct N-alkylation of unprotected α-amino acids with alcohols. This method is highly selective, produces water as the only side product leading to a simple purification procedure, and a variety of α-amino acids are mono- or di-N-alkylated, in most cases with excellent retention of optical purity. The hydrophobicity of the products is tunable, and even simple peptides are selectively alkylated. An iron-catalyzed route to mono-N-alkyl amino acids using renewable fatty alcohols is also described that represents an ideal green transformation for obtaining fully bio-based surfactants. PMID:29226249

Isomeric Detergent Comparison for Membrane Protein Stability: Importance of Inter-Alkyl-Chain Distance and Alkyl Chain Length.

PubMed

Cho, Kyung Ho; Hariharan, Parameswaran; Mortensen, Jonas S; Du, Yang; Nielsen, Anne K; Byrne, Bernadette; Kobilka, Brian K; Loland, Claus J; Guan, Lan; Chae, Pil Seok

2016-12-14

Membrane proteins encapsulated by detergent micelles are widely used for structural study. Because of their amphipathic property, detergents have the ability to maintain protein solubility and stability in an aqueous medium. However, conventional detergents have serious limitations in their scope and utility, particularly for eukaryotic membrane proteins and membrane protein complexes. Thus, a number of new agents have been devised; some have made significant contributions to membrane protein structural studies. However, few detergent design principles are available. In this study, we prepared meta and ortho isomers of the previously reported para-substituted xylene-linked maltoside amphiphiles (XMAs), along with alkyl chain-length variation. The isomeric XMAs were assessed with three membrane proteins, and the meta isomer with a C 12 alkyl chain was most effective at maintaining solubility/stability of the membrane proteins. We propose that interplay between the hydrophile-lipophile balance (HLB) and alkyl chain length is of central importance for high detergent efficacy. In addition, differences in inter-alkyl-chain distance between the isomers influence the ability of the detergents to stabilise membrane proteins. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cardiovascular Responses to Skeletal Muscle Stretching: "Stretching" the Truth or a New Exercise Paradigm for Cardiovascular Medicine?

PubMed

Kruse, Nicholas T; Scheuermann, Barry W

2017-12-01

Stretching is commonly prescribed with the intended purpose of increasing range of motion, enhancing muscular coordination, and preventing prolonged immobilization induced by aging or a sedentary lifestyle. Emerging evidence suggests that acute or long-term stretching exercise may modulate a variety of cardiovascular responses. Specifically, at the onset of stretch, the mechanical deformation of the vascular bed coupled with stimulation of group III muscle afferent fibers initiates a cascade of events resulting in both peripheral vasodilation and a heart rate-driven increase in cardiac output, blood pressure, and muscle blood flow. This potential to increase shear stress and blood flow without the use of excessive muscle energy expenditure may hold important implications for future therapeutic vascular medicine and cardiac health. However, the idea that a cardiovascular component may be involved in human skeletal muscle stretching is relatively new. Therefore, the primary intent of this review is to highlight topics related to skeletal muscle stretching and cardiovascular regulation and function. The current evidence suggests that acute stretching causes a significant macro- and microcirculatory event that alters blood flow and the relationship between oxygen availability and oxygen utilization. These acute vascular changes if performed chronically may result in improved endothelial function, improved arterial blood vessel stiffness, and/or reduced blood pressure. Although several mechanisms have been postulated, an increased nitric oxide bioavailability has been highlighted as one promising candidate for the improvement in vessel function with stretching. Collectively, the evidence provided in this review suggests that stretching acutely or long term may serve as a novel and alternative low intensity therapeutic intervention capable of improving several parameters of vascular function.

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.

Salvage of Failed Protein Targets by Reductive Alkylation

PubMed Central

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

Balancing repair and tolerance of DNA damage caused by alkylating agents.

PubMed

Fu, Dragony; Calvo, Jennifer A; Samson, Leona D

2012-01-12

Alkylating agents constitute a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER) and mismatch repair (MMR), respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for a favourable response of an organism to alkylating agents. Furthermore, the response of an individual to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity.

Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

PubMed

Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

2013-10-01

Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

Rotational spectrum of CH3CN⋯ClF and evidence for the +I effect of a CH3 group on the ‘chlorine’ bond N⋯ClF

NASA Astrophysics Data System (ADS)

Page, M. D.; Waclawik, E. R.; Holloway, J. H.; Legon, A. C.

1999-10-01

The ground-state rotational spectra of the isotopomers CH 3C 14N⋯ 35ClF, CH 3C 14N⋯ 37ClF, CD 3C 14N⋯ 35ClF and CH 3C 15N⋯ 35ClF of a symmetric-rotor complex formed by methyl cyanide and chlorine monofluoride have been observed and analysed to give the spectroscopic constants B0, DJ, DJK, χaa( 14N), χaa(Cl) and Mbb. Interpretations of these quantities on the basis of simple models enabled the geometry and strength of binding of the complex to be determined. It is found that the atoms C-CN⋯ClF lie on the C 3 axis of this complex of C 3v symmetry and that the distance r(N⋯Cl)=2.561(2) Å. The quadratic force constants associated with the intermolecular stretching mode and with the bending motion of the CH 3CN subunit pivoted at its mass centre were determined from the centrifugal distortion constants DJ and 2 DJ+ DJK. Their values were k σ=13.9(3) N m -1 and k α=3.0(1)×10 -20 J rad -2, respectively. A comparison of r(N⋯Cl) values and of k σ values establishes that the +I effect of the CH 3 group when it replaces H in HCN leads to a similar shortening of r(N⋯Cl) and to a similar increase in k σ in the two series RCN⋯ClF and RCN⋯HCl (R=H or CH 3).

Identification of alkyl carbazoles and alkyl benzocarbazoles in Brazilian petroleum derivatives.

PubMed

Oliveira, Eniz Conceição; Vaz de Campos, Maria Cecília; Rodrigues, Maria Regina Alves; Pérez, Valéria Flores; Melecchi, Maria Inês Soares; Vale, Maria Goreti Rodrigues; Zini, Cláudia Alcaraz; Caramão, Elina Bastos

2006-02-10

Carbozoles are important compounds in crude oils, as they may be used as geochemical tracers, being the major type of nitrogen compounds in petroleum. At the same time, they are regarded as undesirable due to the problems they may cause in the refining process, such as catalyst poisoning, corrosion, gum or color formation in final products. As separation and identification of carbazoles are challenging goals, this work presents a chromatographic method, made of a pre-fractionation on neutral alumina followed by the separation and identification of two classes of carbazoles using FeCl(3)/Chromossorb W and gas chromatograph with mass spectrometer (GC/MS) (SIM-single ion monitoring mode) analysis. For the first time, a series of alkyl carbazoles and alkyl benzocarbazoles were identified in heavy gas oil (HGO) and atmospheric residue of distillation (ARD) obtained from Brazilian petroleum.

40 CFR 721.10548 - Mixed alkyl phosphate esters alkoxylated (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed alkyl phosphate esters... Specific Chemical Substances § 721.10548 Mixed alkyl phosphate esters alkoxylated (generic). (a) Chemical... as mixed alkyl phosphate esters alkoxylated (PMN P-04-624) is subject to reporting under this section...

40 CFR 721.10548 - Mixed alkyl phosphate esters alkoxylated (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed alkyl phosphate esters... Specific Chemical Substances § 721.10548 Mixed alkyl phosphate esters alkoxylated (generic). (a) Chemical... as mixed alkyl phosphate esters alkoxylated (PMN P-04-624) is subject to reporting under this section...

Activation of heteroallenes by coordinatively unsaturated nickel(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (Tp(Ph,Me)) ligand.

PubMed

Abubekerov, Mark; Eymann, Léonard Y M; Gianetti, Thomas L; Arnold, John

2016-10-07

Activation of sulfur containing heteroallenes by nickel(ii) alkyl complexes supported by the bulky hydrotris(3-phenyl-5-methylpyrazolyl)borate (Tp(Ph,Me)) ligand is described. Exposure of Tp(Ph,Me)NiCH2Ph (1a) and Tp(Ph,Me)NiCH2Si(CH3)3 (1b) to CS2 resulted in formation of the insertion products Tp(Ph,Me)Ni(η(2)-CS2)CH2Ph (2a) and Tp(Ph,Me)Ni(η(2)-CS2)CH2Si(CH3)3 (2b) in moderate yields. Reaction of 1a and MeNCS produced two species in a 1 : 1 ratio, identified as Tp(Ph,Me)Ni(η(2)-MeNC)CH2Ph (3) and Tp(Ph,Me)Ni(η(2)-MeNCS)SCH2Ph (4). Isolation of the unexpected insertion product (3) prompted an investigation into the activity of 1a-b in the presence of isocyanides (i.e.(t)BuNC), which resulted in isolation of Tp(Ph,Me)Ni(η(2-t)BuNC)CH2Ph (5a) and Tp(Ph,Me)Ni(η(2-t)BuNC)CH2Si(CH3)3 (5b). Similarly, reaction of 1a with OCS led to the isolation of a rare example of a Ni(i) carbonyl species Tp(Ph,Me)NiCO (6). Alternatively, complex 6 was also formed by exposure of 1a-b to an atmosphere of CO. Isolation of the intermediate species (Tp(Ph,Me)Ni(η(2)-CO)CH2TMS (7b) and Tp(Ph,Me)Ni(CO)(C(O)R, (8a-b) with R = Ph, TMS)) shed light on the formation of such species.

Tunneling effects in the unimolecular decay of (CH 3) 2COO Criegee intermediates to OH radical products

DOE PAGES

Fang, Yi; Barber, Victoria P.; Klippenstein, Stephen J.; ...

2017-04-04

Unimolecular decay of the dimethyl substituted Criegee intermediate (CH 3) 2COO is observed at energies significantly below the transition state barrier associated with hydrogen atom transfer with time-resolved detection of the resultant OH radical products. (CH 3) 2COO is prepared at specific energies in the 3900-4600 cm -1 region through IR excitation of combination bands involving CH stretch and another lower frequency mode, and the OH products are detected by UV laser-induced fluorescence. OH appearance times on the order of microseconds are observed in this deep tunneling regime, which are about 100 times slower than that in the vicinity ofmore » the barrier. The experimental rates are in good accord with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical dissociation rates for (CH 3) 2COO that include tunneling. Master equation modeling based on these microcanonical rates is used to predict the thermal decay rate of (CH 3) 2COO to OH products under atmospheric conditions of 276 s -1 at 298 K (high pressure limit). Furthermore, thermal unimolecular decay of (CH 3) 2COO to OH products is shown to have significant contributions from tunneling at energies much below the barrier to H-atom transfer.« less

Tunneling effects in the unimolecular decay of (CH 3) 2COO Criegee intermediates to OH radical products

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

Fang, Yi; Barber, Victoria P.; Klippenstein, Stephen J.

Unimolecular decay of the dimethyl substituted Criegee intermediate (CH 3) 2COO is observed at energies significantly below the transition state barrier associated with hydrogen atom transfer with time-resolved detection of the resultant OH radical products. (CH 3) 2COO is prepared at specific energies in the 3900-4600 cm -1 region through IR excitation of combination bands involving CH stretch and another lower frequency mode, and the OH products are detected by UV laser-induced fluorescence. OH appearance times on the order of microseconds are observed in this deep tunneling regime, which are about 100 times slower than that in the vicinity ofmore » the barrier. The experimental rates are in good accord with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical dissociation rates for (CH 3) 2COO that include tunneling. Master equation modeling based on these microcanonical rates is used to predict the thermal decay rate of (CH 3) 2COO to OH products under atmospheric conditions of 276 s -1 at 298 K (high pressure limit). Furthermore, thermal unimolecular decay of (CH 3) 2COO to OH products is shown to have significant contributions from tunneling at energies much below the barrier to H-atom transfer.« less

Normal Unenhanced Raman Spectra of CO and CH/sub 4/ adsorbed on cobalt(poly)

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

Marzouk, H.A.; Bradley, E.B.; Arunkumar, K.A.

Normal Unenhanced Raman Spectra (NURS) of low-polarizability CO molecules were observed for the first time on cobalt at R.T. and residual gas pressure. We assign five bands observed between 2030--2130 cm/sup -1/ to linear chemisorbed CO species, while those observed between 1840--2010 cm/sup -1/ have been ascribed to the 2--fold chemisorbed species. The three bands observed between 1740--1830 cm/sup -1/ we believe are due to the 3--fold species. The corresponding fourteen Co-C stretches were observed and assigned. A model based upon electron backdonation is proposed for each of the three structures. NURS were also observed at R.T. for physisorbed CH/submore » 4/ and assignments are made to the four frequencies of CH/sub 4/.« less

Selective oxidation of aliphatic C-H bonds in alkylphenols by a chemomimetic biocatalytic system.

PubMed

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Feng, Yingang; Liu, Shuang-Jiang; Li, Shengying

2017-06-27

Selective oxidation of aliphatic C-H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C-H bonds of p - and m -alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity.

40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

40 CFR 721.10493 - Tris-alkyl-alkoxy melamine polymer (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Tris-alkyl-alkoxy melamine polymer... Specific Chemical Substances § 721.10493 Tris-alkyl-alkoxy melamine polymer (generic). (a) Chemical... as tris-alkyl-alkoxy melamine polymer (PMN P-05-417) is subject to reporting under this section for...

40 CFR 721.10493 - Tris-alkyl-alkoxy melamine polymer (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Tris-alkyl-alkoxy melamine polymer... Specific Chemical Substances § 721.10493 Tris-alkyl-alkoxy melamine polymer (generic). (a) Chemical... as tris-alkyl-alkoxy melamine polymer (PMN P-05-417) is subject to reporting under this section for...

Selective alkylation of T–T mismatched DNA using vinyldiaminotriazine–acridine conjugate

PubMed Central

Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato

2018-01-01

Abstract The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T–T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)–acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T–T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T–T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT–acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1. PMID:29309639

Alkyl chitosan film-high strength, functional biomaterials.

PubMed

Lu, Li; Xing, Cao; Xin, Shen; Shitao, Yu; Feng, Su; Shiwei, Liu; Fusheng, Liu; Congxia, Xie

2017-11-01

Biofilm with strong tensile strength is a topic item in the area of tissue engineering, medicine engineering, and so forth. Here we introduced an alkyl chitosan film with strong tensile strength and its possibility for an absorbable anticoagulation material in vivo was tested in the series of blood test, such as dynamic coagulation time, plasma recalcification time and hemolysis. Alkyl chitosan film was a better biomaterial than traditional chitosan film in the anticoagulation, tissue compatibility and cell compatibility. The unique trait of alkyl chitosan film may be for its greater contact angle and hydrophobicity ability to reduce the adsorption capacity for the blood component and the activity of fibrinolytic enzymes, enhance the antibacterial capacity than chitosan film. Moreover, none of chitosan film or butyl chitosan film exhibited quick inflammation or other disadvantage and degraded quickly by implanted test. Therefore, Alkyl chitosan film is of prospective properties as an implantable, absorbable agent for tissue heals, and this material need further research. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 3034-3041, 2017. © 2017 Wiley Periodicals, Inc.

40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated sulfonated diphenyl oxide... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated sulfonated diphenyl oxide... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

Detection and identification of alkylating agents by using a bioinspired "chemical nose".

PubMed

Hertzog-Ronen, Carmit; Borzin, Elena; Gerchikov, Yulia; Tessler, Nir; Eichen, Yoav

2009-10-12

Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical-warfare agents. The detection and identification of alkylating agents is not a trivial issue because of their high reactivity and simple structure. Herein, we report on a new multispot luminescence-based approach to the detection and identification of alkylating agents. In order to demonstrate the potential of the approach, seven pi-conjugated oligomers and polymers bearing nucleophilic pyridine groups, 1-7, were adsorbed onto a solid support and exposed to vapors of alkylators 8-15. The alkylation-induced color-shift patterns of the seven-spot array allow clear discrimination of the different alkylators. The spots are sensitive to minute concentrations of alkylators and, because the detection is based on the formation of new covalent bonds, these spots saturate at about 50 ppb.

Structure-biocompatibility and transfection activity relationships of cationic polyaspartamides with (dialkylamino)alkyl and alkyl or hydroxyalkyl side groups.

PubMed

Salakhieva, Diana; Shevchenko, Vesta; Németh, Csaba; Gyarmati, Benjámin; Szilágyi, András; Abdullin, Timur

2017-01-30

A series of 14 cationic derivatives of poly(aspartic acid) i.e. cationic polyaspartamides with different (dialkylamino)alkyl and alkyl or hydroxyalkyl side groups was synthesized by nucleophilic addition on polysuccinimide. The resulting polyaspartamides have moderate amphiphilic properties. Relationships between the structure and ratio of side groups and in vitro properties of polyaspartamides, including their cytotoxic and membrane-damaging activity towards human cell lines, primary skin fibroblasts and erythrocytes, were established and discussed. Cationic polyaspartamides vary in their DNA-binding, condensing and nuclease-protecting characteristics depending on the concentration ratio of (dialkylamino)alkyl and alkyl or hydroxyalkyl side groups. Effective cell transfection was achieved upon polyaspartamide-mediated plasmid DNA delivery in serum-free medium in the presence of chloroquine. Effect of serum proteins adsorption onto polyaspartamide based polyplexes, and the role of concentration of polyplexes in culture medium in their colloidal stability and transfection process were demonstrated. Synthesized polyaspartamides are biocompatible and long-acting gene carriers, which are applied to cells after dilution and without washing, thus providing transfection level comparable to that of commercial transfection reagent. Copyright © 2016 Elsevier B.V. All rights reserved.

Colloidal Synthesis of CH3 NH3 PbBr3 Nanoplatelets with Polarized Emission through Self-Organization.

PubMed

Liu, Lige; Huang, Sheng; Pan, Longfei; Shi, Li-Jie; Zou, Bingsuo; Deng, Luogen; Zhong, Haizheng

2017-02-06

We report a combined experimental and theoretical study of the synthesis of CH 3 NH 3 PbBr 3 nanoplatelets through self-organization. Shape transformation from spherical nanodots to square or rectangular nanoplatelets can be achieved by keeping the preformed colloidal nanocrystals at a high concentration (3.5 mg mL -1 ) for 3 days, or combining the synthesis of nanodots with self-organization. The average thickness of the resulting CH 3 NH 3 PbBr 3 nanoplatelets is similar to the size of the original nanoparticles, and we also noticed several nanoplatelets with circular or square holes, suggesting that the shape transformation experienced a self-organization process through dipole-dipole interactions along with a realignment of dipolar vectors. Additionally, the CH 3 NH 3 PbBr 3 nanoplatelets exhibit excellent polarized emissions for stretched CH 3 NH 3 PbBr 3 nanoplatelets embedded in a polymer composite film, showing advantageous photoluminescence properties for display backlights. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Grafted self-assembled monolayers derived from naturally occurring phenolic lipids.

PubMed

Pillot, J-P; Birot, M; Tran, T T T; Dao, T M; Belin, C; Desbat, B; Lazare, S

2005-04-12

Self-assembled monolayers grafted onto silicon surfaces were obtained from the hydrosilylation products by trialcoxysilanes of naturally occurring phenolic lipid allyl ethers. The as-obtained materials were characterized by various physical and physicochemical methods. Thus, contact angles of water drops showed that they possess very high hydrophobicity. Their excellent regularity was corroborated by AFM microscopy. The frequencies of the stretching CH2 infrared modes indicate the presence of alkyl chains mainly in the trans/trans conformation. Additionally, optical ellipsometry and quartz microbalance measurements enabled us to estimate the thickness of the films. The results, as a whole, are in good agreement with the formation of densely packed monolayers.

Mechanisms of chemoresistance to alkylating agents in malignant glioma.

PubMed

Sarkaria, Jann N; Kitange, Gaspar J; James, C David; Plummer, Ruth; Calvert, Hilary; Weller, Michael; Wick, Wolfgang

2008-05-15

Intrinsic or acquired chemoresistance to alkylating agents is a major cause of treatment failure in patients with malignant brain tumors. Alkylating agents, the mainstay of treatment for brain tumors, damage the DNA and induce apoptosis, but the cytotoxic activity of these agents is dependent on DNA repair pathways. For example, O6-methylguanine DNA adducts can cause double-strand breaks, but this is dependent on a functional mismatch repair pathway. Thus, tumor cell lines deficient in mismatch repair are resistant to alkylating agents. Perhaps the most important mechanism of resistance to alkylating agents is the DNA repair enzyme O6-methylguanine methyltransferase, which can eliminate the cytotoxic O6-methylguanine DNA adduct before it causes harm. Another mechanism of resistance to alkylating agents is the base excision repair (BER) pathway. Consequently, efforts are ongoing to develop effective inhibitors of BER. Poly(ADP-ribose)polymerase plays a pivotal role in BER and is an important therapeutic target. Developing effective strategies to overcome chemoresistance requires the identification of reliable preclinical models that recapitulate human disease and which can be used to facilitate drug development. This article describes the diverse mechanisms of chemoresistance operating in malignant glioma and efforts to develop reliable preclinical models and novel pharmacologic approaches to overcome resistance to alkylating agents.

40 CFR 721.10711 - Alkyl substituted catechol (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10711 Alkyl substituted catechol (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

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 section...

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 section...

Effect of alkyl chain length on the rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imides.

PubMed

Gangamallaiah, V; Dutt, G B

2013-10-10

Rotational diffusion of a nonpolar solute 9-phenylanthracene (9-PA) and a cationic solute rhodamine 110 (R110) has been examined in a series of 1-alkyl-3-methylimidazolium (alkyl = octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) bis(trifluoromethylsulfonyl)imides to understand the influence of alkyl chain length on solute rotation. In this study, reorientation times (τr) have been measured as a function of viscosity (η) by varying the temperature (T) of the solvents. These results have been analyzed using the Stokes-Einstein-Debye (SED) hydrodynamic theory along with the ones obtained for the same solutes in 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides (Gangamallaiah and Dutt, J. Phys. Chem. B 2012, 116, 12819-12825). It has been noticed that the data for 9-PA and R110 follows the relation τr = A(η/T)(n) with A being the ratio of hydrodynamic volume of the solute to the Boltzmann constant and n = 1 as envisaged by the SED theory. However, upon increasing the alkyl chain length from methyl to octadecyl significant deviations from the SED theory have been observed especially from the octyl derivative onward. From methyl to octadecyl derivatives, the value of A decreases by a factor of 3 for both the solutes and n by a factor of 1.4 and 1.6 for 9-PA and R110, respectively. These observations have been rationalized by taking into consideration the organized structure of the ionic liquids, whose influence appears to be pronounced when the number of carbon atoms in the alkyl chain attached to the imidazolium cation exceeds eight.

Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

PubMed

Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

2015-01-01

A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Iterated Stretching of Viscoelastic Jets

NASA Technical Reports Server (NTRS)

Chang, Hsueh-Chia; Demekhin, Evgeny A.; Kalaidin, Evgeny

1999-01-01

We examine, with asymptotic analysis and numerical simulation, the iterated stretching dynamics of FENE and Oldroyd-B jets of initial radius r(sub 0), shear viscosity nu, Weissenberg number We, retardation number S, and capillary number Ca. The usual Rayleigh instability stretches the local uniaxial extensional flow region near a minimum in jet radius into a primary filament of radius [Ca(1 - S)/ We](sup 1/2)r(sub 0) between two beads. The strain-rate within the filament remains constant while its radius (elastic stress) decreases (increases) exponentially in time with a long elastic relaxation time 3We(r(sup 2, sub 0)/nu). Instabilities convected from the bead relieve the tension at the necks during this slow elastic drainage and trigger a filament recoil. Secondary filaments then form at the necks from the resulting stretching. This iterated stretching is predicted to occur successively to generate high-generation filaments of radius r(sub n), (r(sub n)/r(sub 0)) = square root of 2[r(sub n-1)/r(sub 0)](sup 3/2) until finite-extensibility effects set in.

Design of Warped Stretch Transform

PubMed Central

Mahjoubfar, Ata; Chen, Claire Lifan; Jalali, Bahram

2015-01-01

Time stretch dispersive Fourier transform enables real-time spectroscopy at the repetition rate of million scans per second. High-speed real-time instruments ranging from analog-to-digital converters to cameras and single-shot rare-phenomena capture equipment with record performance have been empowered by it. Its warped stretch variant, realized with nonlinear group delay dispersion, offers variable-rate spectral domain sampling, as well as the ability to engineer the time-bandwidth product of the signal’s envelope to match that of the data acquisition systems. To be able to reconstruct the signal with low loss, the spectrotemporal distribution of the signal spectrum needs to be sparse. Here, for the first time, we show how to design the kernel of the transform and specifically, the nonlinear group delay profile dictated by the signal sparsity. Such a kernel leads to smart stretching with nonuniform spectral resolution, having direct utility in improvement of data acquisition rate, real-time data compression, and enhancement of ultrafast data capture accuracy. We also discuss the application of warped stretch transform in spectrotemporal analysis of continuous-time signals. PMID:26602458

Chiral Brønsted Base-Promoted Nitroalkane Alkylation: Enantioselective Synthesis of sec-Alkyl-3-Substituted Indoles

PubMed Central

Dobish, Mark C.; Johnston, Jeffrey N.

2010-01-01

A Brønsted base-catalyzed reaction of nitroalkanes with alkyl electrophiles provides indole heterocycles substituted at C3 bearing a sec-alkyl group with good enantioselectivity (up to 90% ee). Denitration by hydrogenolysis provides a product with equally high ee. An indolenine intermediate is implicated in the addition step, and surprisingly, water cosolvent was found to have a beneficial effect in this step, leading to a one-pot protocol for elimination/enantioselective addition using PBAM, a bis(amidine) chiral nonracemic base. PMID:21090654

Levator Ani Muscle Stretch Induced by Simulated Vaginal Birth

PubMed Central

Lien, Kuo-Cheng; Mooney, Brian; DeLancey, John O. L.; Ashton-Miller, James A.

2005-01-01

OBJECTIVE: To develop a three-dimensional computer model to predict levator ani muscle stretch during vaginal birth. METHODS: Serial magnetic resonance images from a healthy nulliparous 34-year-old woman, published anatomic data, and engineering graphics software were used to construct a structural model of the levator ani muscles along with related passive tissues. The model was used to quantify pelvic floor muscle stretch induced during the second stage of labor as a model fetal head progressively engaged and then stretched the iliococcygeus, pubococcygeus, and puborectalis muscles. RESULTS: The largest tissue strain reached a stretch ratio (tissue length under stretch/original tissue length) of 3.26 in medial pubococcygeus muscle, the shortest, most medial and ventral levator ani muscle. Regions of the ileococcygeus, pubococcygeus, and puborectalis muscles reached maximal stretch ratios of 2.73, 2.50, and 2.28, respectively. Tissue stretch ratios were proportional to fetal head size: For example, increasing fetal head diameter by 9% increased medial pubococcygeus stretch by the same amount. CONCLUSION: The medial pubococcygeus muscles undergo the largest stretch of any levator ani muscles during vaginal birth. They are therefore at the greatest risk for stretch-related injury. PMID:14704241

Effect of plasma treatment (He/CH4) on glass surface for the reduction of powder flux adhesion in the spray drying process

NASA Astrophysics Data System (ADS)

Ramlan, Nadiah; Zamri, Nazirah Wahidah Mohd; Maskat, Mohd Yusof; Hoong, Chin Oi; Theng, Lau Yen; Zubairi, Saiful Irwan

2018-04-01

A 50Hz glow discharge He/CH4 plasma was generated and applied for the modification of glass surface to reduce powder adhesion on the wall of spray dryer. The hydrophobicity of the glass samples determined by the water droplet contact angle and adhesion weight on glass, dependent on the CH4 flow rate and plasma exposure time. There was a peak that appeared at 1470 cm-1 on the surface of treated glass indicating the presence of CH3 groups from ATR-FTIR data. Surface morphology analysis using scanning electron microscopy (SEM) showed changes of roughness in the surface-treated glass. The presence of alkyl group (CH3) that deposited on the glass surface is one of the factors that contribute to the increase in the surface roughness. The surface roughness will reflect the value of contact angle where hydrophobic surface are rougher compared to hydrophilic surface. The plasma treatment could enhance the value of the contact angle and thus reduced the adhesion on the spray dryer glass surface.

Stretching Micropatterned Cells on a PDMS Membrane

PubMed Central

Carpi, Nicolas; Piel, Matthieu

2014-01-01

Mechanical forces exerted on cells and/or tissues play a major role in numerous processes. We have developed a device to stretch cells plated on a PolyDiMethylSiloxane (PDMS) membrane, compatible with imaging. This technique is reproducible and versatile. The PDMS membrane can be micropatterned in order to confine cells or tissues to a specific geometry. The first step is to print micropatterns onto the PDMS membrane with a deep UV technique. The PDMS membrane is then mounted on a mechanical stretcher. A chamber is bound on top of the membrane with biocompatible grease to allow gliding during the stretch. The cells are seeded and allowed to spread for several hours on the micropatterns. The sample can be stretched and unstretched multiple times with the use of a micrometric screw. It takes less than a minute to apply the stretch to its full extent (around 30%). The technique presented here does not include a motorized device, which is necessary for applying repeated stretch cycles quickly and/or computer controlled stretching, but this can be implemented. Stretching of cells or tissue can be of interest for questions related to cell forces, cell response to mechanical stress or tissue morphogenesis. This video presentation will show how to avoid typical problems that might arise when doing this type of seemingly simple experiment. PMID:24514571

The atmospheric degradation of methyl isocyanate (CH3NCO), a toxic substance

NASA Astrophysics Data System (ADS)

Papanastasiou, D. K.; Bernard, F.; Burkholder, J. B.

2016-12-01

Alkyl isocyanates (R-NCO), as well as isocyanic acid (HNCO), are toxic substances that are emitted into the atmosphere during incomplete combustion of biomass and also formed as products in the atmospheric photooxidation of nitrogen-containing organic species. For example, methyl isocyanate (MIC, CH3NCO) is formed in the atmospheric photochemical transformation of methylisothiocyanate (CH3NCS), a widely used soil fumigant, as well as in the atmospheric photooxidation of amides, such as N-methylformamide. MIC is of particular interest to society because of the possible exposure to this toxic trace compound (recommended exposure limit is 0.02 ppm) in the aftermath of fumigation. Although, there are limited observations of atmospheric MIC (mostly nearby agricultural/fumigation activities) the possibility of emission from combustion processes, such as wildfires, warrants future study. The atmospheric lifetime and fate (gas phase and heterogeneous chemistry) of CH3NCO are presently not well characterized with only a single study of the OH + CH3NCO reaction rate coefficient available in the literature. Additional results from fundamental laboratory studies regarding the major atmospheric degradation pathways of MIC are needed for input to air quality, health, and environmental impact studies. In this study, the reaction of CH3NCO with OH radicals was investigated using pulsed laser photolysis coupled with laser induced fluorescence detection of the OH radical. The rate coefficients, k(OH+CH3NCO), were determined over a range of temperature (295-375 K) and pressure (40-100 Torr, He). The present results are in significant disagreement with the recently published relative rate study. A relative rate kinetic method was also used in this study for comparison and the problems associated with these measurements will be discussed. The atmospheric lifetime of MIC with respect to its gas-phase reaction with OH radicals is estimated to be 85 days, which implies the possibility for

Full-dimensional and reduced-dimensional calculations of initial state-selected reaction probabilities studying the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction on a neural network PES

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

Welsch, Ralph, E-mail: rwelsch@uni-bielefeld.de; Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de

2015-02-14

Initial state-selected reaction probabilities of the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction are calculated in full and reduced dimensionality on a recent neural network potential [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. The quantum dynamics calculation employs the quantum transition state concept and the multi-layer multi-configurational time-dependent Hartree approach and rigorously studies the reaction for vanishing total angular momentum (J = 0). The calculations investigate the accuracy of the neutral network potential and study the effect resulting from a reduced-dimensional treatment. Very good agreement is found betweenmore » the present results obtained on the neural network potential and previous results obtained on a Shepard interpolated potential energy surface. The reduced-dimensional calculations only consider motion in eight degrees of freedom and retain the C{sub 3v} symmetry of the methyl fragment. Considering reaction starting from the vibrational ground state of methane, the reaction probabilities calculated in reduced dimensionality are moderately shifted in energy compared to the full-dimensional ones but otherwise agree rather well. Similar agreement is also found if reaction probabilities averaged over similar types of vibrational excitation of the methane reactant are considered. In contrast, significant differences between reduced and full-dimensional results are found for reaction probabilities starting specifically from symmetric stretching, asymmetric (f{sub 2}-symmetric) stretching, or e-symmetric bending excited states of methane.« less

Effects of pulsed ultrasound on the adsorption of n-alkyl anionic surfactants at the gas/solution interface of cavitation bubbles.

PubMed

Yang, Limei; Sostaric, Joe Z; Rathman, James F; Kuppusamy, Periannan; Weavers, Linda K

2007-02-15

Sonolysis of argon-saturated aqueous solutions of the nonvolatile surfactants sodium dodecyl sulfate (SDS) and sodium 1-pentanesulfonate (SPSo) was investigated at three ultrasonic frequencies under both continuous wave (CW) and pulsed ultrasound. Secondary carbon-centered radicals were detected by spin trapping using 3,5-dibromo-4-nitrosobenzenesulfonic acid (DBNBS) and electron paramagnetic resonance (EPR) spectroscopy. Following sonolysis, -*CH- radicals were observed for both surfactants under both sonication modes. Under CW at 354 kHz, the maximum plateau -*CH- radical yield was higher for SPSo than for SDS, indicating that SDS, which is more surface active under equilibrium conditions, accumulates at the gas/solution interface of cavitation bubbles to a lesser degree, compared with the less surface active surfactant, SPSo. However, after sonolysis (354 kHz) under pulsed ultrasound with a pulse length of 100 ms and an interval of 500 ms, the -*CH- radical yield at the plateau concentrations was higher for SDS than for SPSo due to increased amounts of SDS accumulation on the bubble surfaces. In contrast to the findings following sonolysis at 354 kHz, sonolysis of aqueous surfactant solutions at 620 kHz and 803 kHz showed a higher -*CH- radical yield for SDS compared with SPSo under CW but lower -*CH- radical yield with increasing pulsing interval, indicating a frequency dependence on accumulation. Results indicate that pulsing the ultrasonic wave has a significant effect on the relative adsorption ability of n-alkyl surfactants at the gas/solution surface of cavitation bubbles.

Sleep-inducing N-alkyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)cinnamamides.

PubMed

Houlihan, W J; Gogerty, J H; Ryan, E A; Schmitt, G

1985-01-01

A series of N-alkyl-3-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)-cinnamamides were prepared and screened in a series of tests designed to detect potential sleep inducers. The more active members of the series were evaluated for their ability to induce sleep in Cebus monkeys. The most active compound, N-methyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinone, was equal to methaqualone.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Frequency and peak stretch magnitude affect alveolar epithelial permeability.

PubMed

Cohen, T S; Cavanaugh, K J; Margulies, S S

2008-10-01

The present study measured stretch-induced changes in transepithelial permeability to uncharged tracers (1.5-5.5 A) using cultured monolayers of alveolar epithelial type-I like cells. Cultured alveolar epithelial cells were subjected to uniform cyclic (0, 0.25 and 1.0 Hz) biaxial stretch from 0% to 12, 25 or 37% change in surface area (DeltaSA) for 1 h. Significant changes in permeability of cell monolayers were observed when stretched from 0% to 37% DeltaSA at all frequencies, and from 0% to 25% DeltaSA only at high frequency (1 Hz), but not at all when stretched from 0% to 12% DeltaSA compared with unstretched controls. At stretch oscillation amplitudes of 25 and 37% DeltaSA, imposed at 1 Hz, tracer permeability increased compared with that at 0.25 Hz. Cells subjected to a single stretch cycle at 37% DeltaSA (0.25 Hz), to simulate a deep sigh, were not distinguishable from unstretched controls. Reducing stretch oscillation amplitude while maintaining a peak stretch of 37% DeltaSA (0.25 Hz) via the application of a simulated post-end-expiratory pressure did not protect barrier properties. In conclusion, peak stretch magnitude and stretch frequency were the primary determining factors for epithelial barrier dysfunction, as opposed to oscillation amplitude.

CURRENT CONCEPTS IN MUSCLE STRETCHING FOR EXERCISE AND REHABILITATION

PubMed Central

2012-01-01

Stretching is a common activity used by athletes, older adults, rehabilitation patients, and anyone participating in a fitness program. While the benefits of stretching are known, controversy remains about the best type of stretching for a particular goal or outcome. The purpose of this clinical commentary is to discuss the current concepts of muscle stretching interventions and summarize the evidence related to stretching as used in both exercise and rehabilitation. PMID:22319684

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.

Randomized Controlled Trial Comparing Orthosis Augmented by Either Stretching or Stretching and Strengthening for Stage II Tibialis Posterior Tendon Dysfunction.

PubMed

Houck, Jeff; Neville, Christopher; Tome, Josh; Flemister, Adolph

2015-09-01

The value of strengthening and stretching exercises combined with orthosis treatment in a home-based program has not been evaluated. The purpose of this study was to compare the effects of augmenting orthosis treatment with either stretching or a combination of stretching and strengthening in participants with stage II tibialis posterior tendon dysfunction (TPTD). Participants included 39 patients with stage II TPTD who were recruited from a medical center and then randomly assigned to a strengthening or stretching treatment group. Excluding 3 dropouts, there were 19 participants in the strengthening group and 17 in the stretching group. The stretching treatment consisted of a prefabricated orthosis used in conjunction with stretching exercises. The strengthening treatment consisted of a prefabricated orthosis used in conjunction with the stretching and strengthening exercises. The main outcome measures were self-report (ie, Foot Function Index and Short Musculoskeletal Function Assessment) and isometric deep posterior compartment strength. Two-way analysis of variance was used to test for differences between groups at 6 and 12 weeks after starting the exercise programs. Both groups significantly improved in pain and function over the 12-week trial period. The self-report measures showed minimal differences between the treatment groups. There were no differences in isometric deep posterior compartment strength. A moderate-intensity, home-based exercise program was minimally effective in augmenting orthosis wear alone in participants with stage II TPTD. Level I, prospective randomized study. © The Author(s) 2015.

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. © The Author(s) 2016.

Stretching-induced wrinkling in plastic-rubber composites.

PubMed

Yang, Junyu; Damle, Sameer; Maiti, Spandan; Velankar, Sachin S

2017-01-25

We examine the mechanics of three-layer composite films composed of an elastomeric layer sandwiched between two thin surface layers of plastic. Upon stretching and releasing such composite films, they develop a highly wrinkled surface texture. The mechanism for this texturing is that during stretching, the plastic layers yield and stretch irreversibly whereas the elastomer stretches reversibly. Thus upon releasing, the plastic layers buckle due to compressive stress imposed by the elastomer. Experiments are conducted using SEPS elastomer and 50 micron thick LLDPE plastic films. Stretching and releasing the composites to 2-5 times their original length induces buckles with wavelength on the order of 200 microns, and the wavelength decreases as the stretching increases. FEM simulations reveal that plastic deformation is involved at all stages during this process: (1) during stretching, the plastic layer yields in tension; (2) during recovery, the plastic layer first yields in-plane in compression and then buckles; (3) post-buckling, plastic hinges are formed at high-curvature regions. Homogeneous wrinkles are predicted only within a finite window of material properties: if the yield stress is too low, the plastic layers yield in-plane, without wrinkling, whereas if the yield stress is too high, non-homogeneous wrinkles are predicted. This approach to realizing highly wrinkled textures offers several advantages, most importantly the fact that high aspect ratio wrinkles (amplitude to wavelength ratios exceeding 0.4) can be realized.

Synchrotron Based Fourier Transform Far-Infrared Spectroscopy of CH3NO2

NASA Astrophysics Data System (ADS)

Twagirayezu, Sylvestre; Billinghurst, Brant E.; May, Tim; Dawadi, Mahesh B.; Perry, David S.

2013-06-01

As a slightly asymmetric top molecule (κ = 0.25) with both a free internal rotor and a methyl group, CH_3NO_2 is a benchmark system for studies of torsional motion in a 6-fold potential and of the coupling between a large amplitude vibration and other small-amplitude vibrations. For this purpose, rotationally resolved infrared spectra of CH_3NO_2, have been recorded using the Far-Infrared beamline at the Canadian Light Source, which is equipped with a high resolution Bruker IFS 125HR spectrometer. The observed infrared spectra, in the range 550-1000cm^{-1}, are the average of 300 interferometer scans collected at a nominal resolution of 0.00096cm^{-1}. Two a-type bands, centered at 657.08cm^{-1}for NO symmetric bend and at 917.99cm^{-1}for CN-stretch, have been measured. The initial analysis of a number of torsional states is currently being carried out and the progress will be reported in this talk.

Vacuum ultraviolet photoabsorption spectroscopy of CH2Cl2 and CD2Cl2 in the energy region 50,000-95,000 cm-1

NASA Astrophysics Data System (ADS)

Mandal, Anuvab; Singh, Param Jeet; Shastri, Aparna; Jagatap, B. N.

2014-12-01

A consolidated study of the VUV absorption spectra of CH2Cl2 and CD2Cl2 in the 50,000-95,000 cm-1 region using synchrotron radiation is presented. Rydberg series and vibronic analysis are carried out and supported by quantum chemical calculations. The broad absorption band of CH2Cl2 in the region 50,000-60,000 cm-1 is attributed to the valence states 11B2, 11B1 and 11A1. Most of the bands in the 60,000-95,000 cm-1 region are fitted to Rydberg series of ns, np and nd type converging to the first four ionization potentials 11.320, 11.357, 12.152 and 12.271 eV of CH2Cl2 arising from excitation of an electron from one of the four outermost Cl non-bonding orbitals (2b1, 3b2, 1a2 and 4a1). Vertical excited states of CH2Cl2 calculated using TDDFT are correlated with experimentally observed electronic states based on the symmetries of the initial and final MOs involved in a transition. A few Rydberg transitions viz. 2b1→5s, 4p, 5p, 6p; 3b2→4p, 5p; 1a2→4p are accompanied by vibronic features. Observed vibronic bands are assigned mainly to the CCl symmetric stretch (ν3‧) mode with smaller contributions from the CH symmetric stretch (ν1‧), CH2 bend (ν2‧) and CH2 wag (ν8‧) modes. Assignments are corroborated by comparison with the VUV absorption spectrum of the deuterated isotopologue CD2Cl2, reported here for the first time. The high underlying intensities seen in several sub-regions are explained by valence or valence-Rydberg mixed type transitions predicted with high oscillator strengths by the TDDFT calculations.

Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

PubMed

Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

2018-05-08

A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Discrete Electromechanical Model for Human Cardiac Tissue: Effects of Stretch-Activated Currents and Stretch Conditions on Restitution Properties and Spiral Wave Dynamics

PubMed Central

Weise, Louis D.; Panfilov, Alexander V.

2013-01-01

We introduce an electromechanical model for human cardiac tissue which couples a biophysical model of cardiac excitation (Tusscher, Noble, Noble, Panfilov, 2006) and tension development (adjusted Niederer, Hunter, Smith, 2006 model) with a discrete elastic mass-lattice model. The equations for the excitation processes are solved with a finite difference approach, and the equations of the mass-lattice model are solved using Verlet integration. This allows the coupled problem to be solved with high numerical resolution. Passive mechanical properties of the mass-lattice model are described by a generalized Hooke's law for finite deformations (Seth material). Active mechanical contraction is initiated by changes of the intracellular calcium concentration, which is a variable of the electrical model. Mechanical deformation feeds back on the electrophysiology via stretch-activated ion channels whose conductivity is controlled by the local stretch of the medium. We apply the model to study how stretch-activated currents affect the action potential shape, restitution properties, and dynamics of spiral waves, under constant stretch, and dynamic stretch caused by active mechanical contraction. We find that stretch conditions substantially affect these properties via stretch-activated currents. In constantly stretched medium, we observe a substantial decrease in conduction velocity, and an increase of action potential duration; whereas, with dynamic stretch, action potential duration is increased only slightly, and the conduction velocity restitution curve becomes biphasic. Moreover, in constantly stretched medium, we find an increase of the core size and period of a spiral wave, but no change in rotation dynamics; in contrast, in the dynamically stretching medium, we observe spiral drift. Our results may be important to understand how altered stretch conditions affect the heart's functioning. PMID:23527160

A discrete electromechanical model for human cardiac tissue: effects of stretch-activated currents and stretch conditions on restitution properties and spiral wave dynamics.

PubMed

Weise, Louis D; Panfilov, Alexander V

2013-01-01

We introduce an electromechanical model for human cardiac tissue which couples a biophysical model of cardiac excitation (Tusscher, Noble, Noble, Panfilov, 2006) and tension development (adjusted Niederer, Hunter, Smith, 2006 model) with a discrete elastic mass-lattice model. The equations for the excitation processes are solved with a finite difference approach, and the equations of the mass-lattice model are solved using Verlet integration. This allows the coupled problem to be solved with high numerical resolution. Passive mechanical properties of the mass-lattice model are described by a generalized Hooke's law for finite deformations (Seth material). Active mechanical contraction is initiated by changes of the intracellular calcium concentration, which is a variable of the electrical model. Mechanical deformation feeds back on the electrophysiology via stretch-activated ion channels whose conductivity is controlled by the local stretch of the medium. We apply the model to study how stretch-activated currents affect the action potential shape, restitution properties, and dynamics of spiral waves, under constant stretch, and dynamic stretch caused by active mechanical contraction. We find that stretch conditions substantially affect these properties via stretch-activated currents. In constantly stretched medium, we observe a substantial decrease in conduction velocity, and an increase of action potential duration; whereas, with dynamic stretch, action potential duration is increased only slightly, and the conduction velocity restitution curve becomes biphasic. Moreover, in constantly stretched medium, we find an increase of the core size and period of a spiral wave, but no change in rotation dynamics; in contrast, in the dynamically stretching medium, we observe spiral drift. Our results may be important to understand how altered stretch conditions affect the heart's functioning.

C-H bond functionalization via hydride transfer: formation of α-arylated piperidines and 1,2,3,4-tetrahydroisoquinolines via stereoselective intramolecular amination of benzylic C-H bonds.

PubMed

Vadola, Paul A; Carrera, Ignacio; Sames, Dalibor

2012-08-17

We here report a study of the intramolecular amination of sp(3) C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl aldehydes are subjected to N-toluenesulfonamide in the presence of BF(3)·OEt(2) to effect imine formation and HT-cyclization, leading to 2-arylpiperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexibility. Substrates of higher conformational rigidity were more reactive, giving higher yields of the desired products. However, a single substituent on the alkyl chain linking the N-tosylimine and the benzylic sp(3) C-H bonds was sufficient for HT-cyclization to occur. In addition, an examination of various arenes revealed that the electronic character of the hydridic C-H bonds dramatically affects the efficiency of the reaction. We also found that this transformation is highly stereoselective; 2-substituted aldehydes yield cis-2,5-disubstituted piperidines, while 3-substituted aldehydes afford trans-2,4-disubstituted piperidines. The stereoselectivity is a consequence of thermodynamic control. The pseudoallylic strain between the arene and tosyl group on the piperidine ring is proposed to rationalize the greater stability of the isomer with the aryl ring in the axial position. This preferential placement of the arene is proposed to affect the observed stereoselectivity.

C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

PubMed Central

Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

2012-01-01

We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexibility. Substrates of higher conformational rigidity were more reactive, giving higher yields of the desired products. However, a single substituent on the alkyl chain linking the N-tosylimine and the benzylic sp3 C-H bonds was sufficient for HT-cyclization to occur. In addition, an examination of various arenes revealed that the electronic character of the hydridic C-H bonds dramatically affects the efficiency of the reaction. We also found that this transformation is highly stereoselective; 2-substituted aldehydes yield cis-2,5-disubstituted piperidines, while 3-substituted aldehydes afford trans-2,4-disubstituted piperidines. The stereoselectivity is a consequence of thermodynamic control. The pseudo-allylic strain between the arene and tosyl group on the piperidine ring is proposed to rationalize the greater stability of the isomer with the aryl ring in the axial position. This preferential placement of the arene is proposed to affect the observed stereoselectivity. PMID:22672002

Reinforcement for Stretch Formed Sheet Metal

NASA Technical Reports Server (NTRS)

Lea, J. B.; Baxter, C. R.

1983-01-01

Tearing of aluminum sheet metal durinng stretch forming prevented by flame spraying layer of aluminum on edges held in stretch-forming machine. Technique improves grip of machine on metal and reinforced sheet better able to with stand concentration of force in vicinity of grips.

Alkylation of 6-mercaptopurine (6-MP) with N-alkyl-N-alkoxycarbonylaminomethyl chlorides: S6-(N-alkyl-N-alkoxycarbonyl)aminomethyl-6-MP prodrug structure effect on the dermal delivery of 6-MP.

PubMed

Siver, K G; Sloan, K B

1990-01-01

The S6-(N-alkyl-N-alkoxycarbonyl)aminomethyl-6-MP (6-CARB-6-MP) prodrugs 5-20 were synthesized from the reaction of 6-MP with N-alkyl-N-alkyoxycarbonylaminomethyl chlorides (4) in dimethyl sulfoxide in overall yields of 5-62%, depending on the N-alkyl and the alkoxy groups involved. The derivatives were fully characterized by spectral and microanalyses. The assignment of the substitution pattern as S6-alkyl was based on comparisons of the UV, 1H NMR and 13C NMR spectra with model compounds. A S6, 9-bis-alkyl derivative was obtained from the reaction of 2 equivalents of 4 with 6-MP but the product was unstable and decomposed on standing to a 9-alkyl derivative. The 6-CARB-6-MP prodrugs reverted to 6-MP in water by an SN1-type mechanism involving unimolecular charge separation in the transition state of the rate determining step. There was no effect of dermal enzymes on the rate of hydrolysis. The solubilities in isopropyl myristate (IPM) for all of the 6-CARB-6-MP prodrugs were significantly greater than the solubility of 6-MP in IPM but only one prodrug (5) was apparently even as soluble as 6-MP in water. Selected 6-CARB-6-MP prodrugs were examined in diffusion cell experiments. Only the N-methyl-N-methoxycarbonyl derivative 5 gave a steady-state rate of delivery of 6-MP from IPM that was significantly greater than the steady-state rate of delivery of 6-MP from 6-MP in IPM. All the other derivatives gave steady-state rates of delivery of 6-MP from IPM that were either not significantly different, or were significantly lower than the rate obtained from 6-MP in IPM. In all cases, the effect of the 6-CARB-6-MP:IPM suspensions on the permeability of the skin, as determined by the second application flux of theophylline:propylene glycol, was of the same magnitude as the effect of IPM alone.

Ultrasound promoted N-alkylation of pyrrole using potassium superoxide as base in crown ether.

PubMed

Yim, E S; Park, M K; Han, B H

1997-04-01

Ultrasound accelerates the N-alkylation of pyrrole by alkylating reagents using potassium superoxide as base in the presence of 18-crown-6. A much lower yield of N-alkylated pyrrole was realized in the absence of ultrasound. N-alkylating reagents employed for pyrrole are methyl iodide, ethyl bromide, benzyl bromide, as well as acrylonitrile allyl cyanide and methyl acrylate. In an extension of this work, we have found that ultrasound was not necessary for the N-alkylation of indole and alkyl amine, such as diphenyl amine and piperidine with alkyl halides using our reagents. In all cases we observed that the 18-crown-6 catalyzed N-alkylation reaction gives higher yields of N-alkylated products than that without crown ether, when potassium superoxide was used as base. These observations are probably due to the potassium-crown complex which can be released when the reaction goes to completion.

Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

PubMed

Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

2017-05-22

Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

40 CFR 721.2094 - N,N′-di(alkyl heteromonocycle)amino chlorotriazine.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false N,Nâ²-di(alkyl heteromonocycle)amino... Specific Chemical Substances § 721.2094 N,N′-di(alkyl heteromonocycle)amino chlorotriazine. (a) Chemical... as N,N′-di(alkyl heteromonocycle)amino chlorotriazine (PMN P-93-1369) is subject to reporting under...

40 CFR 721.2094 - N,N′-di(alkyl heteromonocycle)amino chlorotriazine.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false N,Nâ²-di(alkyl heteromonocycle)amino... Specific Chemical Substances § 721.2094 N,N′-di(alkyl heteromonocycle)amino chlorotriazine. (a) Chemical... as N,N′-di(alkyl heteromonocycle)amino chlorotriazine (PMN P-93-1369) is subject to reporting under...

On the Prony series representation of stretched exponential relaxation

NASA Astrophysics Data System (ADS)

Mauro, John C.; Mauro, Yihong Z.

2018-09-01

Stretched exponential relaxation is a ubiquitous feature of homogeneous glasses. The stretched exponential decay function can be derived from the diffusion-trap model, which predicts certain critical values of the fractional stretching exponent, β. In practical implementations of glass relaxation models, it is computationally convenient to represent the stretched exponential function as a Prony series of simple exponentials. Here, we perform a comprehensive mathematical analysis of the Prony series approximation of the stretched exponential relaxation, including optimized coefficients for certain critical values of β. The fitting quality of the Prony series is analyzed as a function of the number of terms in the series. With a sufficient number of terms, the Prony series can accurately capture the time evolution of the stretched exponential function, including its "fat tail" at long times. However, it is unable to capture the divergence of the first-derivative of the stretched exponential function in the limit of zero time. We also present a frequency-domain analysis of the Prony series representation of the stretched exponential function and discuss its physical implications for the modeling of glass relaxation behavior.

DYNAMIC OSCILLATORY STRETCHING EFFICACY ON HAMSTRING EXTENSIBILITY AND STRETCH TOLERANCE: A RANDOMIZED CONTROLLED TRIAL

PubMed Central

Tee, Jason Cameron; Stewart, Aimee

2017-01-01

Background While static stretch (SS), proprioceptive neuromuscular facilitation (PNF) and oscillatory physiological mobilization techniques are documented to have positive effects on a range of motion (ROM), there are no reports on the effect of dynamic oscillatory stretching (DOS), a technique that combines these three techniques, on hamstring extensibility. Purpose To determine whether DOS improves hamstring extensibility and stretch tolerance to a greater degree than SS in asymptomatic young participants. Study Design Randomized Controlled Trial. Methods Sixty participants (47 females, 13 males, mean age 22 ± 1 years, height 166 ± 6 centimeters, body mass 67.6 ± 9.7 kg) completed a passive straight leg (SLR) to establish hamstring extensibility and stretch tolerance as perceived by participants, using a visual analogue scale (VAS). Participants were randomly assigned to one of two treatment groups (SS or DOS) or a placebo control (20 per group). Tests were repeated immediately following and one hour after each intervention. Data were assessed using a two-way repeated measure analysis of variance (ANOVA) and Tukey's post hoc test. Results Immediately post-intervention, there was a significant improvement in the hamstring extensibility as measured by the SLR in both the SS and DOS groups, with the DOS group exhibiting a significantly greater increase than the SS group (Control 73 ± 12°, SS 86 ± 8°, DOS 94 ± 11°, p < 0.001). One hour post-intervention, hamstring extensibility in the DOS group remained elevated, while the SS group no longer differed from the control group (Control 73 ± 12°, SS 80 ± 8°, DOS 89 ± 12°, p = 0.001). Furthermore, the stretch tolerance remained significantly elevated for the SS group, but there was no difference between the control and DOS groups, (Control 4.6 ± 1.3, SS 5.9 ± 0.8, DOS 4.3 ± 1.0 AU, p < 0.001). Conclusion DOS was more effective than SS at achieving

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2007-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2007-06-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2007-09-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2006-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2006-01-18

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2006-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2006-12-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2007-02-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

CH-TRU Waste Content Codes (CH-TRUCON)

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

Washington TRU Solutions LLC

2006-09-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container.more » Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled

Catalytic hydrogenation activity and electronic structure determination of bis(arylimidazol-2-ylidene)pyridine cobalt alkyl and hydride complexes.

PubMed

Yu, Renyuan Pony; Darmon, Jonathan M; Milsmann, Carsten; Margulieux, Grant W; Stieber, S Chantal E; DeBeer, Serena; Chirik, Paul J

2013-09-04

The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, ((iPr)CNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, ((iPr)CNC)CoCH3 is an effective precatalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene, and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, ((iPr)CNC)CoH, was accomplished by hydrogenation of ((iPr)CNC)CoCH3. Over the course of 3 h at 22 °C, migration of the metal hydride to the 4-position of the pyridine ring yielded (4-H2-(iPr)CNC)CoN2. Similar alkyl migration was observed upon treatment of ((iPr)CNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redox-active, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic, and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity, and suggest that a wide family of pyridine-based pincers may also be redox-active.

Asymmetric synthesis of isoindolones by chiral cyclopentadienyl-rhodium(III)-catalyzed C-H functionalizations.

PubMed

Ye, Baihua; Cramer, Nicolai

2014-07-21

Directed Cp*Rh(III)-catalyzed carbon-hydrogen (C-H) bond functionalizations have evolved as a powerful strategy for the construction of heterocycles. Despite their high value, the development of related asymmetric reactions is largely lagging behind due to a limited availability of robust and tunable chiral cyclopentadienyl ligands. Rhodium complexes comprising a chiral Cp ligand with an atropchiral biaryl backbone enables an asymmetric synthesis of isoindolones from arylhydroxamates and weakly alkyl donor/acceptor diazo derivatives as one-carbon component under mild conditions. The complex guides the substrates with a high double facial selectivity yielding the chiral isoindolones in good yields and excellent enantioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alanine, N-(2-carboxyethyl)-N-alkyl... Specific Chemical Substances § 721.520 Alanine, N-(2-carboxyethyl)-N-alkyl-, salt. (a) Chemical substance... alanine, N-(2-carboxyethyl)-N- alkyl-, salt (P-89-336) is subject to reporting under this section for the...

40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alanine, N-(2-carboxyethyl)-N-alkyl... Specific Chemical Substances § 721.520 Alanine, N-(2-carboxyethyl)-N-alkyl-, salt. (a) Chemical substance... alanine, N-(2-carboxyethyl)-N- alkyl-, salt (P-89-336) is subject to reporting under this section for the...

Effects of cervical self-stretching on slow vital capacity.

PubMed

Han, Dongwook; Yoon, Nayoon; Jeong, Yeongran; Ha, Misook; Nam, Kunwoo

2015-07-01

[Purpose] This study investigated the effects of self-stretching of cervical muscles, because the accessory inspiratory muscle is considered to improve pulmonary function. [Subjects] The subjects were 30 healthy university students 19-21 years old who did not have any lung disease, respiratory dysfunction, cervical injury, or any problems upon cervical stretching. [Methods] Spirometry was used as a pulmonary function test to measure the slow vital capacity before and after stretching. The slow vital capacity of the experimental group was measured before and after cervical self-stretching. Meanwhile, the slow vital capacity of the control group, which did not perform stretching, was also measured before and after the intervention. [Results] The expiratory vital capacity, inspiratory reserve volume, and expiratory reserve volume of the experimental group increased significantly after the cervical self-stretching. [Conclusion] Self-stretching of the cervical muscle (i.e., the inspiratory accessory muscle) improves slow vital capacity.

40 CFR 721.644 - Amines, C12-14-tert-alkyl, sulfonates.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amines, C12-14-tert-alkyl, sulfonates... Substances § 721.644 Amines, C12-14-tert-alkyl, sulfonates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amines, C12-14-tert-alkyl, sulfonates (PMN...

40 CFR 721.644 - Amines, C12-14-tert-alkyl, sulfonates.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amines, C12-14-tert-alkyl, sulfonates... Substances § 721.644 Amines, C12-14-tert-alkyl, sulfonates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amines, C12-14-tert-alkyl, sulfonates (PMN...

Cyclic stretching of soft substrates induces spreading and growth

PubMed Central

Cui, Yidan; Hameed, Feroz M.; Yang, Bo; Lee, Kyunghee; Pan, Catherine Qiurong; Park, Sungsu; Sheetz, Michael

2015-01-01

In the body, soft tissues often undergo cycles of stretching and relaxation that may affect cell behaviour without changing matrix rigidity. To determine whether transient forces can substitute for a rigid matrix, we stretched soft pillar arrays. Surprisingly, 1–5% cyclic stretching over a frequency range of 0.01–10 Hz caused spreading and stress fibre formation (optimum 0.1 Hz) that persisted after 4 h of stretching. Similarly, stretching increased cell growth rates on soft pillars comparative to rigid substrates. Of possible factors linked to fibroblast growth, MRTF-A (myocardin-related transcription factor-A) moved to the nucleus in 2 h of cyclic stretching and reversed on cessation; but YAP (Yes-associated protein) moved much later. Knockdown of either MRTF-A or YAP blocked stretch-dependent growth. Thus, we suggest that the repeated pulling from a soft matrix can substitute for a stiff matrix in stimulating spreading, stress fibre formation and growth. PMID:25704457

Triceps stretch (image)

MedlinePlus

... shoulder. Hold for 10 to 20 seconds, then switch sides. Alternate method: raise your arm over your ... elbow. Hold for 10 to 20 seconds, then switch sides. You should feel either of these stretches ...

Stretch induced endothelin-1 secretion by adult rat astrocytes involves calcium influx via stretch-activated ion channels (SACs)

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

Ostrow, Lyle W., E-mail: lostrow1@jhmi.edu; Suchyna, Thomas M.; Sachs, Frederick

2011-06-24

Highlights: {yields} Endothelin-1 expression by adult rat astrocytes correlates with cell proliferation. {yields} Stretch-induced ET-1 is inhibited by GsMtx-4, a specific inhibitor of Ca{sup 2+} permeant SACs. {yields} The less specific SAC inhibitor streptomycin also inhibits ET-1 secretion. {yields} Stretch-induced ET-1 production depends on a calcium influx. {yields} SAC pharmacology may provide a new class of therapeutic agents for CNS pathology. -- Abstract: The expression of endothelins (ETs) and ET-receptors is often upregulated in brain pathology. ET-1, a potent vasoconstrictor, also inhibits the expression of astrocyte glutamate transporters and is mitogenic for astrocytes, glioma cells, neurons, and brain capillary endothelia.more » We have previously shown that mechanical stress stimulates ET-1 production by adult rat astrocytes. We now show in adult astrocytes that ET-1 production is driven by calcium influx through stretch-activated ion channels (SACs) and the ET-1 production correlates with cell proliferation. Mechanical stimulation using biaxial stretch (<20%) of a rubber substrate increased ET-1 secretion, and 4 {mu}M GsMTx-4 (a specific inhibitor of SACs) inhibited secretion by 30%. GsMTx-4 did not alter basal ET-1 levels in the absence of stretch. Decreasing the calcium influx by lowering extracellular calcium also inhibited stretch-induced ET-1 secretion without effecting ET-1 secretion in unstretched controls. Furthermore, inhibiting SACs with the less specific inhibitor streptomycin also inhibited stretch-induced ET-1 secretion. The data can be explained with a simple model in which ET-1 secretion depends on an internal Ca{sup 2+} threshold. This coupling of mechanical stress to the astrocyte endothelin system through SACs has treatment implications, since all pathology deforms the surrounding parenchyma.« less

Importance of Stretching

MedlinePlus

... Kids and Teens Pregnancy and Childbirth Women Men Seniors Your Health Resources Healthcare Management End-of-Life ... pain. Always listen to your body. Stretching for seniors It’s all about maintaining that flexibility when it ...

Alkylation sensitivity screens reveal a conserved cross-species functionome

PubMed Central

Svilar, David; Dyavaiah, Madhu; Brown, Ashley R.; Tang, Jiang-bo; Li, Jianfeng; McDonald, Peter R.; Shun, Tong Ying; Braganza, Andrea; Wang, Xiao-hong; Maniar, Salony; St Croix, Claudette M.; Lazo, John S.; Pollack, Ian F.; Begley, Thomas J.; Sobol, Robert W.

2013-01-01

To identify genes that contribute to chemotherapy resistance in glioblastoma, we conducted a synthetic lethal screen in a chemotherapy-resistant glioblastoma derived cell line with the clinical alkylator temozolomide (TMZ) and an siRNA library tailored towards “druggable” targets. Select DNA repair genes in the screen were validated independently, confirming the DNA glycosylases UNG and MYH as well as MPG to be involved in the response to high dose TMZ. The involvement of UNG and MYH is likely the result of a TMZ-induced burst of reactive oxygen species. We then compared the human TMZ sensitizing genes identified in our screen with those previously identified from alkylator screens conducted in E. coli and S. cerevisiae. The conserved biological processes across all three species composes an Alkylation Functionome that includes many novel proteins not previously thought to impact alkylator resistance. This high-throughput screen, validation and cross-species analysis was then followed by a mechanistic analysis of two essential nodes: base excision repair (BER) DNA glycosylases (UNG, human and mag1, S. cerevisiae) and protein modification systems, including UBE3B and ICMT in human cells or pby1, lip22, stp22 and aim22 in S. cerevisiae. The conserved processes of BER and protein modification were dual targeted and yielded additive sensitization to alkylators in S. cerevisiae. In contrast, dual targeting of BER and protein modification genes in human cells did not increase sensitivity, suggesting an epistatic relationship. Importantly, these studies provide potential new targets to overcome alkylating agent resistance. PMID:23038810

Regulation of DNA Alkylation Damage Repair: Lessons and Therapeutic Opportunities

PubMed Central

Soll, Jennifer M.; Sobol, Robert W.; Mosammaparast, Nima

2016-01-01

Alkylation chemotherapy is one of the most widely used systemic therapies for cancer. While somewhat effective, clinical responses and toxicities of these agents are highly variable. A major contributing factor for this variability is the numerous distinct lesions that are created upon alkylation damage. These adducts activate multiple repair pathways. There is mounting evidence that the individual pathways function cooperatively, suggesting that coordinated regulation of alkylation repair is critical to prevent toxicity. Furthermore, some alkylating agents produce adducts that overlap with newly discovered methylation marks, making it difficult to distinguish between bona fide damaged bases and so called ‘epigenetic’ adducts. We discuss new efforts aimed at deciphering the mechanisms that regulate these repair pathways, emphasizing their implications for cancer chemotherapy. PMID:27816326

Palladium-catalyzed Heck-type cross-couplings of unactivated alkyl iodides.

PubMed

McMahon, Caitlin M; Alexanian, Erik J

2014-06-02

A palladium-catalyzed, intermolecular Heck-type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in the β position. The mild catalytic conditions enable intermolecular C-C bond formations with a diverse set of alkyl iodides and alkenes, including substrates containing base- or nucleophile-sensitive functionality. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral Alkyl Halides: Underexplored Motifs in Medicine

PubMed Central

Gál, Bálint; Bucher, Cyril; Burns, Noah Z.

2016-01-01

While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation. PMID:27827902

Study on the decomposition mechanism of alkyl carbonate on lithium metal by pyrolysis-gas chromatography-mass spectroscopy

NASA Astrophysics Data System (ADS)

Mogi, Ryo; Inaba, Minoru; Iriyama, Yasutoshi; Abe, Takeshi; Ogumi, Zempachi

The surface films formed on deposited lithium in electrolyte solutions based on ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate (DMC) were analyzed by pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS). In 1 M LiClO 4/EC, the main component of the surface film was easily hydrolyzed to give ethylene glycol after exposure to air, and hence was considered to have a chemical structure of ROCH 2CH 2OR', of which OR and OR' are OLi or OCO 2Li. Ethylene oxide, acetaldehyde, and 1,4-dioxane were detected in decomposition products, and they were considered to have been formed by pyrolysis of ROCH 2CH 2OR' in the pyrolyzer. The presence of ethanol in decomposition products confirmed that ring cleavage at the CH 2O bonds of EC occurs by one electron reduction. In addition, the presence of methanol implied the cleavage of the CC bond of EC upon reduction. From the surface films formed in 1 M LiClO 4/DEC and /DMC, ethanol and methanol, respectively, were detected, which suggested that corresponding lithium alkoxides and/or lithium alkyl carbonates were the main components. In 1 M LiClO 4/EC+DEC (1:1), EC dominantly decomposed to form the surface film. The surface film formed in 1 M LiPF 6/EC+DEC (1:1) contained a much smaller amount of organic compounds.

Control of concerted two bond versus single bond dissociation in CH(3)Co(CO)(4) via an intermediate state using pump-dump laser pulses.

PubMed

Ambrosek, David; González, Leticia

2007-10-07

Wavepacket propagations on ab initio multiconfigurational two-dimensional potential energy surfaces for CH(3)Co(CO)(4) indicate that after irradiation to the lowest first and second electronic excited states, concerted dissociation of CH(3) and the axial CO ligand takes place. We employ a pump-dump sequence of pulses with appropriate frequencies and time delays to achieve the selective breakage of a single bond by controlling the dissociation angle. The pump and dump pulse sequence exploits the unbound surface where dissociation occurs in a counterintuitive fashion; stretching of one bond in an intermediate state enhances the single dissociation of the other bond.

mTOR target NDRG1 confers MGMT-dependent resistance to alkylating chemotherapy.

PubMed

Weiler, Markus; Blaes, Jonas; Pusch, Stefan; Sahm, Felix; Czabanka, Marcus; Luger, Sebastian; Bunse, Lukas; Solecki, Gergely; Eichwald, Viktoria; Jugold, Manfred; Hodecker, Sibylle; Osswald, Matthias; Meisner, Christoph; Hielscher, Thomas; Rübmann, Petra; Pfenning, Philipp-Niklas; Ronellenfitsch, Michael; Kempf, Tore; Schnölzer, Martina; Abdollahi, Amir; Lang, Florian; Bendszus, Martin; von Deimling, Andreas; Winkler, Frank; Weller, Michael; Vajkoczy, Peter; Platten, Michael; Wick, Wolfgang

2014-01-07

A hypoxic microenvironment induces resistance to alkylating agents by activating targets in the mammalian target of rapamycin (mTOR) pathway. The molecular mechanisms involved in this mTOR-mediated hypoxia-induced chemoresistance, however, are unclear. Here we identify the mTOR target N-myc downstream regulated gene 1 (NDRG1) as a key determinant of resistance toward alkylating chemotherapy, driven by hypoxia but also by therapeutic measures such as irradiation, corticosteroids, and chronic exposure to alkylating agents via distinct molecular routes involving hypoxia-inducible factor (HIF)-1alpha, p53, and the mTOR complex 2 (mTORC2)/serum glucocorticoid-induced protein kinase 1 (SGK1) pathway. Resistance toward alkylating chemotherapy but not radiotherapy was dependent on NDRG1 expression and activity. In posttreatment tumor tissue of patients with malignant gliomas, NDRG1 was induced and predictive of poor response to alkylating chemotherapy. On a molecular level, NDRG1 bound and stabilized methyltransferases, chiefly O(6)-methylguanine-DNA methyltransferase (MGMT), a key enzyme for resistance to alkylating agents in glioblastoma patients. In patients with glioblastoma, MGMT promoter methylation in tumor tissue was not more predictive for response to alkylating chemotherapy in patients who received concomitant corticosteroids.

Aag DNA Glycosylase Promotes Alkylation-Induced Tissue Damage Mediated by Parp1

PubMed Central

Calvo, Jennifer A.; Moroski-Erkul, Catherine A.; Lake, Annabelle; Eichinger, Lindsey W.; Shah, Dharini; Jhun, Iny; Limsirichai, Prajit; Bronson, Roderick T.; Christiani, David C.; Meira, Lisiane B.; Samson, Leona D.

2013-01-01

Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER) is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG) mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag −/− mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage. PMID:23593019

mTOR target NDRG1 confers MGMT-dependent resistance to alkylating chemotherapy

PubMed Central

Weiler, Markus; Blaes, Jonas; Pusch, Stefan; Sahm, Felix; Czabanka, Marcus; Luger, Sebastian; Bunse, Lukas; Solecki, Gergely; Eichwald, Viktoria; Jugold, Manfred; Hodecker, Sibylle; Osswald, Matthias; Meisner, Christoph; Hielscher, Thomas; Rübmann, Petra; Pfenning, Philipp-Niklas; Ronellenfitsch, Michael; Kempf, Tore; Schnölzer, Martina; Abdollahi, Amir; Lang, Florian; Bendszus, Martin; von Deimling, Andreas; Winkler, Frank; Weller, Michael; Vajkoczy, Peter; Platten, Michael; Wick, Wolfgang

2014-01-01

A hypoxic microenvironment induces resistance to alkylating agents by activating targets in the mammalian target of rapamycin (mTOR) pathway. The molecular mechanisms involved in this mTOR-mediated hypoxia-induced chemoresistance, however, are unclear. Here we identify the mTOR target N-myc downstream regulated gene 1 (NDRG1) as a key determinant of resistance toward alkylating chemotherapy, driven by hypoxia but also by therapeutic measures such as irradiation, corticosteroids, and chronic exposure to alkylating agents via distinct molecular routes involving hypoxia-inducible factor (HIF)-1alpha, p53, and the mTOR complex 2 (mTORC2)/serum glucocorticoid-induced protein kinase 1 (SGK1) pathway. Resistance toward alkylating chemotherapy but not radiotherapy was dependent on NDRG1 expression and activity. In posttreatment tumor tissue of patients with malignant gliomas, NDRG1 was induced and predictive of poor response to alkylating chemotherapy. On a molecular level, NDRG1 bound and stabilized methyltransferases, chiefly O6-methylguanine-DNA methyltransferase (MGMT), a key enzyme for resistance to alkylating agents in glioblastoma patients. In patients with glioblastoma, MGMT promoter methylation in tumor tissue was not more predictive for response to alkylating chemotherapy in patients who received concomitant corticosteroids. PMID:24367102

Characterization of Malaysian coals for carbon dioxide sequestration

NASA Astrophysics Data System (ADS)

Abunowara, M.; Bustam, M. A.; Sufian, S.; Eldemerdash, U.

2016-06-01

Coal samples from Mukah-Balingian and Merit-Pila coal mines were characterized with ultimate, approximate, petrographic analysis, FT-IR spectra patterns, FESEM images and BET measurements to obtain information on the chemical composition and chemical structure in the samples. Two coal samples were obtained from Merit-Pila coal mine namely sample1 (S1) and sample2 (S2). The other two coal samples were obtained from Mukah-Balingian coal mine namely sample3 (S3) and sample4 (S4), Sarawak, Malaysia. The results of ultimate analysis show that coal S1 has the highest carbon percentage by 54.47%, the highest hydrogen percentage by 10.56% and the lowest sulfur percentage by 0.19% and the coal S4 has the highest moisture content by 31.5%. The coal S1 has the highest fixed carbon percentage by 42.6%. The coal S4 has BET surface area by 2.39 m2/g and Langmuir surface area by 3.0684 m2/g respectively. Fourier-Transform Infrared (FT-IR) spectroscopy analysis of all coal samples shows a presence of oxygen containing functional groups which considered are as active sites on coal surface. The oxygen functional groups are mainly carboxyl (-COOH), hydroxyl (-OH), alkyl (-CH, -CH2, -CH3), aliphatic (C-O-C stretching associated with -OH), amino (-NH stretching vibrations), (-NH stretching vibrations), aromatic (C=C), vinylic (C=C) and clay minerals. In all FE-SEM images of coal samples matrix, it can be seen that there are luminous and as non luminous features which refer to the existence of various minerals types distributed in the coal organic matrix. The bright luminosity is due to the presence of sodium, potassium or aluminium. According to petrographic analysis, all coal sample samples are range in vitrinite reflectance from 0.38% to 56% (VRr) are sub-bituminous coals.

Acute effect of constant torque and angle stretching on range of motion, muscle passive properties, and stretch discomfort perception.

PubMed

Cabido, Christian E T; Bergamini, Juliana C; Andrade, André G P; Lima, Fernando V; Menzel, Hans J; Chagas, Mauro H

2014-04-01

The aim of the present study was to compare the acute effects of constant torque (CT) and constant angle (CA) stretching exercises on the maximum range of motion (ROMmax), passive stiffness (PS), and ROM corresponding to the first sensation of tightness in the posterior thigh (FSTROM). Twenty-three sedentary men (age, 19-33 years) went through 1 familiarization session and afterward proceeded randomly to both CA and CT treatment stretching conditions, on separate days. An isokinetic dynamometer was used to analyze hamstring muscles during passive knee extension. The subjects performed 4 stretches of 30 seconds each with a 15-second interval between them. In the CA stretching, the subject reached a certain ROM (95% of ROMmax), and the angle was kept constant. However, in the CT stretching exercise, the volunteer reached a certain resistance torque (corresponding to 95% of ROMmax) and it was kept constant. The results showed an increase in ROMmax for both CA and CT (p < 0.001), but the increase was greater for CT than for CA (CA vs. CT in poststretching, p = 0.002). Although the PS decreased for both CA and CT (p < 0.001), the decrease was greater for CT than for CA (CA vs. CT in poststretching, p = 0.002). The FSTROM increased for both CA and CT, but the increase for CT was greater than that for CA (CA vs. CT in poststretching, p = 0.003). The greater increase in ROMmax for the CT stretch may be explained by greater changes in the biomechanical properties of the muscle-tendon unit and stretch tolerance, as indicated by the results of PS and FSTROM.

Optofluidic time-stretch microscopy: recent advances

NASA Astrophysics Data System (ADS)

Lei, Cheng; Nitta, Nao; Ozeki, Yasuyuki; Goda, Keisuke

2018-06-01

Flow cytometry is an indispensable method for valuable applications in numerous fields such as immunology, pathology, pharmacology, molecular biology, and marine biology. Optofluidic time-stretch microscopy is superior to conventional flow cytometry methods for its capability to acquire high-quality images of single cells at a high-throughput exceeding 10,000 cells per second. This makes it possible to extract copious information from cellular images for accurate cell detection and analysis with the assistance of machine learning. Optofluidic time-stretch microscopy has proven its effectivity in various applications, including microalga-based biofuel production, evaluation of thrombotic disorders, as well as drug screening and discovery. In this review, we discuss the principles and recent advances of optofluidic time-stretch microscopy.

Optofluidic time-stretch microscopy: recent advances

NASA Astrophysics Data System (ADS)

Lei, Cheng; Nitta, Nao; Ozeki, Yasuyuki; Goda, Keisuke

2018-04-01

Flow cytometry is an indispensable method for valuable applications in numerous fields such as immunology, pathology, pharmacology, molecular biology, and marine biology. Optofluidic time-stretch microscopy is superior to conventional flow cytometry methods for its capability to acquire high-quality images of single cells at a high-throughput exceeding 10,000 cells per second. This makes it possible to extract copious information from cellular images for accurate cell detection and analysis with the assistance of machine learning. Optofluidic time-stretch microscopy has proven its effectivity in various applications, including microalga-based biofuel production, evaluation of thrombotic disorders, as well as drug screening and discovery. In this review, we discuss the principles and recent advances of optofluidic time-stretch microscopy.

A randomized controlled comparison of stretching procedures for posterior shoulder tightness.

PubMed

McClure, Philip; Balaicuis, Jenna; Heiland, David; Broersma, Mary Ellen; Thorndike, Cheryl K; Wood, April

2007-03-01

Randomized controlled trial, To compare changes in shoulder internal rotation range of motion (ROM), for 2 stretching exercises, the "cross-body stretch" and the "sleeper stretch," in individuals with posterior shoulder tightness. Recently, some authors have expressed the belief that the sleeper stretch is better than the cross-body stretch to address glenohumeral posterior tightness because the scapula is stabilized. Fifty-four asymptomatic subjects (20 males, 34 females) participated in the study. The control group (n=24) consisted of subjects with a between-shoulder difference in internal rotation ROM of less than 10 degrees, whereas those subjects with more than a 10 degrees difference were randomly assigned to 1 of 2 intervention groups, the sleeper stretch group (n=15) or the cross-body stretch group (n=15). Shoulder internal rotation ROM, with the arm abducted to 90 degrees and scapula motion prevented, was measured before and after a 4-week intervention period. Subjects in the control group were asked not to engage in any new stretching activities, while subjects in the 2 stretching groups were asked to perform stretching exercises on the more limited side only, once daily for 5 repetitions, holding each stretch for 30 seconds. The improvements in internal rotation ROM for the subjects in the cross-body stretch group (mean +/- SD, 20.0 degrees +/- 12.9 degrees) were significantly greater than for the subjects in the control group (5.9 degrees +/- 9.4 degrees, P = .009). The gains in the sleeper stretch group (12.4 degrees +/- 10.4 degrees) were not significant compared to those of the control group (P = .586) and those of the cross-body stretch group (P = .148). The cross-body stretch in individuals with limited shoulder internal rotation ROM appears to be more effective than no stretching in controls without internal rotation asymmetry to improve shoulder internal rotation ROM. While the improvement in internal rotation from the cross-body stretch was

Arylation, alkenylation, and alkylation of 2-halopyridine N-oxides with grignard reagents: a solution to the problem of C2/C6 regioselective functionalization of pyridine derivatives.

PubMed

Zhang, Song; Liao, Lian-Yan; Zhang, Fang; Duan, Xin-Fang

2013-03-15

A facile arylation, alkenylation, and alkylation of functionalized 2-halopyridine N-oxides with various Grignard reagents was developed. It represented a highly efficient and selective C-H bond functionalization of pyridine derivatives in the presence of reactive C-Cl or C-Br bonds. Using Cl or Br as a blocking group, C2/C6 site-controllable functionalization of pyridine derivatives has been achieved. Various pyridine compounds can be prepared as illustrated in the total syntheses of Onychine, dielsine, and PARP-1 inhibitor GPI 16539.

The relevance of stretch intensity and position—a systematic review

PubMed Central

Apostolopoulos, Nikos; Metsios, George S.; Flouris, Andreas D.; Koutedakis, Yiannis; Wyon, Matthew A.

2015-01-01

Stretching exercises to increase the range of motion (ROM) of joints have been used by sports coaches and medical professionals for improving performance and rehabilitation. The ability of connective and muscular tissues to change their architecture in response to stretching is important for their proper function, repair, and performance. Given the dearth of relevant data in the literature, this review examined two key elements of stretching: stretch intensity and stretch position; and their significance to ROM, delayed onset muscle soreness (DOMS), and inflammation in different populations. A search of three databases, Pub-Med, Google Scholar, and Cochrane Reviews, identified 152 articles, which were subsequently categorized into four groups: athletes (24), clinical (29), elderly (12), and general population (87). The use of different populations facilitated a wider examination of the stretching components and their effects. All 152 articles incorporated information regarding duration, frequency and stretch position, whereas only 79 referred to the intensity of stretching and 22 of these 79 studies were deemed high quality. It appears that the intensity of stretching is relatively under-researched, and the importance of body position and its influence on stretch intensity, is largely unknown. In conclusion, this review has highlighted areas for future research, including stretch intensity and position and their effect on musculo-tendinous tissue, in relation to the sensation of pain, delayed onset muscle soreness, inflammation, as well as muscle health and performance. PMID:26347668

High Resolution Infrared Spectra of Plasma Jet-Cooled - and Triacetylene in the C-H Stretch Region by CW Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Zhao, D.; Guss, J.; Walsh, A.; Doney, K.; Linnartz, H.

2013-06-01

Polyacetylenes form an important series of unsaturated hydrocarbons that are of astrophysical interest. Small polyacetylenes have been detected from infrared observations in dense atmosphere of Titan and in a protoplanetary nebula CRL 618. We present here high-resolution mid-infrared spectra of diacetylene (HC_{4}H) and triacetylene (HC_{6}H) that are recorded in a supersonically expanded pulsed planar plasma using an ultra-sensitive detection technique. This method uses an all fiber-laser-based optical parametric oscillator (OPO), in combination with continuous wave cavity ring-down spectroscopy (cw-CRDS) as a direct absorption detection tool. A hardware-based multi-trigger concept is developed to apply cw-CRDS to pulsed plasmas. Vibrationally hot but rotationally cold HC_{4}H and HC_{6}H are produced by discharging a C_{2}H_{2}/He/Ar gas mixture which is supersonically expanded into a vacuum chamber through a slit discharge nozzle. Experimental spectra are recorded at a resolution of ˜100 MHz in the 3305-3340 cm^{-1} region, which is characteristic of the C-H stretch vibrations of HC_{4}H and HC_{6}H. Jet-cooling in our experiment reduces the rotational temperature of both HC_{4}H and HC_{6}H to <20 K. In total, ˜2000 lines are measured. More than fourteen (vibrationally hot) bands for HC_{4}H and four bands for HC_{6}H are assigned based on Loomis-Wood diagrams, and nearly half of these bands are analyzed for the first time. For both molecules improved and new molecular constants of a series of vibrational levels are presented. The accurate molecular data reported here, particularly those for low-lying (bending) vibrational levels may be used to interpret the ro-vibrational transitions in the FIR and submillimeter/THz region. D. Zhao, J. Guss, A. Walsh, H. Linnartz Chem. Phys. Lett., {dx.doi.org/10.1016/j.cplett.2013.02.025}, in press, 2013.

Stretched Inertial Jets

NASA Astrophysics Data System (ADS)

Ghabache, Elisabeth; Antkowiak, Arnaud; Seon, Thomas; Villermaux, Emmanuel

2015-11-01

Liquid jets often arise as short-lived bursting liquid flows. Cavitation or impact-driven jets, bursting champagne bubbles, shaped-charge jets, ballistospores or drop-on-demand inkjet printing are a few examples where liquid jets are suddenly released. The trademark of all these discharge jets is the property of being stretched, due to the quenching injection. the present theoretical and experimental investigation, the structure of the jet flow field will be unraveled experimentally for a few emblematic occurrences of discharge jets. Though the injection markedly depends on each flow configuration, the jet velocity field will be shown to be systematically and rapidly attracted to the universal stretching flow z/t. The emergence of this inertial attractor actually only relies on simple kinematic ingredients, and as such is fairly generic. The universality of the jet velocity structure will be discussed.

Design of a new membrane stretching device

NASA Astrophysics Data System (ADS)

Shao, Yiran

Cell stretching device has been applied into the lab use for many years to help researchers study about the behavior of cells during the stretching process. Because the cell responses to the different mechanical stimuli, especially in the case of disease, the cell stretching device is a necessary tool to study the cell behavior in a controlled environment. However existing devices have limitations, such as too big to fit the culture chamber, unable to be observed during the stretching process and too expensive to fabricate. In this thesis, a new cell stretcher is designed to resolve these limitations. Many typical cell stretching devices only work under simple conditions. For instance they can only apply the strain on the cell in uniaxial or equibiaxial directions. On the other hand the environment of cells' survival is varying. Many new cell stretchers have been developed, which have the same property that cells can be stretched via the radical deformation of the elastomeric membrane. The aim of this new design is to create a cell stretching device that fits in general lab conditions. This device is designed to fit on a microscope to observe, as well as in the incubator. In addition, two small step motors are used to control the strain, adjust the frequency, and maintain the stability precisely. Problems such as the culture media leakage and the membrane breakage are solved by the usage of multiple materials for both the cell stretcher and the membrane. Based on the experimental results, this device can satisfy the requirements of target users with a reduced manufacturing cost. In the future, an auto-focus tracking function will be developed to allow real time observation of the cells' behavior.

Kinetics of OH- and Cl-initiated oxidation of CH2dbnd CHC(O)O(CH2)2CH3 and CH2dbnd CHCH2C(O)O(CH2)2CH3 and fate of the alkoxy radicals formed

NASA Astrophysics Data System (ADS)

Rivela, Cynthia; Blanco, María B.; Teruel, Mariano A.

2016-05-01

Rate coefficients of the reactions of OH and Cl radicals with vinyl and allyl butyrate were determined for the first time at 298 K and 1 atm using the relative method to be (in cm3 molecule-1 s-1): k1(OH + CH2dbnd CHC(O)O(CH2)2CH3) = (2.61 ± 0.31) × 10-11, k2(Cl + CH2dbnd CHC(O)O(CH2)2CH3) = (2.48 ± 0.89) × 10-10, k3(OH + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.89 ± 0.31) × 10-11, and k4(Cl + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.25 ± 0.96) × 10-10. Reactivity trends and atmospheric lifetimes of esters are presented. Additionally, a product study shown butyric acid and polifunctional products for the reactions of vinyl and allyl butyrate, respectively and general mechanism is proposed.

IR-UV double resonance spectroscopic investigation of phenylacetylene-alcohol complexes. Alkyl group induced hydrogen bond switching.

PubMed

Singh, Prashant Chandra; Patwari, G Naresh

2008-06-12

The electronic transitions of phenylacetylene complexes with water and trifluoroethanol are shifted to the blue, while the corresponding transitions for methanol and ethanol complexes are shifted to the red relative to the phenylacetylene monomer. Fluorescence dip infrared (FDIR) spectra in the O-H stretching region indicate that, in all the cases, phenylacetylene is acting as a hydrogen bond acceptor to the alcohols. The FDIR spectrum in the acetylenic C-H stretching region shows Fermi resonance bands for the bare phenylacetylene, which act as a sensitive tool to probe the intermolecular structures. The FDIR spectra reveal that water and trifluoroethanol interact with the pi electron density of the acetylene C-C triple bond, while methanol and ethanol interact with the pi electron density of the benzene ring. It can be inferred that the hydrogen bonding acceptor site on phenylacetylene switches from the acetylene pi to the benzene pi with lowering in the partial charge on the hydrogen atom of the OH group. The most significant finding is that the intermolecular structures of water and methanol complexes are notably distinct, which, to the best of our knowledge, this is first such observation in the case of complexes of substituted benzenes.

Immediate effects of different types of stretching exercises on badminton jump smash.

PubMed

Jang, Hwi S; Kim, Daeho; Park, Jihong

2018-01-01

Since different types of stretching exercises may alter athletic performance, we compared the effects of three types of stretching exercises on badminton jump smash. Sixteen male collegiate badminton players performed one of three different stretching exercises in a counterbalanced order on different days. Static stretching had seven typical stretches, while dynamic stretching involved nine dynamic movements, and resistance dynamic stretching was performed with weighted vests and dumbbells. Before and after each stretching exercise, subjects performed 20 trials of jump smashes. Dependent measurements were the jump heights during jump smashes, velocities of jump-smashed shuttlecocks, and drop point of jump-smashed shuttlecocks. To test the effects of each stretching exercise, we performed mixed model ANOVAs and calculated between-time effect sizes (ES). Each stretching exercise improved the jump heights during jump smashes (type main effect: F(2,75)=1.19, P=0.31; static stretching: 22.1%, P<0.01, ES=0.98; dynamic stretching: 30.1%, P<0.01, ES=1.49; resistance dynamic stretching: 17.7%, P=0.03, ES=0.98) and velocities of jump-smashed shuttlecocks (type main effect: F(2,75)=2.18, P=0.12; static stretching: 5.7%, P=0.61, ES=0.39; dynamic stretching: 3.4%, P=0.94, ES=0.28; resistance dynamic stretching: 6%, P=0.50, ES=0.66). However, there were no differences among the stretching exercises for any measurement. The drop point of jump-smashed shuttlecocks did not change (interaction: F(2,75)=0.88, P=0.42). All stretching exercises improved badminton jump smash performance, but we could not determine the best protocol. Since badminton requires high-speed movement and explosive force, we suggest performing dynamic stretching or resistance dynamic stretching.

Mechanical stretching for tissue engineering: two-dimensional and three-dimensional constructs.

PubMed

Riehl, Brandon D; Park, Jae-Hong; Kwon, Il Keun; Lim, Jung Yul

2012-08-01

Mechanical cell stretching may be an attractive strategy for the tissue engineering of mechanically functional tissues. It has been demonstrated that cell growth and differentiation can be guided by cell stretch with minimal help from soluble factors and engineered tissues that are mechanically stretched in bioreactors may have superior organization, functionality, and strength compared with unstretched counterparts. This review explores recent studies on cell stretching in both two-dimensional (2D) and three-dimensional (3D) setups focusing on the applications of stretch stimulation as a tool for controlling cell orientation, growth, gene expression, lineage commitment, and differentiation and for achieving successful tissue engineering of mechanically functional tissues, including cardiac, muscle, vasculature, ligament, tendon, bone, and so on. Custom stretching devices and lab-specific mechanical bioreactors are described with a discussion on capabilities and limitations. While stretch mechanotransduction pathways have been examined using 2D stretch, studying such pathways in physiologically relevant 3D environments may be required to understand how cells direct tissue development under stretch. Cell stretch study using 3D milieus may also help to develop tissue-specific stretch regimens optimized with biochemical feedback, which once developed will provide optimal tissue engineering protocols.

Mechanical Stretching for Tissue Engineering: Two-Dimensional and Three-Dimensional Constructs

PubMed Central

Riehl, Brandon D.; Park, Jae-Hong; Kwon, Il Keun

2012-01-01

Mechanical cell stretching may be an attractive strategy for the tissue engineering of mechanically functional tissues. It has been demonstrated that cell growth and differentiation can be guided by cell stretch with minimal help from soluble factors and engineered tissues that are mechanically stretched in bioreactors may have superior organization, functionality, and strength compared with unstretched counterparts. This review explores recent studies on cell stretching in both two-dimensional (2D) and three-dimensional (3D) setups focusing on the applications of stretch stimulation as a tool for controlling cell orientation, growth, gene expression, lineage commitment, and differentiation and for achieving successful tissue engineering of mechanically functional tissues, including cardiac, muscle, vasculature, ligament, tendon, bone, and so on. Custom stretching devices and lab-specific mechanical bioreactors are described with a discussion on capabilities and limitations. While stretch mechanotransduction pathways have been examined using 2D stretch, studying such pathways in physiologically relevant 3D environments may be required to understand how cells direct tissue development under stretch. Cell stretch study using 3D milieus may also help to develop tissue-specific stretch regimens optimized with biochemical feedback, which once developed will provide optimal tissue engineering protocols. PMID:22335794

The Impact of Commonly Used Alkylating Agents on Artifactual Peptide Modification.

PubMed

Hains, Peter G; Robinson, Phillip J

2017-09-01

Iodoacetamide is by far the most commonly used agent for alkylation of cysteine during sample preparation for proteomics. An alternative, 2-chloroacetamide, has recently been suggested to reduce the alkylation of residues other than cysteine, such as the N-terminus, Asp, Glu, Lys, Ser, Thr, and Tyr. Here we show that although 2-chloroacetamide reduces the level of off-target alkylation, it exhibits a range of adverse effects. The most significant of these is methionine oxidation, which increases to a maximum of 40% of all Met-containing peptides, compared with 2-5% with iodoacetamide. Increases were also observed for mono- and dioxidized tryptophan. No additional differences between the alkylating reagents were observed for a range of other post-translational modifications and digestion parameters. The deleterious effects were observed for 2-chloroacetamide from three separate suppliers. The adverse impact of 2-chloroacetamide on methionine oxidation suggests that it is not the ideal alkylating reagent for proteomics.

Alkyl gallates, intensifiers of beta-lactam susceptibility in methicillin-resistant Staphylococcus aureus.

PubMed

Shibata, Hirofumi; Kondo, Kyoko; Katsuyama, Ryo; Kawazoe, Kazuyoshi; Sato, Yoichi; Murakami, Kotaro; Takaishi, Yoshihisa; Arakaki, Naokatu; Higuti, Tomihiko

2005-02-01

We found that ethyl gallate purified from a dried pod of tara (Caesalpinia spinosa) intensified beta-lactam susceptibility in methicillin-resistant and methicillin-sensitive strains of Staphylococcus aureus (MRSA and MSSA strains, respectively). This compound and several known alkyl gallates were tested with MRSA and MSSA strains to gain new insights into their structural functions in relation to antimicrobial and beta-lactam susceptibility-intensifying activities. The maximum activity of alkyl gallates against MRSA and MSSA strains occurred at 1-nonyl and 1-decyl gallate, with an MIC at which 90% of the isolates tested were inhibited of 15.6 microg/ml. At concentrations lower than the MIC, alkyl gallates synergistically elevated the susceptibility of MRSA and MSSA strains to beta-lactam antibiotics. Such a synergistic activity of the alkyl gallates appears to be specific for beta-lactam antibiotics, because no significant changes were observed in the MICs of other classes of antibiotics examined in this study. The length of the alkyl chain was also associated with the modifying activity of the alkyl gallates, and the optimum length was C5 to C6. The present work clearly demonstrates that the length of the alkyl chain has a key role in the elevation of susceptibility to beta-lactam antibiotics.

Deep tunneling in the unimolecular decay of CH 3CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Barber, Victoria P.

Unimolecular decay of Criegee intermediates produced in alkene ozonolysis is known to be a significant source of OH radicals in the troposphere. In this work, unimolecular decay of the methyl-substituted Criegee intermediate, syn-CH 3CHOO, to OH products is shown to occur at energies significantly below the transition state barrier for a 1,4 hydrogen transfer that leads to these products [Y. Fang et al., J. Chem. Phys. 144, 061102 (2016)]. The rate of appearance of OH products arising from tunneling through the barrier is obtained through direct time-domain measurements following the vibrational activation of syn-CH 3CHOO. IR excitation of syn-CH 3CHOOmore » at energies nearly 2000 cm -1 below the barrier is achieved through combination bands involving CH stretch and another lower frequency mode, and the resultant OH products are detected by UV laser-induced fluorescence. The observed syn-CH 3CHOO combination bands in the 4100–4350 cm -1 region are identified by comparison with the computed IR absorption spectrum. The experimental decay rates are found to be ca. 106 s -1 in this deep tunneling regime, which is approximately 100-times slower than that in the vicinity of the barrier.The experimental results are consistent with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical decay rates with tunneling through the barrier, and notable deviations may originate from the sparsity in the density of states for syn-CH 3CHOO at lower energies. Thermal unimolecular decay of syn-CH 3CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.« less

Statistics of Advective Stretching in Three-dimensional Incompressible Flows

NASA Astrophysics Data System (ADS)

Subramanian, Natarajan; Kellogg, Louise H.; Turcotte, Donald L.

2009-09-01

We present a method to quantify kinematic stretching in incompressible, unsteady, isoviscous, three-dimensional flows. We extend the method of Kellogg and Turcotte (J. Geophys. Res. 95:421-432, 1990) to compute the axial stretching/thinning experienced by infinitesimal ellipsoidal strain markers in arbitrary three-dimensional incompressible flows and discuss the differences between our method and the computation of Finite Time Lyapunov Exponent (FTLE). We use the cellular flow model developed in Solomon and Mezic (Nature 425:376-380, 2003) to study the statistics of stretching in a three-dimensional unsteady cellular flow. We find that the probability density function of the logarithm of normalised cumulative stretching (log S) for a globally chaotic flow, with spatially heterogeneous stretching behavior, is not Gaussian and that the coefficient of variation of the Gaussian distribution does not decrease with time as t^{-1/2} . However, it is observed that stretching becomes exponential log S˜ t and the probability density function of log S becomes Gaussian when the time dependence of the flow and its three-dimensionality are increased to make the stretching behaviour of the flow more spatially uniform. We term these behaviors weak and strong chaotic mixing respectively. We find that for strongly chaotic mixing, the coefficient of variation of the Gaussian distribution decreases with time as t^{-1/2} . This behavior is consistent with a random multiplicative stretching process.

Jet-cooled electronic and vibrational spectroscopy of crown ethers: benzo-15-crown-5 ether and 4'-amino-benzo-15-crown-5 ether.

PubMed

Shubert, V Alvin; James, William H; Zwier, Timothy S

2009-07-16

Laser-induced fluorescence (LIF), ultraviolet hole-burning (UVHB), and resonant ion-dip infrared (RIDIR) spectroscopies were carried out on isolated benzo-15-crown-5 ether (B15C) and 4'-amino-benzo-15-crown-5 ether (ABC) cooled in a supersonic expansion. Three conformational isomers of B15C and four of ABC were observed and spectroscopically characterized. Full optimizations and harmonic frequency calculations were undertaken for the full set of almost 1700 conformational minima identified in a molecular mechanics force field search. When compared with TDDFT predictions, the S(0)-S(1) origin positions serve as a useful diagnostic of the conformation of the crown ether near the phenyl ring responsible for the UV absorption and to the position of the NH(2) substituent. In-plane orientations for the beta carbons produce red-shifted S(0)-S(1) origins, while out-of-plane "buckling" produces substantial blue shifts of 600 cm(-1) or more. Comparison between the alkyl CH stretch spectra of B15C and ABC divide the spectra into common subgroups shared by the two molecules. The high-frequency CH stretch transitions (above 2930 cm(-1)) reflect the number of CH...O interactions, which in turn track in a general way the degree of buckling of the crown. On this basis, assignments of each of the observed conformational isomers to a class of structure can be made. All the observed structures have some degree of buckling to them, indicating that in the absence of a strong-binding partner, the crown folds in on itself to gain additional stabilization from weak dispersive and CH...O interactions.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the

40 CFR 721.10517 - Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide and...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl methacrylates, polymer with... Substances § 721.10517 Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide... reporting. (1) The chemical substance identified generically as alkyl methacrylates, polymer with...

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.

Catalytic Hydrogenation Activity and Electronic Structure Determination of Bis(arylimidazol-2-ylidene)pyridine Cobalt Alkyl and Hydride Complexes

PubMed Central

Yu, Renyuan Pony; Darmon, Jonathan M.; Milsmann, Carsten; Margulieux, Grant W.; E. Stieber, S. Chantal; DeBeer, Serena

2013-01-01

The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, (iPrCNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, (iPrCNC)CoCH3 is an effective pre-catalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, (iPrCNC)CoH was accomplished by hydrogenation of (iPrCNC)CoCH3. Over the course of 3 hours at 22 °C, migration of the metal-hydride to the 4-position of the pyridine ring yielded (4-H2-iPrCNC)CoN2. Similar alkyl migration was observed upon treatment of (iPrCNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redoxactive, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity and suggest a wide family of pyridine-based pincers may also be redox active. PMID:23968297

Bruxism: Is There an Indication for Muscle-Stretching Exercises?

PubMed

Gouw, Simone; de Wijer, Anton; Creugers, Nico Hj; Kalaykova, Stanimira I

Bruxism is a common phenomenon involving repetitive activation of the masticatory muscles. Muscle-stretching exercises are a recommended part of several international guidelines for musculoskeletal disorders and may be effective in management of the jaw muscle activity that gives rise to bruxism. However, most studies of muscle-stretching exercises have mainly focused on their influence on performance (eg, range of motion, coordination, and muscle strength) of the limb or trunk muscles of healthy individuals or individuals with sports-related injuries. Very few have investigated stretching of the human masticatory muscles and none muscle-stretching exercises in the management of (sleep) bruxism. This article reviews the literature on muscle-stretching exercises and their potential role in the management of sleep bruxism or its consequences in the musculoskeletal system.

A cephalometric study of velar stretch in adolescent subjects.

PubMed

Simpson, R K; Colton, J

1980-01-01

Cephalometric x-rays were used to evaluate velar stretch in 20 normal adolescents during the production of /s/. Radiopaque markers were used so that the behaviors of both the anterior and posterior portions and the total velum cound be evaluated. Velar stretch was found in each of the subjects with the average stretch (15.19%) greater than the amount reported for 10-year-old subjects but less than the average stretch for adults. The correlation between amount of velar stretch and need ratio was not significant. The different stages of involution of adenoid tissue, which is characteristic of this age group, resulted in varying configurations of the naso-pharynx were postulated as one possible explanation for this unexpected finding. Normative data and clinical implications are presented.

Superelastic supercapacitors with high performances during stretching.

PubMed

Zhang, Zhitao; Deng, Jue; Li, Xueyi; Yang, Zhibin; He, Sisi; Chen, Xuli; Guan, Guozhen; Ren, Jing; Peng, Huisheng

2015-01-14

A fiber-shaped supercapacitor that can be stretched over 400% is developed by using two aligned carbon nanotube/polyaniline composite sheets as electrodes. A high specific capacitance of approximately 79.4 F g(-1) is well maintained after stretching at a strain of 300% for 5000 cycles or 100.8 F g(-1) after bending for 5000 cycles at a current density of 1 A g(-1). In particular, the high specific capacitance is maintained by 95.8% at a stretching speed as high as 30 mm s(-1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

When alcohol is the answer: trapping, identifying and quantifying simple alkylating species in aqueous environments

PubMed Central

Penketh, P. G.; Shyam, K.; Baumann, R. P; Zhu, Rui; Ishiguro, K.; Sartorelli, A. C.; Ratner, E. S.

2016-01-01

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

Acute Effects of Three Different Stretching Protocols on the Wingate Test Performance

PubMed Central

Franco, Bruno L.; Signorelli, Gabriel R.; Trajano, Gabriel S.; Costa, Pablo B.; de Oliveira, Carlos G.

2012-01-01

The purpose of this study was to examine the acute effects of different stretching exercises on the performance of the traditional Wingate test (WT). Fifteen male participants performed five WT; one for familiarization (FT), and the remaining four after no stretching (NS), static stretching (SS), dynamic stretching (DS), and proprioceptive neuromuscular facilitation (PNF). Stretches were targeted for the hamstrings, quadriceps, and calf muscles. Peak power (PP), mean power (MP), and the time to reach PP (TP) were calculated. The MP was significantly lower when comparing the DS (7.7 ± 0.9 W/kg) to the PNF (7.3 ± 0.9 W/kg) condition (p < 0.05). For PP, significant differences were observed between more comparisons, with PNF stretching providing the lowest result. A consistent increase of TP was observed after all stretching exercises when compared to NS. The results suggest the type of stretching, or no stretching, should be considered by those who seek higher performance and practice sports that use maximal anaerobic power. Key points The mean power was significantly lower when comparing dynamic stretching.to proprioceptive neuromuscular facilitation. For peak power, significant differences were observed between more comparisons, with proprioceptive neuromuscular facilitation stretching providing the lowest result. A consistent increase of time to reach the peak was observed after all stretching exercises when compared to non-stretching. The type of stretching, or no stretching, should be considered by those who seek higher performance and practice sports that use maximal anaerobic power. PMID:24149116

Cessation of cyclic stretch induces atrophy of C2C12 myotubes.

PubMed

Soltow, Quinlyn A; Zeanah, Elizabeth H; Lira, Vitor A; Criswell, David S

2013-05-03

Cyclic stretch of differentiated myotubes mimics the loading pattern of mature skeletal muscle. We tested a cell culture model of disuse atrophy by the cessation of repetitive bouts of cyclic stretch in differentiated C2C12 myotubes. Myotubes were subjected to cyclic strain (12%, 0.7 Hz, 1 h/d) on collagen-I-coated Bioflex plates using a computer-controlled vacuum stretch apparatus (Flexcell Int.) for 2 (2dSTR) or 5 (5dSTR) consecutive days. Control cultures were maintained in the Bioflex plates without cyclic stretch for 2d or 5d. Additionally, some cultures were stretched for 2 d followed by cessation of stretch for 3d (2dSTR3dCES). Cyclic stretching (5dSTR) increased myotube diameter and overall myotube area by ~2-fold (P<0.05) compared to non-stretched controls, while cessation of stretch (2dSTR3dCES) resulted in ~80% smaller myotubes than 5dSTR cells, and 40-50% smaller than non-stretched controls (P<0.05). Further, the calpain-dependent cleavage products of αII-spectrin (150 kDa) and talin increased (3.5-fold and 2.2-fold, respectively; P<0.05) in 2dSTR3dCES myotubes, compared to non-stretched controls. The 1h cyclic stretching protocol acutely increased the phosphorylation of Akt (+4.5-fold; P<0.05) and its downstream targets, FOXO3a (+4.2-fold; P<0.05) and GSK-3β (+1.8-fold; P<0.05), which returned to baseline by 48 h after cessation of stretch. Additionally, nitric oxide production increased during stretch and co-treatment with the NOS inhibitor, l-NAME, inhibited the effects of stretch and cessation of stretch. We conclude that cessation of cyclic stretching causes myotube atrophy by activating calpains and decreasing activation of Akt. Stretch-induced myotube growth, as well as activation of atrophy signaling with cessation of stretch, are dependent on NOS activity. Copyright © 2013 Elsevier Inc. All rights reserved.

EMG and peak force responses to PNF stretching and the relationship between stretching-induced force deficits and bilateral deficits

PubMed Central

Cengiz, Asim

2015-01-01

[Purpose] The aim of the present study was to investigate the possibility of an interaction between stretching induced deficit (SFD) and bilateral deficits (BLD) during maximal voluntary isometric hand flexion under PNF stretch and no-stretch conditions through measurement of EMG and force production. [Subjects and Methods] Ten physically active male Caucasian students (age, 24.1±2.38 years; body mass, 79.48±11.40 kg; height, 174.15±0.8 cm) volunteered to participate in this study. EMG and force measurements of the subjects were recorded during either unilateral or bilateral 3-second maximal voluntary isometric hand flexion (MVC) against a force transducer. The paired sample t-test was used to examine the significance of differences among several conditions. Pearson product-moment correlation was used to evaluate the associations between different parameters. [Results] Stretching-induced deficits correlated with bilateral deficits in both force (r=0.85) and iEMG (r=0.89). PNF stretching caused significant decrements in the bilateral and unilateral conditions for both the right and left sides. [Conclusion] Since both force and iEMG decreases were observed in most measurements; it suggests there is a neural mechanism behinnd both the BLD and the SFD. PMID:25931696

STRETCH-DEPENDENT SENSITIZATION OF POST-JUNCTIONAL NEURAL EFFECTORS IN COLONIC MUSCLES

PubMed Central

Won, Kyung-Jong; Sanders, Kenton M.; Ward, Sean M.

2012-01-01

Background The colon undergoes distension-induced changes in motor activity as luminal contents or feces increases wall pressure. Input from enteric motor neurons regulates motility. Here we examined stretch-dependent responses in circular muscle strips of murine colon. Methods Length-ramps (6–31μm s−1) were applied in the axis of the circular muscle layer in a controlled manner until 5 mN isometric force was reached. Key Results Length-ramps produced transient membrane potential hyperpolarizations and attenuation of action potential (AP) complexes. Responses were reproducible when ramps were applied every 30s. Stretch-dependent hyperpolarization was blocked by TTX, suggesting AP-dependent release of inhibitory neurotransmitter(s). Atropine did not potentiate stretch-induced hyperpolarizations, but increased compliance of the circular layer. L-NNA inhibited stretch-dependent hyperpolarization and decreased muscle compliance, suggesting release of NO mediates stretch-dependent inhibition. Control membrane potential was restored by the NO donor SNP. Stretch-dependent hyperpolarizations were blocked by L-methionine, an inhibitor of stretch-dependent K+ (SDK) channels in colonic muscles. Loss of ICC, elicited by Kit neutralizing antibody, also inhibited responses to stretch. In presence of L-NNA and apamin, stretch responses became excitatory and were characterized by membrane depolarization and increased AP firing. A neurokinin-1 receptor antagonist inhibited this stretch-dependent increase in excitability. Conclusions & Inferences Our data show that stretch-dependent responses in colonic muscles require tonic firing of enteric inhibitory neurons, but reflex activation of neurons does not appear to be necessary. NO causes activation of SDK channels, and stretch of muscles further activates these channels, explaining the inhibitory response to stretch in colonic muscle strips. PMID:23279087

Optical sensor system for time-resolved quantification of methane densities in CH4-fueled spark ignition engines.

PubMed

Golibrzuch, Kai; Digulla, Finn-Erik; Bauke, Stephan; Wackerbarth, Hainer; Thiele, Olaf; Berg, Thomas

2017-08-01

We present the development and the first application of an optical sensor system that allows single-cycle determination of methane (CH 4 ) concentration inside internal combustion (IC) engines. We use non-dispersive infrared absorption spectroscopy to detect the CH 4 density with a time resolution up to 33 μs at acquisition rates of 30 kHz. The measurement scheme takes advantage of the strong temperature dependence of the absorption band applying two detection channels for CH 4 that detect different spectral regions of the ν 3 anti-symmetric C-H-stretch absorption. The strategy allows the simultaneous determination of fuel concentration as well as gas temperature. We show the proof-of-concept by validation of the measurement strategy in static pressure cell experiments as well as its application to a methane-fueled IC engine using a modified spark plug probe. Our results clearly demonstrate that it is crucial to determine the CH 4 temperature in the probe volume. Due to thermal influences of the sensor probe, the temperature needed to calculate the desired quantities (fuel density, fuel concentration) significantly differs from the gas phase temperature in the rest of the combustion chamber and estimations from standard thermodynamic models, e.g., polytropic compression, will fail.

Extended exposure to alkylator chemotherapy: delayed appearance of myelodysplasia.

PubMed

Chamberlain, Marc C; Raizer, Jeffrey

2009-06-01

A case series of gliomas treated with alkylator-based chemotherapy who subsequently developed myelodysplastic syndrome (tMDS) or acute myelocytic leukemia (AML). Alkylator-based chemotherapy is recognized to be leukemogenic; however, it is infrequently described as a delayed consequence of anti-glioma treatment. Seven patients (4 men; 3 women) ages 34-69 years (median 44), with gliomas (3 Grade 2; 4 Grade 3) were treated with surgery, all but one with involved-field radiotherapy and all with alkylator-based chemotherapy (temozolomide; 6 patients, nitrosoureas; 5 patients, both agents; 5 patients). Exposure to alkylator-based chemotherapy ranged from 8 to 30 months (median 24). The diagnosis of tMDS was determined by bone marrow biopsy in 7 patients. Seven patients showed chromosomal abnormalities consistent with chemotherapy induced MDS. Three patients were diagnosed with AML as well (in two determined by bone marrow and one at autopsy). Interval from last chemotherapy exposure to diagnosis of tMDS/AML ranged from 3 to 31 months (median 24 months). Two patients were treated with bone marrow transplantation and 5 received supportive care only. Five patients have died, 2 as a consequence of recurrent brain tumor, 1 as a complication of transplantation, and 2 due to AML. Although rare, induction of tMDS/AML following extended use of alkylator-based chemotherapy may become more relevant with the evolving practice to treat gliomas for protracted periods. Future work to determine at risk patients would be important.

ChIP-seq.

PubMed

Kim, Tae Hoon; Dekker, Job

2018-05-01

Owing to its digital nature, ChIP-seq has become the standard method for genome-wide ChIP analysis. Using next-generation sequencing platforms (notably the Illumina Genome Analyzer), millions of short sequence reads can be obtained. The densities of recovered ChIP sequence reads along the genome are used to determine the binding sites of the protein. Although a relatively small amount of ChIP DNA is required for ChIP-seq, the current sequencing platforms still require amplification of the ChIP DNA by ligation-mediated PCR (LM-PCR). This protocol, which involves linker ligation followed by size selection, is the standard ChIP-seq protocol using an Illumina Genome Analyzer. The size-selected ChIP DNA is amplified by LM-PCR and size-selected for the second time. The purified ChIP DNA is then loaded into the Genome Analyzer. The ChIP DNA can also be processed in parallel for ChIP-chip results. © 2018 Cold Spring Harbor Laboratory Press.

Alkyl Glucosides in Contact Dermatitis.

PubMed

Loranger, Camille; Alfalah, Maisa; Ferrier Le Bouedec, Marie-Christine; Sasseville, Denis

Ecologically sound because they are synthesized from natural and renewable sources, the mild surfactants alkyl glucosides are being rediscovered by the cosmetic industry. They are currently found in rinse-off products such as shampoos, liquid cleansers, and shower gels, but also in leave-on products that include moisturizers, deodorants, and sunscreens. During the past 15 years, numerous cases of allergic contact dermatitis have been published, mostly to lauryl and decyl glucosides, and these compounds are considered emergent allergens. Interestingly, the sunscreen Tinosorb M contains decyl glucoside as a hidden allergen, and most cases of allergic contact dermatitis reported to this sunscreen ingredient are probably due to sensitization to decyl glucoside. This article will review the chemistry of alkyl glucosides, their sources of exposure, as well as their cutaneous adverse effects reported in the literature and encountered in various patch testing centers.

Selective sp3 C–H alkylation via polarity-match-based cross-coupling

PubMed Central

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-01-01

The functionalization of carbon–hydrogen (C–H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence1. Although many C–H functionalization reactions involve C(sp3)–C(sp2) coupling, there is a growing demand for C–H alkylation reactions, wherein sp3 C–H bonds are replaced with sp3 C–alkyl groups. Here we describe a polarity-match-based selective sp3 C–H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C–H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl–alkyl fragment coupling. The sp3 C–H alkylation is highly selective for the α-C–H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry. PMID:28636596

Merging C-H activation and alkene difunctionalization at room temperature: a palladium-catalyzed divergent synthesis of indoles and indolines.

PubMed

Manna, Manash Kumar; Hossian, Asik; Jana, Ranjan

2015-02-06

A palladium-catalyzed 1,2-carboamination through C-H activation at room temperature is reported for the synthesis of 2-arylindoles, and indolines from readily available, inexpensive aryl ureas and vinyl arenes. The reaction initiates with a urea-directed electrophilic ortho palladation, alkene insertion, and β-hydride elimination sequences to provide the Fujiwara-Moritani arylation product. Subsequently, aza-Wacker cyclization, and β-hydride elimination provide the 2-arylindoles in high yields. Intercepting the common σ-alkyl-Pd intermediate, corresponding indolines are also achieved. The indoline formation is attributed to the generation of stabilized, cationic π-benzyl-Pd species to suppress β-hydride elimination.

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

2015-07-07

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.

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. Copyright © 2016 Elsevier Inc. All rights reserved.

ChIP and ChIP-Related Techniques: Expanding the Fields of Application and Improving ChIP Performance.

PubMed

Visa, Neus; Jordán-Pla, Antonio

2018-01-01

Protein-DNA interactions in vivo can be detected and quantified by chromatin immunoprecipitation (ChIP). ChIP has been instrumental for the advancement of epigenetics and has set the groundwork for the development of a number of ChIP-related techniques that have provided valuable information about the organization and function of genomes. Here, we provide an introduction to ChIP and discuss the applications of ChIP in different research areas. We also review some of the strategies that have been devised to improve ChIP performance.

Nickel-Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates.

PubMed

Chen, Haifeng; Jia, Xiao; Yu, Yingying; Qian, Qun; Gong, Hegui

2017-10-09

The construction of all C(sp 3 ) quaternary centers has been successfully achieved under Ni-catalyzed cross-electrophile coupling of allylic carbonates with unactivated tertiary alkyl halides. For allylic carbonates bearing C1 or C3 substituents, the reaction affords excellent regioselectivity through the addition of alkyl groups to the unsubstituted allylic carbon terminus. The allylic alkylation method also exhibits excellent functional-group compatibility, and delivers the products with high E selectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of multispectral thermal infrared images - Decorrelation contrast stretching

NASA Technical Reports Server (NTRS)

Gillespie, Alan R.

1992-01-01

Decorrelation contrast stretching is an effective method for displaying information from multispectral thermal infrared (TIR) images. The technique involves transformation of the data to principle components ('decorrelation'), independent contrast 'stretching' of data from the new 'decorrelated' image bands, and retransformation of the stretched data back to the approximate original axes, based on the inverse of the principle component rotation. The enhancement is robust in that colors of the same scene components are similar in enhanced images of similar scenes, or the same scene imaged at different times. Decorrelation contrast stretching is reviewed in the context of other enhancements applied to TIR images.

Hybrid ligand-alkylating agents targeting telomeric G-quadruplex structures.

PubMed

Doria, Filippo; Nadai, Matteo; Folini, Marco; Di Antonio, Marco; Germani, Luca; Percivalle, Claudia; Sissi, Claudia; Zaffaroni, Nadia; Alcaro, Stefano; Artese, Anna; Richter, Sara N; Freccero, Mauro

2012-04-14

The synthesis, physico-chemical properties and biological effects of a new class of naphthalene diimides (NDIs) capable of reversibly binding telomeric DNA and alkylate it through an electrophilic quinone methide moiety (QM), are reported. FRET and circular dichroism assays showed a marked stabilization and selectivity towards telomeric G4 DNA folded in a hybrid topology. NDI-QMs' alkylating properties revealed a good reactivity on single nucleosides and selectivity towards telomeric G4. A selected NDI was able to significantly impair the growth of melanoma cells by causing telomere dysfunction and down-regulation of telomerase expression. These findings points to our hybrid ligand-alkylating NDIs as possible tools for the development of novel targeted anticancer therapies. This journal is © The Royal Society of Chemistry 2012

Alkyl Azides, Diazides, Haloazides and Bridged Polycyclic Diazides

DTIC Science & Technology

1991-05-16

temperature. Most of the methyl ether was removed during this process. The ehtyl ether was distilled from the reaction mixture using a water aspirator into a...Street PROGRAM IPROJECT ITASK IWORK li1111? ArliiqIoh, VA 22217-5000 EILIMENT NO I NO. I oACCESSION P10) Alkyl Azides, Dlazides, laloazides and...REPRODUCE LEGIBLY. ALKYL AZIDES, DIAZIDES, HALOAZIDES AND BRIDGED POLYCYCLIC DIAZIDES Final REPORTe July 1, 1989-November 14, 1990 A6jd.%4gi0 F’or

Three Fresh Exposures, Stretched Color

NASA Technical Reports Server (NTRS)

2004-01-01

This panoramic camera image from NASA's Mars Exploration Rover Opportunity has been processed using a technique known as a decorrelation stretch to exaggerate the colors. The area in the image includes three holes created inside 'Endurance Crater' by Opportunity's rock abrasion tool between sols 143 and 148 (June 18 and June 23, 2004). Because color variations are so subtle in the pictured area, stretched images are useful for discriminating color differences that can alert scientists to compositional and textural variations. For example, without the exaggeration, no color difference would be discernable among the tailings left behind after the grinding of these holes, but in this stretched image, the tailings around 'London' (top) appear more red than those of the other holes ('Virginia,' middle, and 'Cobble Hill,' bottom). Scientists believe that is because the rock abrasion tool sliced through two 'blueberries,' or spherules (visible on the upper left and upper right sides of the circle). When the blades break up these spherules, composed of mostly gray hematite, the result is a bright red powder. In this image, you can see the rock layers that made the team want to grind holes in each identified layer. The top layer is yellowish red, the middle is yellowish green and the lower layer is green. Another advantage to viewing this stretched image is the clear detail of the distribution of the rock abrasion tool tailings (heading down-slope) and the differences in rock texture. This image was created using the 753-, 535- and 432-nanometer filters.

Enantiomerically Pure Acetals in Organic Synthesis: Resolutions and Diastereoselective Alkylations of Alpha-Hydroxy Esters

DTIC Science & Technology

1990-01-01

sensitivity of the alkylating agent to the reaction conditions. In either case , a decision was made to use 5-iodo-2- methyl -l-pentene as the alkylating ...agent, and the reaction conditions. In most cases the diastereomeric products of the alkylation were also separated by column chromatography. This...equatorially substituted product. Oxidation of the alcohol to the ketone followed by treatment with an alkyl Grignard reagent gave only the product which

On One-Dimensional Stretching Functions for Finite-Difference Calculations

NASA Technical Reports Server (NTRS)

Vinokur, M.

1980-01-01

The class of one dimensional stretching function used in finite difference calculations is studied. For solutions containing a highly localized region of rapid variation, simple criteria for a stretching function are derived using a truncation error analysis. These criteria are used to investigate two types of stretching functions. One is an interior stretching function, for which the location and slope of an interior clustering region are specified. The simplest such function satisfying the criteria is found to be one based on the inverse hyperbolic sine. The other type of function is a two sided stretching function, for which the arbitrary slopes at the two ends of the one dimensional interval are specified. The simplest such general function is found to be one based on the inverse tangent. The general two sided function has many applications in the construction of finite difference grids.

Lamellar Thickness and Stretching Temperature Dependency of Cavitation in Semicrystalline Polymers

PubMed Central

Wang, Yaotao; Jiang, Zhiyong; Fu, Lianlian; Lu, Ying; Men, Yongfeng

2014-01-01

Polybutene-1 (PB-1), a typical semicrystalline polymer, in its stable form I shows a peculiar temperature dependent strain-whitening behavior when being stretched at temperatures in between room temperature and melting temperature of the crystallites where the extent of strain-whitening weakens with the increasing of stretching temperature reaching a minima value followed by an increase at higher stretching temperatures. Correspondingly, a stronger strain-hardening phenomenon was observed at higher temperatures. The strain-whitening phenomenon in semicrystalline polymers has its origin of cavitation process during stretching. In this work, the effect of crystalline lamellar thickness and stretching temperature on the cavitation process in PB-1 has been investigated by means of combined synchrotron ultrasmall-angle and wide-angle X-ray scattering techniques. Three modes of cavitation during the stretching process can be identified, namely “no cavitation” for the quenched sample with the thinnest lamellae where only shear yielding occurred, “cavitation with reorientation” for the samples stretched at lower temperatures and samples with thicker lamellae, and “cavitation without reorientation” for samples with thinner lamellae stretched at higher temperatures. The mode “cavitation with reorientation” occurs before yield point where the plate-like cavities start to be generated within the lamellar stacks with normal perpendicular to the stretching direction due to the blocky substructure of the crystalline lamellae and reorient gradually to the stretching direction after strain-hardening. The mode of “cavitation without reorientation” appears after yield point where ellipsoidal shaped cavities are generated in those lamellae stacks with normal parallel to the stretching direction followed by an improvement of their orientation at larger strains. X-ray diffraction results reveal a much improved crystalline orientation for samples with thinner lamellae

ChIPpeakAnno: a Bioconductor package to annotate ChIP-seq and ChIP-chip data

PubMed Central

2010-01-01

Background Chromatin immunoprecipitation (ChIP) followed by high-throughput sequencing (ChIP-seq) or ChIP followed by genome tiling array analysis (ChIP-chip) have become standard technologies for genome-wide identification of DNA-binding protein target sites. A number of algorithms have been developed in parallel that allow identification of binding sites from ChIP-seq or ChIP-chip datasets and subsequent visualization in the University of California Santa Cruz (UCSC) Genome Browser as custom annotation tracks. However, summarizing these tracks can be a daunting task, particularly if there are a large number of binding sites or the binding sites are distributed widely across the genome. Results We have developed ChIPpeakAnno as a Bioconductor package within the statistical programming environment R to facilitate batch annotation of enriched peaks identified from ChIP-seq, ChIP-chip, cap analysis of gene expression (CAGE) or any experiments resulting in a large number of enriched genomic regions. The binding sites annotated with ChIPpeakAnno can be viewed easily as a table, a pie chart or plotted in histogram form, i.e., the distribution of distances to the nearest genes for each set of peaks. In addition, we have implemented functionalities for determining the significance of overlap between replicates or binding sites among transcription factors within a complex, and for drawing Venn diagrams to visualize the extent of the overlap between replicates. Furthermore, the package includes functionalities to retrieve sequences flanking putative binding sites for PCR amplification, cloning, or motif discovery, and to identify Gene Ontology (GO) terms associated with adjacent genes. Conclusions ChIPpeakAnno enables batch annotation of the binding sites identified from ChIP-seq, ChIP-chip, CAGE or any technology that results in a large number of enriched genomic regions within the statistical programming environment R. Allowing users to pass their own annotation data such

Selenium carboxylic acids betaine; 3,3‧,3″-selenotris(propanoic acid) betaine, Se(CH2CH2COOH)2(CH2CH2COO)

NASA Astrophysics Data System (ADS)

Doudin, Khalid; Törnroos, Karl W.

2017-06-01

Attempts to prepare [Se(CH2CH2COOH)3]+Cl- from Se(CH2CH2COOH)2 and H2Cdbnd CHCOOH in concentrated hydrochloric acid, for the corresponding sulfonium salt, led exclusively to the Se-betaine, Se(CH2CH2COOH)2(CH2CH2COO). The Se-betaine crystallises in the space group P2l/c with the cell dimensions at 223 K, a = 5.5717(1), b = 24.6358(4), c = 8.4361(1) Å, β = 104.762(1)°, V = 1119.74(3) Å3, Z = 4, Dcalc = 1.763 Mgm- 3, μ = 3.364 Mm-1. The structure refined to RI = 0.0223 for 2801 reflections with Fo > 4σ(Fo). In the crystalline state the molecule is intermolecularly linked to neighbouring molecules by a number of hydrogen bonds; a very strong carboxylic-carboxylate bond with an O⋯O distance of 2.4435(16) Å, a medium strong carboxylic-carboxylate bond with an O⋯O distance of 2.6431(16) Å and several weak O⋯H(CH2) with O⋯C distances between 3.2 and 3.3 Å. In the carboxylic group involved in the very strong hydrogen bond the O⋯H bond is antiperiplanar to the Cdbnd O bond while the Osbnd H bond is periplanar to the Cdbnd O bond in the second carboxylic group. Based upon the Csbnd O bond lengths and the elongation of the Osbnd H bond involved in the strong hydrogen bond one may describe the compound as strongly linked units of Se(CH2CH2COOH)(CH2CH2COO)2 rather than Se(CH2CH2COOH)2(CH2CH2COO). The selenium atom forms two strong intramolecular 1,5-Se⋯O contacts, with a carboxylate oxygen atom, 2.9385(12) Å, and with a carboxylic oxygen atom, 2.8979(11) Å. To allow for these contacts the two organic fragments have been forced into the periplanar conformation. The molecule is only slightly asymmetric with regard to the Csbnd Sesbnd C bond angles but is very asymmetric with regard to the torsion angles.

Stretch That Budget!

ERIC Educational Resources Information Center

Walker, John R.

1976-01-01

Discusses ways in which industrial education teachers can stretch their budgets, which include reducing waste to a minimum, keeping an accurate and up-to-date inventory, trading surplus or excess materials with neighboring schools, and planning programs more carefully. Money-saving tips concerned with metals, plastics, woods, and printing are also…

Rosidal K: a short-stretch compression bandage system.

PubMed

Williams, C

Management of venous leg ulcers account for a large proportion of the work of healthcare professionals, especially for those who are community based. Multilayer and long-stretch bandage systems have been used successfully for many years in venous leg ulcer management. Rosidal K, a short-stretch bandage, is now also becoming more widely accepted in this country as an effective and cost-effective bandage system. This product focus looks at bandage systems and examines the research supporting the use of short-stretch bandages and Rosidal K.

Effects of single bond-ion and single bond-diradical form on the stretching vibration of Cdbnd N bridging bond in 4,4‧-disubstituted benzylidene anilines

NASA Astrophysics Data System (ADS)

Cao, Chao-Tun; Bi, Yakun; Cao, Chenzhong

2016-06-01

Fifty-seven samples of model compounds, 4,4‧-disubstituted benzylidene anilines, p-X-ArCH = NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νCdbnd N of the Cdbnd N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νCdbnd N, that is there are mainly three modes in the stretching vibration of Cdbnd N bond: (I) polar double bond form Cdbnd N, (II) single bond-ion form C+-N- and (III) single bond-diradical form Crad -Nrad . The contributions of the forms (I) and (II) to the change of νCdbnd N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II).

40 CFR 721.5860 - Methylphenol, bis(sub-sti-tuted)alkyl.

Code of Federal Regulations, 2010 CFR

2010-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5860 Methylphenol, bis(sub-sti-tuted)alkyl. (a) Chemical substance and significant new uses...-ed)alkyl (P-84-417) is subject to reporting under this section for the significant new uses described...

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

Laboratory Spectroscopy of CH(+) and Isotopic CH

NASA Technical Reports Server (NTRS)

Pearson, John C.; Drouin, Brian J.

2006-01-01

The A1II - X1(Epsilon) electronic band of the CH(+) ion has been used as a probe of the physical and dynamical conditions of the ISM for 65 years. In spite of being one of the first molecular species observed in the ISM and the very large number of subsequent observations with large derived column densities, the pure rotational spectra of CH+ has remained elusive in both the laboratory and in the ISM as well. We report the first laboratory measurement of the pure rotation of the CH(+) ion and discuss the detection of CH-13(+) in the ISM. Also reported are the somewhat unexpected chemical conditions that resulted in laboratory production.

The vacuum-ultraviolet photoelectron spectra of CH2F2 and CH2Cl2 revisited

NASA Astrophysics Data System (ADS)

Tuckett, Richard; Harvey, Jonelle; Hemberger, Patrick; Bodi, Andras

2015-09-01

The threshold photoelectron spectrum (TPES) of difluoromethane and dichloromethane has been recorded at the Swiss Light Source with a resolution of 2 meV or 16 cm-1. Electronic and vibronic transitions are simulated and assigned with the help of Franck-Condon (FC) calculations based on coupled cluster electronic structure calculations for the equilibrium geometries and harmonic vibrational frequencies of the neutrals, and of the ground and excited electronic states of the cations. Notwithstanding a high-resolution pulsed-field ionisation study on CH2F2 (Forysinski et al., 2010) in which a number of transitions to the X∼+ state have been recorded with unprecedented accuracy, we report the first complete vibrationally resolved overview of the low-lying electronic states of CH2X2+, X = F or Cl. Hydrogen atom loss from CH2F2+ occurs at low energy, making the ground state rather anharmonic and interpretation of the X∼+ band challenging in the harmonic approximation. By Franck-Condon fits, the adiabatic ionisation energies to the A∼+ 2B2, C∼+ 2A2 and D∼+ 2B2 states have been determined as 14.3 ± 0.1, 15.57 ± 0.01 and 18.0 ± 0.1 eV, respectively. The first band in the CH2Cl2 TPES is complex for a different reason, as it is the result of two overlapping ionic states, X∼+ 2B2 and A∼+ 2B1, with derived ionisation energies of 11.0 ± 0.2 and 11.317 ± 0.006 eV, and dominated by an extended progression in the CCl2 bend (in X∼+) and a short progression in the CCl2 symmetric stretch (in A∼+), respectively. Furthermore, even though Koopmans' approximation holds for the vertical ionisations, the X∼+ state of CH2Cl2+ is stabilized by geometry relaxation and corresponds to ionisation from the (HOMO-1) orbital. That is, the first two vertical ionisation energies are in the same order as the negative of the orbital energies of the highest occupied orbitals, but the adiabatic ionisation energy corresponding to electron removal from the (HOMO-1) is lower than the

Detection of transient infrared absorption of SO3 and 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] in the reaction CH2OO+SO2

NASA Astrophysics Data System (ADS)

Wang, Yi-Ying; Dash, Manas Ranjan; Chung, Chao-Yu; Lee, Yuan-Pern

2018-02-01

We recorded time-resolved infrared absorption spectra of transient species produced on irradiation at 308 nm of a flowing mixture of CH2I2/O2/N2/SO2 at 298 K. Bands of CH2OO were observed initially upon irradiation; their decrease in intensity was accompanied by the appearance of an intense band at 1391.5 cm-1 that is associated with the degenerate SO-stretching mode of SO3, two major bands of HCHO at 1502 and 1745 cm-1, and five new bands near >1340, 1225, 1100, 940, and 880 cm-1. The band near 1340 cm-1 was interfered by absorption of SO2 and SO3, so its band maximum might be greater than 1340 cm-1. SO3 in its internally excited states was produced initially and became thermalized at a later period. The rotational contour of the band of thermalized SO3 agrees satisfactorily with the reported spectrum of SO3. These five new bands are tentatively assigned to an intermediate 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] according to comparison with anharmonic vibrational wavenumbers and relative IR intensities predicted for this intermediate. Observation of a small amount of cyc-(CH2)O(SO2)O is consistent with the expected reaction according to the potential energy scheme predicted previously. SO3+HCHO are the major products of the title reaction. The other predicted product channel HCOOH+SO2 was unobserved and its branching ratio was estimated to be <5%.

Detection of transient infrared absorption of SO3 and 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] in the reaction CH2OO+SO2.

PubMed

Wang, Yi-Ying; Dash, Manas Ranjan; Chung, Chao-Yu; Lee, Yuan-Pern

2018-02-14

We recorded time-resolved infrared absorption spectra of transient species produced on irradiation at 308 nm of a flowing mixture of CH 2 I 2 /O 2 /N 2 /SO 2 at 298 K. Bands of CH 2 OO were observed initially upon irradiation; their decrease in intensity was accompanied by the appearance of an intense band at 1391.5 cm -1 that is associated with the degenerate SO-stretching mode of SO 3 , two major bands of HCHO at 1502 and 1745 cm -1 , and five new bands near >1340, 1225, 1100, 940, and 880 cm -1 . The band near 1340 cm -1 was interfered by absorption of SO 2 and SO 3 , so its band maximum might be greater than 1340 cm -1 . SO 3 in its internally excited states was produced initially and became thermalized at a later period. The rotational contour of the band of thermalized SO 3 agrees satisfactorily with the reported spectrum of SO 3 . These five new bands are tentatively assigned to an intermediate 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH 2 )O(SO 2 )O] according to comparison with anharmonic vibrational wavenumbers and relative IR intensities predicted for this intermediate. Observation of a small amount of cyc-(CH 2 )O(SO 2 )O is consistent with the expected reaction according to the potential energy scheme predicted previously. SO 3 +HCHO are the major products of the title reaction. The other predicted product channel HCOOH+SO 2 was unobserved and its branching ratio was estimated to be <5%.

libChEBI: an API for accessing the ChEBI database.

PubMed

Swainston, Neil; Hastings, Janna; Dekker, Adriano; Muthukrishnan, Venkatesh; May, John; Steinbeck, Christoph; Mendes, Pedro

2016-01-01

ChEBI is a database and ontology of chemical entities of biological interest. It is widely used as a source of identifiers to facilitate unambiguous reference to chemical entities within biological models, databases, ontologies and literature. ChEBI contains a wealth of chemical data, covering over 46,500 distinct chemical entities, and related data such as chemical formula, charge, molecular mass, structure, synonyms and links to external databases. Furthermore, ChEBI is an ontology, and thus provides meaningful links between chemical entities. Unlike many other resources, ChEBI is fully human-curated, providing a reliable, non-redundant collection of chemical entities and related data. While ChEBI is supported by a web service for programmatic access and a number of download files, it does not have an API library to facilitate the use of ChEBI and its data in cheminformatics software. To provide this missing functionality, libChEBI, a comprehensive API library for accessing ChEBI data, is introduced. libChEBI is available in Java, Python and MATLAB versions from http://github.com/libChEBI, and provides full programmatic access to all data held within the ChEBI database through a simple and documented API. libChEBI is reliant upon the (automated) download and regular update of flat files that are held locally. As such, libChEBI can be embedded in both on- and off-line software applications. libChEBI allows better support of ChEBI and its data in the development of new cheminformatics software. Covering three key programming languages, it allows for the entirety of the ChEBI database to be accessed easily and quickly through a simple API. All code is open access and freely available.

From old alkylating agents to new minor groove binders.

PubMed

Puyo, Stéphane; Montaudon, Danièle; Pourquier, Philippe

2014-01-01

Alkylating agents represent the oldest class of anticancer agents with the approval of mechloretamine by the FDA in 1949. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in the treatment of specific malignancies, sometimes representing the unique option for the treatment of refractory tumors. Here, we are reviewing the major classes of alkylating agents, with a particular focus on the latest generations of compounds that specifically target the minor groove of the DNA. These naturally occurring derivatives have a unique mechanism of action that explains the recent regain of interest in developing new classes of alkylating agents that could be used in combination with other anticancer drugs to enhance tumor response in the clinic. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Quantum Dynamics Study of the Potential Energy Minima Effect on Energy Efficiency for the F- + CH3Cl → FCH3 + Cl- Reaction.

PubMed

Li, Yida; Wang, Yuping; Wang, Dunyou

2017-04-13

The Polanyi rules on the energy efficiency on reactivity are summarized solely from the locations of barriers on the potential energy surfaces. Here, our quantum dynamics study for the F - + CH 3 Cl → FCH 3 + Cl - reaction shows that the two potential energy minima in the entrance channel on the potential energy surface play an essential role in energy efficiency on reactivity. The reactivity of this reaction is dominated by the low collision energies where two distinctive reaction mechanisms involve the two minima in the entrance channel. Overall, the Cl-CH 3 stretching motion and C-H 3 umbrella motion both are more efficient than the translational motion in promoting this reaction. Although this reaction has a negative energy barrier, our study shows that it is the minima in the entrance channel, together with the energy barrier relative to these minima, that determine the energy efficacy on reactivity.

Methods of producing alkylated hydrocarbons from an in situ heat treatment process liquid

DOEpatents

Roes, Augustinus Wilhelmus Maria [Houston, TX; Mo, Weijian [Sugar Land, TX; Muylle, Michel Serge Marie [Houston, TX; Mandema, Remco Hugo [Houston, TX; Nair, Vijay [Katy, TX

2009-09-01

A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation.

40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

A Japanese Stretching Intervention Can Modify Lumbar Lordosis Curvature.

PubMed

Kadono, Norio; Tsuchiya, Kazushi; Uematsu, Azusa; Kamoshita, Hiroshi; Kiryu, Kazunori; Hortobágyi, Tibor; Suzuki, Shuji

2017-08-01

Eighteen healthy male adults were assigned to either an intervention or control group. Isogai dynamic therapy (IDT) is one of Japanese stretching interventions and has been practiced for over 70 years. However, its scientific quantitative evidence remains unestablished. The objective of this study was to determine whether IDT could modify lumbar curvature in healthy young adults compared with stretching exercises used currently in clinical practice. None of previous studies have provided data that conventional stretching interventions could modify spinal curvatures. However, this study provides the first evidence that a specific form of a Japanese stretching intervention can acutely modify the spinal curvatures. We compared the effects of IDT, a Japanese stretching intervention (n=9 males), with a conventional stretching routine (n=9 males) used widely in clinics to modify pelvic tilt and lumbar lordosis (LL) angle. We measured thoracic kyphosis (TK) and LL angles 3 times during erect standing using the Spinal Mouse before and after each intervention. IDT consisted of: (1) hip joint correction, (2) pelvic tilt correction, (3) lumbar alignment correction, and (4) squat exercise stretch. The control group performed hamstring stretches while (1) standing and (2) sitting. IDT increased LL angle to 25.1 degrees (±5.9) from 21.2 degrees (±6.9) (P=0.047) without changing TK angle (pretest: 36.8 degrees [±6.9]; posttest: 36.1 degrees [±6.5]) (P=0.572). The control group showed no changes in TK (P=0.819) and LL angles (P=0.744). IDT can thus be effective for increasing LL angle, hence anterior pelvic tilt. Such modifications could ameliorate low back pain and improve mobility in old adults with an unfavorable pelvic position.

Alkylation Induced DNA Repair and Mutagenesis in Escherichia coli.

DTIC Science & Technology

1987-11-23

III (Gates and inn, 1977), Micrococcus luteus UV endo- nuclease (Grossman et al, 1978) and bacteriophage T UV endonuclease (Warner et al, 1980) have DNA...34, Garland Publishing, Inc. New York & London USA. Ather, A., Z. Ahmed and S. Riazxxddin, 1984. Adaptive response of Micrococcus luteus to alkylating...Laval, J., 3. Pierre and F. Laval. 1981. Release of 7-nmthylguanine residues frain alkylated ENA by extracts of Micrococcus luteus and Escherichia

Impact of artifact removal on ChIP quality metrics in ChIP-seq and ChIP-exo data

PubMed Central

Carroll, Thomas S.; Liang, Ziwei; Salama, Rafik; Stark, Rory; de Santiago, Ines

2014-01-01

With the advent of ChIP-seq multiplexing technologies and the subsequent increase in ChIP-seq throughput, the development of working standards for the quality assessment of ChIP-seq studies has received significant attention. The ENCODE consortium's large scale analysis of transcription factor binding and epigenetic marks as well as concordant work on ChIP-seq by other laboratories has established a new generation of ChIP-seq quality control measures. The use of these metrics alongside common processing steps has however not been evaluated. In this study, we investigate the effects of blacklisting and removal of duplicated reads on established metrics of ChIP-seq quality and show that the interpretation of these metrics is highly dependent on the ChIP-seq preprocessing steps applied. Further to this we perform the first investigation of the use of these metrics for ChIP-exo data and make recommendations for the adaptation of the NSC statistic to allow for the assessment of ChIP-exo efficiency. PMID:24782889

Stretched size of atrial septal defect predicted by intracardiac echocardiography.

PubMed

Lin, Ming-Chih; Fu, Yun-Ching; Jan, Sheng-Ling; Ho, Chi-Lin; Hwang, Betau

2010-01-01

The stretched size of an atrial septal defect (ASD) is important for device selection during transcatheter closure. However, balloon sizing carries potential risks such as hypotension, bradycardia, or laceration of the atrial septum. The aim of the present study was to investigate the accuracy of the predicted stretched size of ASD by intracardiac echocardiography (ICE). From December 2004 to November 2007, 136 consecutive patients with single secundum type ASD undergoing transcatheter closure of their defect using the Amplatzer septal occluder under ICE guidance were enrolled for analysis. There were 43 males and 93 females. The age ranged from 2.2 to 79.1 years with a median age of 13.4 years. The body weight ranged from 12.1 to 93.2 kg with a median body weight of 45.8 kg. The stretched size of ASD measured by a sizing plate was considered as the standard. ASD sizes measured by ICE in bicaval and short-axis views predicted the stretched size by formulae derived from linear regressions. The predicted stretched sizes obtained using 2 formulae, 1.34 x radicalbicaval xshort axis (formula 1) and 1.22 x larger diameter (formula 2), exhibited good agreement with the standard stretched size with Kappa values of 0.91 and 0.90, respectively. The accuracy rate of predicted stretched sizes within 2 mm, 3 mm, and 4 mm range of the standard size were 32.8%, 45.4%, and 57.7% (formula 1) and 33.1%, 50%, and 63.2% (formula 2). The stretched size of ASD predicted by ICE exhibited good agreement with the standard stretched size. This prediction provides helpful information, especially if balloon sizing cannot be adequately performed.

40 CFR 721.10621 - Distillation bottoms, alkylated benzene by-product (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... benzene by-product (generic). 721.10621 Section 721.10621 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10621 Distillation bottoms, alkylated benzene by... substance identified generically as distillation bottoms, alkylated benzene by-product (PMN P-12-196) is...

40 CFR 721.10621 - Distillation bottoms, alkylated benzene by-product (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... benzene by-product (generic). 721.10621 Section 721.10621 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10621 Distillation bottoms, alkylated benzene by... substance identified generically as distillation bottoms, alkylated benzene by-product (PMN P-12-196) is...

40 CFR 721.10702 - Polyfluorinated alkyl thio polyacrylic acid-acrylamide (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... acid-acrylamide (generic). 721.10702 Section 721.10702 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10702 Polyfluorinated alkyl thio polyacrylic acid... substance identified generically as polyfluorinated alkyl thio polyacrylic acid-acrylamide (PMN P-11-534) is...

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

SERIES: Genomic instability in cancer Balancing repair and tolerance of DNA damage caused by alkylating agents

PubMed Central

Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D

2013-01-01

Alkylating agents comprise a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER), and mismatch repair (MMR) respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for an organism's favorable response to alkylating agents. Furthermore, an individual's response to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity. PMID:22237395

Optofluidic time-stretch quantitative phase microscopy.

PubMed

Guo, Baoshan; Lei, Cheng; Wu, Yi; Kobayashi, Hirofumi; Ito, Takuro; Yalikun, Yaxiaer; Lee, Sangwook; Isozaki, Akihiro; Li, Ming; Jiang, Yiyue; Yasumoto, Atsushi; Di Carlo, Dino; Tanaka, Yo; Yatomi, Yutaka; Ozeki, Yasuyuki; Goda, Keisuke

2018-03-01

Innovations in optical microscopy have opened new windows onto scientific research, industrial quality control, and medical practice over the last few decades. One of such innovations is optofluidic time-stretch quantitative phase microscopy - an emerging method for high-throughput quantitative phase imaging that builds on the interference between temporally stretched signal and reference pulses by using dispersive properties of light in both spatial and temporal domains in an interferometric configuration on a microfluidic platform. It achieves the continuous acquisition of both intensity and phase images with a high throughput of more than 10,000 particles or cells per second by overcoming speed limitations that exist in conventional quantitative phase imaging methods. Applications enabled by such capabilities are versatile and include characterization of cancer cells and microalgal cultures. In this paper, we review the principles and applications of optofluidic time-stretch quantitative phase microscopy and discuss its future perspective. Copyright © 2017 Elsevier Inc. All rights reserved.

Tunable nanoblock lasers and stretching sensors.

PubMed

Lu, T W; Wang, C; Hsiao, C F; Lee, P T

2016-09-22

Reconfigurable, reliable, and robust nanolasers with wavelengths tunable in the telecommunication bands are currently being sought after for use as flexible light sources in photonic integrated circuits. Here, we propose and demonstrate tunable nanolasers based on 1D nanoblocks embedded within stretchable polydimethylsiloxane. Our lasers show a large wavelength tunability of 7.65 nm per 1% elongation. Moreover, this tunability is reconfigurable and reliable under repeated stretching/relaxation tests. By applying excessive stretching, wide wavelength tuning over a range of 80 nm (spanning the S, C, and L telecommunication bands) is successfully demonstrated. Furthermore, as a stretching sensor, an enhanced wavelength response to elongation of 9.9 nm per % is obtained via the signal differential from two nanoblock lasers positioned perpendicular to each other. The minimum detectable elongation is as small as 0.056%. Nanoblock lasers can function as reliable tunable light sources in telecommunications and highly sensitive on-chip structural deformation sensors.

Spontaneous bending of pre-stretched bilayers.

PubMed

DeSimone, Antonio

2018-01-01

We discuss spontaneously bent configurations of pre-stretched bilayer sheets that can be obtained by tuning the pre-stretches in the two layers. The two-dimensional nonlinear plate model we use for this purpose is an adaptation of the one recently obtained for thin sheets of nematic elastomers, by means of a rigorous dimensional reduction argument based on the theory of Gamma-convergence (Agostiniani and DeSimone in Meccanica. doi:10.1007/s11012-017-0630-4, 2017, Math Mech Solids. doi:10.1177/1081286517699991, arXiv:1509.07003, 2017). We argue that pre-stretched bilayer sheets provide us with an interesting model system to study shape programming and morphing of surfaces in other, more complex systems, where spontaneous deformations are induced by swelling due to the absorption of a liquid, phase transformations, thermal or electro-magnetic stimuli. These include bio-mimetic structures inspired by biological systems from both the plant and the animal kingdoms.

Low-level stretching accelerates cell migration into a gap.

PubMed

Toume, Samer; Gefen, Amit; Weihs, Daphne

2017-08-01

We observed that radially stretching cell monolayers at a low level (3%) increases the rate at which they migrate to close a gap formed by in vitro injury. Wound healing has been shown to accelerate in vivo when deformations are topically applied, for example, by negative pressure wound therapy. However, the direct effect of deformations on cell migration during gap closure is still unknown. Thus, we have evaluated the effect of radially applied, sustained (static) tensile strain on the kinematics of en mass cell migration. Monolayers of murine fibroblasts were cultured on stretchable, linear-elastic substrates that were subjected to different tensile strains, using a custom-designed three-dimensionally printed stretching apparatus. Immediately following stretching, the monolayer was 'wounded' at its centre, and cell migration during gap closure was monitored and quantitatively evaluated. We observed a significant increase in normalised migration rates and a reduction of gap closure time with 3% stretching, relative to unstretched controls or 6% stretch. Interestingly, the initial gap area was linearly correlated with the maximum migration rate, especially when stretching was applied. Therefore, small deformations applied to cell monolayers during gap closure enhance en mass cell migration associated with wound healing and can be used to fine-tune treatment protocols. © 2016 Medicalhelplines.com Inc and John Wiley & Sons Ltd.

Biocatalysis: Unmasked by stretching

NASA Astrophysics Data System (ADS)

Kharlampieva, Eugenia; Tsukruk, Vladimir V.

2009-09-01

The biocatalytic activity of enzyme-loaded responsive layer-by-layer films can be switched on and off by simple mechanical stretching. Soft materials could thus be used to trigger biochemical reactions under mechanical action, with potential therapeutic applications.

Poly(ethyleneoxide) functionalization through alkylation

DOEpatents

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.

The acute effect of different stretching methods on sprint performance in taekwondo practitioners.

PubMed

Alemdaroğlu, Utku; Köklü, Yusuf; Koz, Mitat

2017-09-01

The purpose of this study was to compare the acute effects of different stretching types on sprint performance in taekwondo practitioners. Twelve male taekwondo practitioners performed stretching exercises using different types (ballistic, proprioceptive neuromuscular facilitation [PNF], static stretching) in a random order at three-day intervals; there was also a control condition involving no stretching exercises. The subjects performed 2 maximal 20-m sprints (with 10-m split times also recorded) with a recovery period of 1 minute immediately post stretching and at 5, 10, 15 and 20 minutes after stretching. They also performed these sprints before doing the stretching exercises. The study results showed that sprint times significantly increased after static stretching (10-m pre =1.84±0.07 s, 10-m post =1.89±0.08 s; 20-m pre =3.33±0.19 s, 20-m post= 3.38±0.2 s), PNF stretching (10-m pre =1.84±0.07 s, 10-m post =1.89±0.08 s; 20-m pre =3.33±0.19 s, 20-m post =3.38±0.20 s) and ballistic stretching (pre =1.84±0.08 s, post =1.86±0.07 s; 20-m pre =3.33±0.20 s, 20-m post =3.35±0.21 s) (P<0.05). In the static stretching condition, 10-m and 20-m sprint performance had fully returned to normal at 15 minutes after stretching. In the PNF stretching condition, 20-m sprint performance returned to normal levels at 15 minutes after stretching, while 10-m performance took 20 minutes to recover fully. In the ballistic stretching method, both 10-m and 20-m sprint performances had fully recovered at 5 minutes after stretching. It is therefore concluded that the acute effects of static, PNF and ballistic stretching may negatively affect sprint performance, although sprint performance is less affected after ballistic stretching than after the other stretching types. Therefore, it is not advisable to perform PNF or static stretching immediately before sprint performance.

Versatile assembly of p-carboxylatocalix[4]arene-O-alkyl ethers

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

Kennedy, Stuart; Teat, Simon J.; Dalgarno, Scott J.

Crystallisation of lower-rim tetra-O-alkylated p-carboxylatocalix[4]arenes from pyridine results in the formation of both bi-layer and pillar type supramolecular motifs. Full alkylation at the calixarene lower rim has significant influence over the supramolecular self-assembly motif, including preclusion of pyridine guest molecules from the calixarene cavity in the solid state.

40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal oxide, modified with alkyl and... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with alkyl...

Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

NASA Astrophysics Data System (ADS)

Liu, Yan-Yun; Yang, Xu-Heng; Song, Ren-Jie; Luo, Shenglian; Li, Jin-Heng

2017-04-01

Difunctionalization of alkenes has become a powerful tool for quickly increasing molecular complexity in synthesis. Despite significant progress in the area of alkene difunctionalization involving the incorporation of a nitrogen atom across the C-C double bonds, approaches for the direct 1,2-carboamination of alkenes to produce linear N-containing molecules are scarce and remain a formidable challenge. Here we describe a radical-mediated oxidative intermolecular 1,2-alkylamination of alkenes with alkyl nitriles and amines involving C(sp3)-H oxidative functionalization catalysed by a combination of Ag2CO3 with iron Lewis acids. This three-component alkene 1,2-alkylamination method is initiated by the C(sp3)-H oxidative radical functionalization, which enables one-step formation of two new chemical bonds, a C-C bond and a C-N bond, to selectively produce γ-amino alkyl nitriles.

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. © The Author(s) 2015.

Eliminating electromechanical instability in dielectric elastomers by employing pre-stretch

NASA Astrophysics Data System (ADS)

Jiang, Liang; Betts, Anthony; Kennedy, David; Jerrams, Stephen

2016-07-01

Electromechanical instability (EMI) is one of most common failure modes for dielectric elastomers (DEs). It has been reported that pre-stretching a DE sample can suppress EMI due to strain stiffening taking place for larger strains and a higher elastic modulus are achieved at high stretch ratios when a voltage is applied to the material. In this work, the influence of equi-biaxial stretch on DE secant modulus was studied using VHB 4910 and silicone rubber (SR) composites containing barium titanate (BaTiO3, BT) particles and also dopamine coated BT (DP-BT) particles. The investigation of equi-biaxial deformation and EMI failure for VHB 4910 was undertaken by introducing a voltage-stretch function. The results showed that EMI was suppressed by equi-biaxial pre-stretch for all the DEs fabricated and tested. The stiffening properties of the DE materials were also studied with respect to the secant modulus. Furthermore, a voltage-induced strain of above 200% was achieved for the polyacrylate film by applying a pre-stretch ratio of 2.0 without EMI occurring. However, a maximum voltage-induced strain in the polyacrylate film of 78% was obtained by the SR/20 wt% DP-BT composite for a lower applied pre-stretch ratio of 1.6 and again EMI was eliminated.

Experimental and QSAR study on the surface activities of alkyl imidazoline surfactants

NASA Astrophysics Data System (ADS)