Testing the Concept of Hypervalency: Charge Density Analysis of K[subscript 2]SO[subscript 4

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

Schmøkel, Mette S.; Cenedese, Simone; Overgaard, Jacob

2012-10-25

One of the most basic concepts in chemical bonding theory is the octet rule, which was introduced by Lewis in 1916, but later challenged by Pauling to explain the bonding of third-row elements. In the third row, the central atom was assumed to exceed the octet by employing d orbitals in double bonding leading to hypervalency. Ever since, polyoxoanions such as SO{sub 4}{sup 2-}, PO{sub 4}{sup 3-}, and ClO{sub 4}{sup -} have been paradigmatic examples for the concept of hypervalency in which the double bonds resonate among the oxygen atoms. Here, we examine S-O bonding by investigating the charge densitymore » of the sulfate group, SO{sub 4}{sup 2-}, within a crystalline environment based both on experimental and theoretical methods. K{sub 2}SO{sup 4} is a high symmetry inorganic solid, where the crystals are strongly affected by extinction effects. Therefore, high quality, very low temperature single crystal X-ray diffraction data were collected using a small crystal (30 {micro}m) and a high-energy (30 keV) synchrotron beam. The experimental charge density was determined by multipole modeling, whereas a theoretical density was obtained from periodic ab initio DFT calculations. The chemical bonding was jointly analyzed within the framework of the Quantum Theory of Atoms In Molecules only using quantities derived from an experimental observable (the charge density). The combined evidence suggests a bonding situation where the S-O interactions can be characterized as highly polarized, covalent bonds, with the 'single bond' description significantly prevailing over the 'double bond' picture. Thus, the study rules out the hypervalent description of the sulfur atom in the sulfate group.« less

Topology of charge density of flucytosine and related molecules and characteristics of their bond charge distributions.

PubMed

Murgich, Juan; Franco, Héctor J; San-Blas, Gioconda

2006-08-24

The molecular charge distribution of flucytosine (4-amino-5-fluoro-2-pyrimidone), uracil, 5-fluorouracil, and thymine was studied by means of density functional theory calculations (DFT). The resulting distributions were analyzed by means of the atoms in molecules (AIM) theory. Bonds were characterized through vectors formed with the charge density value, its Laplacian, and the bond ellipticity calculated at the bond critical point (BCP). Within each set of C=O, C-H, and N-H bonds, these vectors showed little dispersion. C-C bonds formed three different subsets, one with a significant degree of double bonding, a second corresponding to single bonds with a finite ellipticity produced by hyperconjugation, and a third one formed by a pure single bond. In N-C bonds, a decrease in bond length (an increase in double bond character) was not reflected as an increase in their ellipticity, as in all C-C bonds studied. It was also found that substitution influenced the N-C, C-O, and C-C bond ellipticity much more than density and its Laplacian at the BCP. The Laplacian of charge density pointed to the existence of both bonding and nonbonding maxima in the valence shell charge concentration of N, O, and F, while only bonding ones were found for the C atoms. The nonbonding maxima related to the sites for electrophilic attack and H bonding in O and N, while sites of nucleophilic attack were suggested by the holes in the valence shell of the C atoms of the carbonyl groups.

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1989-01-01

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

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

PubMed Central

Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

2015-01-01

Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism. PMID:25588215

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

PubMed

Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

2015-01-12

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

Double bonds? Studies on the barrier to rotation about the cumulenic C=C bonds of tetraaryl[n]cumulenes (n = 3, 5, 7, 9).

PubMed

Buehringer, Martina U; Padberg, Kevin; Phleps, Martin; Maid, Harald; Placht, Christian; Neiss, Christian; Ferguson, Michael; Goerling, Andreas; Tykwinski, Rik R

2018-03-31

Bonding is the fundamental aspect of organic chemistry, yet the magnitude of C=C bonding in [n]cumulenes as a function of increasing chain length has yet to be experimentally verified for derivatives longer than n = 5. The synthesis of a series of apolar and unsymmetrically substituted tetraaryl[n]cumulenes (n = 3, 5, 7, 9) has been developed and rotational barriers for Z-/E-isomerization have been measured using dynamic VT-NMR spectroscopy. Both experiment and theory confirm a dramatic reduction of the rotational barrier (through estimation of G≠rot for the isomerization) from >24 to 19 to 15 to 11 kcal-1 in [n]cumulenes with n = 3, 5, 7, 9, respectively. Thus, the reduction of cumulenic bonding in longer cumulenes affords bond rotational barriers that are more characteristic of a sterically hindered single bond than that of a double bond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of intra-domain disulfide bonds in heat-induced irreversible denaturation of camelid single domain VHH antibodies

PubMed Central

Akazawa-Ogawa, Yoko; Uegaki, Koichi; Hagihara, Yoshihisa

2016-01-01

Camelid-derived single domain VHH antibodies are highly heat resistant, and the mechanism of heat-induced VHH denaturation predominantly relies on the chemical modification of amino acids. Although chemical modification of disulfide bonds has been recognized as a cause for heat-induced denaturation of many proteins, there have been no mutagenesis studies, in which the number of disulfide bonds was controlled. In this article, we examined a series of mutants of two different VHHs with single, double or no disulfide bonds, and scrutinized the effects of these disulfide bond modifications on VHH denaturation. With the exception of one mutant, the heat resistance of VHHs decreased when the number of disulfide bonds increased. The effect of disulfide bonds on heat denaturation was more striking if the VHH had a second disulfide bond, suggesting that the contribution of disulfide shuffling is significant in proteins with multiple disulfide bonds. Furthermore, our results directly indicate that removal of a disulfide bond can indeed increase the heat resistance of a protein, irrespective of the negative impact on equilibrium thermodynamic stability. PMID:26289739

Electronegativity effects and single covalent bond lengths of molecules in the gas phase.

PubMed

Lang, Peter F; Smith, Barry C

2014-06-07

This paper discusses in detail the calculation of internuclear distances of heteronuclear single bond covalent molecules in the gaseous state. It reviews briefly the effect of electronegativity in covalent bond length. A set of single bond covalent radii and electronegativity values are proposed. Covalent bond lengths calculated by an adapted form of a simple expression (which calculated internuclear separation of different Group 1 and Group 2 crystalline salts to a remarkable degree of accuracy) show very good agreement with observed values. A small number of bond lengths with double bonds as well as bond lengths in the crystalline state are calculated using the same expression and when compared with observed values also give good agreement. This work shows that covalent radii are not additive and that radii in the crystalline state are different from those in the gaseous state. The results also show that electronegativity is a major influence on covalent bond lengths and the set of electronegativity scale and covalent radii proposed in this work can be used to calculate covalent bond lengths in different environments that have not yet been experimentally measured.

Laser desorption single-conformation UV and IR spectroscopy of the sulfonamide drug sulfanilamide, the sulfanilamide-water complex, and the sulfanilamide dimer.

PubMed

Uhlemann, Thomas; Seidel, Sebastian; Müller, Christian W

2017-06-07

We have studied the conformational preferences of the sulfonamide drug sulfanilamide, its dimer, and its monohydrated complex through laser desorption single-conformation UV and IR spectroscopy in a molecular beam. Based on potential energy curves for the inversion of the anilinic and the sulfonamide NH 2 groups calculated at DFT level, we suggest that the zero-point level wave function of the sulfanilamide monomer is appreciably delocalized over all four conformer wells. The sulfanilamide dimer, and the monohydrated complex each exhibit a single isomer in the molecular beam. The isomeric structures of the sulfanilamide dimer and the monohydrated sulfanilamide complex were assigned based on their conformer-specific IR spectra in the NH and OH stretch region. Quantum Theory of Atoms in Molecules (QTAIM) analysis of the calculated electron density in the water complex suggests that the water molecule is bound side-on in a hydrogen bonding pocket, donating one O-HO[double bond, length as m-dash]S hydrogen bond and accepting two hydrogen bonds, a NHO and a CHO hydrogen bond. QTAIM analysis of the dimer electron density suggests that the C i symmetry dimer structure exhibits two dominating N-HO[double bond, length as m-dash]S hydrogen bonds, and three weaker types of interactions: two CHO bonds, two CHN bonds, and a chalcogen OO interaction. Most interestingly, the molecular beam dimer structure closely resembles the R dimer unit - the dimer unit with the greatest interaction energy - of the α, γ, and δ crystal polymorphs. Interacting Quantum Atoms analysis provides evidence that the total intermolecular interaction in the dimer is dominated by the short-range exchange-correlation contribution.

Immediate performance of self-etching versus system adhesives with multiple light-activated restoratives.

PubMed

Irie, M; Suzuki, K; Watts, D C

2004-11-01

The purpose of this study was to evaluate the performance of both single and double applications of (Adper Prompt L-Pop) self-etching dental adhesive, when used with three classes of light-activated restorative materials, in comparison to the performance of each restorative system adhesive. Evaluation parameters to be considered for the adhesive systems were (a) immediate marginal adaptation (or gap formation) in tooth cavities, (b) free setting shrinkage-strain determined by the immediate marginal gap-width in a non-bonding Teflon cavity, and (c) their immediate shear bond-strengths to enamel and to dentin. The maximum marginal gap-width and the opposing-width (if any) in the tooth cavities and in the Teflon cavities were measured immediately (3 min) after light-activation. The shear bond-strengths to enamel and to dentin were also measured at 3 min. For light-activated restorative materials during early setting (<3 min), application of Adper Prompt L-Pop exhibited generally superior marginal adaptation to most system adhesives. But there was no additional benefit from double application. The marginal-gaps in tooth cavities and the marginal-gaps in Teflon cavities were highly correlated (r = 0.86-0.89, p < 0.02-0.01). For enamel and dentin shear bond-strengths, there were no significant differences between single and double applications, for all materials tested except Toughwell and Z 250 with enamel. Single application of a self-etch adhesive was a feasible and beneficial alternative to system adhesives for several classes of restorative. Marginal gap-widths in tooth cavities correlated more strongly with free shrinkage-strain magnitudes than with bond-strengths to tooth structure.

3-Methyl-4,5-di­hydro­oxazolium tetra­phenyl­borate

PubMed Central

Tiritiris, Ioannis; Saur, Stefan; Kantlehner, Willi

2014-01-01

In the cation of the title salt, C4H8NO+·C24H20B−, the C—N bond lengths are 1.272 (2), 1.4557 (19) and 1.4638 (19) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.3098 (19) Å shows that double-bond character and charge delocalization occurs within the NCO plane of the cation. In the crystal, a C—H⋯π inter­action is present between the methyl­ene H atom of the cation and one phenyl ring of the tetra­phenyl­borate ion. The latter forms an aromatic pocket in which the cation is embedded. PMID:24765023

Crystal structure of (1-eth­oxy­ethyl­idene)di­methyl­aza­nium tetra­phenyl­borate

PubMed Central

Tiritiris, Ioannis; Saur, Stefan; Kantlehner, Willi

2015-01-01

In the cation of the title salt, C6H14NO+·C24H20B−, the C—N bond lengths are 1.297 (2), 1.464 (2) and 1.468 (2) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.309 (2) Å shows double-bond character, pointing towards charge delocalization within the NCO plane of the iminium ion. In the crystal, C—H⋯π inter­actions between the iminium H atoms and the phenyl C atoms of the anion are present. The phenyl rings form aromatic pockets, in which the iminium ions are embedded. PMID:26870564

Assessing the distinguishable cluster approximation based on the triple bond-breaking in the nitrogen molecule

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

Rishi, Varun; Perera, Ajith; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu

2016-03-28

Obtaining the correct potential energy curves for the dissociation of multiple bonds is a challenging problem for ab initio methods which are affected by the choice of a spin-restricted reference function. Coupled cluster (CC) methods such as CCSD (coupled cluster singles and doubles model) and CCSD(T) (CCSD + perturbative triples) correctly predict the geometry and properties at equilibrium but the process of bond dissociation, particularly when more than one bond is simultaneously broken, is much more complicated. New modifications of CC theory suggest that the deleterious role of the reference function can be diminished, provided a particular subset of termsmore » is retained in the CC equations. The Distinguishable Cluster (DC) approach of Kats and Manby [J. Chem. Phys. 139, 021102 (2013)], seemingly overcomes the deficiencies for some bond-dissociation problems and might be of use in quasi-degenerate situations in general. DC along with other approximate coupled cluster methods such as ACCD (approximate coupled cluster doubles), ACP-D45, ACP-D14, 2CC, and pCCSD(α, β) (all defined in text) falls under a category of methods that are basically obtained by the deletion of some quadratic terms in the double excitation amplitude equation for CCD/CCSD (coupled cluster doubles model/coupled cluster singles and doubles model). Here these approximate methods, particularly those based on the DC approach, are studied in detail for the nitrogen molecule bond-breaking. The N{sub 2} problem is further addressed with conventional single reference methods but based on spatial symmetry-broken restricted Hartree–Fock (HF) solutions to assess the use of these references for correlated calculations in the situation where CC methods using fully symmetry adapted SCF solutions fail. The distinguishable cluster method is generalized: 1) to different orbitals for different spins (unrestricted HF based DCD and DCSD), 2) by adding triples correction perturbatively (DCSD(T)) and iteratively (DCSDT-n), and 3) via an excited state approximation through the equation of motion (EOM) approach (EOM-DCD, EOM-DCSD). The EOM-CC method is used to identify lower-energy CC solutions to overcome singularities in the CC potential energy curves. It is also shown that UHF based CC and DC methods behave very similarly in bond-breaking of N{sub 2}, and that using spatially broken but spin preserving SCF references makes the CCSD solutions better than those for DCSD.« less

Single Molecule Study of Force-Induced Rotation of Carbon-Carbon Double Bonds in Polymers.

PubMed

Huang, Wenmao; Zhu, Zhenshu; Wen, Jing; Wang, Xin; Qin, Meng; Cao, Yi; Ma, Haibo; Wang, Wei

2017-01-24

Carbon-carbon double bonds (C═C) are ubiquitous in natural and synthetic polymers. In bulk studies, due to limited ways to control applied force, they are thought to be mechanically inert and not to contribute to the extensibility of polymers. Here, we report a single molecule force spectroscopy study on a polymer containing C═C bonds using atomic force microscope. Surprisingly, we found that it is possible to directly observe the cis-to-trans isomerization of C═C bonds at the time scale of ∼1 ms at room temperature by applying a tensile force ∼1.7 nN. The reaction proceeds through a diradical intermediate state, as confirmed by both a free radical quenching experiment and quantum chemical modeling. The force-free activation length to convert the cis C═C bonds to the transition state is ∼0.5 Å, indicating that the reaction rate is accelerated by ∼10 9 times at the transition force. On the basis of the density functional theory optimized structure, we propose that because the pulling direction is not parallel to C═C double bonds in the polymer, stretching the polymer not only provides tension to lower the transition barrier but also provides torsion to facilitate the rotation of cis C═C bonds. This explains the apparently low transition force for such thermally "forbidden" reactions and offers an additional explanation of the "lever-arm effect" of polymer backbones on the activation force for many mechanophores. This work demonstrates the importance of precisely controlling the force direction at the nanoscale to the force-activated reactions and may have many implications on the design of stress-responsive materials.

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).

Power module packaging with double sided planar interconnection and heat exchangers

DOEpatents

Liang, Zhenxian; Marlino, Laura D.; Ning, Puqi; Wang, Fei

2015-05-26

A double sided cooled power module package having a single phase leg topology includes two IGBT and two diode semiconductor dies. Each IGBT die is spaced apart from a diode semiconductor die, forming a switch unit. Two switch units are placed in a planar face-up and face-down configuration. A pair of DBC or other insulated metallic substrates is affixed to each side of the planar phase leg semiconductor dies to form a sandwich structure. Attachment layers are disposed on outer surfaces of the substrates and two heat exchangers are affixed to the substrates by rigid bond layers. The heat exchangers, made of copper or aluminum, have passages for carrying coolant. The power package is manufactured in a two-step assembly and heating process where direct bonds are formed for all bond layers by soldering, sintering, solid diffusion bonding or transient liquid diffusion bonding, with a specially designed jig and fixture.

A Comparison of Cocrystal Structure Solutions from Powder and Single Crystal Techniques

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

S Lapidus; P Stephens; K Arora

We demonstrate the effectiveness and accuracy of high resolution powder diffraction for determination of cocrystal structures through a double-blind study. Structures of 10 cocrystals of varying complexity were determined independently using single crystal and powder techniques. The two methodologies give identical molecular packing and hydrogen bond topology, and an rms difference in covalent bond lengths of 0.035 {angstrom}. Powder techniques are clearly sufficient to establish a complete characterization of cocrystal geometry.

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

The role of intra-domain disulfide bonds in heat-induced irreversible denaturation of camelid single domain VHH antibodies.

PubMed

Akazawa-Ogawa, Yoko; Uegaki, Koichi; Hagihara, Yoshihisa

2016-01-01

Camelid-derived single domain VHH antibodies are highly heat resistant, and the mechanism of heat-induced VHH denaturation predominantly relies on the chemical modification of amino acids. Although chemical modification of disulfide bonds has been recognized as a cause for heat-induced denaturation of many proteins, there have been no mutagenesis studies, in which the number of disulfide bonds was controlled. In this article, we examined a series of mutants of two different VHHs with single, double or no disulfide bonds, and scrutinized the effects of these disulfide bond modifications on VHH denaturation. With the exception of one mutant, the heat resistance of VHHs decreased when the number of disulfide bonds increased. The effect of disulfide bonds on heat denaturation was more striking if the VHH had a second disulfide bond, suggesting that the contribution of disulfide shuffling is significant in proteins with multiple disulfide bonds. Furthermore, our results directly indicate that removal of a disulfide bond can indeed increase the heat resistance of a protein, irrespective of the negative impact on equilibrium thermodynamic stability. © The Authors 2015. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.

Probing phospholipase a(2) with fluorescent phospholipid substrates.

PubMed

Wichmann, Oliver; Gelb, Michael H; Schultz, Carsten

2007-09-03

The Foerster resonance energy transfer-based sensor, PENN, measures intracellular phospholipase A(2) (PLA(2)) activity in living cells and small organisms. In an attempt to modify the probe for the detection of particular isoforms, we altered the sn-2 fatty acid in such a way that either one or three of the Z double bonds in arachidonic acid were present in the sensor molecule. Arachidonic-acid-mimicking fatty acids were prepared by copper-mediated coupling reactions. Probes with a single double bond in the 5-position exhibited favorable substrate properties for secretory PLA(2)s. In vitro experiments with the novel unsaturated doubly labeled phosphatidylethanolamine derivatives showed preferred cleavage of the sensor PENN2 (one double bond) by the physiologically important group V sPLA(2), while the O-methyl-derivative PMNN2 was accepted best by the isoform from hog pancreas. For experiments in living cells, we demonstrated that bioactivation via S-acetylthioethyl (SATE) groups is essential for probe performance. Surprisingly, membrane-permeant versions of the new sensors that contained double bonds, PENN2 and PENN3, were only cleaved to a minor extent in HeLa cells while the saturated form, PENN, was well accepted.

Structure of water clusters on graphene: A classical molecular dynamics approach

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Sasaoka, Kenji; Yamamoto, Takahiro

2018-03-01

The microscopic structure of surface water adsorbed on graphene is elucidated theoretically by classical molecular dynamics simulation. At a low temperature (100 K), the main polygon consisting of hydrogen bonds in single-layered water on graphene is tetragonal, whereas the dominant polygons in double-layered water are tetragonal, pentagonal, and hexagonal. On the other hand, at room temperature, the tetragonal, pentagonal, and hexagonal water clusters are the main structures in both single- and double-layered water.

STM/STS Study of the Sb (111) Surface

NASA Astrophysics Data System (ADS)

Chekmazov, S. V.; Bozhko, S. I.; Smirnov, A. A.; Ionov, A. M.; Kapustin, A. A.

An Sb crystal is a Peierls insulator. Formation of double layers in the Sb structure is due to the shift of atomic planes (111) next but one along the C3 axis. Atomic layers inside the double layer are connected by covalent bonds. The interaction between double layers is determined mainly by Van der Waals forces. The cleave of an Sb single crystal used to be via break of Van der Waals bonds. However, using scanning tunneling microscopy (STM) and spectroscopy (STS) we demonstrated that apart from islands equal in thickness to the double layer, steps of one atomic layer in height also exist on the cleaved Sb (111) surface. Formation of "unpaired" (111) planes on the surface leads to a local break of conditions of Peierls transition. STS experiment reveals higher local density of states (LDOS) measured for "unpaired" (111) planes in comparison with those for the double layer.

Insight into destabilization mechanism of Mg-based hydrides interstitially co-doped with nonmetals: a DFT study

NASA Astrophysics Data System (ADS)

Wu, Zhen; Zhu, Luying; Yang, Fusheng; Zhang, Zaoxiao; Nyamsi, Serge N.

2018-04-01

Mg-based metal hydride is one of the most promising materials for hydrogen energy storage. However, the high thermal stability due to strong bonding effects between the atoms limits its practical application. In order to reduce the thermal stability, a method of doping double nonmetals into Mg-based system was proposed in this study. The density functional theory (DFT) calculation results showed that the thermal stabilities of both the B-N co-doped Mg-based alloy and its hydride are reduced compared with pure Mg-based system. The relative formation enthalpies of the alloy and its hydride are 0.323 and 0.595 eV atom-1, respectively. The values are much higher than those for either singly B- or N-doped Mg-based system. The more significant destabilization by doping double nonmetal elements than single element is mainly attributed to a dual effect in weakening Mg-Ni/NiH4 bonds, caused by criss-cross interactions between B-Ni and N-Mg bonds.

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

PubMed Central

Yoo, Byung-Kuk; Su, Zixue; Thomas, John Meurig; Zewail, Ahmed H.

2016-01-01

Understanding the dynamical nature of the catalytic active site embedded in complex systems at the atomic level is critical to developing efficient photocatalytic materials. Here, we report, using 4D ultrafast electron microscopy, the spatiotemporal behaviors of titanium and oxygen in a titanosilicate catalytic material. The observed changes in Bragg diffraction intensity with time at the specific lattice planes, and with a tilted geometry, provide the relaxation pathway: the Ti4+=O2− double bond transformation to a Ti3+−O1− single bond via the individual atomic displacements of the titanium and the apical oxygen. The dilation of the double bond is up to 0.8 Å and occurs on the femtosecond time scale. These findings suggest the direct catalytic involvement of the Ti3+−O1− local structure, the significance of nonthermal processes at the reactive site, and the efficient photo-induced electron transfer that plays a pivotal role in many photocatalytic reactions. PMID:26729878

Single-chain polybutadiene organometallic nanoparticles: an experimental and theoretical study† †Electronic supplementary information (ESI) available: Detailed experimental procedures and characterization of ONPs including: 1H and 13C NMR, SEC, DLS, DSC, TGA, UV-vis, GC-MS spectra and computational calculations. See DOI: 10.1039/c5sc04535e Click here for additional data file.

PubMed Central

Berkovich, Inbal; Mavila, Sudheendran; Iliashevsky, Olga; Kozuch, Sebastian

2016-01-01

High molecular weight polybutadienes and rhodium complexes were used to produce single chain organometallic nanoparticles. Irradiation of high cis-polybutadiene in the presence of a photosensitizer isomerised the double bonds to produce differing cis/trans ratios within the polymer. Notably, a higher cis percentage of carbon–carbon double bonds within the polymer structure led to faster binding of metal ions, as well as their faster removal by competing phosphine ligands. The experimental results were supported and rationalized by DFT computations. PMID:28936327

The covalently bound diazo group as an infrared probe for hydrogen bonding environments.

PubMed

You, Min; Liu, Liyuan; Zhang, Wenkai

2017-07-26

Covalently bound diazo groups are frequently found in biomolecular substrates. The C[double bond, length as m-dash]N[double bond, length as m-dash]N asymmetric stretching vibration (ν as ) of the diazo group has a large extinction coefficient and appears in an uncongested spectral region. To evaluate the solvatochromism of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band for studying biomolecules, we recorded the infrared (IR) spectra of a diazo model compound, 2-diazo-3-oxo-butyric acid ethyl ester, in different solvents. The width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly dependent on the Kamlet-Taft solvent parameter, which reflects the polarizability and hydrogen bond accepting ability of the solvent. Therefore, the width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band could be used to probe these properties for a solvent. We found that the position of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly correlated with the density of hydrogen bond donor groups in the solvent. We studied the relaxation dynamics and spectral diffusion of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of a natural amino acid, 6-diazo-5-oxo-l-norleucine, in water using nonlinear IR spectroscopy. The relaxation and spectral diffusion time constants of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band were similar to those of the N[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band. We concluded that the position and width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of the diazo group could be used to probe the hydrogen bond donating and accepting ability of a solvent, respectively. These results suggest that the diazo group could be used as a site-specific IR probe for the local hydration environments.

Unveiling the mechanism of photoinduced isomerization of the photoactive yellow protein (PYP) chromophore

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

Gromov, Evgeniy V., E-mail: evgeniy.gromov@pci.uni-heidelberg.de

2014-12-14

A detailed theoretical analysis, based on extensive ab initio second-order approximate coupled cluster calculations, has been performed for the S{sub 1} potential energy surface (PES) of four photoactive yellow protein (PYP) chromophore derivatives that are hydrogen bonded with two water molecules and differ merely in the carbonyl substituent. The main focus is put on contrasting the isomerization properties of these four species in the S{sub 1} excited state, related to torsion around the chromophore's single and double carbon-carbon bonds. The analysis provides evidence of the different isomerization behavior of these four chromophore complexes, which relates to the difference in theirmore » carbonyl substituents. While a stable double-bond torsion pathway exists on the S{sub 1} PES of the chromophores bearing the –O–CH{sub 3} and –NH{sub 2} substituents, this is not the case for the –S–CH{sub 3} and –CH{sub 3} substituted species. The presence of the –S–CH{sub 3} group leads to a strong instability of the chromophore with respect to the single-bond twist, whereas in the case of the –CH{sub 3} substituent a crossing of the S{sub 1} and S{sub 2} PESs occurs, which perturbs the pathway. Based on this analysis, the key factors that support the double-bond torsion have been identified. These are (i) the hydrogen bonds at the phenolic oxygen of the chromophore, (ii) the weak electron-acceptor character of the carbonyl group, and (iii) the ethylene-like pattern of the torsion in the beginning of the process. Our results suggest that the interplay between these factors determines the chromophore's isomerization in the solvent environment and in the native PYP environment.« less

Thermoelectric performance of various benzo-difuran wires

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

Péterfalvi, Csaba G.; Grace, Iain; Manrique, Dávid Zs.

2014-05-07

Using a first principles approach to electron transport, we calculate the electrical and thermoelectrical transport properties of a series of molecular wires containing benzo-difuran subunits. We demonstrate that the side groups introduce Fano resonances, the energy of which is changing with the electronegativity of selected atoms in it. We also study the relative effect of single, double, or triple bonds along the molecular backbone and find that single bonds yield the highest thermopower, approximately 22 μV/K at room temperature, which is comparable with the highest measured values for single-molecule thermopower reported to date.

2-Acetyl-1,1,3,3-tetra­methyl­guanidine

PubMed Central

Tiritiris, Ioannis

2012-01-01

In the mol­ecule of the title compound, C7H15N3O, the central C atom is surrounded in a nearly ideal trigonal–planar geometry by three N atoms. The C—N bond lengths in the CN3 unit are 1.3353 (13), 1.3463 (12) and 1.3541 (13) Å, indicating an inter­mediate character between a single and a double bond for each C—N bond. The bonds between the N atoms and the terminal C-methyl groups all have values close to that of a typical single bond [1.4526 (13)–1.4614 (14) Å]. In the crystal, the guanidine mol­ecules are connected by weak C—H⋯O and C—H⋯N hydrogen bonds, generating layers parallel to the ab plane. PMID:23125768

Bond angles in transition metal tetracarbonyl compounds: A further test of the theory of hybrid bond orbitals*

PubMed Central

Pauling, Linus

1978-01-01

An equation for the bond angles OC—M—CO for tetracarbonyl groups in which the transition metal atom M is enneacovalent, derived from the simple theory of hybrid sp3d5 bond orbitals, is tested by comparison of the calculated values of the angles with the experimental values reported for many compounds containing M(CO)4 groups, especially those with M = Fe, Mn, Re, Cr, or Mo. The importance of the energy of resonance of single bonds and double bonds in stabilizing octahedral complexes of chromium and manganese with carbonyl, phosphine, arsine, and thio groups is also discussed. PMID:16592490

Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheet versus two-dimensional layers in solid-state photochemical [2 + 2] reactions.

PubMed

Garai, Mousumi; Biradha, Kumar

2015-09-01

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N-H⋯Npy versus N-H⋯O=C) and network geometries. In this series, a greater tendency towards the formation of N-H⋯O hydrogen bonds (β-sheets and two-dimensional networks) over N-H⋯N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layer via N-H⋯O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

A QM/MM study of the initial excited state dynamics of green-absorbing proteorhodopsin.

PubMed

Borin, Veniamin A; Wiebeler, Christian; Schapiro, Igor

2018-04-17

The primary photochemical reaction of the green-absorbing proteorhodopsin is studied by means of a hybrid quantum mechanics/molecular mechanics (QM/MM) approach. The simulations are based on a homology model derived from the blue-absorbing proteorhodopsin crystal structure. The geometry of retinal and the surrounding sidechains in the protein binding pocket were optimized using the QM/MM method. Starting from this geometry the isomerization was studied with a relaxed scan along the C13[double bond, length as m-dash]C14 dihedral. It revealed an "aborted bicycle pedal" mechanism of isomerization that was originally proposed by Warshel for bovine rhodopsin and bacteriorhodopsin. However, the isomerization involved the concerted rotation about C13[double bond, length as m-dash]C14 and C15[double bond, length as m-dash]N, with the latter being highly twisted but not isomerized. Further, the simulation showed an increased steric interaction between the hydrogen at the C14 of the isomerizing bond and the hydroxyl group at the neighbouring tyrosine 200. In addition, we have simulated a nonadiabatic trajectory which showed the timing of the isomerization. In the first 20 fs upon excitation the order of the conjugated double and single bonds is inverted, consecutively the C13[double bond, length as m-dash]C14 rotation is activated for 200 fs until the S1-S0 transition is detected. However, the isomerization is reverted due to the specific interaction with the tyrosine as observed along the relaxed scan calculation. Our simulations indicate that the retinal - tyrosine 200 interaction plays an important role in the outcome of the photoisomerization.

The shortest Th-Th distance from a new type of quadruple bond.

PubMed

Hu, Han-Shi; Kaltsoyannis, Nikolas

2017-02-15

Compounds featuring unsupported metal-metal bonds between actinide elements remain highly sought after yet confined experimentally to inert gas matrix studies. Notwithstanding this paucity, actinide-actinide bonding has been the subject of extensive computational research. In this contribution, high level quantum chemical calculations at both the scalar and spin-orbit levels are used to probe the Th-Th bonding in a range of zero valent systems of general formula LThThL. Several of these compounds have very short Th-Th bonds arising from a new type of Th-Th quadruple bond with a previously unreported electronic configuration featuring two unpaired electrons in 6d-based δ bonding orbitals. H 3 AsThThAsH 3 is found to have the shortest Th-Th bond yet reported (2.590 Å). The Th 2 unit is a highly sensitive probe of ligand electron donor/acceptor ability; we can tune the Th-Th bond from quadruple to triple, double and single by judicious choice of the L group, up to 2.888 Å for singly-bonded ONThThNO.

(Meth­oxy­methyl­idene)di­methyl­aza­nium tetra­phenyl­borate aceto­nitrile monosolvate

PubMed Central

Tiritiris, Ioannis; Saur, Stefan; Kantlehner, Willi

2014-01-01

In the cation of the title salt, C4H10NO+·C24H20B−·C2H3N, the C—N bond lengths are 1.2864 (16), 1.4651 (17) and 1.4686 (16) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.2978 (15) Å shows double-bond character, pointing towards charge delocalization within the NCO plane of the iminium ion. C—H⋯π inter­actions are present between the methine H atom and two of the phenyl rings of the tetra­phenyl­borate ion. The latter forms an aromatic pocket in which the cation is embedded. The iminium ion is further connected through a C—H⋯N hydrogen bond to the aceto­nitrile mol­ecule. This leads to the formation of a two-dimensional supramolecular pattern along the bc plane. PMID:24765028

Watson-Crick base pairing controls excited-state decay in natural DNA.

PubMed

Bucher, Dominik B; Schlueter, Alexander; Carell, Thomas; Zinth, Wolfgang

2014-10-13

Excited-state dynamics are essential to understanding the formation of DNA lesions induced by UV light. By using femtosecond IR spectroscopy, it was possible to determine the lifetimes of the excited states of all four bases in the double-stranded environment of natural DNA. After UV excitation of the DNA duplex, we detected a concerted decay of base pairs connected by Watson-Crick hydrogen bonds. A comparison of single- and double-stranded DNA showed that the reactive charge-transfer states formed in the single strands are suppressed by base pairing in the duplex. The strong influence of the Watson-Crick hydrogen bonds indicates that proton transfer opens an efficient decay path in the duplex that prohibits the formation or reduces the lifetime of reactive charge-transfer states. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward reliable modeling of S-nitrosothiol chemistry: Structure and properties of methyl thionitrite (CH3SNO), an S-nitrosocysteine model

NASA Astrophysics Data System (ADS)

Khomyakov, Dmitry G.; Timerghazin, Qadir K.

2017-07-01

Methyl thionitrite CH3SNO is an important model of S-nitrosated cysteine aminoacid residue (CysNO), a ubiquitous biological S-nitrosothiol (RSNO) involved in numerous physiological processes. As such, CH3SNO can provide insights into the intrinsic properties of the —SNO group in CysNO, in particular, its weak and labile S—N bond. Here, we report an ab initio computational investigation of the structure and properties of CH3SNO using a composite Feller-Peterson-Dixon scheme based on the explicitly correlated coupled cluster with single, double, and perturbative triple excitations calculations extrapolated to the complete basis set limit, CCSD(T)-F12/CBS, with a number of additive corrections for the effects of quadruple excitations, core-valence correlation, scalar-relativistic and spin-orbit effects, as well as harmonic zero-point vibrational energy with an anharmonicity correction. These calculations suggest that the S—N bond in CH3SNO is significantly elongated (1.814 Å) and has low stretching frequency and dissociation energy values, νS—N = 387 cm-1 and D0 = 32.4 kcal/mol. At the same time, the S—N bond has a sizable rotation barrier, △E0≠ = 12.7 kcal/mol, so CH3SNO exists as a cis- or trans-conformer, the latter slightly higher in energy, △E0 = 1.2 kcal/mol. The S—N bond properties are consistent with the antagonistic nature of CH3SNO, whose resonance representation requires two chemically opposite (antagonistic) resonance structures, CH3—S+=N—O- and CH3—S-/NO+, which can be probed using external electric fields and quantified using the natural resonance theory approach (NRT). The calculated S—N bond properties slowly converge with the level of correlation treatment, with the recently developed distinguished cluster with single and double excitations approximation (DCSD-F12) performing significantly better than the coupled cluster with single and double excitations (CCSD-F12), although still inferior to the CCSD(T)-F12 method that includes perturbative triple excitations. Double-hybrid density functional theory (DFT) calculations with mPW2PLYPD/def2-TZVPPD reproduce well the geometry, vibrational frequencies, and the S—N bond rotational barrier in CH3SNO, while hybrid DFT calculations with PBE0/def2-TZVPPD give a better S—N bond dissociation energy.

Photoisomerization of Trans Ortho-, Meta-, Para-Nitro Diarylbutadienes: A Case of Regioselectivity.

PubMed

Agnihotri, Harsha; Paramasivam, Mahalingavelar; Palakollu, Veerabhadraiah; Kanvah, Sriram

2015-11-01

A series of ortho-, meta- and para-substituted trans-nitro aryl (phenyl and pyridyl) butadienes have been synthesized and characterized. The effect of substitution and positional selectivity on their fluorescence and photoisomerization were systematically investigated. Among all dienes, meta- and para-nitro phenyl-substituted derivatives exhibit remarkable solvatochromic emission shifts due to intramolecular charge transfer. On the other hand, ortho derivatives undergo regioselective isomerization upon photoexcitation in contrast to inefficient isomerization of para and meta nitro-substituted dienes. Single crystal X-ray analysis revealed existence of intramolecular hydrogen bonding between the nitro group and the hydrogen of the proximal double bond. This restricts the rotation of the proximal double bond thereby allowing regioselective isomerization. The observations were also supported by NMR spectroscopic studies. © 2015 The American Society of Photobiology.

Electron transfer dynamics of bistable single-molecule junctions.

PubMed

Danilov, Andrey V; Kubatkin, Sergey E; Kafanov, Sergey G; Flensberg, Karsten; Bjørnholm, Thomas

2006-10-01

We present transport measurements of single-molecule junctions bridged by a molecule with three benzene rings connected by two double bonds and with thiol end-groups that allow chemical binding to gold electrodes. The I-V curves show switching behavior between two distinct states. By statistical analysis of the switching events, we show that a 300 meV mode mediates the transition between the two states. We propose that breaking and reformation of a S-H bond in the contact zone between molecule and electrode explains the observed bistability.

Evaluation of Disulfide Bond Position to Enhance the Thermal Stability of a Highly Stable Single Domain Antibody

PubMed Central

Zabetakis, Dan; Olson, Mark A.; Anderson, George P.; Legler, Patricia M.; Goldman, Ellen R.

2014-01-01

Single domain antibodies are the small recombinant variable domains derived from camelid heavy-chain-only antibodies. They are renowned for their stability, in large part due to their ability to refold following thermal or chemical denaturation. In addition to refolding after heat denaturation, A3, a high affinity anti-Staphylococcal Enterotoxin B single domain antibody, possesses a melting temperature of ∼84°C, among the highest reported for a single domain antibody. In this work we utilized the recently described crystal structure of A3 to select locations for the insertion of a second disulfide bond and evaluated the impact that the addition of this second bond had on the melting temperature. Four double-disulfide versions of A3 were constructed and each was found to improve the melting temperature relative to the native structure without reducing affinity. Placement of the disulfide bond at a previously published position between framework regions 2 and 3 yielded the largest improvement (>6°C), suggesting this location is optimal, and seemingly provides a universal route to raise the melting temperature of single domain antibodies. This study further demonstrates that even single domain antibodies with extremely high melting points can be further stabilized by addition of disulfide bonds. PMID:25526640

3-[Bis(dimethyl­amino)­methyl­ene]-1,1-diphenyl­urea

PubMed Central

Tiritiris, Ioannis

2012-01-01

In the title compound, C18H22N4O, the C=N and C—N bond lengths in the CN3 unit are 1.3179 (11), 1.3551 (11) and 1.3737 (11) Å, indicating double- and single-bond character, respectively. The N—C—N angles are 115.91 (8), 118.20 (8) and 125.69 (8), showing a deviation of the CN3 plane from an ideal trigonal–planar geometry. The bonds between the N atoms and the terminal C-methyl groups all have values close to a typical single bond [1.4529 (12)–1.4624 (12) Å]. The dihedral angle between the phenyl rings is 79.63 (4)°. In the crystal, the mol­ecules are connected via weak C—H⋯O hydrogen bonds, generating chains along [100]. PMID:23284417

Site-specific binding of a water molecule to the sulfa drugs sulfamethoxazole and sulfisoxazole: a laser-desorption isomer-specific UV and IR study.

PubMed

Uhlemann, Thomas; Seidel, Sebastian; Müller, Christian W

2018-03-07

To determine the preferred water molecule binding sites of the polybasic sulfa drugs sulfamethoxazole (SMX) and sulfisoxazole (SIX), we have studied their monomers and monohydrated complexes through laser-desorption conformer-specific UV and IR spectroscopy. Both the SMX and SIX monomer adopt a single conformer in the molecular beam. On the basis of their conformer-specific IR spectra in the NH stretch region, these conformers were assigned to the SMX and SIX global minimum structures, both exhibiting a staggered sulfonamide group and an intramolecular C-HO[double bond, length as m-dash]S hydrogen bond. The SMX-H 2 O and SIX-H 2 O complexes each adopt a single isomer in the molecular beam. Their isomeric structures were determined based on their isomer-specific IR spectra in the NH/OH stretch region. Quantum Theory of Atoms in Molecules analysis of the calculated electron densities revealed that in the SMX-H 2 O complex the water molecule donates an O-HN hydrogen bond to the heterocycle nitrogen atom and accepts an N-HO hydrogen bond from the sulfonamide NH group. In the SIX-H 2 O complex, however, the water molecule does not bind to the heterocycle but instead donates an O-HO[double bond, length as m-dash]S hydrogen bond to the sulfonamide group and accepts an N-HO hydrogen bond from the sulfonamide NH group. Both water complexes are additionally stabilized by a C ph -HOH 2 hydrogen bond. Interacting Quantum Atoms analysis suggests that all intermolecular hydrogen bonds are dominated by the short-range exchange-correlation contribution.

Development of a QSAR model for predicting aqueous reaction rate constants of organic chemicals with hydroxyl radicals.

PubMed

Luo, Xiang; Yang, Xianhai; Qiao, Xianliang; Wang, Ya; Chen, Jingwen; Wei, Xiaoxuan; Peijnenburg, Willie J G M

2017-03-22

Reaction with hydroxyl radicals (˙OH) is an important removal pathway for organic pollutants in the aquatic environment. The aqueous reaction rate constant (k OH ) is therefore an important parameter for fate assessment of aquatic pollutants. Since experimental determination fails to meet the requirement of being able to efficiently handle numerous organic chemicals at limited cost and within a relatively short period of time, in silico methods such as quantitative structure-activity relationship (QSAR) models are needed to predict k OH . In this study, a QSAR model with a larger and wider applicability domain as compared with existing models was developed. Following the guidelines for the development and validation of QSAR models proposed by the Organization for Economic Co-operation and Development (OECD), the model shows satisfactory performance. The applicability domain of the model has been extended and contained chemicals that have rarely been covered in most previous studies. The chemicals covered in the current model contain functional groups including [double bond splayed left]C[double bond, length as m-dash]C[double bond splayed right], -C[triple bond, length as m-dash]C-, -C 6 H 5 , -OH, -CHO, -O-, [double bond splayed left]C[double bond, length as m-dash]O, -C[double bond, length as m-dash]O(O)-, -COOH, -C[triple bond, length as m-dash]N, [double bond splayed left]N-, -NH 2 , -NH-C(O)-, -NO 2 , -N[double bond, length as m-dash]C-N[double bond splayed right], [double bond splayed left]N-N[double bond splayed right], -N[double bond, length as m-dash]N-, -S-, -S-S-, -SH, -SO 3 , -SO 4 , -PO 4 , and -X (F, Cl, Br, and I).

Single and double C-Cl-activation of methylene chloride by P,N-ligand coordinated rhodium complexes.

PubMed

Blank, Benoît; Glatz, Germund; Kempe, Rhett

2009-02-02

Two in one: The simultaneous formation of bimetallic mu-methylene bridged Rh(III) complexes as well as dimeric Rh(III) complexes with terminal chloromethyl groups is observed for P,N-ligand stabilized Rh(I) complexes by C-Cl bond activation of methylene chloride. A mechanistic proposal for the formation of both activation products is also discussed. The synthesis of Rh(I) complexes with P-functionalized aminopyridine ligands is reported as well as the first simultaneous observation of a single and double activation of C-Cl bonds of methylene chloride affording both a dimeric Rh(III) complex bearing terminal CH(2)Cl groups in addition to a binuclear Rh(III) complex with a bridging mu-CH(2) group. The structures of the oxidative addition products were obtained by X-ray diffraction studies and NMR experiments were performed to elucidate some aspects of the reaction pathway.

Pressure-induced emission band separation of the hybridized local and charge transfer excited state in a TPE-based crystal.

PubMed

Liu, Xuedan; Li, Aisen; Xu, Weiqing; Ma, Zhiyong; Jia, Xinru

2018-05-08

We herein report a newly synthesized simple molecule, named TPE[double bond, length as m-dash]C4, with twisted D-A structure. TPE[double bond, length as m-dash]C4 showed two intrinsic emission bands ascribed to the locally excited (LE) state and the intramolecular charge transfer (ICT) state, respectively. In the crystal state, the LE emission band is usually observed. However, by applying hydrostatic pressure to the powder sample and the single crystal sample of TPE[double bond, length as m-dash]C4, dual-fluorescence (445 nm and 532 nm) was emerged under high pressure, owing to the pressure-induced emission band separation of the hybridized local and charge transfer excited state (HLCT). It is found that the emission of TPE[double bond, length as m-dash]C4 is generally determined by the ratio of the LE state to the ICT state. The ICT emission band is much more sensitive to the external pressure than the LE emission band. The HLCT state leads to a sample with different responsiveness to grinding and hydrostatic pressure. This study is of significance in the molecular design of such D-A type molecules and in the control of photoluminescence features by molecular structure. Such results are expected to pave a new way to further understand the relationship between the D-A molecular structure and stimuli-responsive properties.

Determining Double Bond Position in Lipids Using Online Ozonolysis Coupled to Liquid Chromatography and Ion Mobility-Mass Spectrometry.

PubMed

Harris, Rachel A; May, Jody C; Stinson, Craig A; Xia, Yu; McLean, John A

2018-02-06

The increasing focus on lipid metabolism has revealed a need for analytical techniques capable of structurally characterizing lipids with a high degree of specificity. Lipids can exist as any one of a large number of double bond positional isomers, which are indistinguishable by single-stage mass spectrometry alone. Ozonolysis reactions coupled to mass spectrometry have previously been demonstrated as a means for localizing double bonds in unsaturated lipids. Here we describe an online, solution-phase reactor using ozone produced via a low-pressure mercury lamp, which generates aldehyde products diagnostic of cleavage at a particular double bond position. This flow-cell device is utilized in conjunction with structurally selective ion mobility-mass spectrometry. The lamp-mediated reaction was found to be effective for multiple lipid species in both positive and negative ionization modes, and the conversion efficiency from precursor to product ions was tunable across a wide range (20-95%) by varying the flow rate through the ozonolysis device. Ion mobility separation of the ozonolysis products generated additional structural information and revealed the presence of saturated species in a complex mixture. The method presented here is simple, robust, and readily coupled to existing instrument platforms with minimal modifications necessary. For these reasons, application to standard lipidomic workflows is possible and aids in more comprehensive structural characterization of a myriad of lipid species.

Accurate bond energies of hydrocarbons from complete basis set extrapolated multi-reference singles and doubles configuration interaction.

PubMed

Oyeyemi, Victor B; Pavone, Michele; Carter, Emily A

2011-12-09

Quantum chemistry has become one of the most reliable tools for characterizing the thermochemical underpinnings of reactions, such as bond dissociation energies (BDEs). The accurate prediction of these particular properties (BDEs) are challenging for ab initio methods based on perturbative corrections or coupled cluster expansions of the single-determinant Hartree-Fock wave function: the processes of bond breaking and forming are inherently multi-configurational and require an accurate description of non-dynamical electron correlation. To this end, we present a systematic ab initio approach for computing BDEs that is based on three components: 1) multi-reference single and double excitation configuration interaction (MRSDCI) for the electronic energies; 2) a two-parameter scheme for extrapolating MRSDCI energies to the complete basis set limit; and 3) DFT-B3LYP calculations of minimum-energy structures and vibrational frequencies to account for zero point energy and thermal corrections. We validated our methodology against a set of reliable experimental BDE values of CC and CH bonds of hydrocarbons. The goal of chemical accuracy is achieved, on average, without applying any empirical corrections to the MRSDCI electronic energies. We then use this composite scheme to make predictions of BDEs in a large number of hydrocarbon molecules for which there are no experimental data, so as to provide needed thermochemical estimates for fuel molecules. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tungsten Hydride Phosphorus- and Arsenic-Bearing Molecules with Double and Triple W-P and W-As Bonds.

PubMed

Andrews, Lester; Cho, Han-Gook; Fang, Zongtang; Vasiliu, Monica; Dixon, David A

2018-05-07

Laser ablation of tungsten metal provides W atoms which react with phosphine and arsine during condensation in excess argon and neon, leading to major new infrared (IR) absorptions. Annealing, UV irradiation, and deuterium substitution experiments coupled with electronic structure calculations at the density functional theory level led to the assignment of the observed IR absorptions to the E≡WH 3 and HE═WH 2 molecules for E = P and As. The potential energy surfaces for hydrogen transfer from PH 3 to the W were calculated at the coupled-cluster CCSD(T)/complete basis set level. Additional weak bands in the phosphide and arsenide W-H stretching region are assigned to the molecules with loss of H from W, E≡WH 2 . The electronic structure calculations show that the E≡WH 3 molecules have a W-E triple bond, the HE═WH 2 molecules have a W-E double bond, and the H 2 E-WH molecules have a W-E single bond. The formation of multiple E-W bonds leads to increasing stability for the isomers.

Synthesis, spectroscopic characterization and theoretical calculations of ClF2CC(O)NPCl3 ([chloro(difluor)acetyl]phosphorimidic trichloride).

PubMed

Iriarte, Ana G; Cutin, Edgardo H; Argüello, Gustavo A

2014-01-01

The synthesis of [chloro(difluor)acetyl]phosphorimidic trichloride (ClF2CC(O)NPCl3), together with a tentative assignment of the vibrational, NMR and mass spectra, are reported. Quantum chemical calculations (MP2 and B3LYP methods with 6-311+G(d) and 6-311+G(2df,p) basis sets) predict three stable conformers in the gas phase (syn, gauche and anti, defined according to the rotation around both the ClCCN and the CCNP dihedral angles). However, only a single C1 symmetry conformer is observed in the liquid phase, possessing the CO double bond in synperiplanar orientation with respect to the PN double bond, and the ClC bond distorted from the plane defined by the CC(O)NP entity. A Natural Bond Orbital (NBO) analysis was carried out for the title compound and related molecules in order to provide an explanation about the electronic properties. Copyright © 2013 Elsevier B.V. All rights reserved.

Electron paramagnetic resonance study of radiation-induced paramagnetic centers in succinic anhydride single crystal

NASA Astrophysics Data System (ADS)

Caliskan, Betul; Caliskan, Ali Cengiz; Er, Emine

2017-09-01

Succinic anhydride single crystals were exposed to 60Co-gamma irradiation at room temperature. The irradiated single crystals were investigated at 125 K by Electron Paramagnetic Resonance (EPR) Spectroscopy. The investigation of EPR spectra of irradiated single crystals of succinic anhydride showed the presence of two succinic anhydride anion radicals. The anion radicals observed in gamma-irradiated succinic anhydride single crystal were created by the scission of the carbon-oxygen double bond. The structure of EPR spectra demonstrated that the hyperfine splittings arise from the same radical species. The reduction of succinic anhydride was identified which is formed by the addition of an electron to oxygen of the Csbnd O bond. The g values, the hyperfine structure constants and direction cosines of the radiation damage centers observed in succinic anhydride single crystal were obtained.

A two-color fluorogenic carbene complex for tagging olefins via metathesis reaction

NASA Astrophysics Data System (ADS)

Wirtz, Marcel; Grüter, Andreas; Heib, Florian; Huch, Volker; Zapp, Josef; Herten, Dirk-Peter; Schmitt, Michael; Jung, Gregor

2015-12-01

We describe a fluorogenic ruthenium (II) carbene complex in which the chromophore is directly connected to the metal center. The compound introduces a boron dipyrromethene (BODIPY) moiety into target double bonds by metathesis. Tagging of terminal double bonds is demonstrated on immobilized styrene units on a glass surface. We also show that two compounds with distinguishable fluorescence properties are formed in the model reaction with styrene. The outcome of the metathesis reaction is characterized by 19F-NMR, optical spectroscopy, and, finally, single-molecule trajectories. This labeling scheme, in our perception, is of particular interest in the fields of interfacial science and biorthogonal ligation in combination with super-resolution imaging.

Molecular structure of Ti8C12 and related complexes.

PubMed Central

Pauling, L

1992-01-01

Application of valence-bond theory leads to the assignment to the molecule Ti8C12 of a cubic structure, point group Ohm3m, with 8 Ti at the cube corners, +/-(x x x, x, x x [symbol, see text]) where x = 1.78 A, and with 12 C in pairs in the cube faces, +/-(0 y z, [symbol, see text], 0, y z [symbol, see text]) where y = 1.78 A and z = 0.71 A. The Ti-C and C-C bonds have bond number 4/3, corresponding to resonance of single and double bonds in 2:1 ratio. PMID:11607323

Pulsed EPR measurements on reaction rate constants for addition of photo-generated radicals to double bonds of diethyl fumarate and diethyl maleate

NASA Astrophysics Data System (ADS)

Takahashi, Hirona; Hagiwara, Kenta; Kawai, Akio

2016-11-01

Addition reaction of photo-generated radicals to double bonds of diethyl fumarate (deF) and diethyl maleate (deM), which are geometrical isomers, was studied by means of time-resolved- (TR-) and pulsed-electron paramagnetic resonance (EPR). Analysis of TR-EPR spectra indicates that adduct radicals from deF and deM should have the same structure. The double bonds of these monomers are converted to single ones by addition reaction, which allows hindered internal rotation to give the same structure of adduct radical. The rate constants for addition reaction of photo-generated radicals were determined by Stern-Volmer analysis of the decay time of electron spin-echo intensity of these radicals measured by the pulsed EPR method. Rate constants for deF were found to be larger than those for deM. This relation is in good consistent with efficiency of polymerisation of deF and deM. Experimentally determined rate constants were evaluated by introducing the addition reaction model on the basis of two important factors enthalpy and polar effects.

N-(Diphenyl­carbamo­yl)-N,N′,N′,N′′,N′′-penta­methyl­guanidinium tetra­phenyl­borate

PubMed Central

Tiritiris, Ioannis

2013-01-01

In the title salt, C19H25N4O+·C24H20B−, the C=N and C—N bond lengths in the CN3 unit are 1.3327 (8)/1.3364 (9) and 1.3802 (9) Å, indicating double- and single-bond character, respectively. The N—C—N angles are 118.77 (6), 120.29 (6) and 120.81 (6)°, showing only a small deviation of the CN3 plane from an ideal trigonal-planar geometry. The bonds between the N atoms and the terminal methyl C atoms all have values close to a typical single bond [1.4636 (9)–1.4772 (9) Å]. The crystal packing is caused by electrostatic inter­actions between cations and anions. PMID:23476477

Strong correlation in incremental full configuration interaction

NASA Astrophysics Data System (ADS)

Zimmerman, Paul M.

2017-06-01

Incremental Full Configuration Interaction (iFCI) reaches high accuracy electronic energies via a many-body expansion of the correlation energy. In this work, the Perfect Pairing (PP) ansatz replaces the Hartree-Fock reference of the original iFCI method. This substitution captures a large amount of correlation at zero-order, which allows iFCI to recover the remaining correlation energy with low-order increments. The resulting approach, PP-iFCI, is size consistent, size extensive, and systematically improvable with increasing order of incremental expansion. Tests on multiple single bond, multiple double bond, and triple bond dissociations of main group polyatomics using double and triple zeta basis sets demonstrate the power of the method for handling strong correlation. The smooth dissociation profiles that result from PP-iFCI show that FCI-quality ground state computations are now within reach for systems with up to about 10 heavy atoms.

Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode.

PubMed

Kim, Jeong Soo; Kim, Byung-Man; Kim, Un-Young; Shin, HyeonOh; Nam, Jung Seung; Roh, Deok-Ho; Park, Jun-Hyeok; Kwon, Tae-Hyuk

2017-10-11

We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO 2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 μm transparent and 2.5-μm TiO 2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; V OC = 0.73 V, J SC = 15.4 mA·cm -2 , and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m -2 ), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO 2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only J SC through improved ICT but also V OC through the evenly distributed sensitizer surface coverage.

Dual resin bonded joints in polyetheretherketone (PEEK) matrix composites

NASA Astrophysics Data System (ADS)

Zelenak, Steve; Radford, Donald W.; Dean, Michael W.

1993-04-01

The paper describes applications of the dual resin (miscible polymer) bonding technique (Smiley, 1989) developed as an alternative to traditional bonding approaches to joining thermoplastic matrix composite subassemblies into structures. In the experiments, the performance of joint geometries, such as those that could be used to assemble large truss structures in space, are investigated using truss joint models consisting of woven carbon fiber/PEEK tubes of about 1 mm wall thickness. Specific process conditions and hand-held hardware used to apply heat and pressure were chosen to simulate a field asembly technique. Results are presented on tube/cruciform double lap shear tests, pinned-pinned tube compression tests, and single lap shear bond tests of joints obtained using the dual resin bonding technique.

Reactions of the linear tetranuclear complex Ru sub 4 (CO) sub 10 (CH sub 3 C double bond C(H)C(H) double bond N-i-Pr) sub 2 with oxidizing reagents. Syntheses of halide-bridged (Ru(CO) sub 2 X(CH sub 3 C double bond C(H)C(H) double bond N-i-Pr)) sub 2 and fac-Ru(CO) sub 3 X(CH sub 3 C double bond C(H)C(H) double bond N-i-Pr)

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

Mul, W.P.; Elsevier, C.J.; van Leijen, M.

1991-01-01

The linear tetranuclear complex Ru{sub 4}(CO){sub 10}(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr){sub 2} (1), containing two {eta}{sup 5}-azaruthenacyclopentadienyl systems, reacts with oxidizing reagents (I{sub 2}, Br{sub 2}, NBS, CCl{sub 4}) at elevated temperatures (40-90C) in heptane or benzene to give the new dimeric halide-bridged organoruthenium(II) complexes (Ru(CO){sub 2}X(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr)){sub 2} (X = I (3a), X = Br (3b), Cl (3c); yield 30-80%) together with (Ru(CO){sub 3}X{sub 2}){sub 2}. The reactions of 1 with CX{sub 4} (X = I, Br, Cl) are accelerated by CO, probably because Ru{sub 4}(CO){sub 12}(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr){sub 2} (5), which contains two unbridged metal-metal bonds,more » is formed prior to oxidation. The halide-bridged dimers 3a-c are obtained as mixtures of four isomers, the configurations of which are discussed. Splitting of the halide bridges takes place when a solution of 3a-c is saturated with CO, whereby mononuclear fac-Ru(CO){sub 3}X(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr) (4a-c) is obtained. This process is reversible; ie., passing a stream of nitrogen through a solution of 4a-c or removal of the solvent under vacuum causes the reverse reaction with reformation of 3a-c. Compounds 3a-c and 4a-c have been characterized by IR (3, 4), FD mass (3), {sup 1}H (3, 4), and {sup 13}C{l brace}H{r brace} NMR (4) spectroscopy and satisfactory elemental analyses have been obtained for 3a-c. Compounds 3 and 4 are suitable precursors for the preparation of new homo- and heteronuclear transition-metal complexes.« less

An ab initio study of HCuCO

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.

1994-01-01

HCuCO is studied using a large Gaussian basis set at the coupled cluster singles and doubles level of theory, including a perturbational estimate of the connected triples (CCSD(T)). In contrast with CuCO, HCuCO is linear. The Cu-CO bond in HCuCO is significantly stronger than in CuCO. These differences between HCuCO and CuCO are discussed in terms of theCu-H bond polarizing the Cu 4s electron away from the CO.

Surface shapes and surrounding environment analysis of single- and double-stranded DNA-binding proteins in protein-DNA interface.

PubMed

Wang, Wei; Liu, Juan; Sun, Lin

2016-07-01

Protein-DNA bindings are critical to many biological processes. However, the structural mechanisms underlying these interactions are not fully understood. Here, we analyzed the residues shape (peak, flat, or valley) and the surrounding environment of double-stranded DNA-binding proteins (DSBs) and single-stranded DNA-binding proteins (SSBs) in protein-DNA interfaces. In the results, we found that the interface shapes, hydrogen bonds, and the surrounding environment present significant differences between the two kinds of proteins. Built on the investigation results, we constructed a random forest (RF) classifier to distinguish DSBs and SSBs with satisfying performance. In conclusion, we present a novel methodology to characterize protein interfaces, which will deepen our understanding of the specificity of proteins binding to ssDNA (single-stranded DNA) or dsDNA (double-stranded DNA). Proteins 2016; 84:979-989. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Theoretical study of geometry relaxation following core excitation: H2O, NH3, and CH4

NASA Astrophysics Data System (ADS)

Takahashi, Osamu; Kunitake, Naoto; Takaki, Saya

2015-10-01

Single core-hole (SCH) and double core-hole excited state molecular dynamics (MD) calculations for neutral and cationic H2O, NH3, and CH4 have been performed to examine geometry relaxation after core excitation. We observed faster X-H (X = C, N, O) bond elongation for the core-ionized state produced from the valence cationic molecule and the double-core-ionized state produced from the ground and valence cationic molecules than for the first resonant SCH state. Using the results of SCH MD simulations of the ground and valence cationic molecules, Auger decay spectra calculations were performed. We found that fast bond scission leads to peak broadening of the spectra.

Double proton transfer behavior and one-electron oxidation effect in double H-bonded glycinamide-formic acid complex.

PubMed

Li, Ping; Bu, Yuxiang

2004-11-22

The behavior of double proton transfer occurring in a representative glycinamide-formic acid complex has been investigated at the B3LYP/6-311 + + G( * *) level of theory. Thermodynamic and, especially, kinetic parameters, such as tautomeric energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the double proton transfer process, such as geometrical changes, interaction energies, and intrinsic reaction coordinate calculations have also been studied. Computational results show that the participation of a formic acid molecule favors the proceeding of the proton transfer for glycinamide compared with that without mediate-assisted case. The double proton transfer process proceeds with a concerted mechanism rather than a stepwise one since no ion-pair complexes have been located during the proton transfer process. The calculated barrier heights are 11.48 and 0.85 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 2.95 and 2.61 kcal/mol to 8.53 and -1.76 kcal/mol if further inclusion of zero-point vibrational energy corrections, where the negative barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to that occurring between glycinamide and formamide. Furthermore, solvent effects on the thermodynamic and kinetic processes have also been predicted qualitatively employing the isodensity surface polarized continuum model within the framework of the self-consistent reaction field theory. Additionally, the oxidation process for the double H-bonded glycinamide-formic acid complex has also been investigated. Contrary to that neutral form possessing a pair of two parallel intermolecular H bonds, only a single H bond with a comparable strength has been found in its ionized form. The vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 9.40 and 8.69 eV, respectively, where ionization is mainly localized on the glycinamide fragment. Like that ionized glycinamide-formamide complex, the proton transfer in the ionized complex is characterized by a single-well potential, implying that the proton initially attached to amide N4 in the glycinamide fragment cannot be transferred to carbonyl O13 in the formic acid fragment at the geometry of the optimized complex. Copyright 2004 American Institute of Physics.

Catalytic coupling of sp2- and sp-hybridized carbon-hydrogen bonds with vinylmetalloid compounds.

PubMed

Marciniec, Bogdan

2007-10-01

In the Account given herein, it has been shown that silylative coupling of olefins, well-recognized as a new catalytic route for the activation of double bond C-H bond of olefins and double bond C-Si bond of vinylsilicon compounds with ethylene elimination, can be extended over both other vinylmetalloid derivatives (double bond C-E) (where E = Ge, B, and others) as well as the activation of triple bond C-H, double bond C aryl-H, and -O-H bond of alcohols and silanols. This general transformation is catalyzed by transition-metal complexes (mainly Ru and Rh) containing or initiating TM-H and/or TM-E bonds (inorganometallics). This new general catalytic route for the activation of double bond C-H and triple bond C-H as well as double bond C-E bonds called metallative coupling or trans-metalation (cross-coupling, ring-closing, and polycondensation) constitutes an efficient method (complementary to metathesis) for stereo- and regioselective synthesis of a variety of molecular and macromolecular compounds of vinyl-E (E = Si, B, and Ge) and ethynyl-E (E = Si and Ge) functionality, also potent organometallic reagents for efficient synthesis of highly pi-conjugated organic compounds. The mechanisms of the catalysis of this deethenative metalation have been supported by equimolar reactions of TM-H and/or TM-E with initial substances and reactions with deuterium-labeled reagents.

Reductive amination of glutaraldehyde 2,4-dinitrophenylhydrazone using 2-picoline borane and high-performance liquid chromatographic analysis.

PubMed

Uchiyama, Shigehisa; Sakamoto, Hironari; Ohno, Akiko; Inaba, Yohei; Nakagome, Hideki; Kunugita, Naoki

2012-09-21

A typical method for the measurement of glutaraldehyde (GLA) employs 2,4-dinitrophenylhydrazine (DNPH) to form GLA-DNPhydrazone derivatives. However, this method is subject to analytical errors because GLA-DNPhydrazone is a quaternary bis-derivative and forms three geometric isomers (E-E, E-Z and Z-Z) as a result of the two C[double bond, length as m-dash]N double bonds. To overcome this issue, a method for transforming the C[double bond, length as m-dash]N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been applied. The amination reaction of GLA-DNPhydrazones with 2-picoline borane is accelerated with catalytic amounts of acid and is completed within 10 minutes in the presence of 100 mmol L(-1) phosphoric acid. Reduction of GLA-DNPhydrazone by 2-picoline borane is unique and results in the formation of N-(2,4-dinitrophenyl)-1-piperidinamine (DNPPA). NMR and LC-APCI-MS data confirmed the product identification. DNPPA is very stable and did not change when stored for at least four weeks at room temperature. DNPPA has excellent solubility of 14.6 g L(-1) at 20 °C in acetonitrile. The absorption maximum wavelength and the molar absorptivity of DNPPA were 351 nm and 4.2 × 10(4) L mol(-1) cm(-1) respectively. Complete separation between the reduced forms of C1-C10 aldehyde DNPhydrazones, including DNPPA, can be achieved by operating the reversed-phase high-performance liquid chromatograph at 351 nm in gradient mode using a C18 amide column. The reductive amination method for GLA overcomes analytical errors caused by E-E, E-Z and Z-Z geometrical isomers.

Purification and characterization of 9-hexadecenoic acid cis-trans isomerase from pseudomonas sp. strain E-3

PubMed

Okuyama; Ueno; Enari; Morita; Kusano

1998-01-01

A 9-hexadecenoic acid cis-trans isomerase (9-isomerase) that catalyzed the cis-to-trans isomerization of the double bond of free 9-cis-hexadecenoic acid [16:1(9c)] was purified to homogeneity from an extract of Pseudomonas sp. strain E-3 and characterized. Electrophoresis of the purified enzyme on both incompletely denaturing and denaturing polyacrylamide gels yielded a single band of a protein with a molecular mass of 80 kDa, suggesting that the isomerase is a monomeric protein of 80 kDa. The 9-isomerase, assayed with 16:1(9c) as a substrate, had a specific activity of 22.8 &mgr;mol h-1 (mg protein)-1 and a Km of 117.6 mM. The optimal pH and temperature for catalysis were approximately pH 7-8 and 30 degrees C, respectively. The 9-isomerase catalyzed the cis-to-trans conversion of a double bond at positions 9, 10, or 11, but not that of a double bond at position 6 or 7 of cis-mono-unsaturated fatty acids with carbon chain lengths of 14, 15, 16, and 17. Octadecenoic acids with a double bond at position 9 or 11 were not susceptible to isomerization. These results suggest that 9-isomerase has a strict specificity for both the position of the double bond and the chain length of the fatty acid. The enzyme catalyzed the cis-to-trans isomerization of fatty acids in a free form, and in the presence of a membrane fraction it was also able to isomerize 16:1(9c) esterified to phosphatidylethanolamine. The 9-isomerase was strongly inhibited by catecholic antioxidants such as alpha-tocopherol and nordihydroguaiaretic acid, but was not inhibited by 1, 10-phenanthroline or EDTA or under anoxic conditions. Based on these results, the possible mechanism of catalysis by this enzyme is discussed.

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

DOEpatents

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

2002-01-01

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

Acetonitrile covalent adduct chemical ionization mass spectrometry for double bond localization in non-methylene-interrupted polyene fatty acid methyl esters.

PubMed

Lawrence, Peter; Brenna, J Thomas

2006-02-15

Covalent adduct chemical ionization (CACI) using a product of acetonitrile self-reaction, (1-methyleneimino)-1-ethenylium (MIE; CH2=C=N+=CH2), has been investigated as a method for localizing double bonds in a series of 16 non-methylene-interrupted fatty acid methyl esters (NMI-FAME) of polyenes with three and more double bonds. As with polyunsaturated homoallylic (methylene-interrupted) FAME and conjugated dienes, MIE (m/z 54) reacts across double bonds to yield molecular ions 54 mass units above the parent analyte. [M + 54]+ ions of several 20- and 22-carbon FAME that include one double bond in the C2-C3 position separated by two to five methylene units from a three, four, or five C homoallylic system dissociated according to rules for the homoallylic system, with an additional fragment corresponding to cleavage between the lone double bond and the carboxyl group and defining the position of the lone double bond. Triene FAME with both methylene and ethylene interruption yielded characteristic fragments distinguishable from homoallylic trienes. Fragmentation of fully conjugated trienes in the MS-1 spectra yields ratios of [M + 54]+/[M + 54 - 32]+ (loss of methanol) near unity, which distinguishes them from homoallylic FAME having a ratio of 8 or more; collisionally activated dissociation of [M + 54]+ yields a series of ions, including some rearrangement products, indicative of double bond position. Unlike conjugated dienes, fully conjugated triene diagnostic ion signal ratios did not follow any pattern based on double bond geometry. Partially conjugated trienes behave similarly to monoenes and conjugated dienes, yielding [M + 54]+/[M + 54 - 32]+ of 2-3 and, permitting them to be assigned as partially conjugated FAME using the MS-1 spectrum. They yield unique MS/MS spectra with weaker but assignable fragment ions, along with a diagnostic fragment that locates the lone double bond and permits 6,10,12-octatrienoate to be distinguished from 6,8,12-octatrienoate. The presence of a triple bond did not affect fragment formation in a methylene-interrupted yne-ene but did change fragments in a conjugated yne-ene. These data extend the principle of double bond localization by acetonitrile CACI-MS/MS to double bond structure in complex FAME found in nature.

Studies of Single Biomolecules, DNA Conformational Dynamics, and Protein Binding

DTIC Science & Technology

2008-07-11

Nucleotide Base pairs Hydrogen bonds FIG. 1: Ladder structure of DNA showing the Watson - Crick bonding of the bases A, T, G, and C which are suspended by a...protected against unwanted action of chemicals and proteins. The three-dimensional structure of DNA is the famed Watson - Crick double-helix, the equilibrium...quantitative analysis [88]. [1] A. Kornberg and T. A. Baker, DNA Replication (W. H. Freeman, New York, 1992). [2] J. D. Watson and F. H. C. Crick

Role of Secondary Low-Energy Electrons in the Concomitant Chemoradiation Therapy of Cancer

NASA Astrophysics Data System (ADS)

Zheng, Yi; Hunting, Darel J.; Ayotte, Patrick; Sanche, Léon

2008-05-01

Solid films of DNA with and without the chemotherapeutic agent cisplatin bonded to guanine were bombarded with electrons of 1, 10, 100, and 60 000 eV causing single and double strand breaks. In the presence of cisplatin this damage was increased by factors varying from 1.3 to 4.4 owing to an increase in bond dissociation triggered by the formation of transient anions. This mechanism may lie at the basis of the efficiency of concomitant cisplatin-radiation therapy.

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

PubMed

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

2017-08-15

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

Hardening Mechanisms of Silicon Nanospheres: A Molecular Dynamics Study

DTIC Science & Technology

2011-05-01

in single oxide system 111 Figure 5.9 Dislocation motion in double oxide systems 112 x Figure 5.10 Dislocation response to incremental...addressed as no single dislocation loops were ever separated and no diffraction peaks indicative of the -Sn phase were observed. The load vs. displacement...as the diamond cubic structure has angle dependent covalent bonds. Therefore, other potentials have been 20 developed that model the

Stereoselective rhodium-catalysed [2+2+2] cycloaddition of linear allene-ene/yne-allene substrates: reactivity and theoretical mechanistic studies.

PubMed

Haraburda, Ewelina; Torres, Óscar; Parella, Teodor; Solà, Miquel; Pla-Quintana, Anna

2014-04-22

Allene-ene-allene (2 and 5) and allene-yne-allene (3 and 7) N-tosyl and O-linked substrates were satisfactorily synthesised. The [2+2+2] cycloaddition reaction catalysed by the Wilkinson catalyst [RhCl(PPh3 )3 ] was evaluated. Substrates 2 and 5, which bear a double bond in the central position, gave a tricyclic structure in a reaction in which four contiguous stereogenic centres were formed as a single diastereomer. The reaction of substrates 3 and 7, which bear a triple bond in the central position, gave a tricyclic structure with a cyclohexenic ring core, again in a diastereoselective manner. All cycloadducts were formed by a regioselective reaction of the inner allene double bond and, therefore, feature an exocyclic diene motif. A Diels-Alder reaction on N-tosyl linked cycloadducts 8 and 10 allowed pentacyclic scaffolds to be diastereoselectively constructed. The reactivity of the allenes on [2+2+2] cycloaddition reactions was studied for the first time by density functional theory calculations. This mechanistic study rationalizes the order in which the unsaturations take part in the catalytic cycle, the reactivity of the two double bonds of the allene towards the [2+2+2] cycloaddition reaction, and the diastereoselectivity of the reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction of the thermo-labile triazenide Na[tBu3SiNNNSiMe3] with CO2: formation of the imido carbonate (tBu3SiO)(Me3SiO)C[double bond, length as m-dash]N-SitBu3 and carbamine acid (tBu3SiO)CONH2.

PubMed

Lerner, H-W; Bolte, M; Wagner, M

2017-07-11

The thermo-labile triazenide Na[tBu 3 SiNNNSiMe 3 ] was prepared by the reaction of Me 3 SiN 3 with Na(thf) 2 [SitBu 3 ] in pentane at -78 °C. Treatment of Na[tBu 3 SiNNNSiMe 3 ] with an excess of carbon dioxide in pentane at -78 °C yielded the imido carbonate (tBu 3 SiO)(Me 3 SiO)C[double bond, length as m-dash]N-SitBu 3 and the carbamine acid (tBu 3 SiO)CONH 2 along with other products. From the reaction solution we could isolate the imido carbonate (tBu 3 SiO)(Me 3 SiO)C[double bond, length as m-dash]N-SitBu 3 and carbamine acid (tBu 3 SiO)CONH 2 . At first single crystals of the carbamine acid (tBu 3 SiO)CONH 2 (triclinic, space group P1[combining macron]) were grown from this solution at room temperature. A second crop of crystals were obtained by concentrating the solution. The second charge consisted of the imido carbonate (tBu 3 SiO)(Me 3 SiO)C[double bond, length as m-dash]N-SitBu 3 (monoclinic, space group P2 1 /n).

Maxima of |Ψ|2: a connection between quantum mechanics and Lewis structures.

PubMed

Lüchow, Arne

2014-04-30

The maxima of squared electronic wave functions |Ψ|2 are analyzed for a number of small molecules. They are in principle observables and show considerable chemical insight from first principles. The maxima contain substantial information about the relative electron positions in a molecule, such as the pairing of opposite spin electrons and the Pauli repulsion which are lost in the electron density. Single bond and double bond as well as polar bond pairs and lone pairs are obtained from the maximum analysis. In many cases, we find a correspondence to the electron arrangements in molecules as assumed by Lewis in 1916. Copyright © 2014 Wiley Periodicals, Inc.

Enhanced production of a single domain antibody with an engineered stabilizing extra disulfide bond.

PubMed

Liu, Jinny L; Goldman, Ellen R; Zabetakis, Dan; Walper, Scott A; Turner, Kendrick B; Shriver-Lake, Lisa C; Anderson, George P

2015-10-09

Single domain antibodies derived from the variable region of the unique heavy chain antibodies found in camelids yield high affinity and regenerable recognition elements. Adding an additional disulfide bond that bridges framework regions is a proven method to increase their melting temperature, however often at the expense of protein production. To fulfill their full potential it is essential to achieve robust protein production of these stable binding elements. In this work, we tested the hypothesis that decreasing the isoelectric point of single domain antibody extra disulfide bond mutants whose production fell due to the incorporation of the extra disulfide bond would lead to recovery of the protein yield, while maintaining the favorable melting temperature and affinity. Introduction of negative charges into a disulfide bond mutant of a single domain antibody specific for the L1 antigen of the vaccinia virus led to approximately 3.5-fold increase of protein production to 14 mg/L, while affinity and melting temperature was maintained. In addition, refolding following heat denaturation improved from 15 to 70 %. It also maintained nearly 100 % of its binding function after heating to 85 °C for an hour at 1 mg/mL. Disappointingly, the replacement of neutral or positively charged amino acids with negatively charged ones to lower the isoelectric point of two anti-toxin single domain antibodies stabilized with a second disulfide bond yielded only slight increases in protein production. Nonetheless, for one of these binders the charge change itself stabilized the structure equivalent to disulfide bond addition, thus providing an alternative route to stabilization which is not accompanied by loss in production. The ability to produce high affinity, stable single domain antibodies is critical for their utility. While the addition of a second disulfide bond is a proven method for enhancing stability of single domain antibodies, it frequently comes at the cost of reduced yields. While decreasing the isoelectric point of double disulfide mutants of single domain antibodies may improve protein production, charge addition appears to consistently improve refolding and some charge changes can also improve thermal stability, thus providing a number of benefits making the examination of such mutations worth consideration.

A general mixture equation of state for double bonding carboxylic acids with ≥2 association sites

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2018-05-01

In this paper, we obtain the first general multi-component solution to Wertheim's thermodynamic perturbation theory for the case that molecules can participate in cyclic double bonds. In contrast to previous authors, we do not restrict double bonding molecules to a 2-site association scheme. Each molecule in a multi-component mixture can have an arbitrary number of donor and acceptor association sites. The one restriction on the theory is that molecules can have at most one pair of double bonding sites. We also incorporate the effect of hydrogen bond cooperativity in cyclic double bonds. We then apply this new association theory to 2-site and 3-site models for carboxylic acids within the polar perturbed chain statistical associating fluid theory equation of state. We demonstrate the accuracy of the approach by comparison to both pure and multi-component phase equilibria data. It is demonstrated that the 3-site association model gives substantially a different hydrogen bonding structure than a 2-site approach. We also demonstrate that inclusion of hydrogen bond cooperativity has a substantial effect on a liquid phase hydrogen bonding structure.

Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment

NASA Astrophysics Data System (ADS)

Fernández-Ramos, Antonio; Smedarchina, Zorka; Rodríguez-Otero, Jesús

2001-01-01

To test the approximate instanton approach to intermolecular proton-transfer dynamics, we report multidimensional ab initio bimolecular rate constants of HH, HD, and DD exchange in the complex of acetic acid with methanol in tetrahydrofuran-d8, and compare them with the NMR (nuclear magnetic resonance) experiments of Gerritzen and Limbach. The bimolecular rate constants are evaluated as products of the exchange rates and the equilibrium rate constants of complex formation in solution. The two molecules form hydrogen-bond bridges and the exchange occurs via concerted transfer of two protons. The dynamics of this transfer is evaluated in the complete space of 36 vibrational degrees of freedom. The geometries of the two isolated molecules, the complex, and the transition states corresponding to double proton transfer are fully optimized at QCISD (quadratic configuration interaction including single and double substitutions) level of theory, and the normal-mode frequencies are calculated at MP2 (Møller-Plesset perturbation theory of second order) level with the 6-31G (d,p) basis set. The presence of the solvent is taken into account via single-point calculations over the gas phase geometries with the PCM (polarized continuum model). The proton exchange rate constants, calculated with the instanton method, show the effect of the structure and strength of the hydrogen bonds, reflected in the coupling between the tunneling motion and the other vibrations of the complex. Comparison with experiment, which shows substantial kinetic isotopic effects (KIE), indicates that tunneling prevails over classic exchange for the whole temperature range of observation. The unusual behavior of the experimental KIE upon single and double deuterium substitution is well reproduced and is related to the synchronicity of two-atom tunneling.

Laboratory spectroscopic analyses of electron irradiated alkanes and alkenes in solar system ices

NASA Astrophysics Data System (ADS)

Hand, K. P.; Carlson, R. W.

2012-03-01

We report results from laboratory experiments of 10 keV electron irradiation of thin ice films of water and short-chain hydrocarbons at ˜10-8 Torr and temperatures ranging from 70-100 K. Hydrocarbon mixtures include water with C3H8, C3H6, C4H10 (butane and isobutane), and C4H8, (1-butene and cis/trans-2-butene). The double bonds of the alkenes in our initial mixtures were rapidly destroyed or converted to single carbon bonds, covalent bonds with hydrogen, bonds with -OH (hydroxyl), bonds with oxygen (C-O), or double bonds with oxygen (carbonyl). Spectra resulting from irradiation of alkane and alkene ices are largely indistinguishable; the initial differences in film composition are destroyed and the resulting mixture includes long-chain, branched aliphatics, aldehydes, ketones, esters, and alcohols. Methane was observed as a product during radiolysis but CO was largely absent. We find that while some of the carbon is oxidized and lost to CO2 formation, some carbon is sequestered into highly refractory, long-chain aliphatic compounds that remain as a thin residue even after the ice film has been raised to standard temperature and pressure. We conclude that the high availability of hydrogen in our experiments leads to the formation of the formyl radical which then serves as the precursor for formaldehyde and polymerization of longer hydrocarbon chains.

A noniterative asymmetric triple excitation correction for the density-fitted coupled-cluster singles and doubles method: Preliminary applications

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

Bozkaya, Uğur, E-mail: ugrbzky@gmail.com

2016-04-14

An efficient implementation of the asymmetric triples correction for the coupled-cluster singles and doubles [ΛCCSD(T)] method [S. A. Kucharski and R. J. Bartlett, J. Chem. Phys. 108, 5243 (1998); T. D. Crawford and J. F. Stanton, Int. J. Quantum Chem. 70, 601 (1998)] with the density-fitting [DF-ΛCCSD(T)] approach is presented. The computational time for the DF-ΛCCSD(T) method is compared with that of ΛCCSD(T). Our results demonstrate that the DF-ΛCCSD(T) method provide substantially lower computational costs than ΛCCSD(T). Further application results show that the ΛCCSD(T) and DF-ΛCCSD(T) methods are very beneficial for the study of single bond breaking problems as wellmore » as noncovalent interactions and transition states. We conclude that ΛCCSD(T) and DF-ΛCCSD(T) are very promising for the study of challenging chemical systems, where the coupled-cluster singles and doubles with perturbative triples method fails.« less

Metal-Free Multiple Carbon-Carbon and Carbon-Hydrogen Bond Activations via Charge-Switching Mechanism in Unstrained Diindolylmethanes.

PubMed

Challa, Chandrasekhar; Varughese, Sunil; Suresh, Cherumuttathu H; Lankalapalli, Ravi S

2017-08-18

A transformation of the unstrained phenol substituted 3,3'-diindolylmethanes (DIPMs) to 2,3'-diindolylketones (DIKs) by double C-C single bond cleavage with associated rearrangements, triggered by phenyliodine(III) diacetate (PIDA), is reported. Density functional theory studies reveal a mechanism involving multiple "charge-switching" steps by synergistic involvement of the two indole units with overall low activation energy. The indole 'charge-switching' mechanism in DIPMs was further extended toward synthesis of a natural product motif cyclohepta[b]indole from biaryl appended DIBM.

The 1-((diorganooxyphosphonyl)-methyl)-2,4- and -2,6-diamido benzenes

NASA Technical Reports Server (NTRS)

Mikroyannidis, John A. (Inventor); Kourtides, Demetrius A. (Inventor)

1989-01-01

1-((Diorgano oxyphosphonyl) methyl)-2,4- and -2,6-dinitro and diamino benzenes are prepared by nitrating an (organophosphonyl) methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo grounds (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids (HO)2P(double bond O)single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

Some 1-(diorganooxyphosphonyl)methyl-2,4- and -2,6-dinitro-benzenes

NASA Technical Reports Server (NTRS)

Mikroyannidis, John A. (Inventor); Kourtides, Demetrius A. (Inventor)

1989-01-01

1-(Diorgano oxyphosphonyl) methyl) 2,4- and 2,6-dinitro- and diamino benzenes are prepared by nitrating an (organophosphonyl)methly benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo group (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids, (HO)2P(double bond O) single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

Selective aliphatic carbon-hydrogen bond activation of protected alcohol substrates by cytochrome P450 enzymes.

PubMed

Bell, Stephen G; Spence, Justin T J; Liu, Shenglan; George, Jonathan H; Wong, Luet-Lok

2014-04-21

Protected cyclohexanol and cyclohex-2-enol substrates, containing benzyl ether and benzoate ester moieties, were designed to fit into the active site of the Tyr96Ala mutant of cytochrome P450cam. The protected cyclohexanol substrates were efficiently and selectively hydroxylated by the mutant enzyme at the trans C-H bond of C-4 on the cyclohexyl ring. The selectivity of oxidation of the benzoate ester protected cyclohexanol could be altered by making alternative amino acid substitutions in the P450cam active site. The addition of the double bond in the cyclohexyl ring of the benzoate ester protected cyclohex-2-enol has a debilitative effect on the activity of the Tyr96Ala mutant with this substrate. However, the Phe87Ala/Tyr96Phe double mutant, which introduces space at a different location in the active site than the Tyr96Ala mutant, was able to efficiently hydroxylate the C-H bonds of 1-cyclohex-2-enyl benzoate at the allylic C-4 position. Mutations at Phe87 improved the selectivity of the oxidation of 1-phenyl-1-cyclohexylethylene to trans-4-phenyl-ethenylcyclohexanol (92%) when compared to single mutants at Tyr96 of P450cam.

An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

NASA Astrophysics Data System (ADS)

Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

2012-12-01

The crystal chemistry of armenite, ideally BaCa2Al6Si9O30.2H2O, a double-ring structure belonging to the milarite group, was studied to better understand the nature of extra-framework "Ca-oxygen-anion-H2O-molecule quasi-clusters" and H bonding behavior in microporous silicates. Neutron and X-ray single-crystal diffraction and IR powder and 1H NMR spectroscopic measurements were made. Four crystallographically independent Ca and H2O molecule sites were refined from the diffraction data, whereby both sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming a quasi cluster around it. The neutron results give the first static description of the protons in armenite, allowing bond distances and angles relating to the H2O molecules and H bonds to be determined. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two broad bands at roughly 3470 and 3410 cm-1 and by a single H2O bending mode at 1654 cm-1. At 10 K four intense OH bands are located at 3479, 3454, 3401 and 3384 cm-1 and two H2O bending modes at 1650 and 1606 cm-1. The 1H MAS NMR spectrum shows a single strong resonance near 5.3 ppm and a smaller one near 2.7 ppm. The former can be assigned to H2O molecules bonded to Ca and the latter to weakly bonded H2O located at a site at the center of the structural double ring and it is partially occupied. The nature of H bonding in the microporous Ca-bearing zeolites scolecite, wairakite and epistilbite are also analyzed. The average OH stretching wavenumber shown by the IR spectra of armenite (~3435 cm-1) and scolecite (~3430 cm-1) are similar, while the average OH wavenumbers for wairakite (~3475 cm-1) and epistilbite (~3500 cm-1) are greater. In all cases the average OH stretching wavenumber is more similar to that of liquid water (~3400 cm-1) than of ice (~3220 cm-1). The strength of hydrogen bonding of the H2O molecules in microporous silicates does not appear to change greatly with decreasing temperatures from 300 K down to 10 K. The reason for this and also understanding better the ion-dipole interaction and its effect on H-bonding strength in Ca-quasi clusters need further study. The crystal structure of armenite viewed down [001] and [010].

Piperidine-1-carboximidamide

PubMed Central

Tiritiris, Ioannis

2012-01-01

In the title compound, C6H13N3, the C=N and C—N bond lengths in the CN3 unit are 1.3090 (17), and 1.3640 (17) (C–NH2) and 1.3773 (16) Å, indicating double- and single-bond character, respectively. The N—C—N angles are 116.82 (12), 119.08 (11) and 124.09 (11)°, showing a deviation of the CN3 plane from an ideal trigonal–planar geometry. The piperidine ring is in a chair conformation. In the crystal, mol­ecules are linked by N—H⋯N hydrogen bonds, forming a two-dimensional network along the ac plane. PMID:23284550

Systematic oxidation of polystyrene by ultraviolet-ozone, characterized by near-edge X-ray absorption fine structure and contact angle.

PubMed

Klein, Robert J; Fischer, Daniel A; Lenhart, Joseph L

2008-08-05

The process of implanting oxygen in polystyrene (PS) via exposure to ultraviolet-ozone (UV-O) was systematically investigated using the characterization technique of near-edge X-ray absorption fine structure (NEXAFS). Samples of PS exposed to UV-O for 10-300 s and washed with isopropanol were analyzed using the carbon and oxygen K-edge NEXAFS partial electron yields, using various retarding bias voltages to depth-profile the oxygen penetration into the surface. Evaluation of reference polymers provided a scale to quantify the oxygen concentration implanted by UV-O treatment. We find that ozone initially reacts with the double bonds on the phenyl rings, forming carbonyl groups, but within 1 min of exposure, the ratio of double to single oxygen bonds stabilizes at a lower value. Oxygen penetrates the film with relative ease, creating a fairly uniform distribution of oxygen within at least the first 4 nm (the effective depth probed by NEXAFS here). Before oxygen accumulates in large concentrations, however, it preferentially degrades the uppermost layer of the film by removing oxygenated low-molecular-weight oligomers. The failure to accumulate high concentrations of oxygen is seen in the nearly constant carbon edge jump, the low concentration of oxygen even at 5 min exposure (58% of that in poly(4-acetoxystyrene), the polymer with the most similarities to UV-O-treated PS), and the relatively high contact angles. At 5 min exposure the oxygen concentration contains ca. 7 atomic % oxygen. The oxygen species that are implanted consist predominantly of single O-C bonds and double O=C bonds but also include a small fraction of O-H. UV-O treatment leads a plateau after 2 min exposure in the water contact angle hysteresis, at a value of 67 +/- 2 degrees , due primarily to chemical heterogeneity. Annealing above T(g) allows oxygenated species to move short distances away from the surface but not diffuse further than 1-2 nm.

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

ERIC Educational Resources Information Center

Grayson, Scott M.

2012-01-01

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

N,N,N′,N′-Tetra­methyl­guanidinium tetra­phenyl­borate

PubMed Central

Tiritiris, Ioannis

2012-01-01

In the title salt, C5H14N3 +·C24H20B−, the C—N bond lengths in the central CN3 unit are 1.3322 (11), 1.3385 (12) and 1.3422 (12) Å, indicating partial double-bond character. The central C atom is bonded to the three N atoms in a nearly ideal trigonal-planar geometry [N—C—N angles = 119.51 (8), 119.81 (9) and 120.69 (8)°] and the positive charge is delocalized in the CN3 plane. The bond lengths between the N atoms and the terminal methyl groups all have values close to a typical single bond [1.4597 (12)–1.4695 (13) Å]. The crystal packing is caused by electrostatic inter­actions between cations and anions. PMID:23476307

Understanding Rotation about a C=C Double Bond

ERIC Educational Resources Information Center

Barrows, Susan E.; Eberlein, Thomas H.

2005-01-01

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

Superplastic Forming/Diffusion Bonding Without Interlayer of 5A90 Al-Li Alloy Hollow Double-Layer Structure

NASA Astrophysics Data System (ADS)

Jiang, Shaosong; Jia, Yong; Lu, Zhen; Shi, Chengcheng; Zhang, Kaifeng

2017-09-01

The hollow double-layer structure of 5A90 Al-Li alloy was fabricated by SPF/DB process in this study. The characteristics and mechanism of 5A90 Al-Li alloy with respect to superplasticity and diffusion bonding were investigated. Tensile tests showed that the optimal elongation of tensile specimens was 243.97% at the temperature of 400 °C and the strain rate of 0.001 s-1. Effect of the surface roughness, bonding temperature and bonding time to determine the microstructure and mechanical properties of diffusion bonding joints was investigated, and the optimum bonding parameters were 540 °C/2.5 h/Ra18. Through the finite element simulation, it could be found that the SPF/DB process of hollow double-layer structure was feasible. The hollow double-layer structure of 5A90 Al-Li alloy was manufactured, showing that the thickness distribution of the bonding area was uniform and the thinnest part was the round corner. The SEM images of diffusion bonding joints showed that sound bonding interfaces were obtained in which no discontinuity existed.

Infrared and Raman Spectroscopy: A Discovery-Based Activity for the General Chemistry Curriculum

ERIC Educational Resources Information Center

Borgsmiller, Karen L.; O'Connell, Dylan J.; Klauenberg, Kathryn M.; Wilson, Peter M.; Stromberg, Christopher J.

2012-01-01

A discovery-based method is described for incorporating the concepts of IR and Raman spectroscopy into the general chemistry curriculum. Students use three sets of springs to model the properties of single, double, and triple covalent bonds. Then, Gaussian 03W molecular modeling software is used to illustrate the relationship between bond…

Microwave emulations and tight-binding calculations of transport in polyacetylene

NASA Astrophysics Data System (ADS)

Stegmann, Thomas; Franco-Villafañe, John A.; Ortiz, Yenni P.; Kuhl, Ulrich; Mortessagne, Fabrice; Seligman, Thomas H.

2017-01-01

A novel approach to investigate the electron transport of cis- and trans-polyacetylene chains in the single-electron approximation is presented by using microwave emulation measurements and tight-binding calculations. In the emulation we take into account the different electronic couplings due to the double bonds leading to coupled dimer chains. The relative coupling constants are adjusted by DFT calculations. For sufficiently long chains a transport band gap is observed if the double bonds are present, whereas for identical couplings no band gap opens. The band gap can be observed also in relatively short chains, if additional edge atoms are absent, which cause strong resonance peaks within the band gap. The experimental results are in agreement with our tight-binding calculations using the nonequilibrium Green's function method. The tight-binding calculations show that it is crucial to include third nearest neighbor couplings to obtain the gap in the cis-polyacetylene.

Partially linearized external models to active-space coupled-cluster through connected hextuple excitations.

PubMed

Xu, Enhua; Ten-No, Seiichiro L

2018-06-05

Partially linearized external models to active-space coupled-cluster through hextuple excitations, for example, CC{SDtqph} L , CCSD{tqph} L , and CCSD{tqph} hyb, are implemented and compared with the full active-space CCSDtqph. The computational scaling of CCSDtqph coincides with that for the standard coupled-cluster singles and doubles (CCSD), yet with a much large prefactor. The approximate schemes to linearize the external excitations higher than doubles are significantly cheaper than the full CCSDtqph model. These models are applied to investigate the bond dissociation energies of diatomic molecules (HF, F 2 , CuH, and CuF), and the potential energy surfaces of the bond dissociation processes of HF, CuH, H 2 O, and C 2 H 4 . Among the approximate models, CCSD{tqph} hyb provides very accurate descriptions compared with CCSDtqph for all of the tested systems. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

A P-H functionalized Al/P-based frustrated Lewis pair - hydrophosphination of nitriles, ring opening with cyclopropenones and evidence of P[double bond, length as m-dash]C double bond formation.

PubMed

Keweloh, Lukas; Aders, Niklas; Hepp, Alexander; Pleschka, Damian; Würthwein, Ernst-Ulrich; Uhl, Werner

2018-06-12

Hydroalumination of R-P(H)-C[triple bond, length as m-dash]C-tBu with bulky H-Al[CH(SiMe3)2]2 afforded the new P-H functionalized Al/P-based frustrated Lewis pair R-P(H)-C[[double bond, length as m-dash]C(H)-tBu]-AlR2 [R = CH(SiMe3)2; FLP 7]. A weak adduct of 7 with benzonitrile (8) was detected by NMR spectroscopy, but could not be isolated. tert-Butyl isocyanide afforded a similar, but isolable adduct (9), in which the isocyanide C atom was coordinated to aluminium. The unique reactivity of 7 became evident from its reactions with the heteroatom substituted nitriles PhO-C[triple bond, length as m-dash]N, PhCH2S-C[triple bond, length as m-dash]N and H8C4N-C[triple bond, length as m-dash]N. Hydrophosphination of the C[triple bond, length as m-dash]N triple bonds afforded imines at room temperature which were coordinated to the FLP by Al-N and P-C bonds to yield AlCPCN heterocycles (10 to 12). These processes depend on substrate activation by the FLP. Diphenylcyclopropenone and its sulphur derivative reacted with 7 by addition of the P-H bond to a C-C bond of the strained C3 ring and ring opening to afford the fragment (Z)-Ph-C(H)[double bond, length as m-dash]C(Ph)-C-X-Al (X = O, S). The C-O or C-S groups were coordinated to the FLP to yield AlCPCX heterocycles (13 and 14). The thiocarbonyl derived compound 14 contains an internally stabilized phosphenium cation with a localized P[double bond, length as m-dash]C bond, a trigonal planar coordinated P atom and a short P[double bond, length as m-dash]C distance (168.9 pm). Insight into formation mechanisms, the structural and energetic properties of FLP 7 and compounds 13 and 14 was gained by quantum chemical DFT calculations.

Laser performance and modeling of RE3+:YAG double-clad crystalline fiber waveguides

NASA Astrophysics Data System (ADS)

Li, Da; Lee, Huai-Chuan; Meissner, Stephanie K.; Meissner, Helmuth E.

2018-02-01

We report on laser performance of ceramic Yb:YAG and single crystal Tm:YAG double-clad crystalline fiber waveguide (CFW) lasers towards the goal of demonstrating the design and manufacturing strategy of scaling to high output power. The laser component is a double-clad CFW, with RE3+:YAG (RE = Yb, Tm respectively) core, un-doped YAG inner cladding, and ceramic spinel or sapphire outer cladding. Laser performance of the CFW has been demonstrated with 53.6% slope efficiency and 27.5-W stable output power at 1030-nm for Yb:YAG CFW, and 31.6% slope efficiency and 46.7-W stable output power at 2019-nm for Tm:YAG CFW, respectively. Adhesive-Free Bond (AFB®) technology enables a designable refractive index difference between core and inner cladding, and designable core and inner cladding sizes, which are essential for single transverse mode CFW propagation. To guide further development of CFW designs, we present thermal modeling, power scaling and design of single transverse mode operation of double-clad CFWs and redefine the single-mode operation criterion for the double-clad structure design. The power scaling modeling of double-clad CFW shows that in order to achieve the maximum possible output power limited by the physical properties, including diode brightness, thermal lens effect, and simulated Brillion scattering, the length of waveguide is in the range of 0.5 2 meters. The length of an individual CFW is limited by single crystal growth and doping uniformity to about 100 to 200 mm lengths, and also by availability of starting crystals and manufacturing complexity. To overcome the limitation of CFW lengths, end-to-end proximity-coupling of CFWs is introduced.

Design fabrication and test of graphite/polyimide composite joints and attachments for advanced aerospace vehicles

NASA Technical Reports Server (NTRS)

1979-01-01

Graphite/polyimide (Gr/PI) bolted and bonded joints were investigated. Possible failure modes and the design loads for the four generic joint types are discussed. Preliminary sizing of a type 1 joint, bonded and bolted configuration is described, including assumptions regarding material properties and sizing methodology. A general purpose finite element computer code is described that was formulated to analyze single and double lap joints, with and without tapered adherends, and with user-controlled variable element size arrangements. An initial order of Celion 6000/PMR-15 prepreg was received and characterized.

(But­oxy­methyl­idene)di­methyl­aza­nium tetra­phenyl­borate aceto­nitrile monosolvate

PubMed Central

Tiritiris, Ioannis; Saur, Stefan; Kantlehner, Willi

2014-01-01

In the title solvated salt, C7H16NO+·C24H20B−·C2H3N, the C—N bond lengths in the cation are 1.2831 (19), 1.467 (2) and 1.465 (2) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.2950 (18) Å shows a double-bond character, pointing towards charge delocalization within the NCO plane of the iminium ion. The two C atoms of the n-butyl group are disordered over the two sites, with refined occupancy ratios of 0.890 (5):0.110 (5) and 0.888 (4):0.112 (4). In the crystal, C—H⋯π inter­actions occur between the methine H atom, H atoms of the –N(CH3)2 and –CH2 groups of the cation, and two of the phenyl rings of the tetra­phenyl­borate anion. The latter inter­action forms an aromatic pocket in which the cation is embedded. Thus, a two-dimensional pattern is created in the ac plane. PMID:24826158

Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine–acetylene hydrogen-bonded complex

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

Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu

2015-09-14

a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pairmore » of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.« less

Formation of conjugated delta8,delta10-double bonds by delta12-oleic-acid desaturase-related enzymes: biosynthetic origin of calendic acid.

PubMed

Cahoon, E B; Ripp, K G; Hall, S E; Kinney, A J

2001-01-26

Divergent forms of the plant Delta(12)-oleic-acid desaturase (FAD2) have previously been shown to catalyze the formation of acetylenic bonds, epoxy groups, and conjugated Delta(11),Delta(13)-double bonds by modification of an existing Delta(12)-double bond in C(18) fatty acids. Here, we report a class of FAD2-related enzymes that modifies a Delta(9)-double bond to produce the conjugated trans-Delta(8),trans-Delta(10)-double bonds found in calendic acid (18:3Delta(8trans,10trans,12cis)), the major component of the seed oil of Calendula officinalis. Using an expressed sequence tag approach, cDNAs for two closely related FAD2-like enzymes, designated CoFADX-1 and CoFADX-2, were identified from a C. officinalis developing seed cDNA library. The deduced amino acid sequences of these polypeptides share 40-50% identity with those of other FAD2 and FAD2-related enzymes. Expression of either CoFADX-1 or CoFADX-2 in somatic soybean embryos resulted in the production of calendic acid. In embryos expressing CoFADX-2, calendic acid accumulated to as high as 22% (w/w) of the total fatty acids. In addition, expression of CoFADX-1 and CoFADX-2 in Saccharomyces cerevisiae was accompanied by calendic acid accumulation when induced cells were supplied exogenous linoleic acid (18:2Delta(9cis,12cis)). These results are thus consistent with a route of calendic acid synthesis involving modification of the Delta(9)-double bond of linoleic acid. Regiospecificity for Delta(9)-double bonds is unprecedented among FAD2-related enzymes and further expands the functional diversity found in this family of enzymes.

Nucleation-dependant chemical bonding paradigm: the effect of rare earth ions on the nucleation of urea in aqueous solution.

PubMed

Chen, Xiaoyan; Sun, Congting; Wu, Sixin; Xue, Dongfeng

2017-03-29

Rare earth ions can be used to construct a variety of novel structures and are favorable to chemical bonding regulation and design. In this study, the chemical bonding paradigm between rare earth ions (Ln 3+ ) and urea molecules in an aqueous solution can be tracked by the evolution of C[double bond, length as m-dash]O, NH 2 , and CN vibration bands during the urea nucleation stage. Rare earth ions such as La 3+ , Gd 3+ , and Lu 3+ can manipulate the nucleation time of urea via regulating the nucleation-dependant N-C[double bond, length as m-dash]OH-N hydrogen-bonding between urea molecules. Two types of chemical bondings between Ln 3+ and urea molecules have been confirmed, which are Ln 3+ O[double bond, length as m-dash]C-N and Ln 3+ NH 2 -C. Compared with Ln 3+ NH 2 -C, Ln 3+ prefers to coordinate with the O[double bond, length as m-dash]C bond in urea. With a higher concentration of rare earth ions in the solution, some N-C[double bond, length as m-dash]OH-N hydrogen bonds are broken as a consequence of the incorporation of Ln 3+ into the lattice, resulting in the decreased symmetry of local urea molecules in the crystalline nuclei and the consequent Ln 3+ concentration-dependent nucleation time of urea. Moreover, using the ionic electronegativity scale of Ln 3+ , the different effects of La 3+ , Gd 3+ , and Lu 3+ on urea nucleation can be further distinguished. The present study provides basic data for unrevealing the chemical bonding regulation role of rare earth ions in the formation of hydrogen bonded materials, which may give insight into the design and fabrication of novel materials utilizing rare earth ions to adjust the chemical bonding process.

Test and analysis of Celion 3000/PMR-15, graphite/polyimide bonded composite joints: Data report

NASA Technical Reports Server (NTRS)

Cushman, J. B.; Mccleskey, S. F.; Ward, S. H.

1982-01-01

Standard single lap, double lap and symmetric step lap bonded joints of Celion 3000/PMR-15 graphite/polyimide composite were evaluated. Composite to composite and composite to titanium joints were tested at 116 K (-250 F), 294 K (70 F) and 561 K (550 F). Joint parameters evaluated are lap length, adherend thickness, adherend axial stiffness, lamina stacking sequence and adherend tapering. Advanced joint concepts were examined to establish the change in performance of preformed adherends, scalloped adherends and hybrid systems. The material properties of the high temperature adhesive, designated A7F, used for bonding were established. The bonded joint tests resulted in interlaminar shear or peel failures of the composite and there were very few adhesive failures. Average test results agree with expected performance trends for the various test parameters. Results of finite element analyses and of test/analysis correlations are also presented.

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

PubMed

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

2015-11-11

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

The selective activation of a C-F bond with an auxiliary strong Lewis acid: a method to change the activation preference of C-F and C-H bonds.

PubMed

Wang, Lin; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

2016-11-15

The selective activation of the C-F bonds in substituted (2,6-difluorophenyl)phenylimines (2,6-F 2 H 3 C 6 -(C[double bond, length as m-dash]NH)-n'-R-C 6 H 4 (n' = 2, R = H (1); n' = 2, R = Me (2); n' = 4, R = tBu (3))) by Fe(PMe 3 ) 4 with an auxiliary strong Lewis acid (LiBr, LiI, or ZnCl 2 ) was explored. As a result, iron(ii) halides ((H 5 C 6 -(C[double bond, length as m-dash]NH)-2-FH 3 C 6 )FeX(PMe 3 ) 3 (X = Br (8); Cl (9)) and (n-RH 4 C 6 -(C[double bond, length as m-dash]NH)-2'-FH 3 C 6 )FeX(PMe 3 ) 3 (n = 2, R = Me, X = Br (11); n = 4, R = tBu, X = I (12))) were obtained. Under similar reaction conditions, using LiBF 4 instead of LiBr or ZnCl 2 , the reaction of (2,6-difluorophenyl)phenylimine with Fe(PMe 3 ) 4 afforded an ionic complex [(2,6-F 2 H 3 C 6 -(C[double bond, length as m-dash]NH)-H 4 C 6 )Fe(PMe 3 ) 4 ](BF 4 ) (10) via the activation of a C-H bond. The method of C-F bond activation with an auxiliary strong Lewis acid is appropriate for monofluoroarylmethanimines. Without the Lewis acid, iron(ii) hydrides ((2-RH 4 C 6 -(C[double bond, length as m-dash]NH)-2'-FH 3 C 6 )FeH(PMe 3 ) 3 (R = H (13); Me (14))) were generated from the reactions of Fe(PMe 3 ) 4 with the monofluoroarylmethanimines (2-FH 4 C 6 -(C[double bond, length as m-dash]NH)-2'-RC 6 H 4 (R = H (4); Me (5))); however, in the presence of ZnCl 2 or LiBr, iron(ii) halides ((2-RH 4 C 6 -(C[double bond, length as m-dash]NH)-H 4 C 6 )FeX(PMe 3 ) 3 (R = H, X = Cl (15); R = Me, X = Br (16))) could be obtained through the activation of a C-F bond. Furthermore, a C-F bond activation with good regioselectivity in (pentafluorophenyl)arylmethanimines (F 5 C 6 -(C[double bond, length as m-dash]NH)-2,6-Y 2 C 6 H 3 (Y = F (6); H (7))) could be realized in the presence of ZnCl 2 to produce iron(ii) chlorides ((2,6-Y 2 H 3 C 6 -(C[double bond, length as m-dash]NH)-F 4 C 6 )FeCl(PMe 3 ) 3 (Y = F (17); H (18))). This series of iron(ii) halides could be used to catalyze the hydrosilylation reaction of aldehydes. Due to the stability of iron(ii) halides to high temperature, the reaction mixture was allowed to be heated to 100 °C and the reaction could finish within 0.5 h.

Mapping the Excited State Potential Energy Surface of a Retinal Chromophore Model with Multireference and Equation-of-Motion Coupled-Cluster Methods.

PubMed

Gozem, Samer; Melaccio, Federico; Lindh, Roland; Krylov, Anna I; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

2013-10-08

The photoisomerization of the retinal chromophore of visual pigments proceeds along a complex reaction coordinate on a multidimensional surface that comprises a hydrogen-out-of-plane (HOOP) coordinate, a bond length alternation (BLA) coordinate, a single bond torsion and, finally, the reactive double bond torsion. These degrees of freedom are coupled with changes in the electronic structure of the chromophore and, therefore, the computational investigation of the photochemistry of such systems requires the use of a methodology capable of describing electronic structure changes along all those coordinates. Here, we employ the penta-2,4-dieniminium (PSB3) cation as a minimal model of the retinal chromophore of visual pigments and compare its excited state isomerization paths at the CASSCF and CASPT2 levels of theory. These paths connect the cis isomer and the trans isomer of PSB3 with two structurally and energetically distinct conical intersections (CIs) that belong to the same intersection space. MRCISD+Q energy profiles along these paths provide benchmark values against which other ab initio methods are validated. Accordingly, we compare the energy profiles of MRPT2 methods (CASPT2, QD-NEVPT2, and XMCQDPT2) and EOM-SF-CC methods (EOM-SF-CCSD and EOM-SF-CCSD(dT)) to the MRCISD+Q reference profiles. We find that the paths produced with CASSCF and CASPT2 are topologically and energetically different, partially due to the existence of a "locally excited" region on the CASPT2 excited state near the Franck-Condon point that is absent in CASSCF and that involves a single bond, rather than double bond, torsion. We also find that MRPT2 methods as well as EOM-SF-CCSD(dT) are capable of quantitatively describing the processes involved in the photoisomerization of systems like PSB3.

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.

Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation

DOE PAGES

Zaporozhets, Irina A.; Ivanov, Vladimir V.; Lyakh, Dmitry I.; ...

2015-07-13

The earlier proposed multi-reference state-specific coupled-cluster theory with the complete active space reference suffered from a problem of energy discontinuities when the formal reference state was changing in the calculation of the potential energy curve (PEC). A simple remedy to the discontinuity problem is found and is presented in this work. It involves using natural complete active space self-consistent field active orbitals in the complete active space coupled-cluster calculations. As a result, the approach gives smooth PECs for different types of dissociation problems, as illustrated in the calculations of the dissociation of the single bond in the hydrogen fluorine moleculemore » and of the symmetric double-bond dissociation in the water molecule.« less

Programming Recognition Arrays through Double Chalcogen-Bonding Interactions.

PubMed

Biot, Nicolas; Bonifazi, Davide

2018-04-11

In this work, we have programmed and synthesized a recognition motif constructed around a chalcogenazolo-pyridine scaffold (CGP) that, through the formation of frontal double chalcogen-bonding interactions, associates into dimeric EX-type complexes. The reliability of the double chalcogen-bonding interaction has been shown at the solid-state by X-ray analysis, depicting the strongest recognition persistence for a Te-congener. The high recognition fidelity, chemical and thermal stability and easy derivatization at the 2-position makes CGP a convenient motif for constructing supramolecular architectures through programmed chalcogen-bonding interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoisomerization in bacteriorhodopsin studied by FTIR, linear dichroism and photoselection experiments combined with quantum chemical theoretical analysis

NASA Astrophysics Data System (ADS)

Fahmy, K.; Siebert, F.; Großjean, M. F.; Tavan, P.

1989-12-01

Orientations of IR transition moments of the retinal chromophore of bacteriorhodopsin (BR) and of the apo-protein are investigated by FTIR linear dichroism and photoselection measurements. Low temperature difference spectra for the photoinduced transitions of BR to its photocycle intermediates K and L are evaluated using improved methods. Quantum chemical calculations of directions of IR and electronic transition moments of model chromophores are employed to analyze corresponding observations. The chromophore of light-adapted BR 568 is shown to exhibit small (15-30°) twists around the CC single bonds of retinals polyene chain but no large overall helicity (⩽15°). The average retinal plane is demonstrated to form an angle of 90±20° with the plane of the purple membrane. The C 9C 10 double bond of retinal is found approximately parallel to the plane of the membrane. Upon photoisomerization the orientation of the chromophore moiety from C 1 to C 13 is estimated to be largely conserved. The single bond twists of the chromophore in L are shown to be larger than those in BR 568. This result is in agreement with the previous prediction of increased single bond twists in L, which can cause a p K decrease of the chromophore and, thereby, enforce its deprotonation in the L→M transition [Schulten and Tavan, Nature, 272 (1978) 85].

Insights into structure and activity of natural compound inhibitors of pneumolysin

PubMed Central

Li, Hongen; Zhao, Xiaoran; Deng, Xuming; Wang, Jianfeng; Song, Meng; Niu, Xiaodi; Peng, Liping

2017-01-01

Pneumolysin is the one of the major virulence factor of the bacterium Streptococcus pneumoniae. In previous report, it is shown that β-sitosterol, a natural compound without antimicrobial activity, is a potent antagonist of pneumolysin. Here, two new pneumolysin natural compound inhibitors, with differential activity, were discovered via haemolysis assay. To explore the key factor of the conformation for the inhibition activity, the interactions between five natural compound inhibitors with differential activity and pneumolysin were reported using molecular modelling, the potential of mean force profiles. Interestingly, it is found that incorporation of the single bond (C22-C23-C24-C25) to replace the double bond (hydrocarbon sidechain) improved the anti-haemolytic activity. In view of the molecular modelling, binding of the five inhibitors to the conserved loop region (Val372, Leu460, and Tyr461) of the cholesterol binding sites led to stable complex systems, which was consistent with the result of β-sitosterol. Owing to the single bond (C22-C23-C24-C25), campesterol and brassicasterol could form strong interactions with Val372 and show higher anti-haemolytic activity, which indicated that the single bond (C22-C23-C24-C25) in inhibitors was required for the anti-haemolytic activity. Overall, the current molecular modelling work provides a starting point for the development of rational design and higher activity pneumolysin inhibitors. PMID:28165051

Effective fragment potential study of the interaction of DNA bases.

PubMed

Smith, Quentin A; Gordon, Mark S; Slipchenko, Lyudmila V

2011-10-20

Hydrogen-bonded and stacked structures of adenine-thymine and guanine-cytosine nucleotide base pairs, along with their methylated analogues, are examined with the ab inito based general effective fragment potential (EFP2) method. A comparison of coupled cluster with single, double, and perturbative triple (CCSD(T)) energies is presented, along with an EFP2 energy decomposition to illustrate the components of the interaction energy.

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2015-04-22

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

The behavior of bonded doubler splices for composite sandwich panels

NASA Technical Reports Server (NTRS)

Zeller, T. A.; Weisahaar, T. A.

1980-01-01

The results of an investigation into the behavior of adhesively bonded doubler splices of two composite material sandwich panels are presented. The splices are studied from three approaches: analytical; numerical (finite elements); and experimental. Several parameters that characterize the splice are developed to determine their influence upon joint strength. These parameters are: doubler overlap length; core stiffness; laminate bending stiffness; the size of the gap between the spliced sandwich panels; and room and elevated temperatures. Similarities and contrasts between these splices and the physically similar single and double lap joints are discussed. The results of this investigation suggest several possible approaches to improving the strength of the sandwich splices.

Ground state structure of high-energy-density polymeric carbon monoxide

NASA Astrophysics Data System (ADS)

Xia, Kang; Sun, Jian; Pickard, Chris J.; Klug, Dennis D.; Needs, Richard J.

2017-04-01

Crystal structure prediction methods and first-principles calculations have been used to explore low-energy structures of carbon monoxide (CO). Contrary to the standard wisdom, the most stable structure of CO at ambient pressure was found to be a polymeric structure of P n a 21 symmetry rather than a molecular solid. This phase is formed from six-membered (four carbon + two oxygen) rings connected by C=C double bonds with two double-bonded oxygen atoms attached to each ring. Interestingly, the polymeric P n a 21 phase of CO has a much higher energy density than trinitrotoluene (TNT). On compression to about 7 GPa, P n a 21 is found to transform into another chainlike phase of C c symmetry which has similar ring units to P n a 21 . On compression to 12 GPa, it is energetically favorable for CO to polymerize into a purely single bonded C m c a phase, which is stable over a wide pressure range and transforms into the previously known C m c m phase at around 100 GPa. Thermodynamic stability of these structures was verified using calculations with different density functionals, including hybrid and van der Waals corrected functionals.

Triplet Excitation Transfer between Carotenoids in the LH2 Complex from Photosynthetic Bacterium Rhodopseudomonas palustris.

PubMed

Feng, Juan; Wang, Qian; Wu, Yi-Shi; Ai, Xi-Cheng; Zhang, Xu-Jia; Huang, You-Guo; Zhang, Xing-Kang; Zhang, Jian-Ping

2004-01-01

We have studied, by means of sub-microsecond time-resolved absorption spectroscopy, the triplet-excited state dynamics of carotenoids (Cars) in the intermediate-light adapted LH2 complex (ML-LH2) from Rhodopseudomonas palustris containing Cars with different numbers of conjugated double bonds. Following pulsed photo-excitation at 590 nm at room temperature, rapid spectral equilibration was observed either as a red shift of the isosbestic wavelength on a time scale of 0.6-1.0 mus, or as a fast decay in the shorter-wavelength side of the T(n)<--T(1) absorption of Cars with a time constant of 0.5-0.8 mus. Two major spectral components assignable to Cars with 11 and 12 conjugated double bonds were identified. The equilibration was not observed in the ML-LH2 at 77 K, or in the LH2 complex from Rhodobacter sphaeroides G1C containing a single type of Car. The unique spectral equilibration was ascribed to temperature-dependent triplet excitation transfer among different Car compositions. The results suggest that Cars of 11 and 12 conjugated bonds, both in close proximity of BChls, may coexist in an alpha,beta-subunit of the ML-LH2 complex.

Derivatization of carbonyl compounds with 2,4-dinitrophenylhydrazine and their subsequent determination by high-performance liquid chromatography.

PubMed

Uchiyama, Shigehisa; Inaba, Yohei; Kunugita, Naoki

2011-05-15

Derivatization of carbonyl compounds with 2,4-dinitrophenylhydrazine (DNPH) is one of the most widely used analytical methods. In this article, we highlight recent advances using DNPH provided by our studies over past seven years. DNPH reacts with carbonyls to form corresponding stable 2,4-DNPhydrazone derivatives (DNPhydrazones). This method may result in analytical error because DNPhydrazones have both E- and Z-stereoisomers caused by the CN double bond. Purified aldehyde-2,4-DNPhydrazone demonstrated only the E-isomer, but under UV irradiation and the addition of acid, both E- and Z-isomers were seen. In order to resolve the isometric problem, a method for transforming the CN double bond of carbonyl-2,4-DNPhydrazone into a C-N single bond, by reductive amination using 2-picoline borane, has been developed. The amination reactions of C1-C10 aldehyde DNPhydrazones are completely converted into the reduced forms and can be analyzed with high-performance liquid chromatography. As a new application using DNPH derivatization, the simultaneous measurement of carbonyls with carboxylic acids or ozone is described in this review. Copyright © 2010 Elsevier B.V. All rights reserved.

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

PubMed

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

2014-11-01

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

Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate

NASA Astrophysics Data System (ADS)

Ding, Aishun; Lu, Guolin; Guo, Hao; Huang, Xiaoyu

2017-03-01

A series of ABA triblock copolymers, consisting of double-bond-containing poly(phenoxyallene) (PPOA), poly(methyl methacrylate) (PMMA), or poly(butyl acrylate) (PBA) segments, were synthesized by sequential free radical polymerization and atom transfer radical polymerization (ATRP). A new bifunctional initiator bearing azo and halogen-containing ATRP initiating groups was first prepared followed by initiating conventional free radical homopolymerization of phenoxyallene with cumulated double bond to give a PPOA-based macroinitiator with ATRP initiating groups at both ends. Next, PMMA-b-PPOA-b-PMMA and PBA-b-PPOA-b-PBA triblock copolymers were synthesized by ATRP of methyl methacrylate and n-butyl acrylate initiated by the PPOA-based macroinitiator through the site transformation strategy. These double-bond-containing triblock copolymers are stable under UV irradiation and free radical circumstances.

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

PubMed

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

2016-10-07

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

Facile synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks under ambient conditions.

PubMed

Ding, San-Yuan; Cui, Xiao-Hui; Feng, Jie; Lu, Gongxuan; Wang, Wei

2017-10-31

We reported herein a facile approach for the synthesis of -C[double bond, length as m-dash]N- linked covalent organic frameworks under ambient conditions. Three known (COF-42, COF-43, and COF-LZU1) and one new (Pr-COF-42) COF materials were successfully synthesized using this method. Furthermore, this simple synthetic approach makes the large-scale synthesis of -C[double bond, length as m-dash]N- linked COFs feasible.

A facile and efficient method of enzyme immobilization on silica particles via Michael acceptor film coatings: immobilized catalase in a plug flow reactor.

PubMed

Bayramoglu, Gulay; Arica, M Yakup; Genc, Aysenur; Ozalp, V Cengiz; Ince, Ahmet; Bicak, Niyazi

2016-06-01

A novel method was developed for facile immobilization of enzymes on silica surfaces. Herein, we describe a single-step strategy for generating of reactive double bonds capable of Michael addition on the surfaces of silica particles. This method was based on reactive thin film generation on the surfaces by heating of impregnated self-curable polymer, alpha-morpholine substituted poly(vinyl methyl ketone) p(VMK). The generated double bonds were demonstrated to be an efficient way for rapid incorporation of enzymes via Michael addition. Catalase was used as model enzyme in order to test the effect of immobilization methodology by the reactive film surface through Michael addition reaction. Finally, a plug flow type immobilized enzyme reactor was employed to estimate decomposition rate of hydrogen peroxide. The highly stable enzyme reactor could operate continuously for 120 h at 30 °C with only a loss of about 36 % of its initial activity.

Effect of cationic substitution on the double-well hydrogen-bond potential in [K1-x(NH4)x]3H(SO4)2 proton conductors: a single-crystal neutron diffraction study.

PubMed

Choudhury, R R; Chitra, R; Selezneva, E V; Makarova, I P

2017-10-01

The structure of the mixed crystal [K 1-x (NH 4 ) x ] 3 H(SO 4 ) 2 as obtained from single-crystal neutron diffraction is compared with the previously reported room-temperature neutron structure of crystalline K 3 H(SO 4 ) 2 . The two structures are very similar, as indicated by the high value of their isostructurality index (94.8%). It was found that the replacement of even a small amount (3%) of K + with NH 4 + has a significant influence on the short strong hydrogen bond connecting the two SO 4 2- ions. Earlier optical measurements had revealed that the kinetics of the superionic transition in the solid solution [K 1-x (NH 4 ) x ] 3 H(SO 4 ) 2 are much faster than in K 3 H(SO 4 ) 2 ; this reported difference in the kinetics of the superionic phase transition in this class of crystal is explained on the basis of the difference in strength of the hydrogen-bond interactions in the two structures.

Zr 2Ir 6B with an eightfold superstructure of the cubic perovskite-like boride ZrIr 3B 0.5: Synthesis, crystal structure and bonding analysis

NASA Astrophysics Data System (ADS)

Hermus, Martin; Fokwa, Boniface P. T.

2010-04-01

Single phase powder samples and single crystals of Zr 2Ir 6B were successfully synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. Superstructure reflections were observed both on powder and on single crystal diffraction data, leading to an eightfold superstructure of ZrIr 3B x phase. The new phase, which has a metallic luster, crystallizes in space group Fm3¯m (no. 225) with the lattice parameters a=7.9903(4) Å, V=510.14(4) Å 3. Its crystal structure was refined on the basis of powder as well as single crystal data. The single crystal refinement converged to R1=0.0239 and w R2=0.0624 for all 88 unique reflections and 6 parameters. Zr 2Ir 6B is isotypic to Ti 2Rh 6B and its structure can be described as a defect double perovskite, A2BB' O6, where the A site is occupied by zirconium, the B site by boron, the O site by iridium but the B' site is vacant, leading to the formation of empty and boron-filled octahedral Ir 6 clusters. According to the result of tight-binding electronic structure calculations, Ir-B and Ir-Zr interactions are mainly responsible for the structural stability of the phase. According to COHP bonding analysis, the strongest bonding occurs for the Ir-B contacts, and the Ir-Ir bonding within the empty clusters is two times stronger than that in the BIr 6 octahedra.

The Existence of a Designer Al=Al Double Bond in the LiAl2 H4- Cluster Formed by Electronic Transmutation.

PubMed

Lundell, Katie A; Zhang, Xinxing; Boldyrev, Alexander I; Bowen, Kit H

2017-12-22

The Al=Al double bond is elusive in chemistry. Herein we report the results obtained via combined photoelectron spectroscopy and ab initio studies of the LiAl 2 H 4 - cluster that confirm the formation of a conventional Al=Al double bond. Comprehensive searches for the most stable structures of the LiAl 2 H 4 - cluster have shown that the global minimum isomer I possesses a geometric structure which resembles that of Si 2 H 4 , demonstrating a successful example of the transmutation of Al atoms into Si atoms by electron donation. Theoretical simulations of the photoelectron spectrum discovered the coexistence of two isomers in the ion beam, including the one with the Al=Al double bond. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereocontrolled Additions to a Rigid Bicyclo [3.3.0] Octane Ring System

DTIC Science & Technology

2008-05-05

bridgehead carbon. The metals studied were palladium, platinum, and the Raney nickel catalyst . The catalysts themselves are usually absorbed on an...Catalytic Hydrogenation Reaction The Raney nickel catalyst yielded extremely pure product in a single isomeric form when the reaction was run with...ethyl acetate was 68.7%, a noted increase over that obtained with the Raney nickel catalyst . 31 Disappearance of the double bond peak again

Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C 2H 4, C 2H 3F, and 1,1-C 2H 2F 2) near and above threshold

DOE PAGES

Gaire, B.; Gatton, A. S.; Wiegandt, F.; ...

2016-09-14

We have investigated bond-rearrangement driven by photo-double-ionization (PDI) near and above the double ionization threshold in a sequence of carbon-carbon double bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy (COLTRIMS) method to resolve all photo-double-ionization events leading to two-ionic fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of none, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing as evident by the re-ordering of the threshold energies of the PDI in the fluorinatedmore » molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molcules and drives bond-rearrangement during the dissociation process. The energy sharing and the relative angle between the 3D-momentum vectors of the two electrons provide clear evidence of direct and indirect PDI processes.« less

Ce and La single- and double-substitutional defects in yttrium aluminum garnet: first-principles study.

PubMed

Muñoz-García, Ana Belén; Seijo, Luis

2011-02-10

The atomistic structure, energetics, and electronic structure of single-substitutional Ce and La defects and double-substitutional Ce-La defects in Ce,La-codoped yttrium aluminum garnet (YAG) Y(3)Al(5)O(12) have been studied by means of first-principles periodic boundary conditions density functional theory calculations. Single substitution of Y by Ce or by La produces atomistic expansions around the impurities, which are significantly smaller than the ionic radii mismatches and the overall lattice distortions are found to be confined within their second coordination spheres. In double-substitutional defects, the impurities tend to be as close as possible. La-codoping Ce:YAG provokes an anisotropic expansion around Ce defects. The Ce impurity introduces 4f occupied states in the 5.0 eV computed gap of YAG, peaking 0.25 eV above the top of the valence band, and empty 4f, 5d, and 6s states starting at 3.8 eV in the gap and spreading over the conduction band. La-codoping produces very small effects on the electronic structure of Ce:YAG, the most visible one being the decrease in covalent bonding with one of the oxygen atoms, which shifts 0.05 Å away from Ce and gets 0.04 Å closer to La in the most stable Ce-La double-substitutional defect.

Utilisation of an eta(3)-allyl hydride complex, formed by UV irradiation, as a controlled source of 16-electron (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe).

PubMed

Sexton, Catherine J; López-Serrano, Joaquín; Lledós, Agustí; Duckett, Simon B

2008-10-21

Low temperature UV irradiation of solutions of (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe)(2) yields (eta(5)-C(5)Me(5))Rh(eta(3)-CH(2)CHCH(2))(H), which provides controlled access to the 16-electron fragment (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe).

Communication: Infrared spectroscopy of protonated allyl-trimethylsilane: Evidence for the β-silyl effect

NASA Astrophysics Data System (ADS)

Chiavarino, Barbara; Crestoni, Maria Elisa; Lemaire, Joel; Maitre, Philippe; Fornarini, Simonetta

2013-08-01

β-trimethylsilyl-2-propyl cation has been formed by the gas phase protonation of allyl-trimethylsilane and characterized by infrared multiple photon dissociation spectroscopy. The experimental Cβ-Cα+ stretching feature at 1586 cm-1, remarkably blue-shifted with respect to a C-C single bond stretching mode, is indicative of high double bond character, a signature of β-stabilizing effect due to hyperconjugation of the trimethylsilyl group in the β-position with respect to the positively charged carbon. Density functional theory calculations at the B3LYP/6-311++G(2df,2p) level yield the optimized geometries and IR spectra for candidate isomeric cations and for neutral and charged reference species.

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

Zaporozhets, Irina A.; Ivanov, Vladimir V.; Lyakh, Dmitry I.

The earlier proposed multi-reference state-specific coupled-cluster theory with the complete active space reference suffered from a problem of energy discontinuities when the formal reference state was changing in the calculation of the potential energy curve (PEC). A simple remedy to the discontinuity problem is found and is presented in this work. It involves using natural complete active space self-consistent field active orbitals in the complete active space coupled-cluster calculations. As a result, the approach gives smooth PECs for different types of dissociation problems, as illustrated in the calculations of the dissociation of the single bond in the hydrogen fluorine moleculemore » and of the symmetric double-bond dissociation in the water molecule.« less

IR spectroscopy as a source of data on bond strengths

NASA Astrophysics Data System (ADS)

Finkelshtein, E. I.; Shamsiev, R. S.

2018-02-01

The aim of this work is the estimation of double bond strength, namely Cdbnd O bonds in ketones and aldehydes and Cdbnd C bonds in various compounds. By the breaking of these bonds one or both fragments formed are carbenes, for which experimental data on the enthalpies of formation (ΔHf298) are scarce. Thus for the estimation of ΔHf298 of the corresponding carbenes, the empirical equations were proposed based on different approximations. In addition, a quantum chemical calculations of the ΔHf298 values of carbenes were performed, and the data obtained were compared with experimental values and the results of earlier calculations. Equations for the calculation of Cdbnd O bond strengths of different ketones and aldehydes from the corresponding stretching frequencies ν(Cdbnd O) were derived. Using the proposed equations, the strengths of Cdbnd O bonds of 25 ketones and 12 conjugated aldehydes, as well as Cdbnd C bonds of 13 hydrocarbons and 7 conjugated aldehydes were estimated for the first time. Linear correlations of Cdbnd C and Cdbnd O bond strengths with the bond lengths were established, and the equations permitting the estimation of the double bond strengths and lengths with acceptable accuracy were obtained. Also, the strength of central Cdbnd C bond of stilbene was calculated for the first time. The uncertainty of the strengths of double bonds obtained may be regarded as accurate ±10-15 kJ/mol.

Capture of SO3 isomers in the oxidation of sulfur monoxide with molecular oxygen.

PubMed

Wu, Zhuang; Lu, Bo; Feng, Ruijuan; Xu, Jian; Lu, Yan; Wan, Huabin; Eckhardt, André K; Schreiner, Peter R; Xie, Changjian; Guo, Hua; Zeng, Xiaoqing

2018-02-13

When mixing SO with O 2 in N 2 , Ne, or Ar, an end-on complex OS-OO forms in the gas phase and can subsequently be trapped at cryogenic temperatures (2.8-15.0 K). Upon infrared light irradiation, OS-OO converts to SO 3 and SO 2 + O with the concomitant formation of a rare 1,2,3-dioxathiirane 2-oxide, i.e., cyclic OS([double bond, length as m-dash]O)O. Unexpectedly, the ring-closure of 16 OS- 18 O 18 O yields a ca. 2 : 1 mixture of cyclic 18 OS([double bond, length as m-dash] 16 O) 18 O and 16 OS([double bond, length as m-dash] 18 O) 18 O. The characterization of OS-OO and OS([double bond, length as m-dash]O)O with IR and UV/Vis spectroscopy is supported by high-level ab initio computations.

N,N,N′,N′,N′′-Penta­methyl-N′′-[3-(1,3,3-trimethyl­ureido)prop­yl]guanidinium tetra­phenyl­borate

PubMed Central

Tiritiris, Ioannis; Kantlehner, Willi

2012-01-01

In the crystal structure of the title molecular salt, C13H30N5O+·C24H20B−, discrete guanidinium cations and tetra­phenyl­borate anions are present. The C—N bond lengths in the CN3 unit are 1.3427 (12), 1.3445 (12) and 1.3453 (13) Å, indicating double-bond character. The central C atom is surrounded in a nearly ideal trigonal-planar geometry by three N atoms and the positive charge is delocalized on the CN3 plane. The bonds between the N atoms and the terminal C-methyl groups all have values close to a typical single bond [1.4595 (15)–1.4688 (12) Å]. In the crystal, cations are connected by C—H⋯O contacts generating a chain along the c axis. PMID:22798881

Crystal structure of 2-bromo-3-di­methyl­amino-N,N,N′,N′,4-penta­methyl-4-(tri­methyl­sil­yloxy)pent-2-eneamidinium bromide

PubMed Central

Tiritiris, Ioannis; Kress, Ralf; Kantlehner, Willi

2015-01-01

The reaction of the ortho­amide 1,1,1-tris­(di­methyl­amino)-4-methyl-4-(tri­methyl­sil­yloxy)pent-2-yne with bromine in benzene, yields the title salt, C15H33BrN3OSi+·Br−. The C—N bond lengths in the amidinium unit are 1.319 (6) and 1.333 (6) Å, indicating double-bond character, pointing towards charge delocalization within the NCN plane. The C—Br bond length of 1.926 (5) Å is characteristic for a C—Br single bond. Additionally, there is a bromine–bromine inter­action [3.229 (3) Å] present involving the anion and cation. In the crystal, weak C—H⋯Br inter­actions between the methyl H atoms of the cation and the bromide ions are present. PMID:26870498

Detection and structural characterization of nitrosamide H2NNO: A central intermediate in deNOx processes.

PubMed

McCarthy, Michael C; Lee, Kin Long Kelvin; Stanton, John F

2017-10-07

The structure and bonding of H 2 NNO, the simplest N-nitrosamine, and a key intermediate in deNO x processes, have been precisely characterized using a combination of rotational spectroscopy of its more abundant isotopic species and high-level quantum chemical calculations. Isotopic spectroscopy provides compelling evidence that this species is formed promptly in our discharge expansion via the NH 2 + NO reaction and is collisionally cooled prior to subsequent unimolecular rearrangement. H 2 NNO is found to possess an essentially planar geometry, an NNO angle of 113.67(5)°, and a N-N bond length of 1.342(3) Å; in combination with the derived nitrogen quadrupole coupling constants, its bonding is best described as an admixture of uncharged dipolar (H 2 N-N=O, single bond) and zwitterion (H 2 N + =N-O - , double bond) structures. At the CCSD(T) level, and extrapolating to the complete basis set limit, the planar geometry appears to represent the minimum of the potential surface, although the torsional potential of this molecule is extremely flat.

Detection and structural characterization of nitrosamide H2NNO: A central intermediate in deNOx processes

NASA Astrophysics Data System (ADS)

McCarthy, Michael C.; Lee, Kin Long Kelvin; Stanton, John F.

2017-10-01

The structure and bonding of H2NNO, the simplest N-nitrosamine, and a key intermediate in deNOx processes, have been precisely characterized using a combination of rotational spectroscopy of its more abundant isotopic species and high-level quantum chemical calculations. Isotopic spectroscopy provides compelling evidence that this species is formed promptly in our discharge expansion via the NH2 + NO reaction and is collisionally cooled prior to subsequent unimolecular rearrangement. H2NNO is found to possess an essentially planar geometry, an NNO angle of 113.67(5)°, and a N-N bond length of 1.342(3) Å; in combination with the derived nitrogen quadrupole coupling constants, its bonding is best described as an admixture of uncharged dipolar (H2N-N=O, single bond) and zwitterion (H2N+=N-O-, double bond) structures. At the CCSD(T) level, and extrapolating to the complete basis set limit, the planar geometry appears to represent the minimum of the potential surface, although the torsional potential of this molecule is extremely flat.

Structural analysis by reductive cleavage with LiAlH4 of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri

PubMed Central

Nishihara, Masateru; Morii, Hiroyuki; Matsuno, Koji; Ohga, Mami; Stetter, Karl O.; Koga, Yosuke

2002-01-01

A choline-containing phospholipid (PL-4) in Methanopyrus kandleri cells was identified as archaetidylcholine, which has been described by Sprott et al. (1997). The PL-4 consisted of a variety of molecular species differing in hydrocarbon composition. Most of the PL-4 was acid-labile because of its allyl ether bond. The identity of PL-4 was confirmed by thin-layer chromatography (TLC) followed by positive staining with Dragendorff-reagent and fast-atom bombardment–mass spectrometry. A new method of LiAlH4 hydrogenolysis was developed to cleave allyl ether bonds and recover the corresponding hydrocarbons. We confirmed the validity of the LiAlH4 method in a study of the model compound synthetic unsaturated archaetidic acid (2,3-di-O-geranylgeranyl-sn-glycerol-1-phosphate). Saturated ether bonds were not cleaved by the LiAlH4 method. The hydrocarbons formed following LiAlH4 hydrogenolysis of PL-4 were identified by gas–liquid chromatography and mass spectrometry. Four kinds of hydrocarbons with one to four double bonds were detected: 47% of the hydrocarbons had four double bonds; 11% had three double bonds; 14% had two double bonds; 7% had one double bond; and 6% were saturated species. The molecular species composition of PL-4 was also estimated based on acid lability: 77% of the molecular species had two acid-labile hydrocarbons; 11% had one acid-labile and one acid-stable hydrocarbon; and 11% had two acid-stable hydrocarbons. To our knowledge, this is the first report of a specific chemical degradation method for the structural analysis of allyl ether phospholipid in archaea. PMID:15803650

Amylases and Their Importance during Glycan Degradation: Genome Sequence Release of Salmonella Amylase Knockout Strains.

PubMed

Arabyan, Narine; Huang, Bihua C; Weimer, Bart C

2017-05-18

Amylases catalyze the cleavage of α-d-1,4 and α-d-1,6-glycosidic bonds in starch and related carbohydrates. Amylases are widely distributed in nature and are important in carbohydrate metabolism. This is the release of four single and two double deletions in Salmonella enterica serovar Typhimurium LT2 that are important for glycan degradation during infection. Copyright © 2017 Arabyan et al.

Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

PubMed

Piou, Tiffany; Rovis, Tomislav

2015-11-05

Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

Molecular self-assembly in substituted alanine derivatives: XRD, Hirshfeld surfaces and DFT studies

NASA Astrophysics Data System (ADS)

Rajalakshmi, Periasamy; Srinivasan, Navaneethakrishnan; Sivaraman, Gandhi; Razak, Ibrahim Abdul; Rosli, Mohd Mustaqim; Krishnakumar, Rajaputi Venkatraman

2014-06-01

The molecular assemblage in the crystal structures of three modified chiral amino acids, two of which are isomeric D- and L-pairs boc-L-benzothienylalanine (BLA), boc-D-benzothienylalanine (BDA) and the other boc-D-naphthylalanine (NDA) differing from this pair very slightly in the chemical modification introduced, is accurately described. The aggregation of amino acid molecules is similar in all the crystals and may be described as a twisted double helical ladder in which two complementary long helical chains formed through O-H⋯O hydrogen bonds are interconnected through the characteristic head-to-tail N-H⋯O hydrogen bonds. Thus the molecular aggregation enabled through classical hydrogen bonds may be regarded as a mimic of the characteristic double helical structure of DNA. Also, precise structural information involving these amino acid molecules with lower symmetry exhibiting higher trigonal symmetry in their self-assembly is expected to throw light on the nature and strength of intermolecular interactions and their role in self-assembly of molecular aggregates, which are crucial in developing new or at least supplement existing crystal engineering strategies. Single crystal X-ray analysis and their electronic structures were calculated at the DFT level with a detailed analysis of Hirshfeld surfaces and fingerprint plots facilitating a comparison of intermolecular interactions in building different supramolecular architectures.

Hydridosilylamido complexes of Ta and Mo isolobal with Berry's zirconocenes: syntheses, β-Si-H agostic interactions, catalytic hydrosilylation, and insight into mechanism.

PubMed

McLeod, Nicolas A; Kuzmina, Lyudmila G; Korobkov, Ilia; Howard, Judith A K; Nikonov, Georgii I

2016-02-14

The syntheses of novel Group 5 and Group 6 hydrosilylamido complexes of the type R(ArN[double bond, length as m-dash])M{N((t)Bu)SiMe2-H}X (M = Ta, R = Cp; M = Mo, R = ArN; X = Cl, H, OBn, Me) are described. The various substituents in the X position seem to play the key role in determining the extent of β-agostic interaction with the Si-H bond. The Mo agostic hydrido complex (ArN[double bond, length as m-dash])2Mo{η(3)-N((t)Bu)SiMe2-H}H is a pre-catalyst for the hydrosilylation of carbonyls. The stoichiometric reaction between benzaldehyde and (ArN[double bond, length as m-dash])2Mo{η(3)-N((t)Bu)SiMe2-H}H gives the benzoxy complex (ArN[double bond, length as m-dash])2Mo{N((t)Bu)SiMe2-H}(OBn), which showed a similar catalytic reactivity compared to the parent hydride. Mechanistic studies suggest that a non-hydride mechanism is operative.

Water transport and desalination through double-layer graphyne membranes.

PubMed

Akhavan, Mojdeh; Schofield, Jeremy; Jalili, Seifollah

2018-05-16

Non-equilibrium molecular dynamics simulations of water-salt solutions driven through single and double-layer graphyne membranes by a pressure difference created by rigid pistons are carried out to determine the relative performance of the membranes as filters in a reverse osmosis desalination process. It is found that the flow rate of water through a graphyne-4 membrane is twice that of a graphyne-3 membrane for both single and double-layer membranes. Although the addition of a second layer to a single-layer membrane reduces the membrane permeability, the double-layer graphyne membranes are still two or three orders of magnitude more permeable than commercial reverse osmosis membranes. The minimum reduction in flow rate for double-layer membranes occurs at a layer spacing of 0.35 nm with an AA stacking configuration, while at a spacing of 0.6 nm the flow rate is close to zero due to a high free energy barrier for permeation. This is caused by the difference in the environments on either side of the membrane sheets and the formation of a compact two-dimensional layer of water molecules in the interlayer space which slows down water permeation. The distribution of residence times of water molecules in the interlayer region suggests that at the critical layer spacing of 0.6 nm, a cross-over occurs in the mechanism of water flow from the collective movement of hydrogen-bonded water sheets to the permeation of individual water molecules. All membranes are demonstrated to have a high salt rejection fraction and the double-layered graphyne-4 membranes can further increase the salt rejection by trapping ions that have passed through the first membrane from the feed solution in the interlayer space.

Solution structure, mutagenesis, and NH exchange studies of the MutT enzyme-Mg 2+-8-oxo-dGMP complex

NASA Astrophysics Data System (ADS)

Massiah, M. A.; Saraswat, V.; Azurmendi, H. F.; Mildvan, A. S.

2004-08-01

The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a KD=52 nM, (Δ G°=-9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (Δ G°=-3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable Δ Hbinding (-32 kcal/mol) despite an unfavorable - TΔ S° binding (+22 kcal/mol). The solution structure of the MutT-Mg 2+-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in 1H- 15N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position -119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3-0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT-Mg 2+-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of Asn-119 in the selective binding of 8-oxo-dGMP, likely donating a single hydrogen bond to its C6O. The R78K+N119A double mutant weakened the binding of 8-oxo-dGMP ( KIslope=3.1 mM) by 6.5±0.2 kcal/mol which overlaps, within error with the sum of the effects of the two single mutants (6.0±0.3 kcal/mol). Such additive effects of the two single mutants in the double mutant are most simply explained by the independent functioning of Asn-119 and Arg-78 in the binding of 8-oxo-dGMP. Independent functioning of these two residues in nucleotide binding is consistent with their locations in the MutT-Mg 2+-8-oxo-dGMP complex, on opposite sides of the active site cleft, with a distance of 8.4±0.5 Å between their side chain nitrogens.

Molecular design of flotation collectors: A recent progress.

PubMed

Liu, Guangyi; Yang, Xianglin; Zhong, Hong

2017-08-01

The nature of froth flotation is to selectively hydrophobize valuable minerals by collector adsorption so that the hydrophobized mineral particles can attach air bubbles. In recent years, the increasing commercial production of refractory complex ores has been urgent to develop special collectors for enhancing flotation separation efficiency of valuable minerals from these ores. Molecular design methods offer an effective way for understanding the structure-property relationship of flotation collectors and developing new ones. The conditional stability constant (CSC), molecular mechanics (MM), quantitative structure-activity relationship (QSAR), and first-principle theory, especially density functional theory (DFT), have been adopted to build the criteria for designing flotation collectors. Azole-thiones, guanidines, acyl thioureas and thionocarbamates, amide-hydroxamates, and double minerophilic-group surfactants such as Gemini, dithiourea and dithionocarbamate molecules have been recently developed as high-performance collectors. To design hydrophobic groups, the hydrophilic-hydrophobic balance parameters have been extensively used as criteria. The replacement of aryl group with aliphatic group or CC single bond(s) with CC double bond(s), reduction of carbon numbers, introduction of oxygen atom(s) and addition of trisiloxane to the tail terminal have been proved to be useful approaches for adjusting the surface activity of collectors. The role of molecular design of collectors in practical flotation applications was also summarized. Based on the critical review, some comments and prospects for further research on molecular design of flotation collectors were also presented in the paper. Copyright © 2017 Elsevier B.V. All rights reserved.

Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH2CH3. Isolation of CH3CH2OC(O)SH

NASA Astrophysics Data System (ADS)

Juncal, Luciana C.; Cozzarín, Melina V.; Romano, Rosana M.

2015-03-01

ROC(S)SC(O)OCH2CH3, with R = CH3sbnd , (CH3)2CHsbnd and CH3(CH2)2sbnd , were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by 1H and 13C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R = CH3sbnd and (CH3)2CHsbnd , while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the Cdbnd S double bond anti (A) with respect to the Csbnd S single bond and the Ssbnd C single bond syn (S) with respect to the Cdbnd O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(Cdbnd O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(Cdbnd S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n → π∗ electronic transition associated with the Cdbnd S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.

Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH₂CH₃. Isolation of CH₃CH₂OC(O)SH.

PubMed

Juncal, Luciana C; Cozzarín, Melina V; Romano, Rosana M

2015-03-15

ROC(S)SC(O)OCH2CH3, with R=CH3-, (CH3)2CH- and CH3(CH2)2-, were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by (1)H and (13)C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R=CH3- and (CH3)2CH-, while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the C=S double bond anti (A) with respect to the C-S single bond and the S-C single bond syn (S) with respect to the C=O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(C=O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(C=S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n→π∗ electronic transition associated with the C=S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. Copyright © 2014 Elsevier B.V. All rights reserved.

Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

PubMed

Xiao, Qing; Zhang, Yan; Wang, Jianbo

2013-02-19

Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo compounds or N-tosylhydrazones show that these transformations also work with other transition metals, demonstrating the generality of the diazo compounds as new cross-coupling partners in transition-metal-catalyzed coupling reactions.

Reactions in 1,1,1-trifluoroacetone triggered by low energy electrons (0-10 eV): from simple bond cleavages to complex unimolecular reactions.

PubMed

Illenberger, Eugen; Meinke, Martina C

2014-08-21

The impact of low energy electrons (0-10 eV) to 1,1,1-trifluoroacetone yields a variety of fragment anions which are formed via dissociative electron attachment (DEA) through three pronounced resonances located at 0.8 eV, near 4 eV, and in the energy range 8-9 eV. The fragment ions arise from different reactions ranging from the direct cleavage of one single or double bond (formation of F(-), CF3(-), O(-), (M-H)(-), and M-F)(-)) to remarkably complex unimolecular reactions associated with substantial geometric and electronic rearrangement in the transitory intermediate (formation of OH(-), FHF(-), (M-HF)(-), CCH(-), and HCCO(-). The ion CCH(-), for example, is formed by an excision of unit from the target molecule through the concerted cleavage of four bonds and recombination to H2O within the neutral component of the reaction.

Ab Initio Study of Polarizabilities of Oligothiophene, Oligocyclopentadiene and Oligofulvene and their Cyano Substituted Oligomers

NASA Astrophysics Data System (ADS)

Lagowski, Jolanta; Ferdous, Sultana

2005-03-01

Ab Initio polarizabilities of thiophene, fulvene and cyclopentadiene based conducting oligomers and polymers and their cyano derivatives have been calculated using the Hartree-Fock (HF), configuration interaction (singles) (CIS ) and density functional (DF) theories with 3-21G* basis using Gaussian software. The main motivation of this investigation is to determine the correlation between the excitation energies and polarizabilities for the conjugated systems studied. It has been found that HF and DF approaches give similar magnitudes for polarizabilities whereas CIS theory provides results that are considerably different. All three methods predict similar trends in polarizabilities as a function of oligomer length and bond alternation along the backbone of the oligomers. It has also been observed that the end groups and the number of `double' bonds have a significant effect on the magnitude of polarizability per C-C bond. Comparison with experimental results will be made where possible.

A new approach to construct a fused 2-ylidene chromene ring: highly regioselective synthesis of novel chromeno quinoxalines.

PubMed

Kumar, K Shiva; Rambabu, D; Prasad, Bagineni; Mujahid, Mohammad; Krishna, G Rama; Rao, M V Basaveswara; Reddy, C Malla; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-06-28

Regioselective construction of a fused 2-ylidene chromene ring was achieved for the first time by using AlCl(3)-induced C-C bond formation followed by Pd/C-Cu mediate coupling-cyclization strategy. A number of chromeno[4,3-b]quinoxaline derivatives were prepared by using this strategy. Single crystal X-ray diffraction study of a representative compound e.g. 6-(2,2-dimethylpropylidene)-4-methyl-6H-chromeno[4,3-b]quinoxalin-3-ol confirmed the presence of an exocyclic C-C double bond with Z-geometry. The crystal structure analysis and hydrogen bonding patterns of the same compound along with its structure elaboration via propargylation followed by Sonogashira coupling of the resulting terminal alkyne is presented. A probable mechanism for the formation of 2-ylidene chromene ring is discussed. Some of the compounds synthesized showed anticancer properties when tested in vitro.

Fused electron deficient semiconducting polymers for air stable electron transport.

PubMed

Onwubiko, Ada; Yue, Wan; Jellett, Cameron; Xiao, Mingfei; Chen, Hung-Yang; Ravva, Mahesh Kumar; Hanifi, David A; Knall, Astrid-Caroline; Purushothaman, Balaji; Nikolka, Mark; Flores, Jean-Charles; Salleo, Alberto; Bredas, Jean-Luc; Sirringhaus, Henning; Hayoz, Pascal; McCulloch, Iain

2018-01-29

Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare polymers where double bonds lock-in a rigid backbone conformation, thus eliminating free rotation along the conjugated backbone. This polymerisation route requires neither organometallic monomers nor transition metal catalysts and offers a reliable design strategy to facilitate delocalisation of frontier molecular orbitals, elimination of energetic disorder arising from rotational torsion and allowing closer interchain electronic coupling. These characteristics are desirable for high charge carrier mobilities. Our polymers with a high electron affinity display long wavelength NIR absorption with air stable electron transport in solution processed organic thin film transistors.

Assessing the issue of instability due to Michael adduct formation in novel chemical entities possessing a carbon-carbon double bond during early drug development--applicability of common laboratory analytical protocols.

PubMed

Polepally, Akshanth Reddy; Kumar, Venkata V Pavan; Bhamidipati, Ravikanth; Kota, Jagannath; Naveed, Shaik Abdul; Reddy, Karnati Harinder; Mamidi, Rao N V S; Selvakumar, N; Mullangi, Ramesh; Srinivas, Nuggehally R

2008-09-01

The discovery of small-molecule novel chemical entities (NCEs) is often a complex play between appropriate structural requirements and optimization of the desired efficacy, safety and pharmacokinetic properties. One of the typical structural variants such as having an active carbon-carbon double bond (alpha, beta-unsaturated carbonyl group) in xenobiotics may lead to stability issues. Such functionalities are extremely reactive, paving way to nucleophilic attack by endogenously occurring and ubiquitous nucleophiles like thiols. While it is easy to make a unilateral decision to not pursue the development of xenobiotics with such functionalities, we question the wisdom of such a decision. In this report, we present in vitro methodologies with appropriate examples to illustrate the ease of assessing the reactivity of the xenobiotics containing double bonds with a known nucleophile. The protocols involve simple reaction procedures followed by measurements using standard laboratory equipments (UV spectrophotometer, HPLC and LC-MS). Our data suggests that not all xenobiotics with carbon-carbon double bonds readily form a Michael's adduct product with glutathione. Hence, the criterion for dropping discovery compounds because of alpha,beta-unsaturated double bonds needs to be reconsidered.

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

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

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

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

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

DOE PAGES

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

2015-06-03

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

MOIL-opt: Energy-Conserving Molecular Dynamics on a GPU/CPU system

PubMed Central

Ruymgaart, A. Peter; Cardenas, Alfredo E.; Elber, Ron

2011-01-01

We report an optimized version of the molecular dynamics program MOIL that runs on a shared memory system with OpenMP and exploits the power of a Graphics Processing Unit (GPU). The model is of heterogeneous computing system on a single node with several cores sharing the same memory and a GPU. This is a typical laboratory tool, which provides excellent performance at minimal cost. Besides performance, emphasis is made on accuracy and stability of the algorithm probed by energy conservation for explicit-solvent atomically-detailed-models. Especially for long simulations energy conservation is critical due to the phenomenon known as “energy drift” in which energy errors accumulate linearly as a function of simulation time. To achieve long time dynamics with acceptable accuracy the drift must be particularly small. We identify several means of controlling long-time numerical accuracy while maintaining excellent speedup. To maintain a high level of energy conservation SHAKE and the Ewald reciprocal summation are run in double precision. Double precision summation of real-space non-bonded interactions improves energy conservation. In our best option, the energy drift using 1fs for a time step while constraining the distances of all bonds, is undetectable in 10ns simulation of solvated DHFR (Dihydrofolate reductase). Faster options, shaking only bonds with hydrogen atoms, are also very well behaved and have drifts of less than 1kcal/mol per nanosecond of the same system. CPU/GPU implementations require changes in programming models. We consider the use of a list of neighbors and quadratic versus linear interpolation in lookup tables of different sizes. Quadratic interpolation with a smaller number of grid points is faster than linear lookup tables (with finer representation) without loss of accuracy. Atomic neighbor lists were found most efficient. Typical speedups are about a factor of 10 compared to a single-core single-precision code. PMID:22328867

Disulfide bond exchanges in integrins αIIbβ3 and αvβ3 are required for activation and post-ligation signaling during clot retraction.

PubMed

Mor-Cohen, Ronit; Rosenberg, Nurit; Averbukh, Yulia; Seligsohn, Uri; Lahav, Judith

2014-05-01

Integrin αIIbβ3 mediates platelet adhesion, aggregation and fibrin clot retraction. These processes require activation of αIIbβ3 and post-ligation signaling. Disulfide bond exchanges are involved in αIIbβ3 and αvβ3 activation. In order to investigate the role of integrin activation and disulfide bond exchange during αIIbβ3- and αvβ3-mediated clot retraction, we co-expressed in baby hamster kidney cells wild-type (WT) human αIIb and WT or mutated human β3 that contain single or double cysteine substitutions disrupting C523-C544 or C560-C583 bonds. Flow cytometry was used to measure surface expression and activation state of the integrins. Time-course of fibrin clot retraction was examined. Cells expressed WT or mutated human αIIbβ3 as well as chimeric hamster/human αvβ3. The αIIbβ3 mutants were constitutively active and the thiol blocker dithiobisnitrobenzoic acid (DTNB) did not affect their activation state. WT cells retracted the clot and addition of αvβ3 inhibitors decreased the retraction rate. The active mutants and WT cells activated by anti-LIBS6 antibody retracted the clot faster than untreated WT cells, particularly in the presence of αvβ3 inhibitor. DTNB substantially inhibited clot retraction by WT or double C523S/C544S mutant expressing cells, but minimally affected single C523S, C544S or C560S mutants. Anti-LIBS6-enhanced clot retraction was significantly inhibited by DTNB when added prior to anti-LIBS6. Both αIIbβ3 and αvβ3 contribute to clot retraction without prior activation of the integrins. Activation of αIIbβ3, but not of αvβ3 enhances clot retraction. Both αIIbβ3 activation and post-ligation signaling during clot retraction require disulfide bond exchange. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Heat of Formation of HNO

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

1995-01-01

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO reversible reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HNO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X double bond H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate (Delta)H(sub f, sup o) value for HNO using state-of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +/- 0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Ammonolysis of ketene as a potential source of acetamide in the troposphere: a quantum chemical investigation.

PubMed

Sarkar, Saptarshi; Mallick, Subhasish; Kumar, Pradeep; Bandyopadhyay, Biman

2018-05-16

Quantum chemical calculations at the CCSD(T)/CBS//MP2/aug-cc-pVTZ levels of theory have been carried out to investigate a potential new source of acetamide in Earth's atmosphere through the ammonolysis of the simplest ketene. It was found that the reaction can occur via the addition of ammonia at either the C[double bond, length as m-dash]C or C[double bond, length as m-dash]O bond of ketene. The potential energy surface as well as calculated rate coefficients indicate that under tropospheric conditions, ammonolysis would occur almost exclusively via ammonia addition at the C[double bond, length as m-dash]O bond with negligible contribution from addition at the C[double bond, length as m-dash]C bond. The reaction of ketene with water has also been investigated in order to compare between hydrolysis and ammonolysis, as the former is known to be responsible for the formation of acetic acid. The rate coefficient for the formation of acetamide was found to be ∼106 to 109 times higher than that for the formation of acetic acid from the same ketene source in the troposphere. By means of the relative rate of ammonolysis with respect to hydrolysis, it was shown that acetamide formation would dominate over acetic acid formation at various altitudes in the troposphere.

Crystal structure of N-[3-(di­methyl­aza­nium­yl)prop­yl]-N′,N′,N′′,N′′-tetra­methyl-N-(N,N,N′,N′-tetra­methyl­form­am­id­in­ium­yl)­guanidinium dibromide hydroxide monohydrate

PubMed Central

Tiritiris, Ioannis; Kantlehner, Willi

2015-01-01

The asymmetric unit of the title hydrated salt, C15H37N6 3+·2Br−·OH−·H2O, contains one cation, three partial-occupancy bromide ions, one hydroxide ion and one water mol­ecule. Refinement of the site-occupancy factors of the three disordered bromide ions converges with occupancies 0.701 (2), 0.831 (2) and 0.456 (2) summing to approximately two bromide ions per formula unit. The structure was refined as a two-component inversion twin with volume fractions 0.109 (8):0.891 (8) for the two domains. The central C3N unit of the bis­amidinium ion is linked to the aliphatic propyl chain by a C—N single bond. The other two bonds in this unit have double-bond character as have the four C—N bonds to the outer NMe2 groups. In contrast, the three C—N bonds to the central N atom of the (di­methyl­aza­nium­yl)propyl group have single-bond character. Delocalization of the two positive charges occurs in the N/C/N and C/N/C planes, while the third positive charge is localized on the di­methyl­ammonium group. The crystal structure is stabilized by O—H⋯O, N—H⋯Br, O—H⋯Br and C—H⋯Br hydrogen bonds, forming a three-dimensional network. PMID:26870507

On the Involvement of Single-Bond Rotation in the Primary Photochemistry of Photoactive Yellow Protein

PubMed Central

Stahl, Andreas D.; Hospes, Marijke; Singhal, Kushagra; van Stokkum, Ivo; van Grondelle, Rienk; Groot, Marie Louise; Hellingwerf, Klaas J.

2011-01-01

Prior experimental observations, as well as theoretical considerations, have led to the proposal that C4-C7 single-bond rotation may play an important role in the primary photochemistry of photoactive yellow protein (PYP). We therefore synthesized an analog of this protein's 4-hydroxy-cinnamic acid chromophore, (5-hydroxy indan-(1E)-ylidene)acetic acid, in which rotation across the C4-C7 single bond has been locked with an ethane bridge, and we reconstituted the apo form of the wild-type protein and its R52A derivative with this chromophore analog. In PYP reconstituted with the rotation-locked chromophore, 1), absorption spectra of ground and intermediate states are slightly blue-shifted; 2), the quantum yield of photochemistry is ∼60% reduced; 3), the excited-state dynamics of the chromophore are accelerated; and 4), dynamics of the thermal recovery reaction of the protein are accelerated. A significant finding was that the yield of the transient ground-state intermediate in the early phase of the photocycle was considerably higher in the rotation-locked samples than in the corresponding samples reconstituted with p-coumaric acid. In contrast to theoretical predictions, the initial photocycle dynamics of PYP were observed to be not affected by the charge of the amino acid residue at position 52, which was varied by 1), varying the pH of the sample between 5 and 10; and 2), site-directed mutagenesis to construct R52A. These results imply that C4-C7 single-bond rotation in PYP is not an alternative to C7=C8 double-bond rotation, in case the nearby positive charge of R52 is absent, but rather facilitates, presumably with a compensatory movement, the physiological Z/E isomerization of the blue-light-absorbing chromophore. PMID:21889456

Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

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

Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk, E-mail: hammer@phys.au.dk

2016-04-28

The adsorption, diffusion, and dissociation of pyridine, C{sub 5}H{sub 5}N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom.more » The origin of the diffusion pathway is discussed in terms of the C{sub 2}–Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).« less

The Nature of the Idealized Triple Bonds Between Principal Elements and the σ Origins of Trans-Bent Geometries-A Valence Bond Study.

PubMed

Ploshnik, Elina; Danovich, David; Hiberty, Philippe C; Shaik, Sason

2011-04-12

We describe herein a valence bond (VB) study of 27 triply bonded molecules of the general type X≡Y, where X and Y are main element atoms/fragments from groups 13-15 in the periodic table. The following conclusions were derived from the computational data: (a) Single π-bond and double π-bond energies for the entire set correlate with the "molecular electronegativity", which is the sum of the X and Y electronegativites for X≡Y. The correlation with the molecular electronegativity establishes a simple rule of periodicity: π-bonding strength generally increases from left to right in a period and decreases down a column in the periodic table. (b) The σ frame invariably prefers trans bending, while π-bonding gets destabilized and opposes the trans distortion. In HC≡CH, the π-bonding destabilization overrides the propensity of the σ frame to distort, while in the higher row molecules, the σ frame wins out and establishes trans-bent molecules with 2(1)/2 bonds, in accord with recent experimental evidence based on solid state (29)Si NMR of the Sekiguchi compound. Thus, in the trans-bent molecules "less bonds pay more". (c) All of the π bonds show significant bonding contributions from the resonance energy due to covalent-ionic mixing. This quantity is shown to correlate linearly with the corresponding "molecular electronegativity" and to reflect the mechanism required to satisfy the equilibrium condition for the bond. The π bonds for molecules possessing high molecular electronegativity are charge-shift bonds, wherein bonding is dominated by the resonance energy of the covalent and ionic forms, rather than by either form by itself.

Osmium (VI) complexes of the 3', 5'-dinucleoside monophosphates, ApU and UpA.

PubMed

Daniel, F B; Behrman, E J

1976-02-10

The dinucleoside monophosphates, ApU and UpA, react with potassium osmate (VI) and 2,2'-bipyridyl to form the corresponding oxo-osmium (VI) bipyridyl sugar ester in which the osmate group is bonded to the terminal 2',3'-glycol. Osmium (VIII) tetroxide and 2,2'-bipyridyl react with the dinucleosides to form the corresponding oxo-osmium (VI) bipyridyl heterocyclic esters which result from addition of the tetroxide to the 5,6-double bond of the uracil residue. Although capable of transesterification reactions, these heterocyclic esters are exceptionally stable toward exchange reactions in solution. No apparent exchange was observed after 1 month. This reaction thus seems promising for single-site osmium labeling in polynucleotides.

Dipropyl 3,6-diphenyl-1,2-dihydro-1,2,4,5-tetrazine-1,2-dicarboxylate.

PubMed

Rao, Guo-Wu; Hu, Wei-Xiao

2003-05-01

The title compound, C(22)H(24)N(4)O(4), was prepared from propyl chloroformate and 3,6-diphenyl-1,2-dihydro-s-tetrazine. This reaction yields the title compound rather than dipropyl 3,6-diphenyl-1,4-dihydro-s-tetrazine-1,4-dicarboxylate. The 2,3-diazabutadiene group in the central six-membered ring is not planar; the C=N double-bond length is 1.285 (2) A, and the average N-N single-bond length is 1.401 (3) A, indicating a lack of conjugation. The ring has a twist conformation, in which adjacent N atoms lie +/- 0.3268 (17) A from the plane of the ring. The molecule has twofold crystallographic symmetry.

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

Breton, J.; Berger, G.; Nabedryk, E.

The photoreduction of the secondary quinone acceptor Q{sub B} in reaction centers (RCs) of the photosynthetic bacteria Rhodobacter sphaeroides and Rhodopseudomonas viridis has been investigated by light-induced FTIR difference spectroscopy of RCs reconstituted with several isotopically labeled ubiquinones. The labels used were {sup 18}O on both carbonyls and {sup 13}C either uniformly or selectively at the 1- or the 4-position, i.e., on either one of the two carbonyls. The Q{sub B}{sup {minus}}/Q{sub B} spectra of RCs reconstituted with the isotopically labeled and unlabeled quinones as well as the double differences calculated form these spectra exhibit distinct isotopic shifts for amore » numer of bands attributed to vibrations of Q{sub B} and Q{sub B}{sup {minus}}. The vibrational modes of the quinone in the Q{sub B} site are compared to those of ubiquinone in vitro, leading to band assignments for the C{double_bond}O and C{double_bond}C vibrations of the neutral Q{sub B} and for the C---O and C---C of the semiquinone. The C{double_bond}O frequency of each of the carbonyls of the unlabeled quinone is revealed at 1641 cm{sup {minus}1} for both species. This demonstrates symmetrical and weak hydrogen bonding of the two C{double_bond}O groups to the protein at the Q{sub B} site. In contrast, the C{double_bond}C vibrations are not equivalent for selective labeling at C{sub 1} or at C{sub 4}, although they both contribute to the {approximately}1611-cm{sup {minus}1} band in the Q{sub B}{sup {minus}}/Q{sub B} spectra of the two species. Compared to the vibrations of isolated ubiquinone, the C{double_bond}C mode of Q{sub B} does not involve displacement of the C{sub 4} carbon atom, while the motion of C{sub 1} is not hindered. Further analysis of the spectra suggests that the protein at the binding site imposes a specific constraint on the methoxy and/or the methyl group proximal to the C{sub 4} carbonyl. 49 refs., 5 figs.« less

Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: an ab initio study.

PubMed

Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D

2014-10-07

We perform an ab initio computational study of molecular complexes with the general formula CF3X-B that involve one trifluorohalomethane CF3X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH3 and PH3), two n-pairs (H2O and H2S), two n-pairs with an unsaturated bond (H2CO and H2CS), and a single π-pair (C2H4) and two π-pairs (C2H2). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C-X bond lengths shorten, while the C-X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.

Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: An ab initio study

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

Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D., E-mail: sdchao@spring.iam.ntu.edu.tw

2014-10-07

We perform an ab initio computational study of molecular complexes with the general formula CF{sub 3}X—B that involve one trifluorohalomethane CF{sub 3}X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH{sub 3} and PH{sub 3}), two n-pairs (H{sub 2}O and H{sub 2}S), two n-pairs with an unsaturated bond (H{sub 2}CO and H{sub 2}CS), and a single π-pairmore » (C{sub 2}H{sub 4}) and two π-pairs (C{sub 2}H{sub 2}). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C–X bond lengths shorten, while the C–X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.« less

The Bacillus subtilis Acyl Lipid Desaturase Is a Δ5 Desaturase

PubMed Central

Altabe, Silvia G.; Aguilar, Pablo; Caballero, Gerardo M.; de Mendoza, Diego

2003-01-01

Bacillus subtilis was recently reported to synthesize unsaturated fatty acids (UFAs) with a double bond at positions Δ5, Δ7, and Δ9 (M. H. Weber, W. Klein, L. Muller, U. M. Niess, and M. A. Marahiel, Mol. Microbiol. 39:1321-1329, 2001). Since this finding would have considerable importance in the double-bond positional specificity displayed by the B. subtilis acyl lipid desaturase, we have attempted to confirm this observation. We report that the double bond of UFAs synthesized by B. subtilis is located exclusively at the Δ5 position, regardless of the growth temperature and the length chain of the fatty acids. PMID:12730185

Preparation of mesoporous alumina particles by spray pyrolysis and application to double bond migration of 2-butene.

PubMed

Song, Ki Chang; Kim, Joo Hyun; Kim, Jin Han; Jung, Kyeong Youl; Park, Young-Kwon; Jeon, Jong-Ki

2011-07-01

The objective of the present study is to investigate the catalytic performance of mesoporous alumina that were prepared via spray pyrolysis for double bond migration from 2-butene to 1-butene. The mesoporous alumina particles were prepared via spray pyrolysis by changing the types of organic surfactants and Al precursors. The texture and acidic properties of mesoporous alumina were analyzed through N2 adsorption, SEM, ammonia-temperature programmed desorption, and FT-IR of adsorbed pyridine. The morphologies and texture properties of the mesoporous alumina were found to have been strongly influenced by the combination of the Al precursor and the structure-directing agents. The mesoporous alumina samples had two kinds of acidic sites: a Lewis acid site and a H-bonded weak acid site. 1-Butene was produced selectively through double bond migration of 2-butene over all of the mesoporous alumina catalysts. The catalyst prepared by using a chloride compound as an aluminium precursor and CTAC as a structure-directing agent showed the highest activity in the double bond migration of 2-butene, which was attributed to its large surface area and an overall high amount of acid sites.

Band structures in coupled-cluster singles-and-doubles Green's function (GFCCSD)

NASA Astrophysics Data System (ADS)

Furukawa, Yoritaka; Kosugi, Taichi; Nishi, Hirofumi; Matsushita, Yu-ichiro

2018-05-01

We demonstrate that the coupled-cluster singles-and-doubles Green's function (GFCCSD) method is a powerful and prominent tool drawing the electronic band structures and the total energies, which many theoretical techniques struggle to reproduce. We have calculated single-electron energy spectra via the GFCCSD method for various kinds of systems, ranging from ionic to covalent and van der Waals, for the first time: the one-dimensional LiH chain, one-dimensional C chain, and one-dimensional Be chain. We have found that the bandgap becomes narrower than in HF due to the correlation effect. We also show that the band structures obtained from the GFCCSD method include both quasiparticle and satellite peaks successfully. Besides, taking one-dimensional LiH as an example, we discuss the validity of restricting the active space to suppress the computational cost of the GFCCSD method. We show that the calculated results without bands that do not contribute to the chemical bonds are in good agreement with full-band calculations. With the GFCCSD method, we can calculate the total energies and spectral functions for periodic systems in an explicitly correlated manner.

Defect-induced magnetism in two-dimensional NbSe2

NASA Astrophysics Data System (ADS)

Manchanda, P.; Skomski, R.

2017-01-01

The energetics and magnetism of perfect and vacancy-containing two-dimensional NbSe2 monolayers is investigated by first-principle calculations. It has been found the single Se vacancy has the lowest formation energy. Perfect NbSe2 monolayers, as well as monolayers containing single-selenium and double-selenium vacancies, are nonmagnetic metallic. However, Nb vacancies create a magnetic moment of 1.5 μB per vacancy. The moment is highly localized, confined nearly exclusively on the Se atoms adjacent to the vacancy, and mainly originates from the Se 4p electrons. The moment distribution indicates strongly anisotropic exchange bonds between vacancy moments.

Gas-phase infrared spectroscopy for determination of double bond configuration of monounsaturated compounds.

PubMed

Attygalle, A B; Svatos, A; Wilcox, C; Voerman, S

1994-05-15

Gas-phase Fourier-transform infrared spectra allow unambiguous determination of the configuration of the double bonds of long-chain unsaturated compounds bearing RCH=CHR' type bonds. Although the infrared absorption at 970-967 cm-1 has been used previously for the identification of trans bonds, the absorption at 3028-3011 cm-1 is conventionally considered to be incapable of distinguishing cis and trans isomers. In this paper, we present a large number of gas-phase spectra of monounsaturated long-chain acetates which demonstrate that an absorption, highly characteristic for the cis configuration, occurs at 3013-3011 cm-1, while trans compounds fail to show any bands in this region. However, if a double bond is present at the C-2 or C-3 carbon atoms, this cis=CH stretch absorption shows a hypsochromic shift to 3029-3028 and 3018-3017 cm-1, respectively. Similarly, if a cis double bond is present at the penultimate carbon atom, this band appears at 3022-3021 cm-1. All the spectra of trans alkenyl acetates showed the expected C-H wag absorption at 968-964 cm-1. In addition, the spectra of (E)-2-alkenyl acetates show a unique three-peak "finger-print" pattern which allows the identification of the position and configuration of this bond. Furthermore, by synthesizing and obtaining spectra of appropriate deuteriated compounds, we have proved that the 3013-3011 cm-1 band is representative of the C-H stretching vibration of cis compounds of RCH=CHR' type.

TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4‧-dimethylaminoflavonol in ethanol solvent

NASA Astrophysics Data System (ADS)

Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

2015-02-01

Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4‧-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

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

USDA-ARS?s Scientific Manuscript database

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

Theoretical study of the H/D isotope effect on phase transition of hydrogen-bonded organic conductor κ-H3(Cat-EDT-TTF)2.

PubMed

Yamamoto, Kaichi; Kanematsu, Yusuke; Nagashima, Umpei; Ueda, Akira; Mori, Hatsumi; Tachikawa, Masanori

2016-11-02

κ-H 3 (Cat-EDT-TTF) 2 (H-TTF) is a hydrogen-bonded π-electron system which was found to reveal C2/c symmetry at 50-293 K, while its isotopologue, κ-D 3 (Cat-EDT-TTF) 2 (D-TTF), showed the phase transition at 185 K from C2/c to P1[combining macron]. To elucidate the origin of such a difference, we calculated the potential energy curves (PECs) for the hydrogen transfer along the H-bonds in these conductors. We found that both the π-stacking and the hydrogen nuclear quantum effect drastically affected the hydrogen transfer energy. By taking account of both effects, we obtained a symmetric single-well effective PEC for H-TTF, which indicated that the hydrogen was always located at the center of the H-bond. By contrast, the effective PEC of D-TTF was a low-barrier double-well, indicating that the position of the H-bonded deuterium would change according to the temperature. We concluded that the π-stacking and the nuclear quantum effect were the key factors for the appearance of phase transition only in D-TTF.

Controlled double emulsification utilizing 3D PDMS microchannels

NASA Astrophysics Data System (ADS)

Chang, Fu-Che; Su, Yu-Chuan

2008-06-01

This paper presents a PDMS emulsification device that is capable of generating water-in-oil-in-water double emulsions in a controlled manner. Specially designed 3D microchannels are utilized to steer the independently driven water- and oil-phase flows (especially to restrict the attachment of the middle oil-phase flow on the channel surfaces), and to break the continuous flows into monodisperse double emulsions. In addition to channel geometries and fluid flow rates, surfactants and osmotic agents are employed to facilitate the breakup process and stabilize the resulting emulsion structures. In the prototype demonstration, two-level SU-8 molds were fabricated to duplicate PDMS microstructures, which were surface treated and bonded irreversibly to form 3D microchannels. Throughout the emulsification trials, dripping was intentionally induced to generate monodisperse double emulsions with single or multiple aqueous droplets inside each oil drop. It is found that the overall and core sizes of the resulting double emulsions could be adjusted independently, mainly by varying the outer and inner fluid flow rates, respectively. As such, the presented double emulsification device could potentially realize the controllability on emulsion structure and size distribution, which is desired for a variety of biological and pharmaceutical applications.

Crystal structure of N′′-benzyl-N′′-[3-(benzyl­dimethyl­aza­nium­yl)prop­yl]-N,N,N′,N′-tetra­methyl­guanidinium bis­(tetra­phenyl­borate)

PubMed Central

Tiritiris, Ioannis; Kantlehner, Willi

2015-01-01

In the crystal structure of the title salt, C24H38N4 2+·2C24H20B−, the C—N bond lengths in the central CN3 unit of the guanidinium ion are 1.3364 (13), 1.3407 (13) and 1.3539 (13) Å, indicating partial double-bond character. The central C atom is bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charge is delocalized in the CN3 plane. The bonds between the N atoms and the terminal methyl groups of the guanidinium moiety and the four C—N bonds to the central N atom of the (benzyl­dimethyl­aza­nium­yl)propyl group have single-bond character. In the crystal, C—H⋯π inter­actions between the guanidin­ium H atoms and the phenyl C atoms of the tetra­phenyl­borate ions are present, leading to the formation of a two-dimensional supra­molecular pattern parallel to the ac plane. PMID:26870511

Analysis of bonded joints. [shear stress and stress-strain diagrams

NASA Technical Reports Server (NTRS)

Srinivas, S.

1975-01-01

A refined elastic analysis of bonded joints which accounts for transverse shear deformation and transverse normal stress was developed to obtain the stresses and displacements in the adherends and in the bond. The displacements were expanded in terms of polynomials in the thicknesswise coordinate; the coefficients of these polynomials were functions of the axial coordinate. The stress distribution was obtained in terms of these coefficients by using strain-displacement and stress-strain relations. The governing differential equations were obtained by integrating the equations of equilibrium, and were solved. The boundary conditions (interface or support) were satisfied to complete the analysis. Single-lap, flush, and double-lap joints were analyzed, along with the effects of adhesive properties, plate thicknesses, material properties, and plate taper on maximum peel and shear stresses in the bond. The results obtained by using the thin-beam analysis available in the literature were compared with the results obtained by using the refined analysis. In general, thin-beam analysis yielded reasonably accurate results, but in certain cases the errors were high. Numerical investigations showed that the maximum peel and shear stresses in the bond can be reduced by (1) using a combination of flexible and stiff bonds, (2) using stiffer lap plates, and (3) tapering the plates.

Base pairing and base mis-pairing in nucleic acids

NASA Technical Reports Server (NTRS)

Wang, A. H. J.; Rich, A.

1986-01-01

In recent years we have learned that DNA is conformationally active. It can exist in a number of different stable conformations including both right-handed and left-handed forms. Using single crystal X-ray diffraction analysis we are able to discover not only additional conformations of the nucleic acids but also different types of hydrogen bonded base-base interactions. Although Watson-Crick base pairings are the predominant type of interaction in double helical DNA, they are not the only types. Recently, we have been able to examine mismatching of guanine-thymine base pairs in left-handed Z-DNA at atomic resolution (1A). A minimum amount of distortion of the sugar phosphate backbone is found in the G x T pairing in which the bases are held together by two hydrogen bonds in the wobble pairing interaction. Because of the high resolution of the analysis we can visualize water molecules which fill in to accommodate the other hydrogen bonding positions in the bases which are not used in the base-base interactions. Studies on other DNA oligomers have revealed that other types of non-Watson-Crick hydrogen bonding interactions can occur. In the structure of a DNA octamer with the sequence d(GCGTACGC) complexed to an antibiotic triostin A, it was found that the two central AT base pairs are held together by Hoogsteen rather than Watson-Crick base pairs. Similarly, the G x C base pairs at the ends are also Hoogsteen rather than Watson-Crick pairing. Hoogsteen base pairs make a modified helix which is distinct from the Watson-Crick double helix.

Triple Nucleophilic Attack of Nitromethane on (2-Iminoaryl)divinyl Ketones: A Domino Synthetic Strategy for Hexahydrophenanthridinones.

PubMed

Feng, Chengjie; Li, Yifei; Xu, Qi; Pan, Ling; Liu, Qun; Xu, Xianxiu

2018-02-02

A novel domino reaction of (2-iminoaryl)divinyl ketones with nitromethane was developed for the efficient synthesis of hexahydrophenanthridin-9(5H)-ones. The reaction proceeded smoothly from readily available starting materials under mild reaction conditions to construct three new bonds and two rings with high diastereoselectivities in good to excellent yields in a single step. A mechanism is proposed, involving a stepwise double Michael addition/aza-Henry reaction cascade, and in this transformation, nitromethane acts as a trinucleophile.

B-DNA Structure and Stability as Function of Nucleic Acid Composition: Dispersion-Corrected DFT Study of Dinucleoside Monophosphate Single and Double Strands

PubMed Central

Barone, Giampaolo; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2013-01-01

We have computationally investigated the structure and stability of all 16 combinations of two out of the four natural DNA bases A, T, G and C in a di-2′-deoxyribonucleoside-monophosphate model DNA strand as well as in 10 double-strand model complexes thereof, using dispersion-corrected density functional theory (DFT-D). Optimized geometries with B-DNA conformation were obtained through the inclusion of implicit water solvent and, in the DNA models, of sodium counterions, to neutralize the negative charge of the phosphate groups. The results obtained allowed us to compare the relative stability of isomeric single and double strands. Moreover, the energy of the Watson–Crick pairing of complementary single strands to form double-helical structures was calculated. The latter furnished the following increasing stability trend of the double-helix formation energy: d(TpA)2

Rational Design of Disulfide Bonds Increases Thermostability of a Mesophilic 1,3-1,4-β-Glucanase from Bacillus terquilensis

PubMed Central

Xu, Xin; Li, Qi

2016-01-01

1,3–1,4-β-glucanase is an important biocatalyst in brewing industry and animal feed industry, while its low thermostability often reduces its application performance. In this study, the thermostability of a mesophilic β-glucanase from Bacillus terquilensis was enhanced by rational design and engineering of disulfide bonds in the protein structure. Protein spatial configuration was analyzed to pre-exclude the residues pairs which negatively conflicted with the protein structure and ensure the contact of catalytic center. The changes in protein overall and local flexibility among the wild-type enzyme and the designated mutants were predicted to select the potential disulfide bonds for enhancement of thermostability. Two residue pairs (N31C-T187C and P102C-N125C) were chosen as engineering targets and both of them were proved to significantly enhance the protein thermostability. After combinational mutagenesis, the double mutant N31C-T187C/P102C-N125C showed a 48.3% increase in half-life value at 60°C and a 4.1°C rise in melting temperature (Tm) compared to wild-type enzyme. The catalytic property of N31C-T187C/P102C-N125C mutant was similar to that of wild-type enzyme. Interestingly, the optimal pH of double mutant was shifted from pH6.5 to pH6.0, which could also increase its industrial application. By comparison with mutants with single-Cys substitutions, the introduction of disulfide bonds and the induced new hydrogen bonds were proved to result in both local and overall rigidification and should be responsible for the improved thermostability. Therefore, the introduction of disulfide bonds for thermostability improvement could be rationally and highly-effectively designed by combination with spatial configuration analysis and molecular dynamics simulation. PMID:27100881

Correlated hydrogen bonding fluctuations and vibrational cross peaks in N-methyl acetamide: simulation based on a complete electrostatic density functional theory map.

PubMed

Hayashi, Tomoyuki; Mukamel, Shaul

2006-11-21

The coherent nonlinear response of the entire amide line shapes of N-methyl acetamide to three infrared pulses is simulated using an electrostatic density functional theory map. Positive and negative cross peaks contain signatures of correlations between the fundamentals and the combination state. The amide I-A and I-III cross-peak line shapes indicate positive correlation and anticorrelation of frequency fluctuations, respectively. These can be ascribed to correlated hydrogen bonding at C[double bond]O and N-H sites. The amide I frequency is negatively correlated with the hydrogen bond on carbonyl C[double bond]O, whereas the amide A and III are negatively and positively correlated, respectively, with the hydrogen bond on amide N-H.

Formation of a 1,4-diamino-2,3-disila-1,3-butadiene derivative.

PubMed

Mondal, Kartik Chandra; Roesky, Herbert W; Dittrich, Birger; Holzmann, Nicole; Hermann, Markus; Frenking, Gernot; Meents, Alke

2013-10-30

A 1,4-diamino-2,3-disila-1,3-butadiene derivative of composition (Me2-cAAC)2(Si2Cl2) (Me2-cAAC = :C(CMe2)2(CH2)N-2,6-iPr2C6H3) was synthesized by reduction of the Me2-cAAC:SiCl4 adduct with KC8. This compound is stable at 0 °C for 3 months in an inert atmosphere. Theoretical studies reveal that the silicon atoms exhibit pyramidal coordination, where the Cl-Si-Si-Cl dihedral angle is twisted by 43.3° (calcd 45.9°). The two silicon-carbon bonds are intermediates between single and double Si-C bonds due to twisting of the C-Si-Si-C dihedral angle (163.6°).

Molecular-specific urokinase antibodies

NASA Technical Reports Server (NTRS)

Atassi, M. Zouhair (Inventor); Morrison, Dennis R. (Inventor)

2009-01-01

Antibodies have been developed against the different molecular forms of urokinase using synthetic peptides as immunogens. The peptides were synthesized specifically to represent those regions of the urokinase molecules which are exposed in the three-dimensional configuration of the molecule and are uniquely homologous to urokinase. Antibodies are directed against the lysine 158-isoleucine 159 peptide bond which is cleaved during activation from the single-chain (ScuPA) form to the bioactive double chain (54 KDa and 33 KDa) forms of urokinase and against the lysine 135 lysine 136 bond that is cleaved in the process of removing the alpha-chain from the 54 KDa form to produce the 33 KDa form of urokinase. These antibodies enable the direct measurement of the different molecular forms of urokinase from small samples of conditioned medium harvested from cell cultures.

Single and double acceptor-levels of a carbon-hydrogen defect in n-type silicon

NASA Astrophysics Data System (ADS)

Stübner, R.; Scheffler, L.; Kolkovsky, Vl.; Weber, J.

2016-05-01

In the present study, we discuss the origin of two dominant deep levels (E42 and E262) observed in n-type Si, which is subjected to hydrogenation by wet chemical etching or a dc H-plasma treatment. Their activation enthalpies determined from Laplace deep level transient spectroscopy measurements are EC-0.06 eV (E42) and EC-0.51 eV (E262). The similar annealing behavior and identical depth profiles of E42 and E262 correlate them with two different charge states of the same defect. E262 is attributed to a single acceptor state due to the absence of the Poole-Frenkel effect and the lack of a capture barrier for electrons. The emission rate of E42 shows a characteristic enhancement with the electric field, which is consistent with the assignment to a double acceptor state. In samples with different carbon and hydrogen content, the depth profiles of E262 can be explained by a defect with one H-atom and one C-atom. From a comparison with earlier calculations [Andersen et al., Phys. Rev. B 66, 235205 (2002)], we attribute E42 to the double acceptor and E262 to the single acceptor state of the CH1AB configuration, where one H atom is directly bound to carbon in the anti-bonding position.

Single and double acceptor-levels of a carbon-hydrogen defect in n-type silicon

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

Stübner, R.; Scheffler, L.; Kolkovsky, Vl., E-mail: kolkov@ifpan.edu.pl

In the present study, we discuss the origin of two dominant deep levels (E42 and E262) observed in n-type Si, which is subjected to hydrogenation by wet chemical etching or a dc H-plasma treatment. Their activation enthalpies determined from Laplace deep level transient spectroscopy measurements are E{sub C}-0.06 eV (E42) and E{sub C}-0.51 eV (E262). The similar annealing behavior and identical depth profiles of E42 and E262 correlate them with two different charge states of the same defect. E262 is attributed to a single acceptor state due to the absence of the Poole-Frenkel effect and the lack of a capture barrier formore » electrons. The emission rate of E42 shows a characteristic enhancement with the electric field, which is consistent with the assignment to a double acceptor state. In samples with different carbon and hydrogen content, the depth profiles of E262 can be explained by a defect with one H-atom and one C-atom. From a comparison with earlier calculations [Andersen et al., Phys. Rev. B 66, 235205 (2002)], we attribute E42 to the double acceptor and E262 to the single acceptor state of the CH{sub 1AB} configuration, where one H atom is directly bound to carbon in the anti-bonding position.« less

Chiral self-discrimination of the enantiomers of alpha-phenylethylamine derivatives in proton NMR.

PubMed

Huang, Shao-Hua; Bai, Zheng-Wu; Feng, Ji-Wen

2009-05-01

Two types of chiral analytes, the urea and amide derivatives of alpha-phenylethylamine, were prepared. The effect of inter-molecular hydrogen-bonding interaction on self-discrimination of the enantiomers of analytes has been investigated using high-resolution (1)H NMR. It was found that the urea derivatives with double-hydrogen-bonding interaction exhibit not only the stronger hydrogen-bonding interaction but also better self-recognition abilities than the amide derivatives (except for one bearing two NO(2) groups). The present results suggest that double-hydrogen-bonding interaction promotes the self-discrimination ability of the chiral compounds. Copyright (c) 2009 John Wiley & Sons, Ltd.

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

PubMed

Stinson, Craig A; Xia, Yu

2016-06-21

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

Two-dimensional Electronic Double-Quantum Coherence Spectroscopy

PubMed Central

Kim, Jeongho; Mukamel, Shaul

2009-01-01

CONSPECTUS The theory of electronic structure of many-electron systems like molecules is extraordinarily complicated. A lot can be learned by considering how electron density is distributed, on average, in the average field of the other electrons in the system. That is, mean field theory. However, to describe quantitatively chemical bonds, reactions, and spectroscopy requires consideration of the way that electrons avoid each other by the way they move; this is called electron correlation (or in physics, the many-body problem for fermions). While great progress has been made in theory, there is a need for incisive experimental tests that can be undertaken for large molecular systems in the condensed phase. Here we report a two-dimensional (2D) optical coherent spectroscopy that correlates the double excited electronic states to constituent single excited states. The technique, termed two-dimensional double-coherence spectroscopy (2D-DQCS), makes use of multiple, time-ordered ultrashort coherent optical pulses to create double- and single-quantum coherences over time intervals between the pulses. The resulting two-dimensional electronic spectrum maps the energy correlation between the first excited state and two-photon allowed double-quantum states. The principle of the experiment is that when the energy of the double-quantum state, viewed in simple models as a double HOMO to LUMO excitation, equals twice that of a single excitation, then no signal is radiated. However, electron-electron interactions—a combination of exchange interactions and electron correlation—in real systems generates a signal that reveals precisely how the energy of the double-quantum resonance differs from twice the single-quantum resonance. The energy shift measured in this experiment reveals how the second excitation is perturbed by both the presence of the first excitation and the way that the other electrons in the system have responded to the presence of that first excitation. We compare a series of organic dye molecules and find that the energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of milli-electronvolts, and it depends quite sensitively on molecular geometry. These results demonstrate the effectiveness of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wavefunctions, and electron correlation in electronic excited states and excitons. PMID:19552412

Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

NASA Astrophysics Data System (ADS)

Veals, Jeffrey D.; Thompson, Donald L.

2014-04-01

Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.

Molecular motions of [Beta]-carotene and a carotenoporphyrin dyad in solution. A carbon-13 NMR spin-lattice relaxation time study

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

Li, S.; Swindle, S.L.; Smith, S.K.

1995-03-09

Analysis of [sup 13]C NMR spin-lattice relaxation times (T[sub 1]) yields information concerning both overall tumbling of molecules in solution and internal rotations about single bonds. Relaxation time and nuclear Overhauser effect data have been obtained for [Beta]-carotene and two related molecules, squalane and squalene, for zinc meso-tetraphenylporphyrin, and for a dyad consisting of a porphyrin covalently linked to a carotenoid polyene through a trimethylene bridge. Squalane and squalene, which lack conjugated double bonds, behave essentially as limp string, with internal rotations at least as rapid as overall isotropic tumbling motions. In contrast, [Beta]-carotene reorients as a rigid rod, withmore » internal motions which are too slow to affect relaxation times. Modeling it as an anisotropic rotor yields a rotational diffusion coefficient for motion about the major axis which is 14 times larger than that for rotation about axes perpendicular to that axis. The porphyrin reorients more nearly isotropically and features internal librational motions about the single bonds to the phenyl groups. The relaxation time data for the carotenoporphyrin are consistent with internal motions similar to those of a medieval military flail. 31 refs., 3 figs., 5 tabs.« less

New antioxidants and antioxidant systems for improvement of the stability of vegetable oils and fish oils

USDA-ARS?s Scientific Manuscript database

Most vegetable oils and fish oils contain polyunsaturated fatty acids ranging from 18 carbons with two to three double bonds, to 22 or 24 carbons, and up to six double bonds. Nutritional research over the years has indicated that individual fatty acids from the diet play a complex role in nutrition ...

Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

PubMed Central

Jiang, Lei; Wang, Wei; Xu, Yi-Sheng

2009-01-01

The addition reactions of NO3 to limonene have been investigated using ab initio methods. Six different possibilities for NO3 addition to the double bonds, which correspond to the two C–C double bonds (endocyclic or exocyclic) have been considered. The negative activation energies for the addition of NO3 to limonene are calculated and the energies of NO3-limonene radical adducts are found to be 14.55 to 20.17 kcal mol-1 more stable than the separated NO3 and limonene at the CCSD(T)/6–31G(d) + CF level. The results also indicate that the endocyclic addition reaction is more energetically favorable than the exocyclic one. PMID:19865516

Evidence for cis-trans isomerization of a double bond in the fatty acids of the psychrophilic bacterium Vibrio sp. strain ABE-1.

PubMed

Morita, N; Shibahara, A; Yamamoto, K; Shinkai, K; Kajimoto, G; Okuyama, H

1993-02-01

Vibrio sp. strain ABE-1 was grown in a medium that contained as its stable isotope tracer either [2,2-2H2]cis-9-hexadecenoic or [2,2-2H2]trans-9-hexadecenoic acid. Gas chromatographic-mass spectrometric analysis of the cis-9-hexadecenoic and trans-9-hexadecenoic acid fractions from the cells revealed the formation of an intracellularly isomerized 2,2-2H2-fatty acid which differed from the tracer only in the geometrical configuration of the double bond. This observation shows that cis-trans isomerization without a shift in double-bond position between these two geometric hexadecenoic acid isomers can occur in the cells.

Evidence for cis-trans isomerization of a double bond in the fatty acids of the psychrophilic bacterium Vibrio sp. strain ABE-1.

PubMed Central

Morita, N; Shibahara, A; Yamamoto, K; Shinkai, K; Kajimoto, G; Okuyama, H

1993-01-01

Vibrio sp. strain ABE-1 was grown in a medium that contained as its stable isotope tracer either [2,2-2H2]cis-9-hexadecenoic or [2,2-2H2]trans-9-hexadecenoic acid. Gas chromatographic-mass spectrometric analysis of the cis-9-hexadecenoic and trans-9-hexadecenoic acid fractions from the cells revealed the formation of an intracellularly isomerized 2,2-2H2-fatty acid which differed from the tracer only in the geometrical configuration of the double bond. This observation shows that cis-trans isomerization without a shift in double-bond position between these two geometric hexadecenoic acid isomers can occur in the cells. PMID:8423164

Poly(ADP-ribose) polymerases covalently modify strand break termini in DNA fragments in vitro

PubMed Central

Talhaoui, Ibtissam; Lebedeva, Natalia A.; Zarkovic, Gabriella; Saint-Pierre, Christine; Kutuzov, Mikhail M.; Sukhanova, Maria V.; Matkarimov, Bakhyt T.; Gasparutto, Didier; Saparbaev, Murat K.; Lavrik, Olga I.; Ishchenko, Alexander A.

2016-01-01

Poly(ADP-ribose) polymerases (PARPs/ARTDs) use nicotinamide adenine dinucleotide (NAD+) to catalyse the synthesis of a long branched poly(ADP-ribose) polymer (PAR) attached to the acceptor amino acid residues of nuclear proteins. PARPs act on single- and double-stranded DNA breaks by recruiting DNA repair factors. Here, in in vitro biochemical experiments, we found that the mammalian PARP1 and PARP2 proteins can directly ADP-ribosylate the termini of DNA oligonucleotides. PARP1 preferentially catalysed covalent attachment of ADP-ribose units to the ends of recessed DNA duplexes containing 3′-cordycepin, 5′- and 3′-phosphate and also to 5′-phosphate of a single-stranded oligonucleotide. PARP2 preferentially ADP-ribosylated the nicked/gapped DNA duplexes containing 5′-phosphate at the double-stranded termini. PAR glycohydrolase (PARG) restored native DNA structure by hydrolysing PAR-DNA adducts generated by PARP1 and PARP2. Biochemical and mass spectrometry analyses of the adducts suggested that PARPs utilise DNA termini as an alternative to 2′-hydroxyl of ADP-ribose and protein acceptor residues to catalyse PAR chain initiation either via the 2′,1″-O-glycosidic ribose-ribose bond or via phosphodiester bond formation between C1′ of ADP-ribose and the phosphate of a terminal deoxyribonucleotide. This new type of post-replicative modification of DNA provides novel insights into the molecular mechanisms underlying biological phenomena of ADP-ribosylation mediated by PARPs. PMID:27471034

Isotope effects associated with tunneling and double proton transfer in the hydrogen bonds of benzoic acid

NASA Astrophysics Data System (ADS)

Xue, Q.; Horsewill, A. J.; Johnson, M. R.; Trommsdorff, H. P.

2004-06-01

The isotope effects associated with double proton transfer in the hydrogen bonds of benzoic acid (BA) dimers have been measured using field-cycling 1H NMR relaxometry and quasielastic neutron scattering. By studying mixed isotope (hydrogen and deuterium) samples, the dynamics of three isotopologues, BA-HH, BA-HD, and BA-DD, have been investigated. Low temperature measurements provide accurate measurements of the incoherent tunneling rate, k0. This parameter scales accurately with the mass number, m, according to the formula k0=(E/m)e-F√m providing conclusive evidence that the proton transfer process is a strongly correlated motion of two hydrons. Furthermore, we conclude that the tunneling pathway is the same for the three isotopologue species. Measurements at higher temperatures illuminate the through barrier processes that are mediated via intermediate or excited vibrational states. In parallel with the investigation of proton transfer dynamics, the theoretical and experimental aspects of studying spin-lattice relaxation in single crystals of mixed isotope samples are investigated in depth. Heteronuclear dipolar interactions between 1H and 2H isotopes contribute significantly to the overall proton spin-lattice relaxation and it is shown that these must be modeled correctly to obtain accurate values for the proton transfer rates. Since the sample used in the NMR measurements was a single crystal, full account of the orientation dependence of the spin-lattice relaxation with respect to the applied B field was incorporated into the data analysis.

Hindered Csbnd N bond rotation in triazinyl dithiocarbamates

NASA Astrophysics Data System (ADS)

Jung, Taesub; Do, Hee-Jin; Son, Jongwoo; Song, Jae Hee; Cha, Wansik; Kim, Yeong-Joon; Lee, Kyung-Koo; Kwak, Kyungwon

2018-01-01

The substituent and solvent effects on the rotation around a Csbnd N amide bond were studied for a series of triazine dibenzylcarbamodithioates. The Gibbs free energies (ΔG‡) were measured to be 16-18 kcal/mol in DMSO-d6 and toluene-d8 using variable-temperature nuclear magnetic resonance (VT-1H NMR) spectroscopy. Density functional theory (DFT) calculations reproduced the experimental observations with various substituents, as well as solvents. From the detailed analysis of the DFT results, we found that the electron donating dibenzyl amine group increased the electron population on the triazinyl ring, which decreased the rotational barrier of the Csbnd N bond in the dithiocarbamate group attached to the triazinyl ring. The higher electron population on the triazine moiety stabilizes the partial double bond character of the Ssbnd C bond, which competitively excludes the double bond character of the Csbnd N bond. Therefore, the rotational dynamics of the Csbnd N bond in dithiocarbamates can be a sensitive probe to small differences in the electron population of substituents on sulfur.

Electronic communication in phosphine substituted bridged dirhenium complexes - clarifying ambiguities raised by the redox non-innocence of the C4H2- and C4-bridges.

PubMed

Li, Yan; Blacque, Olivier; Fox, Thomas; Luber, Sandra; Polit, Walther; Winter, Rainer F; Venkatesan, Koushik; Berke, Heinz

2016-04-07

The mononuclear rhenium carbyne complex trans-[Re(C[triple bond, length as m-dash]CSiMe3)([triple bond, length as m-dash]C-Me)(PMe3)4][PF6] (2) was prepared in 90% yield by heating a mixture of the dinitrogen complex trans-[ReCl(N2)(PMe3)4] (1), TlPF6, and an excess of HC[triple bond, length as m-dash]CSiMe3. 2 could be deprotonated with KOtBu to the vinylidene complex trans-[Re(C[triple bond, length as m-dash]CSiMe3)([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(PMe3)4] (3) in 98% yield. Oxidation of 3 with 1.2 equiv. of [Cp2Fe][PF6] at -78 °C gave the Cβ-C'β coupled dinuclear rhenium biscarbyne complex trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-CH2-CH2-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 (5) in 92% yield. Deprotonation of 5 with an excess of KOtBu in THF produced the diamagnetic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[double bond, length as m-dash]C[double bond, length as m-dash]CH-CH[double bond, length as m-dash]C[double bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)] complex (E-6(S)) in 87% yield with an E-butadienediylidene bridge. Density functional theory (DFT) calculations of E-6(S) confirmed its singlet ground state. The Z-form of 6 (Z-6(S)) could not be observed, which is in accord with its DFT calculated 17.8 kJ mol(-1) higher energy. Oxidation of E-6 with 2 equiv. of [Cp2Fe][PF6] resulted in the stable diamagnetic dicationic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-CH[double bond, length as m-dash]CH-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 complex (E-6[PF6]2) with an ethylenylidene dicarbyne structure of the bridge. The paramagnetic mixed-valence (MV) complex E-6[PF6] was obtained by comproportionation of E-6(S) and E-6[PF6]2 or by oxidation of E-6(S) with 1 equiv. of [Cp2Fe][PF6]. The dicationic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-C[triple bond, length as m-dash]C-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 (7[PF6]2) complex, attributed a butynedi(triyl) bridge structure, was obtained by deprotonation of E-6[PF6]2 with KOtBu followed by oxidation with 2 equiv. of [Cp2Fe][PF6]. The neutral complex 7 could be accessed best by reduction of 7[PF6]2 with KH in the presence of 18-crown-6. According to DFT calculations 7 possesses two equilibrating electronic states: diamagnetic 7(S) and triplet 7(F) with ferromagnetically coupled spins. The latter is calculated to be 5.2 kcal mol(-1) lower in energy than 7(S). There is experimental evidence that 7(S) prevails in solution. 7 could not be isolated in the crystalline state and is unstable transforming mainly by H-abstraction to give E-6(S). UV-Vis-NIR spectroscopy for the dinuclear rhenium complexes E-6(S), E-6[PF6] and E-6[PF6]2, as well as EPR spectroscopic and variable-temperature magnetization measurements for the MV complex E-6[PF6] were also conducted. Spectro-electrochemical reduction studies on 7[PF6]2 allowed the characterization of the mono- and direduced forms of 7(+) and 7 by means of IR- and UV-Vis-NIR-spectroscopy and revealed the chemical fate of the higher reduced form.

On the inversion of the 1 Bu and 2 Ag electronic states in α,ω-diphenylpolyenes

NASA Astrophysics Data System (ADS)

Catalán, J.

2003-07-01

An alternative model to that of the inversion of the states 1Bu and 2Ag is proposed for interpreting the photophysics of the α,ω-diphenylpolyenes. This model is based upon the existence of two chemical structures with Bu symmetry, which may be ascribed to the same excited electronic state 1Bu. One of the two chemical structures corresponds to the Franck-Condon structure with conjugated single and double bonds for the polyene chain, and another consists of a nearly equivalent series of partial double bonds along the polyene chain. The latter relaxed structure is consistent with the observation of high torsional energy barriers and low photoisomerization quantum yields for diphenylhexatriene in the singlet excited state manifold. Interestingly, such a simple quantum model as that of the particle in a one-dimensional box provides quite an accurate description of the absorption spectroscopic properties of these major compounds. This is partly the result of the most stable structures for these compounds being of the all-trans type; such structures increase in length as additional ethylene units are added, which makes them very similar to a one-dimensional box becoming increasingly longer.

Effects of double and triple bonds on the spatial representations of odorants in the rat olfactory bulb.

PubMed

Johnson, Brett A; Ong, Joan; Lee, Kaman; Ho, Sabrina L; Arguello, Spart; Leon, Michael

2007-02-01

Many naturally occurring volatile chemicals that are detected through the sense of smell contain unsaturated (double or triple) carbon-carbon bonds. These bonds can affect odors perceived by humans, yet in a prior study of unsaturated hydrocarbons we found only very minor effects of unsaturated bonds. In the present study, we tested the possibility that unsaturated bonds affect the recognition of oxygen-containing functional groups, because humans perceive odor differences between such molecules. We therefore compared spatial activity patterns across the entire glomerular layer of the rat olfactory bulb evoked by oxygen-containing odorants differing systematically in the presence, position, number, and stereochemistry of unsaturated bonds. We quantified activity patterns by mapping [(14)C]2-deoxyglucose uptake into anatomically standardized data matrices, which we compared statistically. We found that the presence and number of unsaturated bonds consistently affected activity patterns, with the largest effect related to the presence of a triple bond. Effects of bond saturation included a loss of activity in glomeruli strongly activated by the corresponding saturated odorants and/or the presence of activity in areas not stimulated by the corresponding saturated compounds. The position of double bonds also affected patterns of activity, but cis vs. trans configuration had no measurable impact in all five sets of stereoisomers that we studied. These results simultaneously indicate the importance of interactions between carbon-carbon bond types and functional groups in the neural coding of odorant chemical information and highlight the emerging concept that the rat olfactory system is more sensitive to certain types of chemical differences than others. (c) 2006 Wiley-Liss, Inc.

Photoelectron spectroscopy of B4O4-: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

NASA Astrophysics Data System (ADS)

Tian, Wen-Juan; Zhao, Li-Juan; Chen, Qiang; Ou, Ting; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin; Li, Si-Dian

2015-04-01

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O40/- clusters. The measured PES spectra of B4O4- exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4- (2A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4- (2B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O40/- clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O40/- clusters. This work is the first experimental study on a molecular system with an o-bond.

Attosecond Spectroscopy Probing Electron Correlation Dynamics

NASA Astrophysics Data System (ADS)

Winney, Alexander H.

Electrons are the driving force behind every chemical reaction. The exchange, ionization, or even relaxation of electrons is behind every bond broken or formed. According to the Bohr model of the atom, it takes an electron 150 as to orbit a proton[6]. With this as a unit time scale for an electron, it is clear that a pulse duration of several femtoseconds will not be sufficient to understanding electron dynamics. Our work demonstrates both technical and scientific achievements that push the boundaries of attosecond dynamics. TDSE studies show that amplification the yield of high harmonic generation (HHG) may be possible with transverse confinement of the electron. XUV-pump-XUV-probe shows that the yield of APT train can be sufficient for 2-photon double ionization studies. A zero dead-time detection system allows for the measurement of state-resolved double ionization for the first time. Exploiting attosecond angular streaking[7] probes sequential and non-sequential double ionization via electron-electron correlations with attosecond time resolution. Finally, using recoil frame momentum correlation, the fast dissociation of CH 3I reveals important orbital ionization dynamics of non-dissociative & dissociative, single & double ionization.

Bond angle variations in XH3 [X = N, P, As, Sb, Bi]: the critical role of Rydberg orbitals exposed using a diabatic state model.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

Ammonia adopts sp(3) hybridization (HNH bond angle 108°) whereas the other members of the XH3 series PH3, AsH3, SbH3, and BiH3 instead prefer octahedral bond angles of 90-93°. We use a recently developed general diabatic description for closed-shell chemical reactions, expanded to include Rydberg states, to understand the geometry, spectroscopy and inversion reaction profile of these molecules, fitting its parameters to results from Equation of Motion Coupled-Cluster Singles and Doubles (EOM-CCSD) calculations using large basis sets. Bands observed in the one-photon absorption spectrum of NH3 at 18.3 eV, 30 eV, and 33 eV are reassigned from Rydberg (formally forbidden) double excitations to valence single-excitation resonances. Critical to the analysis is the inclusion of all three electronic states in which two electrons are placed in the lone-pair orbital n and/or the symmetric valence σ* antibonding orbital. An illustrative effective two-state diabatic model is also developed containing just three parameters: the resonance energy driving the high-symmetry planar structure, the reorganization energy opposing it, and HXH bond angle in the absence of resonance. The diabatic orbitals are identified as sp hybrids on X; for the radical cations XH3(+) for which only 2 electronic states and one conical intersection are involved, the principle of orbital following dictates that the bond angle in the absence of resonance is acos(-1/5) = 101.5°. The multiple states and associated multiple conical intersection seams controlling the ground-state structure of XH3 renormalize this to acos[3 sin(2)(2(1/2)atan(1/2))/2 - 1/2] = 86.7°. Depending on the ratio of the resonance energy to the reorganization energy, equilibrium angles can vary from these limiting values up to 120°, and the anomalously large bond angle in NH3 arises because the resonance energy is unexpectedly large. This occurs as the ordering of the lowest Rydberg orbital and the σ* orbital swap, allowing Rydbergization to compresses σ* to significantly increase the resonance energy. Failure of both the traditional and revised versions of the valence-shell electron-pair repulsion (VSEPR) theory to explain the ground-state structures in simple terms is attributed to exclusion of this key physical interaction.

Sequential Diels–Alder/[3,3]-sigmatropic rearrangement reactions of β-nitrostyrene with 3-methyl-1,3-pentadiene

PubMed Central

Pipic, Alma; Zeller, Matthias; Tsetsakos, Panagiota

2013-01-01

Summary The tin(IV)-catalyzed reaction of β-nitrostyrene with (E)-3-methyl-1,3-pentadiene in toluene afforded two major nitronic ester cycloadducts in 27% and 29% yield that arise from the reaction at the less substituted diene double bond. Also present were four cycloadducts from the reaction at the higher substituted diene double bond, two of which were the formal cycloadducts of (Z)-3-methyl-1,3-pentadiene. A Friedel–Crafts alkylation product from the reaction of the diene, β-nitrostyrene, and toluene was also obtained in 10% yield. The tin(IV)-catalyzed reaction of β-nitrostyrene with (Z)-3-methyl-1,3-pentadiene in dichloromethane afforded four nitronic ester cycloadducts all derived from the reaction at the higher substituted double bond. One cycloadduct was isolated in 45% yield and two others are formal adducts of the E-isomer of the diene. The product formation in these reactions is consistent with a stepwise mechanism involving a zwitterionic intermediate. The initially isolated nitronic ester cycloadducts underwent tin(IV)-catalyzed interconversion, presumably via zwitterion intermediates. Cycloadducts derived from the reaction at the less substituted double bond of (E)-3-methyl-1,3-pentadiene underwent a [3,3]-sigmatropic rearrangement on heating to afford 4-nitrocyclohexenes. Cycloadducts derived from the reaction at the higher substituted diene double bond of either diene failed to undergo a thermal rearrangement. Rates and success of the rearrangement are consistent with a concerted mechanism possessing a dipolar transition state. An initial assessment of substituent effects on the rearrangement process is presented. PMID:24204426

Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons.

PubMed

Ng, Nga L; Kroll, Jesse H; Keywood, Melita D; Bahreini, Roya; Varutbangkul, Varuntida; Flagan, Richard C; Seinfeld, John H; Lee, Anita; Goldstein, Allen H

2006-04-01

Biogenic hydrocarbons emitted by vegetation are important contributors to secondary organic aerosol (SOA), but the aerosol formation mechanisms are incompletely understood. In this study, the formation of aerosols and gas-phase products from the ozonolysis and photooxidation of a series of biogenic hydrocarbons (isoprene, 8 monoterpenes, 4 sesquiterpenes, and 3 oxygenated terpenes) are examined. By comparing aerosol growth (measured by Differential Mobility Analyzers, DMAs) and gas-phase concentrations (monitored by a Proton Transfer Reaction Mass Spectrometer, PTR-MS), we study the general mechanisms of SOA formation. Aerosol growth data are presented in terms of a "growth curve", a plot of aerosol mass formed versus the amount of hydrocarbon reacted. From the shapes of the growth curves, it is found that all the hydrocarbons studied can be classified into two groups based entirely on the number of double bonds of the hydrocarbon, regardless of the reaction systems (ozonolysis or photooxidation) and the types of hydrocarbons studied: compounds with only one double bond and compounds with more than one double bond. For compounds with only one double bond, the first oxidation step is rate-limiting, and aerosols are formed mainly from low volatility first-generation oxidation products; whereas for compounds with more than one double bond, the second oxidation step may also be rate-limiting and second-generation products contribute substantially to SOA growth. This behavior is characterized by a vertical section in the growth curve, in which continued aerosol growth is observed even after all the parent hydrocarbon is consumed.

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

PubMed

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

2014-06-17

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

Gas Chromatographic Determination of Fatty Acids in Oils with Regard to the Assessment of Fire Hazard

NASA Astrophysics Data System (ADS)

Bartošová, Alica; Štefko, Tomáš

2017-06-01

The aim of the paper was to study and research the application of processing gas chromatographic method for the rapid and accurate determination of the composition of different types of oils, such as substances with the possibility of an adverse event spontaneous combustion or self-heating. Tendency to spontaneous combustion is chemically characterized mainly by the amount of unsaturated fatty acids, which have one or more double bonds in their molecule. Vegetable oils essentially consist of the following fatty acids: palmitic, stearic, oleic, linoleic, and linoleic. For the needs of assessment, the fire hazard must be known, in which the double bond is present, as well as their number in a molecule. As an analytical method, GCMS was used for determination of oils content. Three types of oil were used - rapeseed, sunflower, and coconut oil. Owing to the occurrence of linoleic acid C18:2 (49.8 wt.%) and oleic acid C18:1 (43.3 wt.%) with double bonds, sunflower oil is the most prone to self-heating. The coconut and rapeseed oils contain double bond FAME in lesser amount, and their propensity to self-heating is relatively low.

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

NASA Technical Reports Server (NTRS)

Hart-Smith, L. J.

1973-01-01

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

New ruthenium carboxylate complexes having a 1-5-. eta. sup 5 -cyclooctadienyl ligand

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

Osakada, Kohtaro; Grohmann, A.; Yamamoto, Akio

1990-07-01

Reaction of 3-butenoic acid with Ru(cod)(cot) (cod) = 1-2-{eta}{sup 2}:5-6-{eta}{sup 2}-cyclooctadiene; cot = 1-6-{eta}{sup 6}-cyclooctatriene in the presence of PMe{sub 3} gives a new ruthenium(II) complex formulated as Ru(1-5-{eta}{sup 5}-C{sub 8}H{sub 11}){eta}{sup 1}(O),{eta}{sup 2}(C,C{prime}-OCOCH{sub 2}CH{double bond}CH{sub 2})(PMe{sub 3}) (1). X-ray crystallography revealed its structure as having a piano-stool coordination around the ruthenium center. Crystals of 1 are tetragonal, space group P4{sub 3}2{sub 1}2, with a = 12.559 (3) {angstrom}, c = 20.455 (4) {angstrom}, and Z = 8. {sup 1}H and {sup 13}C({sup 1}H) NMR spectra of 1 agree well for the structure with the allyl entity of the carboxylatemore » {pi}-bonded through the C{double bond}C double bond to ruthenium.« less

Boundary of Phase Co-existence in Docosahexaenoic Acid System

NASA Astrophysics Data System (ADS)

Lor, Chai; Hirst, Linda S.

2011-11-01

Docosahexaenoic acid (DHA) is a highly polyunsaturated fatty acid (PUFA) that exhibits six double bonds in the hydrocarbon tail. It induces phase separation of the membrane into liquid order and liquid disorder in mixtures containing other lipids with more saturation and cholesterol. With the utilization of atomic force microscopy, phase co-existence is observed in lipid mixtures containing DHA on a single supported lipid bilayer. The boundary of phase co-existence with decreasing DHA concentration is explored. The elastic force, thickness, and roughness of the different phases are investigated.

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

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

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

2015-03-14

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

The concept, reality and utility of single-site heterogeneous catalysts (SSHCs).

PubMed

Thomas, John Meurig

2014-05-07

Very substantial advances have recently been made in the design and construction of solid catalysts and in elucidating both their mode of operation and the factors that determine their selectivity and longevity. This Perspective explains how and why such progress has been made. One important factor, the deployment of single-site heterogeneous and enzymatic catalysts, used either alone or in conjunction with other strategies, including metabolic engineering, enables a multitude of new products (for example, environmentally clean jet fuel) to be readily manufactured. In a practical sense SSHCs enable the advantages of homogeneous and to a lesser degree enzymatic catalysts to be united with those of heterogeneous ones. With the aid of the vastly increasing families of nanoporous solids, desired catalytically active sites may be engineered in atomic detail on their inner, accessible surfaces, thereby opening up new possibilities in synthetic organic chemistry - as in the smooth formation of C-C and C[double bond, length as m-dash]N bonds in a number of intermolecular reactions - as well as in photocatalysts and in fluidized catalytic cracking of hydrocarbons.

Complete indium-free CW 200W passively cooled high power diode laser array using double-side cooling technology

NASA Astrophysics Data System (ADS)

Wang, Jingwei; Zhu, Pengfei; Liu, Hui; Liang, Xuejie; Wu, Dihai; Liu, Yalong; Yu, Dongshan; Zah, Chung-en; Liu, Xingsheng

2017-02-01

High power diode lasers have been widely used in many fields. To meet the requirements of high power and high reliability, passively cooled single bar CS-packaged diode lasers must be robust to withstand thermal fatigue and operate long lifetime. In this work, a novel complete indium-free double-side cooling technology has been applied to package passively cooled high power diode lasers. Thermal behavior of hard solder CS-package diode lasers with different packaging structures was simulated and analyzed. Based on these results, the device structure and packaging process of double-side cooled CS-packaged diode lasers were optimized. A series of CW 200W 940nm high power diode lasers were developed and fabricated using hard solder bonding technology. The performance of the CW 200W 940nm high power diode lasers, such as output power, spectrum, thermal resistance, near field, far field, smile, lifetime, etc., is characterized and analyzed.

Probing Fe-V Bonding in a C3-Symmetric Heterobimetallic Complex.

PubMed

Greer, Samuel M; McKay, Johannes; Gramigna, Kathryn M; Thomas, Christine M; Stoian, Sebastian A; Hill, Stephen

2018-04-30

Direct metal-metal bonding of two distinct first-row transition metals remains relatively unexplored compared to their second- and third-row heterobimetallic counterparts. Herein, a recently reported Fe-V triply bonded species, [V( i PrNPPh 2 ) 3 FeI] (1; Kuppuswamy, S.; Powers, T. M.; Krogman, J. P.; Bezpalko, M. W.; Foxman, B. M.; Thomas, C. M. Vanadium-iron complexes featuring metal-metal multiple bonds. Chem. Sci. 2013, 4, 3557-3565), is investigated using high-frequency electron paramagnetic resonance, field- and temperature-dependent 57 Fe nuclear gamma resonance (Mössbauer) spectroscopy, and high-field electron-electron double resonance detected nuclear magnetic resonance. From the use of this suite of physical methods, we have assessed the electronic structure of 1. These studies allow us to establish the effective g̃ tensors as well as the Fe/V electro-nuclear hyperfine interaction tensors of the spin S = 1 / 2 ground state. We have rationalized these tensors in the context of ligand field theory supported by quantum chemical calculations. This theoretical analysis suggests that the S = 1 / 2 ground state originates from a single unpaired electron predominately localized on the Fe site.

A detailed experimental and theoretical study of two novel substituted trifluoromethylchromones. The influence of the bulky bromine atom on the crystal packing.

PubMed

Alcívar León, C D; Echeverría, G A; Piro, O E; Ulic, S E; Jios, J L

2015-02-05

The new 3-methyl-2-trifluoromethylchromone (1) and 3-bromomethyl-2-trifluoromethylchromone (2) compounds were synthesized and characterized by vibrational (IR, Raman), UV-Vis and NMR ((1)H, (13)C and (19)F) spectroscopy and MS spectrometry. The crystal structures of 1 and 2 were determined by X-ray diffraction methods. Both compounds crystallize in the monoclinic P21/c space group with Z=4 molecules per unit cell. The structures were solved from 1423 (1) and 1856 (2) reflections with I>2σ (I) and refined by full-matrix least-squares to agreement R1-values of 0.0403 (1) and 0.0554 (2). Because of π-bonding delocalization, the organic molecular skeletons are planar and the molecular bonding structures can be described by formally single, double and resonant bonds. In 2, the CF3 group revealed a strong rotational disorder around the CCF3 bond, which could be explained in terms of four split positions with about uniform angular distribution. The vibrational, electronic and NMR, spectra were discussed and assigned with the assistance of DFT calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

Detection of carbon-fluorine bonds in organofluorine compounds by Raman spectroscopy using a copper-vapor laser

NASA Astrophysics Data System (ADS)

Sharts, Clay M.; Gorelik, Vladimir S.; Agoltsov, A. M.; Zlobina, Ludmila I.; Sharts, Olga N.

1999-02-01

The Raman spectra of fluoro-organic compounds show specific emission bands for carbon-fluorine bonds in the range 500- 800 wave numbers (cm-1)). With very limited exceptions, biological materials do not contain carbon- fluorine bonds. Fluoro-organic compounds introduced into biological samples can be detected by a Raman emission signal. Normal mode C-F bond bands are observed: (1) at 710- 785 cm -1 for trifluoromethyl groups; (2) at 530-610 cm -1 for aromatic organofluorine bonds; (3) a range centered at 690 cm -1 for difluoromethylene groups. Specific examples of normal mode C-F bond emissions for organofluorine compounds containing trifluoromethyl groups are: 1-bromoperfluorooctane, 726 cm -1; perfluorodecanoic acid, 730 cm -1; triperfluoropropylamine, 750 cm -1; 1,3,5-tris- (trifluoromethyl)-benzene, 730 cm -1; Fluoxetine (Prozac) commercial powdered pill at 782 cm -1. Compounds containing aromatic C-F bonds are: hexafluorobenzene, 569 cm MIN1; pentafluoropyridine, 589 cm -1. Difluoromethylene groups: perfluorodecalin, 692 cm-1; perfluorocyclohexane, 691 cm -1. Raman spectra were observed with a standard single monochromator. The 510.8 nm light source was a copper-vapor laser operated at 3-10 watts with 10-12 nanosecond pulses at 10 kHz repetition rate. Detection was made with a time-gated photomultiplier tube. Resonance Raman spectra were also observed at 255.4 nm, using a frequency doubling crystal. Observed spectra were free of fluorescence with very sharp strong C-F lines.

Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties

DOE PAGES

Bai, Yang; He, Hui-Min; Li, Ying; ...

2015-02-19

Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this study, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field,more » the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (H 2O) 2 cluster. Below the critical electric field, it is observed that with increasing field strength, H-bonding orbitals display gradual evolutions in the orbital energy, orbital ordering, and orbital nature (i.e., from typical -style orbital to unusual -style double H-bonding orbital). We also show that beyond the critical electric field, a single water whisker may disintegrate to form a loosely bound zwitterionic chain due to a relay-style proton transfer, whereas two water whiskers may undergo intermolecular cross-linking to form a quasi-two-dimensional water network. In conclusion, these results help shed new insight on the effects of electric fields on water whisker formation.« less

Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

PubMed

Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

2016-07-28

Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom transfer reaction.

Fast and accurate predictions of covalent bonds in chemical space.

PubMed

Chang, K Y Samuel; Fias, Stijn; Ramakrishnan, Raghunathan; von Lilienfeld, O Anatole

2016-05-07

We assess the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated σ bonding to hydrogen, as well as σ and π bonding between main-group elements, occurring in small sets of iso-valence-electronic molecules with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order Taylor expansions of covalent bonding potentials can achieve high accuracy if (i) the alchemical interpolation is vertical (fixed geometry), (ii) it involves elements from the third and fourth rows of the periodic table, and (iii) an optimal reference geometry is used. This leads to near linear changes in the bonding potential, resulting in analytical predictions with chemical accuracy (∼1 kcal/mol). Second order estimates deteriorate the prediction. If initial and final molecules differ not only in composition but also in geometry, all estimates become substantially worse, with second order being slightly more accurate than first order. The independent particle approximation based second order perturbation theory performs poorly when compared to the coupled perturbed or finite difference approach. Taylor series expansions up to fourth order of the potential energy curve of highly symmetric systems indicate a finite radius of convergence, as illustrated for the alchemical stretching of H2 (+). Results are presented for (i) covalent bonds to hydrogen in 12 molecules with 8 valence electrons (CH4, NH3, H2O, HF, SiH4, PH3, H2S, HCl, GeH4, AsH3, H2Se, HBr); (ii) main-group single bonds in 9 molecules with 14 valence electrons (CH3F, CH3Cl, CH3Br, SiH3F, SiH3Cl, SiH3Br, GeH3F, GeH3Cl, GeH3Br); (iii) main-group double bonds in 9 molecules with 12 valence electrons (CH2O, CH2S, CH2Se, SiH2O, SiH2S, SiH2Se, GeH2O, GeH2S, GeH2Se); (iv) main-group triple bonds in 9 molecules with 10 valence electrons (HCN, HCP, HCAs, HSiN, HSiP, HSiAs, HGeN, HGeP, HGeAs); and (v) H2 (+) single bond with 1 electron.

Nanostructured 2D cellular materials in silicon by sidewall transfer lithography NEMS

NASA Astrophysics Data System (ADS)

Syms, Richard R. A.; Liu, Dixi; Ahmad, Munir M.

2017-07-01

Sidewall transfer lithography (STL) is demonstrated as a method for parallel fabrication of 2D nanostructured cellular solids in single-crystal silicon. The linear mechanical properties of four lattices (perfect and defected diamond; singly and doubly periodic honeycomb) with low effective Young’s moduli and effective Poisson’s ratio ranging from positive to negative are modelled using analytic theory and the matrix stiffness method with an emphasis on boundary effects. The lattices are fabricated with a minimum feature size of 100 nm and an aspect ratio of 40:1 using single- and double-level STL and deep reactive ion etching of bonded silicon-on-insulator. Nanoelectromechanical systems (NEMS) containing cellular materials are used to demonstrate stretching, bending and brittle fracture. Predicted edge effects are observed, theoretical values of Poisson’s ratio are verified and failure patterns are described.

Concise synthesis of the bryostatin A-ring via consecutive C-C bond forming transfer hydrogenations.

PubMed

Lu, Yu; Krische, Michael J

2009-07-16

Under the conditions of C-C bond forming transfer hydrogenation, 1,3-propanediol 1 engages in double asymmetric carbonyl allylation to furnish the C(2)-symmetric diol 2. Double ozonolysis of 2 followed by TBS protection delivers aldehyde 3, which is subject to catalyst directed carbonyl reverse prenylation via transfer hydrogenation to deliver neopentyl alcohol 4 and, ultimately, the bryostatin A-ring 7. Through use of two consecutive C-C bond forming transfer hydrogenations, the Evans' bryostatin A-ring 7 is prepared in less than half the manipulations previously reported.

Tough, high performance, addition-type thermoplastic polymers

NASA Technical Reports Server (NTRS)

Pater, Ruth H. (Inventor)

1992-01-01

A tough, high performance polyimide is provided by reacting a triple bond conjugated with an aromatic ring in a bisethynyl compound with the active double bond in a compound containing a double bond activated toward the formation of a Diels-Adler type adduct, especially a bismaleimide, a biscitraconimide, or a benzoquinone, or mixtures thereof. Addition curing of this product produces a high linear polymeric structure and heat treating the highly linear polymeric structure produces a thermally stable aromatic addition-type thermoplastic polyimide, which finds utility in the preparation of molding compounds, adhesive compositions, and polymer matrix composites.

Determination of phospholipid regiochemistry by Ag(I) adduction and tandem mass spectrometry.

PubMed

Yoo, Hyun Ju; Håkansson, Kristina

2011-02-15

Collision-activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD) of Ag-adducted phospholipids were investigated as structural tools. Previously, determination of the acyl chains at the two phospholipid esterification sites has been performed based on the R(1)COO(-)/R(2)COO(-) ratio in negative ion mode CAD tandem mass spectrometry. However, the observed product ion ratio is dependent on the extent of unsaturation of the fatty acyl group at sn-2 as well as on the total chain length. Similarly, in positive ion mode CAD with/without alkaline or alkaline earth metal adduction, the ratio of product ions resulting from either R(1)COOH or R(2)COOH neutral losses is dependent on the nature of the phospholipid polar headgroup. Ag(+) ion chromatography, in which silver ions are part of the stationary phase, can provide information on double bond number/distribution as well as double bond configuration (cis/trans) because of interaction between Ag(+) ions and olefinic π electrons of fatty acids and lipids. We hypothesized that interactions between double bonds and Ag(+) may be utilized to also reveal phospholipid esterification site information in tandem mass spectrometry. CAD and IRMPD of Ag-adducted phospholipids with unsaturated fatty acids (R(x)COOH, x = 1 or 2) provided characteristic product ions, [R(x)COOH + Ag](+), and their neutral losses. The characteristic product ions and their abundances do not depend on the type of polar headgroup or the number of double bonds of unsaturated acyl chains. Tandem mass spectrometry of Cu-adducted phospholipids was also performed for comparison based on the Lewis acid and base properties of Cu(+) and phospholipid double bonds, respectively.

Carotenoid diagenesis in a marine sediment

NASA Technical Reports Server (NTRS)

Watts, C. D.; Maxwell, J. R.

1977-01-01

The major carotenoids at three levels (3, 40, and 175 m below the sediment-water interface) in a core from a marine sediment (Cariaco Trench, off Venezuela) have been examined. Mass and electronic spectral data have provided evidence for the onset of a progressive reduction of carotenoids in the geological column. The time scale of the process appears to depend on the particular carotenoid. Reduction of up to two double bonds is observed for the diol, zeaxanthin, in the oldest sediment (about 340,000 years old) but no reduction is observed in the younger samples (about 5000 and 56,000 years old). The diketone, canthaxanthin, shows evidence of reduction of up to two double bonds in the 56,000-yr sample and up to five double bonds in the oldest sample. No reduction of beta-carotene was observed in any of the samples.

Constructing Models in Teaching of Chemical Bonds: Ionic Bond, Covalent Bond, Double and Triple Bonds, Hydrogen Bond and Molecular Geometry

ERIC Educational Resources Information Center

Uce, Musa

2015-01-01

Studies in chemistry education show that chemistry topics are considered as abstract, complicated and hard to understand by students. For this reason, it is important to develop new materials and use them in classes for better understanding of abstract concepts. Moving from this point, a student-centered research guided by a teacher was conducted…

Bonding properties and bond activation of ylides: recent findings and outlook.

PubMed

Urriolabeitia, Esteban P

2008-11-14

The interaction of phosphorus and nitrogen ylides with metallic precursors has been examined from different points of view. The first one is related to the bonding properties of the ylides. Ylides with a unique stabilizing group bond through different atoms (the Calpha or the heteroatoms); while ylides with two stabilizing groups never coordinate through the Calpha atom. In the second section we examine the cause of the stereoselective coordination of bisylides of phosphorus, nitrogen and arsenic, and of mixed bisylides. We describe here the very interesting conformational preferences found in these systems, which have been determined and characterized. The DFT study of these bisylides has allowed for the characterization of strong intramolecular PO and AsO interactions, as well as moderate CHO[double bond, length as m-dash]C hydrogen bonds as the source of these conformational preferences. The third topic is related to the amazing reactivity of phosphorus ylides in bond activation processes. Depending on the nature of the metallic precursors, ylides can behave as sources of carbenes, of phosphine derivatives, of other ylides or of orthometallated complexes through P[double bond, length as m-dash]C, P-C or C-H bond activation reactions.

Construction of Injectable Double-Network Hydrogels for Cell Delivery.

PubMed

Yan, Yan; Li, Mengnan; Yang, Di; Wang, Qian; Liang, Fuxin; Qu, Xiaozhong; Qiu, Dong; Yang, Zhenzhong

2017-07-10

Herein we present a unique method of using dynamic cross-links, which are dynamic covalent bonding and ionic interaction, for the construction of injectable double-network (DN) hydrogels, with the objective of cell delivery for cartilage repair. Glycol chitosan and dibenzaldhyde capped poly(ethylene oxide) formed the first network, while calcium alginate formed the second one, and in the resultant DN hydrogel, either of the networks could be selectively removed. The moduli of the DN hydrogel were significantly improved compared to that of the parent single-network hydrogels and were tunable by changing the chemical components. In situ 3D cell encapsulation could be easily performed by mixing cell suspension to the polymer solutions and transferred through a syringe needle before sol-gel transition. Cell proliferation and mediated differentiation of mouse chondrogenic cells were achieved in the DN hydrogel extracellular matrix.

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

PubMed

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

2010-02-04

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

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

PubMed

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

2012-03-07

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

High-Performance Epoxy-Resin-Bonded Magnets Produced from the Sm2Fe17Nx Powders Coated by Copper and Zinc Metals

NASA Astrophysics Data System (ADS)

Noguchi, Kenji; Machida, Ken-ichi; Adachi, Gin-ya

2001-04-01

Fine powders of Sm2Fe17Nx coated with copper metal reduced from CuCl2 and/or zinc metal subsequently derived by photo-decomposition of diethylzinc [Zn(C2H5)2] were prepared, and their magnetic properties were characterized in addition to those of epoxy-resin-bonded magnets produced from the coated powders (Cu/Sm2Fe17Nx, Zn/Sm2Fe17Nx and Zn/Cu/Sm2Fe17Nx). The remanence (Br) and maximum energy product [(\\mathit{BH})max] of double metal-coated Zn/Cu/Sm2Fe17Nx powders were maintained at higher levels than those of single Zn metal-coated Sm2Fe17Nx ones (Zn/Sm2Fe17Nx) even after heat treatment at 673 K since the oxidation resistance and thermal stability were effectively improved by formation of the thick and uniform protection layer on the surface of Sm2Fe17Nx particles. Moreover, the epoxy-resin-bonded magnets produced from the Zn/Cu/Sm2Fe17Nx powders possessed good corrosion resistance in air at 393 K which it resulted in the smaller thermal irreversible flux loss than that of uncoated and single Zn metal-coated Sm2Fe17Nx powders in the temperature range of above 393 K.

Probing the interaction of archaeal DNA polymerases with deaminated bases using X-ray crystallography and non-hydrogen bonding isosteric base analogues.

PubMed

Killelea, Tom; Ghosh, Samantak; Tan, Samuel S; Heslop, Pauline; Firbank, Susan J; Kool, Eric T; Connolly, Bernard A

2010-07-13

Archaeal family-B DNA polymerases stall replication on encountering the pro-mutagenic bases uracil and hypoxanthine. This publication describes an X-ray crystal structure of Thermococcus gorgonarius polymerase in complex with a DNA containing hypoxanthine in the single-stranded region of the template, two bases ahead of the primer-template junction. Full details of the specific recognition of hypoxanthine are revealed, allowing a comparison with published data that describe uracil binding. The two bases are recognized by the same pocket, in the N-terminal domain, and make very similar protein-DNA interactions. Specificity for hypoxanthine (and uracil) arises from a combination of polymerase-base hydrogen bonds and shape fit between the deaminated bases and the pocket. The structure with hypoxanthine at position 2 explains the stimulation of the polymerase 3'-5' proofreading exonuclease, observed with deaminated bases at this location. A beta-hairpin element, involved in partitioning the primer strand between the polymerase and exonuclease active sites, inserts between the two template bases at the extreme end of the double-stranded DNA. This denatures the two complementary primer bases and directs the resulting 3' single-stranded extension toward the exonuclease active site. Finally, the relative importance of hydrogen bonding and shape fit in determining selectivity for deaminated bases has been examined using nonpolar isosteres. Affinity for both 2,4-difluorobenzene and fluorobenzimidazole, non-hydrogen bonding shape mimics of uracil and hypoxanthine, respectively, is strongly diminished, suggesting polar protein-base contacts are important. However, residual interaction with 2,4-difluorobenzene is seen, confirming a role for shape recognition.

Theoretical studies of chemisorption and dimer model systems: Moller-Plesset and configuration interaction calculations on PdH, PdC, PdO, PdF, Pd sub 2 , and PdCO

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

Schwerdtfeger, P.; McFeaters, J.S.; Moore, J.J.

1991-01-01

Ab initio SCF studies have been performed to study the molecular properties of several single-bonded palladium compounds, PdH, PdC, PdO, PdF, Pd{sub 2}, and PdCO, which are important in surface and materials science. Electron correlation effects were evaluated by a second- and third-order Moller-Plesset (MP) perturbation theory and a size-consistency-corrected configuration interaction with single and double substitutions (CISC). Relativistic effects were investigated for PdH and PdF. The ground state of PdC has been calculated at the CISC level to be a {sup 3}{Pi} state which is only 0.26 eV below the {sup 3}{Sigma}{sup {minus}} state (previously assigned ground state) andmore » 0.51 eV below the {sup 1}{Sigma}{sup +} state. PdC is predicted to be stable in the gas phase, and the possibility of preparing this compound is investigated. The bonding in CO chemisorbed on palladium is studied by using the model Pd-CO system. The effect of d{sub {pi}}-{pi}{sup *} back-bonding, discussed at the Hartree-Fock and CI level, is compared with results from multiple-scattering {Chi}{alpha} calculations. The C-O stretching frequency shift for CO on palladium was analyzed at various levels of theory, and the results indicated that the decrease in the CO force constant associated with chemisorption is not solely the result of d{sub {pi}}-{pi}{sup *} back-bonding.« less

The Pariser-Parr-Pople model for trans-polyenes. I. Ab initio and semiempirical study of the bond alternation in trans-butadiene

NASA Astrophysics Data System (ADS)

Förner, Wolfgang

1992-03-01

Ab initio investigations of the bond alternation in butadiene are presented. The atomic basis sets applied range from minimal to split valence plus polarization quality. With the latter one the Hartree-Fock limit for the bond alternation is reached. Correlation is considered on Møller-Plesset many-body perturbation theory of second order (MP2), linear coupled cluster doubles (L-CCD) and coupled cluster doubles (CCD) level. For the smaller basis sets it is shown that for the bond alternation π-π correlations are essential while the effects of σ-σ and σ-π correlations are, though large, nearly independent of bond alternation. On MP2 level the variation of σ-π correlation with bond alternation is surprisingly large. This is discussed as an artefact of MP2. Comparative Su-Schrieffer-Heeger (SSH) and Pariser-Parr-Pople (PPP) calculations show that these models in their usual parametrizations cannot reproduce the ab initio results.

A stable silicon(0) compound with a Si=Si double bond.

PubMed

Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; King, R Bruce; Schaefer, Henry F; von R Schleyer, Paul; Robinson, Gregory H

2008-08-22

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.

Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

DOE PAGES

Abergel, Rebecca J.; de Jong, Wibe A.; Deblonde, Gauthier J. -P.; ...

2017-10-11

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U 6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theorymore » (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.« less

Organometallic benzylidene anilines: donor-acceptor features in NCN-pincer Pt(ii) complexes with a 4-(E)-[(4-R-phenyl)imino]methyl substituent.

PubMed

Batema, Guido D; Lutz, Martin; Spek, Anthony L; van Walree, Cornelis A; van Klink, Gerard P M; van Koten, Gerard

2014-08-28

A series of organometallic 4,4'-substituted benzylidene aniline complexes 4-ClPt-3,5-(CH2NMe2)2C6H2CH[double bond, length as m-dash]NC6H4R'-4', abbreviated as PtCl[NCN(CH[double bond, length as m-dash]NC6H4R'-4')-4], with R' = NMe2, Me, H, Cl, CN (, respectively), was synthesized via a Schiff-base condensation reaction involving reaction of PtCl[NCN(CH[double bond, length as m-dash]O)-4] () with the appropriate 4-R'-substituted aniline derivative () in toluene. The resulting arylplatinum(ii) products were obtained in 75-88% yield. Notably, product was also obtained in 68% yield from a reaction in the solid state by grinding solid with aniline . The structures of , , and in the solid state (single crystal X-ray diffraction) showed a non-planar geometry, in particular for compound . The electronic interaction between the donor benzylidene fragment PtCl(NCN-CH) and the para-R' aniline substituent through the azomethine bridge was studied with NMR and UV/Vis spectroscopy. Linear correlations were found between the azomethine (1)H, the (195)Pt NMR and various (13)C NMR chemical shifts, and the substituent parameters σF and σR of R' at the aniline site. In common with organic benzylidene anilines, the azomethine (1)H NMR chemical shift showed anomalous substituent behavior. The (195)Pt NMR chemical shift of the platinum center can be used as a probe for the electronic properties of the delocalized π-system of the benzylidene aniline framework, to which it is connected. The dual substituent parameter treatment of the azomethine (13)C NMR shift gave important insight into the unique behaviour of the Pt-pincer group as a substituent. Inductively, it is a very strong electron-withdrawing group, whereas mesomerically it behaves like a very strong electron donating group.

Structure-Activity Correlations with Compounds Related to Abscisic Acid 1

PubMed Central

Sondheimer, Ernest; Walton, Daniel C.

1970-01-01

Inhibition of cell expansion of excised embryonic axes of Phaseolus vulgaris was used to evaluate the growth-inhibiting activity of abscisic acid and related compounds. None of the 13 compounds tested was as active as abscisic acid. 4-Hydroxyisophorone, a substance representative of the abscisic acid ring system was essentially inactive; cis, trans-3-methylsorbic acid, a compound resembling the side chain of abscisic acid, had low activity; and cis, trans-β-ionylideneacetic acid was one-sixth as active. Loss of the ring double bond results in a drastic decrease in biological activity. Comparison of our results with those reported previously leads to the suggestion that the double bond of the cyclohexyl moiety may have an important function in determining the degree of activity of cis, trans-ionylideneacetic acids. Two modes of action are discussed. It seems possible that the ring double bond is involved in covalent bonding in binding of the abscisic acid analogue to macromolecules. This may require formation of an intermediate epoxide. It can also be argued that stereochemical differences between cyclohexane derivatives are important factors in determining the degree of biological activity. PMID:5423465

Wafer bonded epitaxial templates for silicon heterostructures

DOEpatents

Atwater, Jr., Harry A.; Zahler, James M [Pasadena, CA; Morral, Anna Fontcubera I [Paris, FR

2008-03-11

A heterostructure device layer is epitaxially grown on a virtual substrate, such as an InP/InGaAs/InP double heterostructure. A device substrate and a handle substrate form the virtual substrate. The device substrate is bonded to the handle substrate and is composed of a material suitable for fabrication of optoelectronic devices. The handle substrate is composed of a material suitable for providing mechanical support. The mechanical strength of the device and handle substrates is improved and the device substrate is thinned to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. An upper portion of the device film exfoliated from the device substrate is removed to provide a smoother and less defect prone surface for an optoelectronic device. A heterostructure is epitaxially grown on the smoothed surface in which an optoelectronic device may be fabricated.

Reduction of the coupling vibration between the bending vibrators of the frequency-change-type two-axis acceleration sensor

NASA Astrophysics Data System (ADS)

Sugawara, Sumio; Sasaki, Yoshifumi; Kudo, Subaru

2018-07-01

The frequency-change-type two-axis acceleration sensor uses a cross-type vibrator consisting of four bending vibrators. When coupling vibration exists between these four bending vibrators, the resonance frequency of each vibrator cannot be adjusted independently. In this study, methods of reducing the coupling vibration were investigated by finite-element analysis. A method of adjusting the length of the short arm of each vibrator was proposed for reducing the vibration. When piezoelectric ceramics were bonded to the single-sided surface of the vibrator, the method was not sufficient. Thus, the ceramics with the same dimensions were bonded to double-sided surfaces. As a result, a marked reduction was obtained in this case. Also, the linearity of the sensor characteristics was significantly improved in a small acceleration range. Accordingly, it was clarified that considering the symmetry along the thickness direction of the vibrator is very important.

Wafer bonded epitaxial templates for silicon heterostructures

NASA Technical Reports Server (NTRS)

Atwater, Harry A., Jr. (Inventor); Zahler, James M. (Inventor); Morral, Anna Fontcubera I (Inventor)

2008-01-01

A heterostructure device layer is epitaxially grown on a virtual substrate, such as an InP/InGaAs/InP double heterostructure. A device substrate and a handle substrate form the virtual substrate. The device substrate is bonded to the handle substrate and is composed of a material suitable for fabrication of optoelectronic devices. The handle substrate is composed of a material suitable for providing mechanical support. The mechanical strength of the device and handle substrates is improved and the device substrate is thinned to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. An upper portion of the device film exfoliated from the device substrate is removed to provide a smoother and less defect prone surface for an optoelectronic device. A heterostructure is epitaxially grown on the smoothed surface in which an optoelectronic device may be fabricated.

IR-UV spectroscopy of jet-cooled 1-indanol: Restriction of the conformational space by hydration

NASA Astrophysics Data System (ADS)

Bouchet, Aude; Altnöder, Jonas; Broquier, Michel; Zehnacker, Anne

2014-11-01

The effect of hydration on a flexible amphiphilic molecule has been studied on the example of 1-hydroxyindan (1-indanol). Studies in jet-cooled conditions by means of resonance-enhanced two-photon ionization and IR-UV double resonance experiments show that the mono-hydrate 1-indanol(H2O) is formed in a dominant isomer, as well as the di-hydrate 1-indanol(H2O)2. 1-Indanol(H2O) favors a cooperative hydrogen bond pattern with -OH⋯O(H)-H⋯π topology, while 1-indanol(H2O)2 forms a cyclic hydrogen bond network with three OH⋯O interactions. The single conformation observed for the hydrates contrasts with the bare molecule which shows two dominant conformations, with the hydroxyl in axial or in equatorial position, respectively. Hydration therefore results in a restriction of the conformational space and conformational locking.

Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

1992-01-01

Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

The Electronic Structure and Spectra of Triphenylamines Functionalized by Phenylethynyl Groups

NASA Astrophysics Data System (ADS)

Baryshnikov, G. V.; Minaeva, V. A.; Minaev, B. F.; Grigoras, M.

2018-01-01

We study the features of the electronic structure and the IR, UV, and visible spectra of a series of triphenylamines substituted with phenylethynyl groups. The analysis is performed at the level of the density functional theory (DFT) and its nonstationary version in comparison with the experimental data of IR and electron spectroscopy. It is shown that, in the excited state, there is a change in the alternation of single, double, and triple bonds in accordance with the character of bonding and antibonding in the lowest vacant molecular orbital. The gradual introduction of additional phenylethynyl groups does not cause frequency shifts in the IR spectra of the molecules under study, but significantly affects the intensity of the corresponding IR bands. A similar effect is also observed in the electronic-absorption spectra of these compounds. This can be used for optical tuning of triphenylamines as promising materials for organic light-emitting diodes and solar cells.

Exactly solvable Schrödinger equation with double-well potential for hydrogen bond

NASA Astrophysics Data System (ADS)

Sitnitsky, A. E.

2017-05-01

We construct a double-well potential for which the Schrödinger equation can be exactly solved via reducing to the confluent Heun's one. Thus the wave function is expressed via the confluent Heun's function. The latter is tabulated in Maple so that the obtained solution is easily treated. The potential is infinite at the boundaries of the final interval that makes it to be highly suitable for modeling hydrogen bonds (both ordinary and low-barrier ones). We exemplify theoretical results by detailed treating the hydrogen bond in KHCO3 and show their good agreement with literature experimental data.

Highly Stable Double-Stranded DNA Containing Sequential Silver(I)-Mediated 7-Deazaadenine/Thymine Watson-Crick Base Pairs.

PubMed

Santamaría-Díaz, Noelia; Méndez-Arriaga, José M; Salas, Juan M; Galindo, Miguel A

2016-05-17

The oligonucleotide d(TX)9 , which consists of an octadecamer sequence with alternating non-canonical 7-deazaadenine (X) and canonical thymine (T) as the nucleobases, was synthesized and shown to hybridize into double-stranded DNA through the formation of hydrogen-bonded Watson-Crick base pairs. dsDNA with metal-mediated base pairs was then obtained by selectively replacing W-C hydrogen bonds by coordination bonds to central silver(I) ions. The oligonucleotide I adopts a duplex structure in the absence of Ag(+) ions, and its stability is significantly enhanced in the presence of Ag(+) ions while its double-helix structure is retained. Temperature-dependent UV spectroscopy, circular dichroism spectroscopy, and ESI mass spectrometry were used to confirm the selective formation of the silver(I)-mediated base pairs. This strategy could become useful for preparing stable metallo-DNA-based nanostructures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiroptical Properties of Imines Derived from R-(+)-Norbornenone: The Role of Electronegativity Differences.

PubMed

Wiberg, Kenneth B

2017-11-02

To allow a comparison with the specific rotations of R-(+)-5-methylenenorbornene (1) and R-(+)-norbornenone (2) we performed calculations at the LC-wPBE/aug-cc-pVTZ level for the imines (5a and 5b) derived from norbornenone and also for their protonated derivative (6). In accord with our results for simpler systems, the specific rotations increase in the order of 1 < 5 < 2 ≈ 6. In addition, the specific rotation of the protonated ketone was calculated and found to be considerably larger than that for 2 or 6. These rotations were found to be linearly dependent on the Hirshfeld charges at the carbon of the exocyclic double bond. This leads to the conclusion that charge transfer from the endocyclic double bond to the π* MO of the exocyclic double bond is an important component of the process that leads to the optical activity of these compounds.

Dihydroceramide desaturase inhibition by a cyclopropanated dihydroceramide analog in cultured keratinocytes.

PubMed

Brodesser, Susanne; Kolter, Thomas

2011-01-01

Most mammalian sphingolipids contain a 4,5-(E)-double bond. We report on the chemical synthesis of a dihydroceramide derivative that prevents the introduction of the double bond into sphingolipids. Minimal alteration of the parent structure by formally replacing the hydrogen atoms in the 5- and in the 6-position of the sphinganine backbone by a methylene group leads to an inhibitor of dihydroceramide desaturase in cultured cells. In the presence of 10-50 μM of compound (1), levels of biosynthetically formed dihydroceramide and-surprisingly-also of phytoceramide are elevated at the expense of ceramide. The cells respond to the lack of unsaturated sphingolipids by an elevation of mRNAs of enzymes required for sphingosine formation. At the same time, the analysis of proliferation and differentiation markers indicates that the sphingolipid double bond is required to keep the cells in a differentiated state.

Dihydroceramide Desaturase Inhibition by a Cyclopropanated Dihydroceramide Analog in Cultured Keratinocytes

PubMed Central

Brodesser, Susanne; Kolter, Thomas

2011-01-01

Most mammalian sphingolipids contain a 4,5-(E)-double bond. We report on the chemical synthesis of a dihydroceramide derivative that prevents the introduction of the double bond into sphingolipids. Minimal alteration of the parent structure by formally replacing the hydrogen atoms in the 5- and in the 6-position of the sphinganine backbone by a methylene group leads to an inhibitor of dihydroceramide desaturase in cultured cells. In the presence of 10–50 μM of compound (1), levels of biosynthetically formed dihydroceramide and—surprisingly—also of phytoceramide are elevated at the expense of ceramide. The cells respond to the lack of unsaturated sphingolipids by an elevation of mRNAs of enzymes required for sphingosine formation. At the same time, the analysis of proliferation and differentiation markers indicates that the sphingolipid double bond is required to keep the cells in a differentiated state. PMID:21490810

Experimental and theoretical distribution of electron density and thermopolimerization in crystals of Ph3Sb(O2CCH=CH2)2 complex

NASA Astrophysics Data System (ADS)

Fukin, Georgy K.; Samsonov, Maxim A.; Arapova, Alla V.; Mazur, Anton S.; Artamonova, Tatiana O.; Khodorkovskiy, Mikhail A.; Vasilyev, Aleksander V.

2017-10-01

In this paper we present the results of a high-resolution single crystal X-ray diffraction experiment of a triphenylantimony diacrylate (Ph3Sb(O2CCH=CH2)2 (1)) and a subsequent charge density study based on a topological analysis according to quantum theory of atoms in molecules (QTAIM) together with density functional theory (DFT) calculation of isolated molecule. The QTAIM was used to investigate nature of the chemical bonds and molecular graph of Ph3Sb(O2CCH=CH2)2 complex. The molecular graph shows that only in one acrylate group there is an evidence of bonding between antimony and carbonyl oxygen atom in terms of the presence of a bond path. Thus the molecular graph for this class of compounds does not provide a definitive picture of the chemical bonding and should be complemented with other descriptors, such as and a source function (SF), noncovalent interaction (NCI) index and delocalization index (DI). Moreover the realization of π…π interactions between double bonds of acrylate groups in adjacent molecules allowed us to carry out a thermopolimerization reaction in crystals of Ph3Sb(O2CCH=CH2)2 complex and to determine a probable structure of polymer by solid state CP/MAS 13C NMR.

Atomic-scale analysis of cation ordering in reduced calcium titanate.

PubMed

Li, Luying; Hu, Xiaokang; Jiang, Fan; Jing, Wenkui; Guo, Cong; Jia, Shuangfeng; Gao, Yihua; Wang, Jianbo

2017-11-03

The phenomenon of cation ordering is closely related to certain physical properties of complex oxides, which necessitates the search of underlying structure-property relationship at atomic resolution. Here we study the superlattices within reduced calcium titanate single crystal micro-pillars, which are unexpected from the originally proposed atomic model. Bright and dark contrasts at alternating Ti double layers perpendicular to b axis are clearly observed, but show no signs in corresponding image simulations based on the proposed atomic model. The multi-dimensional chemical analyses at atomic resolution reveal periodic lower Ti concentrations at alternating Ti double layers perpendicular to b axis. The following in-situ heating experiment shows no phase transition at the reported T c and temperature independence of the superlattices. The dimerization of the Ti-Ti bonds at neighboring double rutile-type chains within Ti puckered sheets are directly observed, which is found to be not disturbed by the cation ordering at alternating Ti double layers. The characterization of cation ordering of complex oxides from chemical and structural point of view at atomic resolution, and its reaction to temperature variations are important for further understanding their basic physical properties and exploiting potential applications.

Palladium-catalyzed Kumada coupling reaction of bromoporphyrins with silylmethyl Grignard reagents: preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems.

PubMed

Sugita, Noriaki; Hayashi, Satoshi; Hino, Fumio; Takanami, Toshikatsu

2012-12-07

We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH(2)OH, CH(2)OMe, and CH(2)F functionalities and the fluoride ion-mediated desilylative introduction of carbon-carbon single and double bonds.

A Study of the X(sup 2) Sigma(sup +) and A(sup 2) Pi States of MgAr(sup +) and MgKr(sup +)

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The ground (sup 2)Sigma(sup +) and lowest excited (sup 2)Pi states of MgAr(sup +) and MgKr(sup +) are studied using the singles and doubles configuration interaction (SDCI) approach, in conjunction with large basis sets. The effect of Mg core correlation and core polarization are accounted for using the core-polarization potential (CPP) approach. Franck-Condon factors, oscillator strengths, radiative lifetimes, dissociation energies, bond lengths, and excitation energies are reported. The computed results are in good agreement with the available experimental data.

Photoelectron spectroscopy of B4O4 (-): Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters.

PubMed

Tian, Wen-Juan; Zhao, Li-Juan; Chen, Qiang; Ou, Ting; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin; Li, Si-Dian

2015-04-07

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O4 (0/-) clusters. The measured PES spectra of B4O4 (-) exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4 (-) ((2)A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4 (-) ((2)B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O4 (0/-) clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O4 (0/-) clusters. This work is the first experimental study on a molecular system with an o-bond.

Laser-assisted patterning of double-sided adhesive tapes for optofluidic chip integration

NASA Astrophysics Data System (ADS)

Zamora, Vanessa; Janeczka, Christian; Arndt-Staufenbiel, Norbert; Havlik, George; Queisser, Marco; Schröder, Henning

2018-02-01

Portable high-sensitivity biosensors exhibit a growing demand in healthcare, food industry and environmental monitoring sectors. Optical biosensors based on photonic integration platforms are attractive candidates due to their high sensitivity, compactness and multiplexing capabilities. However, they need a low-cost and reliable integration with the microfluidic system. Laser-micropatterned double-sided biocompatible adhesive tapes are promising bonding layers for hybrid integration of an optofluidic biochip. As a part of the EU-PHOCNOSIS project, double-sided adhesive tapes have been proposed to integrate the polymer microfluidic system with the optical integrated waveguide sensor chip. Here the adhesive tape should be patterned in a micrometer scale in order to create an interaction between the sample that flows through the polymer microchannel and the photonic sensing microstructure. Three laser-assisted structuring methods are investigated to transfer microchannel patterns to the adhesive tape. The test structure design consists of a single channel with 400 μm wide, 30 mm length and two circular receivers with 3 mm radius. The best structuring results are found by using the picosecond UV laser where smooth and straight channel cross-sections are obtained. Such patterned tapes are used to bond blank polymer substrates to blank silicon substrates. As a proof of concept, the hybrid integration is tested using colored DI-water. Structuring tests related to the reduction of channel widths are also considered in this work. The use of this technique enables a simple and rapid manufacturing of narrow channels (50-60 μm in width) in adhesive tapes, achieving a cheap and stable integration of the optofluidic biochip.

Structure-spectrophotometric selectivity relationship in interactions of quercetin related flavonoids with double stranded and single stranded RNA

NASA Astrophysics Data System (ADS)

Piantanida, Ivo; Mašić, Lozika; Rusak, Gordana

2009-04-01

Interactions of five flavonoids with dsRNA and single stranded ssRNA were studied by UV/vis titrations. The results obtained supported the intercalative binding mode as a dominant interaction of studied flavonoids with dsRNA as well as major interaction with ssRNA. Furthermore, changes of the UV/vis spectra of flavonoids induced by addition of poly G or poly C, respectively, are significantly stronger than changes induced by double stranded poly G-poly C, pointing to essential role of the free poly G or poly C sequence (not hydrogen bonded in double helix). Exclusively poly G caused significant batochromic shift of the UV/vis maxima of all studied flavonoids, whereby the intensity of batochromic shift is nicely correlated to the number of OH groups of flavonoid. Unlikely to poly G, addition of poly A and poly U induced measurable changes only in the UV/vis spectra of flavonoids characterised by no OH (galangin) or three OH groups (myricetin) on the phenyl part of the molecule. Consequently, flavonoids with one- or two-OH groups on the phenyl part of the molecule (luteolin, fisetin, kaempferol) specifically differentiate between poly A, poly U (negligible changes in the UV/Vis spectra) and poly G (strong changes in the UV/Vis spectra) as well as poly C (moderate changes in the UV/Vis spectra).

Probing the origin of structural stability of single and double stapled p53 peptide analogs bound to MDM2.

PubMed

Guo, Zuojun; Streu, Kristina; Krilov, Goran; Mohanty, Udayan

2014-06-01

The stabilization of secondary structure is believed to play an important role in the peptide-protein binding interaction. In this study, the α-helical conformation and structural stability of single and double stapled all-hydrocarbon cross-linked p53 peptides when bound and unbound to MDM2 are investigated. We determined the effects of the peptide sequence, the stereochemistry of the cross-linker, the conformation of the double bond in the alkene bridge, and the length of the bridge, to the relative stability of the α-helix structure. The binding affinity calculations by WaterMap provided over one hundred hydration sites in the MDM2 binding pocket where water density is greater than twice that of the bulk, and the relative value of free energy released by displacing these hydration sites. In agreement with the experimental data, potentials of mean force obtained by weighted histogram analysis methods indicated the order of peptides from lowest to highest binding affinity. Our study provides a comprehensive rationalization of the relationship between peptide stapling strategy, the secondary structural stability, and the binding affinity of p53/MDM2 complex. We hope our efforts can help to further the development of a new generation p53/MDM2 inhibitors that can reactivate the function of p53 as tumor suppressor gene. © 2014 John Wiley & Sons A/S.

Double channel emission from a redox active single component quantum dot complex.

PubMed

Bhandari, Satyapriya; Roy, Shilaj; Pramanik, Sabyasachi; Chattopadhyay, Arun

2015-01-13

Herein we report the generation and control of double channel emission from a single component system following a facile complexation reaction between a Mn(2+) doped ZnS colloidal quantum dot (Qdot) and an organic ligand (8-hydroxy quinoline; HQ). The double channel emission of the complexed quantum dot-called the quantum dot complex (QDC)-originates from two independent pathways: one from the complex (ZnQ2) formed on the surface of the Qdot and the other from the dopant Mn(2+) ions of the Qdot. Importantly, reaction of ZnQ2·2H2O with the Qdot resulted in the same QDC formation. The emission at 500 nm with an excitation maximum at 364 nm is assigned to the surface complex involving ZnQ2 and a dangling sulfide bond. On the other hand, the emission at 588 nm-with an excitation maximum at 330 nm-which is redox tunable, is ascribed to Mn(2+) dopant. The ZnQ2 complex while present in QDC has superior thermal stability in comparison to the bare complex. Interestingly, while the emission of Mn(2+) was quenched by an electron quencher (benzoquinone), that due to the surface complex remained unaffected. Further, excitation wavelength dependent tunability in chromaticity color coordinates makes the QDC a potential candidate for fabricating a light emitting device of desired color output.

Anionic water pentamer and hexamer clusters: An extensive study of structures and energetics

NASA Astrophysics Data System (ADS)

Ünal, Aslı; Bozkaya, Uǧur

2018-03-01

An extensive study of structures and energetics for anionic pentamer and hexamer clusters is performed employing high level ab initio quantum chemical methods, such as the density-fitted orbital-optimized linearized coupled-cluster doubles (DF-OLCCD), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] methods. In this study, sixteen anionic pentamer clusters and eighteen anionic hexamer clusters are reported. Relative, binding, and vertical detachment energies (VDE) are presented at the complete basis set limit (CBS), extrapolating energies of aug4-cc-pVTZ and aug4-cc-pVQZ custom basis sets. The largest VDE values obtained at the CCSD(T)/CBS level are 9.9 and 11.2 kcal mol-1 for pentamers and hexamers, respectively, which are in very good agreement with the experimental values of 9.5 and 11.1 kcal mol-1. Our binding energy results, at the CCSD(T)/CBS level, indicate strong bindings in anionic clusters due to hydrogen bond interactions. The average binding energy per water molecules is -5.0 and -5.3 kcal mol-1 for pentamers and hexamers, respectively. Furthermore, our results demonstrate that the DF-OLCCD method approaches to the CCSD(T) quality for anionic clusters. The inexpensive analytic gradients of DF-OLCCD compared to CCSD or CCSD(T) make it very attractive for high-accuracy studies.

Anionic water pentamer and hexamer clusters: An extensive study of structures and energetics.

PubMed

Ünal, Aslı; Bozkaya, Uğur

2018-03-28

An extensive study of structures and energetics for anionic pentamer and hexamer clusters is performed employing high level ab initio quantum chemical methods, such as the density-fitted orbital-optimized linearized coupled-cluster doubles (DF-OLCCD), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] methods. In this study, sixteen anionic pentamer clusters and eighteen anionic hexamer clusters are reported. Relative, binding, and vertical detachment energies (VDE) are presented at the complete basis set limit (CBS), extrapolating energies of aug4-cc-pVTZ and aug4-cc-pVQZ custom basis sets. The largest VDE values obtained at the CCSD(T)/CBS level are 9.9 and 11.2 kcal mol -1 for pentamers and hexamers, respectively, which are in very good agreement with the experimental values of 9.5 and 11.1 kcal mol -1 . Our binding energy results, at the CCSD(T)/CBS level, indicate strong bindings in anionic clusters due to hydrogen bond interactions. The average binding energy per water molecules is -5.0 and -5.3 kcal mol -1 for pentamers and hexamers, respectively. Furthermore, our results demonstrate that the DF-OLCCD method approaches to the CCSD(T) quality for anionic clusters. The inexpensive analytic gradients of DF-OLCCD compared to CCSD or CCSD(T) make it very attractive for high-accuracy studies.

(2E,5E)-2,5-Bis(4-hy-droxy-3-meth-oxy-benzyl-idene)cyclo-penta-none ethanol monosolvate.

PubMed

Da'i, Muhammad; Yanuar, Arry; Meiyanto, Edy; Jenie, Umar Anggara; Supardjan, Amir Margono

2013-04-01

In the title structure, C21H20O5·C2H5OH, the curcumine-type mol-ecule has a double E conformation for the two benzyl-idene double bonds [C=C = 1.342 (4) and 1.349 (4) Å] and is nearly planar with respect to the non-H atoms (r.m.s. deviation from planarity = 0.069 Å). The two phenolic OH groups form bifurcated hydrogen bonds with intra-molecular branches to adjacent meth-oxy O atoms and inter-molecular branches to either a neighbouring mol-ecule or an ethanol solvent mol-ecule. The ethanol O atom donates a hydrogen bond to the keto O atom. These hydrogen bonds link the constituents into layers parallel to (101) in the crystal structure.

Contamination removal using various solvents and methodologies

NASA Technical Reports Server (NTRS)

Jeppsen, J. C.

1989-01-01

Critical and non-critical bonding surfaces must be kept free of contamination that may cause potential unbonds. For example, an aft-dome section of a redesigned solid rocket motor that had been contaminated with hydraulic oil did not appear to be sufficiently cleaned when inspected by the optically stimulated electron emission process (Con Scan) after it had been cleaned using a hand double wipe cleaning method. As a result, current and new cleaning methodologies as well as solvent capability in removing various contaminant materials were reviewed and testing was performed. Bonding studies were also done to verify that the cleaning methods used in removing contaminants provide an acceptable bonding surface. The removal of contaminants from a metal surface and the strength of subsequent bonds were tested using the Martin Marietta and double-wipe cleaning methods. Results are reported.

Molecular analysis on the utilization of oil palm empty fruit bunches fiber as reinforcement for acrylonitrile butadiene styrene biocomposites

NASA Astrophysics Data System (ADS)

Hermawan, B.; Nikmatin, S.; Alatas, H.; Sudaryanto; Sukaryo, S. G.

2017-05-01

Oil palm empty fruit bunches (OPEFB) was one of the solid waste produced by the palm oil factory and were totally plentiful in biomass. OPEFB fiber used as reinforcement of polymer matrix acrylonitrile butadiene styrene (ABS). The use of FTIR is to see that there is no changes in the molecules of the constituent biocomposite ABS and OPEFB. The reactivity of butadiene and styrene through the double bond- π conjugated system, contributed to the bond reaction with the maleic acid as compatibilizer witch is grafted to the system. It is concluded that the posible grafting reaction occurs by the addition of the MAH to the double bond of the butadiene and styrene. The hydroxyl group of cellulose can interact with this maleic acid to form a bond through the carboxyl group.

TiO(2) doping by hydroxyurea at the nucleation stage: towards a new photocatalyst in the visible spectral range.

PubMed

Azouani, R; Tieng, S; Chhor, K; Bocquet, J-F; Eloy, P; Gaigneaux, E M; Klementiev, K; Kanaev, A V

2010-10-07

We report an original method of preparation of OCN-doped TiO(2) for photocatalysis in the visible spectral range. The preparation is achieved by a sol-gel route using titanium tetraisopropoxide precursor. Special attention was paid to fluid micromixing, which enables homogeneous reaction conditions in the reactor bulk and monodispersity of the produced clusters/nanoparticles. The dopant hydroxyurea (HyU, CH(4)N(2)O(2)) is injected into the reactive fluid at the nucleation stage, which lasts tens of milliseconds. The doping results in a strong yellow coloration of the nanocolloids due to the absorption band in the spectral range 380-550 nm and accelerates the aggregation kinetics of both nuclei at the induction stage and sub-nuclei units (clusters) at the nucleation stage. FTIR, Raman and UV-visible absorption analyses show the formation of a stable HyU-TiO(2) complex. EXAFS spectra indicate no appreciable changes of the first-shell Ti atom environment. The doping agent takes available surface sites of TiO(2) clusters/nanoparticles attaining ∼10% molar loading. The reaction kinetics then accelerates due to a longer collisional lifetime between nanoparticles induced by the formation of a weak [double bond, length as m-dash]OTi bond. The OCN-group bonding to titanium atoms produces a weakening of the C[double bond, length as m-dash]O double bond and a strengthening of the C-N and N-O bonds.

Nature of Bonding in Bowl-Like B36 Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location.

PubMed

Li, Rui; You, Xue-Rui; Wang, Kang; Zhai, Hua-Jin

2018-05-04

The bowl-shaped C 6v B 36 cluster with a central hexagon hole is considered an ideal molecular model for low-dimensional boron-based nanosystems. Owing to the electron deficiency of boron, chemical bonding in the B 36 cluster is intriguing, complicated, and has remained elusive despite a couple of papers in the literature. Herein, a bonding analysis is given through canonical molecular orbitals (CMOs) and adaptive natural density partitioning (AdNDP), further aided by natural bond orbital (NBO) analysis and orbital composition calculations. The concerted computational data establish the idea of concentric double π aromaticity for the B 36 cluster, with inner 6π and outer 18π electron counting, which both conform to the (4n+2) Hückel rule. The updated bonding picture differs from existing knowledge of the system. A refined bonding model is also proposed for coronene, of which the B 36 cluster is an inorganic analogue. It is further shown that concentric double π aromaticity in the B 36 cluster is retained and spatially fixed, irrespective of the migration of the hexagonal hole; the latter process changes the system energetically. The hexagonal hole is a destabilizing factor for σ/π CMOs. The central hexagon hole affects substantially fewer CMOs, thus making the bowl-shaped C 6v B 36 cluster the global minimum. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Targeting excited states in all-trans polyenes with electron-pair states.

PubMed

Boguslawski, Katharina

2016-12-21

Wavefunctions restricted to electron pair states are promising models for strongly correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and heavy-element containing compounds with multiple quasi-degenerate single-particle states. Here, we extend the pCCD method to model excited states using the equation of motion (EOM) formalism. As the cluster operator of pCCD is restricted to electron-pair excitations, EOM-pCCD allows us to target excited electron-pair states only. To model singly excited states within EOM-pCCD, we modify the configuration interaction ansatz of EOM-pCCD to contain also single excitations. Our proposed model represents a simple and cost-effective alternative to conventional EOM-CC methods to study singly excited electronic states. The performance of the excited state models is assessed against the lowest-lying excited states of the uranyl cation and the two lowest-lying excited states of all-trans polyenes. Our numerical results suggest that EOM-pCCD including single excitations is a good starting point to target singly excited states.

A 26-Membered Macrocycle Obtained by a Double Diels-Alder Cycloaddition Between Two 2H-Pyran-2-one Rings and Two 1,1'-(Hexane-1,6-diyl)bis (1H-pyrrole-2,5-dione)s.

PubMed

Turek, Bor Lucijan; Kočevar, Marijan; Kranjc, Krištof; Perdih, Franc

2017-12-01

With the application of a double dienophile 1,1'-(hexane-1,6-diyl)bis(1H-pyrrole-2,5-dione) for a [4+2] cycloaddition with a substituted 2H-pyran-2-one a novel 26-membered tetraaza heteromacrocyclic system 3 was prepared via a direct method under solvent-free conditions with microwave irradiation. The macrocycle prepared is composed of two units of the dienophile and two of the diene. The structure of the macrocycle was characterized on the basis of IR, 1H and 13C NMR and mass spectroscopy, as well as by the elemental analysis and melting point determination. With X-ray diffraction of a single crystal of the macrocycle we have determined that the two acetyl groups (attached to the bridging double bond of the bicyclo[2.2.2]octene fragments) are oriented towards each other (and also towards the inside of the cavity of the macrocycle), therefore, mostly filling it completely.

Moving beyond Watson-Crick models of coarse grained DNA dynamics.

PubMed

Linak, Margaret C; Tourdot, Richard; Dorfman, Kevin D

2011-11-28

DNA produces a wide range of structures in addition to the canonical B-form of double-stranded DNA. Some of these structures are stabilized by Hoogsteen bonds. We developed an experimentally parameterized, coarse-grained model that incorporates such bonds. The model reproduces many of the microscopic features of double-stranded DNA and captures the experimental melting curves for a number of short DNA hairpins, even when the open state forms complicated secondary structures. We demonstrate the utility of the model by simulating the folding of a thrombin aptamer, which contains G-quartets, and strand invasion during triplex formation. Our results highlight the importance of including Hoogsteen bonding in coarse-grained models of DNA.

Tensile bond strength of filled and unfilled adhesives to dentin.

PubMed

Braga, R R; Cesar, P F; Gonzaga, C C

2000-04-01

To determine the tensile bond strength of three filled and two unfilled adhesives applied to bovine dentin. Fragments of the labial dentin of bovine incisors were embedded in PVC cylinders with self-cure acrylic resin, and ground flat using 200 grit and 600 grit sandpaper. The following adhesive systems were tested (n=10): Prime & Bond NT, Prime & Bond NT dual cure, Prime & Bond 2.1, OptiBond Solo and Single Bond. A 3 mm-diameter bonding surface was delimited using a perforated adhesive tape. After etching with 37% phosphoric acid and adhesive application, a resin-based composite truncated cone (TPH, shade A3) was built. Tensile test was performed after 24 hrs storage in distilled water at 37 degrees C. Failure mode was accessed using a x10 magnification stereomicroscope. Weibull statistical analysis revealed significant differences in the characteristic strength between Single Bond and Prime & Bond NT dual cure, and between Single Bond and Prime & Bond 2.1. The Weibull parameter (m) was statistically similar among the five groups. Single Bond and Prime & Bond NT showed areas of dentin cohesive failure in most of the specimens. For OptiBond Solo, Prime & Bond NT dual cure and Prime & Bond 2.1 failure was predominantly adhesive.

Vibrational states and optical transitions in hydrogen bonds

NASA Astrophysics Data System (ADS)

Johannsen, P. G.

1998-03-01

Proton energies in hydrogen bonds are mostly calculated using a double Morse potential (the DMP model). This form, however, does not reproduce the experimentally observed correlation between the proton stretching frequency and the bond length in an extended bond-length region sufficiently well. An alternative potential is proposed in the present paper. The quantum states of this non-symmetric double-well potential are calculated numerically using the Numerov (Fox-Goodwin) algorithm. It is shown that the optical spectra of hydrogen bonds in various substances can be well approximated on the basis of the transition frequencies and intensities predicted by the present model. For weakly interacting OH impurities in 0953-8984/10/10/008/img1, the overtone spectrum and line intensities are well reproduced, whereas the line broadenings and the decrease of the fundamental stretching frequencies in intermediate and strong hydrogen bonds are traced back to the influence of the reduced height of the central barrier. The model is also extrapolated to the range of symmetric hydrogen bonds, and the calculated transition frequencies are discussed with respect to most recent infra-red experiments on ice under strong compression. A possible artificial infra-red signal from strained diamond anvils is thereby noted.

Molecular Simulations of The Formation of Gold-Molecule-Gold Junctions

NASA Astrophysics Data System (ADS)

Wang, Huachuan

2013-03-01

We perform classical molecular simulations by combining grand canonical Monte Carlo (GCMC) sampling with molecular dynamics (MD) simulation to explore the dynamic gold nanojunctions in a Alkenedithiol (ADT) solvent. With the aid of a simple driving-spring model, which can reasonably represent the long-range elasticity of the gold electrode, the spring forces are obtained during the dynamic stretching procedure. A specific multi-time-scale double reversible reference system propagator (double-RESPA) algorithm has been designed for the metal-organic complex in MD simulations to identify the detailed metal-molecule bonding geometry at metal-molecule-metal interface. We investigate the variations of bonding sites of ADT molecules on gold nanojunctions at Au (111) surface at a constant chemical potential. Simulation results show that an Au-ADT-Au interface is formed on Au nanojunctions, bond-breaking intersection is at 1-1 bond of the monatomic chain of the cross-section, instead of at the Au-S bond. Breaking force is around 1.5 nN. These are consistent with the experimental measurements.

Experimental (X-ray, FT-IR and UV-vis spectra) and theoretical methods (DFT study) of (E)-3-methoxy-2-[(p-tolylimino)methyl]phenol.

PubMed

Demircioğlu, Zeynep; Albayrak, Çiğdem; Büyükgüngör, Orhan

2014-07-15

A suitable single crystal of (E)-3-methoxy-2-[(p-tolylimino)methyl]phenol, formulated as C15H15N1O2, reveals that the structure is adopted to its E configuration about the azomethine C=N double bond. The compound adopts a enol-imine tautomeric form with a strong intramolecular O-H⋯N hydrogen bond. The single crystal X-ray diffraction analysis at 296K crystallizes in the monoclinic space group P21/c with a = 13.4791(11) Å, b = 6.8251(3) Å, c = 18.3561(15) Å, α = 90°, β = 129.296(5)°, γ = 90° and Z = 4. Comprehensive theoretical and experimental structural studies on the molecule have been carried out by FT-IR and UV-vis spectrometry. Optimized molecular structure and harmonic vibrational frequencies have been investigated by DFT/B3LYP method with 6-31G(d,p) basis set. Stability of the molecule, hyperconjugative interactions, charge delocalization and intramolecular hydrogen bond has been analyzed by using natural bond orbital (NBO) analysis. Electronic structures were discussed by TD-DFT method and the relocation of the electron density were determined. The energetic behavior of the title compound has been examined in solvent media using polarizable continuum model (PCM). Molecular electrostatic potential (MEP), Mulliken population method and natural population analysis (NPA) have been studied. Nonlinear optical (NLO) properties were also investigated. In addition, frontier molecular orbitals analysis have been performed from the optimized geometry. An ionization potential (I), electron affinity (A), electrophilicity index (ω), chemical potential (μ), electronegativity (χ), hardness (η), and softness (S), have been investigated. Copyright © 2014 Elsevier B.V. All rights reserved.

Revisiting Molecular Dynamics on a CPU/GPU system: Water Kernel and SHAKE Parallelization.

PubMed

Ruymgaart, A Peter; Elber, Ron

2012-11-13

We report Graphics Processing Unit (GPU) and Open-MP parallel implementations of water-specific force calculations and of bond constraints for use in Molecular Dynamics simulations. We focus on a typical laboratory computing-environment in which a CPU with a few cores is attached to a GPU. We discuss in detail the design of the code and we illustrate performance comparable to highly optimized codes such as GROMACS. Beside speed our code shows excellent energy conservation. Utilization of water-specific lists allows the efficient calculations of non-bonded interactions that include water molecules and results in a speed-up factor of more than 40 on the GPU compared to code optimized on a single CPU core for systems larger than 20,000 atoms. This is up four-fold from a factor of 10 reported in our initial GPU implementation that did not include a water-specific code. Another optimization is the implementation of constrained dynamics entirely on the GPU. The routine, which enforces constraints of all bonds, runs in parallel on multiple Open-MP cores or entirely on the GPU. It is based on Conjugate Gradient solution of the Lagrange multipliers (CG SHAKE). The GPU implementation is partially in double precision and requires no communication with the CPU during the execution of the SHAKE algorithm. The (parallel) implementation of SHAKE allows an increase of the time step to 2.0fs while maintaining excellent energy conservation. Interestingly, CG SHAKE is faster than the usual bond relaxation algorithm even on a single core if high accuracy is expected. The significant speedup of the optimized components transfers the computational bottleneck of the MD calculation to the reciprocal part of Particle Mesh Ewald (PME).

Probing the interaction of archaeal DNA polymerases with deaminated bases using X-ray crystallography and non-hydrogen bonding isosteric base analogues†

PubMed Central

Killelea, Tom; Ghosh, Samantak; Tan, Samuel S.; Heslop, Pauline; Firbank, Susan; Kool, Eric T.; Connolly, Bernard A.

2010-01-01

Archaeal family-B DNA polymerases stall replication on encountering the pro-mutagenic bases uracil and hypoxanthine. This publication describes an X-ray crystal structure of Thermococcus gorgonarius polymerase in complex with a DNA containing hypoxanthine in the single-stranded region of the template, two bases ahead of the primer-template junction. Full details of the specific recognition of hypoxanthine are revealed, allowing a comparison with published data that describes uracil binding. The two bases are recognized by the same pocket, in the N-terminal domain, and make very similar protein-DNA interactions. Specificity for hypoxanthine (and uracil) arises from a combination of polymerase-base hydrogen bonds and shape fit between the deaminated bases and the pocket. The structure with hypoxanthine at the +2 position explains the stimulation of the polymerase 3′-5′ proof reading exonuclease, observed with deaminated bases at this location. A β hairpin element, involved in partitioning the primer strand between the polymerase and exonuclease active sites, inserts between the two template bases at the extreme end of the double stranded DNA. This denatures the two complementary primer bases and directs the resulting 3′ single-stranded extension towards the exonuclease active site. Finally the relative importance of hydrogen bonding and shape fit in determining selectivity for deaminated bases has been examined using non-polar isosteres. Affinity for both 2,4 difluorobenzene and fluorobenzimidazole, non-hydrogen bonding shape mimics of uracil and hypoxanthine respectively, is strongly diminished, suggesting polar protein-base contacts are important. However, residual interaction with 2,4 difluorobenzene is seen, confirming a role for shape recognition. PMID:20527806

Singlet oxygenation of 1,2-poly/1,4-hexadiene/s

NASA Technical Reports Server (NTRS)

Golub, M. A.; Rosenberg, M. L.; Gemmer, R. V.

1979-01-01

The microstructural changes that occur in cis and trans forms of 1,2-poly(1,4-hexadiene) during methylene blue-photosensitized oxidation were examined by infrared and (C-13)-NMR spectroscopy. The singlet oxygenation of these polymers yielded the expected allylic hydroperoxides accompanied by double bond shifts to new vinyl and trans-vinylene double bonds. The photosensitized oxidation exhibited zero-order kinetics; the relative rates for the cis- and trans-1,2-poly(1,4-hexadiene)s were approximately 3.8:1.0.

Synthesis and SMM behaviour of trinuclear versus dinuclear 3d-5f uranyl(v)-cobalt(ii) cation-cation complexes.

PubMed

Chatelain, Lucile; Tuna, Floriana; Pécaut, Jacques; Mazzanti, Marinella

2017-05-02

Trinuclear versus dinuclear heterodimetallic U V O 2 + Co 2+ complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study.

PubMed

Sato, Ryuhei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

2017-08-02

Hydration reactions on a carbonate-terminated cubic ZrO 2 (110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H 2 O molecules (Zr-OH 2 ) and monodentate hydroxyl groups (Zr-OH - ). Similar to a carbonate-free hydrated surface, Zr-OH 2 , Zr-OH - , and polydentate hydroxyl groups ([double bond splayed left]OH + ) were observed, while the ratio of acidic Zr-OH 2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO 2 adsorption significantly decreases the basicity of surface oxide ions ([double bond splayed left]O), whereas the acidity of Zr-OH 2 is not affected. As a result, protons released from [double bond splayed left]OH + react with Zr-OH - to form Zr-OH 2 , leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

Maximum-valence radii of transition metals

PubMed Central

Pauling, Linus

1975-01-01

In many of their compounds the transition metals have covalence 9, forming nine bonds with use of nine hybrid spd bond orbitals. A set of maximum-valence single-bond radii is formulated for use in these compounds. These radii are in reasonably good agreement with observed bond lengths. Quadruple bonds between two transition metal atoms are about 50 pm (iron-group atoms) or 55 pm (palladium and platinum-group atoms) shorter than single bonds. This amount of shortening corresponds to four bent single bonds with the best set of bond angles, 79.24° and 128.8°. PMID:16578730

Structural evolution of the [(CO2)n(H2O)]- cluster anions: quantifying the effect of hydration on the excess charge accommodation motif.

PubMed

Muraoka, Azusa; Inokuchi, Yoshiya; Hammer, Nathan I; Shin, Joong-Won; Johnson, Mark A; Nagata, Takashi

2009-08-06

The [(CO2)n(H2O)]- cluster anions are studied using infrared photodissociation (IPD) spectroscopy in the 2800-3800 cm(-1) range. The observed IPD spectra display a drastic change in the vibrational band features at n = 4, indicating a sharp discontinuity in the structural evolution of the monohydrated cluster anions. The n = 2 and 3 spectra are composed of a series of sharp bands around 3600 cm(-1), which are assignable to the stretching vibrations of H2O bound to C2O4- in a double ionic hydrogen-bonding (DIHB) configuration, as was previously discussed (J. Chem. Phys. 2005, 122, 094303). In the n > or = 4 spectrum, a pair of intense bands additionally appears at approximately 3300 cm(-1). With the aid of ab initio calculations at the MP2/6-31+G* level, the 3300 cm(-1) bands are assigned to the bending overtone and the hydrogen-bonded OH vibration of H2O bound to CO2- via a single O-H...O linkage. Thus, the structures of [(CO2)n(H2O)]- evolve with cluster size such that DIHB to C2O4- is favored in the smaller clusters with n = 2 and 3 whereas CO2- is preferentially stabilized via the formation of a single ionic hydrogen-bonding (SIHB) configuration in the larger clusters with n > or = 4.

Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers

NASA Astrophysics Data System (ADS)

Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

2018-01-01

La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C4H6) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C4H6) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH2)3] (Iso A) and La(CH2CHCHCH2) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2A1 (C3v) for Iso A and 2A' (Cs) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1A1 ion of Iso A and the 1A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp3)—H bonds, and H2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C—H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C—H bond activation.

Boron-containing organosilane polymers and ceramic materials thereof

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore R. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)

1989-01-01

The present invention relates to a polyorgano borosilane ceramic precursor polymer comprising a plurality of repeating units of the formula: (R(sup 1) single bond B)(sub p) being linked together at B by second units of the formula: single bond (R sup 2) single bond (Si single bond R sup 3) single bond (sub q), where R(sup 1) is a lower alkyl, cycloalkyl, phenyl, or (R(sup 2)R(sup 3) single bond Si single bond B single bond)(sub n) and R(sup 2) and R(sup 3) are each independently selected from hydrogen, lower alkyl, vinyl, cycloalkyl, or aryl, n is an integer between 1 and 100; p is an integer between 1 and 100; and q is an integer between 1 and 100. These materials are prepared by combining an organo borohalide of the formula R(sup 4) single bond B single bond (X sup 1) (sub 2) where R(sup 4) is selected from halogen, lower alkyl, cycloalkyl, or aryl, and an organo halosilane of the formula: R(sup 2)(R sup 3)Si(X sup 2)(sub 2) where R(sup 2) and R (sup 3) are each independently selected from lower alkyl, cycloalkyl, or aryl, and X(sup 1) and X(sup 2) are each independently selected from halogen, in an anhydrous aprotic solvent having a boiling point at ambient pressure of not greater than 160 C with in excess of four equivalents of an alkali metal, heating the reaction mixture and recovering the polyorgano borosilane. These silicon boron polymers are useful to generate high-temperature ceramic materials, such as SiC, SiB4, and B4C, upon thermal degradation above 600 C.

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Bonding in O3 and SO2.

PubMed

Takeshita, Tyler Y; Lindquist, Beth A; Dunning, Thom H

2015-07-16

There are many well-known differences in the physical and chemical properties of ozone (O3) and sulfur dioxide (SO2). O3 has longer and weaker bonds than O2, whereas SO2 has shorter and stronger bonds than SO. The O-O2 bond is dramatically weaker than the O-SO bond, and the singlet-triplet gap in SO2 is more than double that in O3. In addition, O3 is a very reactive species, while SO2 is far less so. These disparities have been attributed to variations in the amount of diradical character in the two molecules. In this work, we use generalized valence bond (GVB) theory to characterize the electronic structure of ozone and sulfur dioxide, showing O3 does indeed possess significant diradical character, whereas SO2 is effectively a closed shell molecule. The GVB results provide critical insights into the genesis of the observed difference in these two isoelectronic species. SO2 possesses a recoupled pair bond dyad in the a"(π) system, resulting in SO double bonds. The π system of O3, on the other hand, has a lone pair on the central oxygen atom plus a pair of electrons in orbitals on the terminal oxygen atoms that give rise to a relatively weak π interaction.

Mathematical analysis of compressive/tensile molecular and nuclear structures

NASA Astrophysics Data System (ADS)

Wang, Dayu

Mathematical analysis in chemistry is a fascinating and critical tool to explain experimental observations. In this dissertation, mathematical methods to present chemical bonding and other structures for many-particle systems are discussed at different levels (molecular, atomic, and nuclear). First, the tetrahedral geometry of single, double, or triple carbon-carbon bonds gives an unsatisfying demonstration of bond lengths, compared to experimental trends. To correct this, Platonic solids and Archimedean solids were evaluated as atoms in covalent carbon or nitrogen bond systems in order to find the best solids for geometric fitting. Pentagonal solids, e.g. the dodecahedron and icosidodecahedron, give the best fit with experimental bond lengths; an ideal pyramidal solid which models covalent bonds was also generated. Second, the macroscopic compression/tension architectural approach was applied to forces at the molecular level, considering atomic interactions as compressive (repulsive) and tensile (attractive) forces. Two particle interactions were considered, followed by a model of the dihydrogen molecule (H2; two protons and two electrons). Dihydrogen was evaluated as two different types of compression/tension structures: a coaxial spring model and a ring model. Using similar methods, covalent diatomic molecules (made up of C, N, O, or F) were evaluated. Finally, the compression/tension model was extended to the nuclear level, based on the observation that nuclei with certain numbers of protons/neutrons (magic numbers) have extra stability compared to other nucleon ratios. A hollow spherical model was developed that combines elements of the classic nuclear shell model and liquid drop model. Nuclear structure and the trend of the "island of stability" for the current and extended periodic table were studied.

Fixed-Node Diffusion Quantum Monte Carlo Method on Dissociation Energies and Their Trends for R-X Bonds (R = Me, Et, i-Pr, t-Bu).

PubMed

Hou, Aiqiang; Zhou, Xiaojun; Wang, Ting; Wang, Fan

2018-05-15

Achieving both bond dissociation energies (BDEs) and their trends for the R-X bonds with R = Me, Et, i-Pr, and t-Bu reliably is nontrivial. Density functional theory (DFT) methods with traditional exchange-correlation functionals usually have large error on both the BDEs and their trends. The M06-2X functional gives rise to reliable BDEs, but the relative BDEs are determined not as accurately. More demanding approaches such as some double-hybrid functionals, for example, G4 and CCSD(T), are generally required to achieve the BDEs and their trends reliably. The fixed-node diffusion quantum Monte Carlo method (FN-DMC) is employed to calculated BDEs of these R-X bonds with X = H, CH 3 , OCH 3 , OH, and F in this work. The single Slater-Jastrow wave function is adopted as trial wave function, and pseudopotentials (PPs) developed for quantum Monte Carlo calculations are chosen. Error of these PPs is modest in wave function methods, while it is more pronounced in DFT calculations. Our results show that accuracy of BDEs with FN-DMC is similar to that of M06-2X and G4, and trends in BDEs are calculated more reliably than M06-2X. Both BDEs and trends in BDEs of these bonds are reproduced reasonably with FN-DMC. FN-DMC using PPs can thus be applied to BDEs and their trends of similar chemical bonds in larger molecules reliably and provide valuable information on properties of these molecules.

(2E,5E)-2,5-Bis(4-hy­droxy-3-meth­oxy­benzyl­idene)cyclo­penta­none ethanol monosolvate

PubMed Central

Da’i, Muhammad; Yanuar, Arry; Meiyanto, Edy; Jenie, Umar Anggara; Supardjan, Amir Margono

2013-01-01

In the title structure, C21H20O5·C2H5OH, the curcumine-type mol­ecule has a double E conformation for the two benzyl­idene double bonds [C=C = 1.342 (4) and 1.349 (4) Å] and is nearly planar with respect to the non-H atoms (r.m.s. deviation from planarity = 0.069 Å). The two phenolic OH groups form bifurcated hydrogen bonds with intra­molecular branches to adjacent meth­oxy O atoms and inter­molecular branches to either a neighbouring mol­ecule or an ethanol solvent mol­ecule. The ethanol O atom donates a hydrogen bond to the keto O atom. These hydrogen bonds link the constituents into layers parallel to (101) in the crystal structure. PMID:23634071

Why soft UV-A damages DNA: An optical micromanipulation study

NASA Astrophysics Data System (ADS)

Rapp, A.; Greulich, K. O.

2013-09-01

Optical micromanipulation studies have solved a puzzle on DNA damage and repair. Such knowledge is crucial for understanding cancer and ageing. So far it was not understood, why the soft UV component of sunlight, UV-A, causes the dangerous DNA double strand breaks. The energy of UV-A photons is below 4 eV per photon, too low to directly cleave the corresponding chemical bonds in DNA. This is occasionally used to claim that artificial sunbeds, which mainly use UV-A, would not impose a risk on health. UV-A is only sufficient for induction of single strand breaks. The essential new observation is that, when on the opposite strand there is another single strand break at a distance of up to 20 base pairs. These two breaks will be converted into a break of the whole double strand with all its known consequences for cancer and ageing. However, in natural sun the effect is counteracted. Simultaneous red light illumination reduces UV induced DNA damages to 1/3. Since sunlight has a red component, skin tanning with natural sun is not as risky as might appear at a first glance.

Metal-metal bond lengths in complexes of transition metals.

PubMed

Pauling, L

1976-12-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

[The adhesive properties of two bonding systems to tetracycline stained dentin].

PubMed

Liu, H L; Liang, K N; Cheng, L; Li, J Y; He, L B

2016-01-01

To investigate and compare the bonding properties of Single Bond 2 and SE Bond to tetracycline stained dentin in vitro. Ten extracted tetracycline stained human teeth and ten extracted normal human teeth were collected and the occlusal dentin surfaces of all extracted teeth were exposed. The tetracycline stained teeth and normal teeth were divided into two groups, respectively and randomly, based on the adhesives applied. Total-etch adhesive(Single Bond 2) and self-etch adhesive(SE Bond) were used. After application of the adhesives to the dentin surfaces, composite crowns were built up. After 24 h water storage, the teeth were sectioned longitudinally into sticks(0.9 mm×0.9 mm bonding area) for micro tensile testing or micro Raman spectroscopy detection. Bonding strength(μTBS) and resin conversion rate were analyzed using one-way ANOVA. The tetracycline Single Bond 2 group presented lower bonding strength[(16.17 ± 3.16) MPa] than the tetracycline SE Bond group[(25.82 ± 2.62) MPa], and also demonstrated lower bonding strength than the normal Single Bond 2 group[(29.13 ± 2.44) MPa] and the normal SE Bond group[(24.29±2.83) MPa] (P<0.05) , while there was no statistical differences among the other three groups(P>0.05). The resin conversion rate of tetracycline Single Bond 2 group[(55±6)%] was significantly lower than the tetracycline SE Bond group[(66±3)% ](P<0.05) and also lower than the normal Single Bond 2 group[(64 ± 5)%] and the normal SE Bond group[(65 ± 4)%] (P<0.05). No statistically significant differences were observed among the other three groups(P>0.05). The bonding strength of total-etch adhesive system to the tetracycline stained dentin was significantly lower than that to the normal dentin.

Do Practical Standard Coupled Cluster Calculations Agree Better than Kohn–Sham Calculations with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals?

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

Xu, Xuefei; Zhang, Wenjing; Tang, Mingsheng

2015-05-12

Coupled-cluster (CC) methods have been extensively used as the high-level approach in quantum electronic structure theory to predict various properties of molecules when experimental results are unavailable. It is often assumed that CC methods, if they include at least up to connected-triple-excitation quasiperturbative corrections to a full treatment of single and double excitations (in particular, CCSD(T)), and a very large basis set, are more accurate than Kohn–Sham (KS) density functional theory (DFT). In the present work, we tested and compared the performance of standard CC and KS methods on bond energy calculations of 20 3d transition metal-containing diatomic molecules againstmore » the most reliable experimental data available, as collected in a database called 3dMLBE20. It is found that, although the CCSD(T) and higher levels CC methods have mean unsigned deviations from experiment that are smaller than most exchange-correlation functionals for metal–ligand bond energies of transition metals, the improvement is less than one standard deviation of the mean unsigned deviation. Furthermore, on average, almost half of the 42 exchange-correlation functionals that we tested are closer to experiment than CCSD(T) with the same extended basis set for the same molecule. The results show that, when both relativistic and core–valence correlation effects are considered, even the very high-level (expensive) CC method with single, double, triple, and perturbative quadruple cluster operators, namely, CCSDT(2)Q, averaged over 20 bond energies, gives a mean unsigned deviation (MUD(20) = 4.7 kcal/mol when one correlates only valence, 3p, and 3s electrons of transition metals and only valence electrons of ligands, or 4.6 kcal/mol when one correlates all core electrons except for 1s shells of transition metals, S, and Cl); and that is similar to some good xc functionals (e.g., B97-1 (MUD(20) = 4.5 kcal/mol) and PW6B95 (MUD(20) = 4.9 kcal/mol)) when the same basis set is used. We found that, for both coupled cluster calculations and KS calculations, the T1 diagnostics correlate the errors better than either the M diagnostics or the B1 DFT-based diagnostics. The potential use of practical standard CC methods as a benchmark theory is further confounded by the finding that CC and DFT methods usually have different signs of the error. We conclude that the available experimental data do not provide a justification for using conventional single-reference CC theory calculations to validate or test xc functionals for systems involving 3d transition metals.« less

Halogenated 2,5-pyrrolidinediones: synthesis, bacterial mutagenicity in Ames tester strain TA-100 and semi-empirical molecular orbital calculations.

PubMed

Freeman, B A; Wilson, R E; Binder, R G; Haddon, W F

2001-02-20

The chloroimide 3,3-dichloro-4-(dichloromethylene)-2,5-pyrrolidinedione, a tetrachloroitaconimide, is the principal mutagen produced by chlorination of simulated poultry chiller water. It is the second most potent mutagenic disinfection by-product of chlorination ever reported. Six of seven new synthetic analogs of this compound are direct-acting mutagens in Ames tester strain TA-100. Computed energies of the lowest unoccupied molecular orbital (E(LUMO)) and of the radical anion stability (DeltaH(f)(rad)-DeltaH(f)) from MNDO-PM3 for the chloroimides show a quantitative correlation with the Ames TA-100 bacterial mutagenicity values. The molar mutagenicities of these direct acting mutagenic imides having an exocyclic double bond fit the same linear correlation (lnM(m) vs. E(LUMO); lnM(m) vs. DeltaH(f)(rad)--DeltaH(f)) as the chlorinated 2(5H)-furanones, including the potent mutagen MX, 3-chloro-4-(dichloro-methyl)-5-hydroxy-2(5H)-furanone, a by-product of water chlorination and paper bleaching with chlorine. Mutagenicity data for related haloimides having endocyclic double bonds are also given. For the same number of chlorine atoms, the imides with endocyclic double bonds have significantly higher Ames mutagenicity compared to their structural analogs with exocyclic double bonds, but do not follow the same E(LUMO) or DeltaH(f)(rad)-DeltaH(f) correlation as the exocyclic chloroimides and the chlorinated 2(5H)-furanones.

Cyclometalated gold(III) trioxadiborrin complexes: studies of the bonding and excited states.

PubMed

Ayoub, Nicholas A; Browne, Amberle R; Anderson, Bryce L; Gray, Thomas G

2016-03-07

Trioxadiborrins are chelating ligands that assemble in dehydration reactions of boronic acids. They are structurally related to β-diketonate ligands, but have a 2-charge. Little is known of the bonding properties of trioxadiborrin ligands. Presented here are density-functional theory (DFT) studies of cyclometalated gold(III) trioxadiborrins. Substituent effects are evaluated, and comparison is made to the cyclometalating 2-(4-tolyl)pyridine (tpy) ligand on gold. The tpy ligand binds more strongly than any trioxadiborrin ligand considered here, and the two ligands bind competitively to gold. The 1,3-diphenyl trioxadiborrin ligand of 1 has a larger absolute binding enthalpy to gold than its β-diketonate analogue. Conjugation between boron and aryl substituents delocalizes charge and attenuates the trioxadiborrin's binding capacity. Steric effects that disrupt conjugation between boron and aryl substituents cause the trioxadiborrin to chelate more tightly. Fragment bond orders are divided into in-plane and out-of-plane contributions for square planar 1. In-plane bonding accounts for 88% of bond order between (tpy)Au2+ and the trioxadiborrin ligand. Cyclometalated gold(III) trioxadiborrin complexes were previously shown to be phosphorescent. Spin-unrestricted triplet-state geometry optimizations find that the ten largest excited-state distortions all occur on the tpy ligand. A plot of spin density in triplet 1 shows spin to reside predominantly on tpy. The 77 K luminescence spectrum of 1 is reported here. Time-dependent DFT and configuration interaction singles calculations (corrected for doubles excitations) overestimate the emission energy by ∼ 0.12 eV.

Isopeptide bonds of the major pilin protein BcpA influence pilus structure and bundle formation on the surface of Bacillus cereus

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

Hendrickx, Antoni P.A.; Poor, Catherine B.; Jureller, Justin E.

Bacillus cereus strains elaborate pili on their surface using a mechanism of sortase-mediated cross-linking of major and minor pilus components. Here we used a combination of electron microscopy and atomic force microscopy to visualize these structures. Pili occur as single, double or higher order assemblies of filaments formed from monomers of the major pilin, BcpA, capped by the minor pilin, BcpB. Previous studies demonstrated that within assembled pili, four domains of BcpA -- CNA{sub 1}, CNA{sub 2}, XNA and CNA{sub 3} -- each acquire intramolecular lysine-asparagine isopeptide bonds formed via catalytic glutamic acid or aspartic acid residues. Here we showedmore » that mutants unable to form the intramolecular isopeptide bonds in the CNA2 or CNA3 domains retain the ability to form pilus bundles. A mutant lacking the CNA{sub 1} isopeptide bond assembled deformed pilin subunits that failed to associate as bundles. X-ray crystallography revealed that the BcpA variant Asp{sup 312}Ala, lacking an aspartyl catalyst, did not generate the isopeptide bond within the jelly-roll structure of XNA. The Asp{sup 312}Ala mutant was also unable to form bundles and promoted the assembly of deformed pili. Thus, structural integrity of the CNA{sub 1} and XNA domains are determinants for the association of pili into higher order bundle structures and determine native pilus structure.« less

A DSC and FTIR spectroscopic study of the effects of the epimeric 4-cholesten-3-ols and 4-cholesten-3-one on the thermotropic phase behaviour and organization of dipalmitoylphosphatidylcholine bilayer membranes: comparison with their 5-cholesten analogues.

PubMed

Benesch, Matthew G K; Mannock, David A; Lewis, Ruthven N A H; McElhaney, Ronald N

2014-01-01

We present the results of a comparative differential calorimetric and Fourier transform infrared spectroscopic study of the effect of cholesterol and five of its analogues on the thermotropic phase behaviour and organization of dipalmitoylphosphatidylcholine bilayer membranes. These sterols/steroids differ in both the nature and stereochemistry of the polar head group at C3 (βOH, αOH or C=O) and in the position of the double bond (C4-C5 in ring A or C5-C6 in ring B). In the three Δ(5) sterols/steroid series, the concentration of these compounds required to abolish the DPPC pretransition, inversely related to their relative ability to disorder gel state DPPC bilayers, decreases in the order βOH>αOH>C=O and these differences in concentration are significant. However, in the Δ(4) series, these concentrations are more similar, regardless of polar head group nature or stereochemistry. Similarly, the residual enthalpy of the main phase transition of DPPC at 50 mol.% sterol/steroid, which is inversely related to the miscibility of these compounds in the DPPC bilayer, also increases in the order βOH>αOH>C=O, but this effect is attenuated in the Δ(4) as opposed to the Δ(5) series. Both of these results indicate that the presence of a double bond at C4-C5 in ring A, as compared to a C5-C6 double bond in ring B, reduces the effect of variations in the structure of the polar group at C3 on the properties of the host DPPC bilayer. The movement of the double bond from C5 to C4 in the two sterol pairs results in a greater decrease in the temperature and enthalpy of both the pretransition and the main phase transition, whereas the opposite result is observed in the ketosteroid pair. Similarly, the ability of these compounds to order the DPPC hydrocarbon chains decreases in the order βOH>αOH>C=O in both series of compounds, but in the two sterol pairs, hydrocarbon chain ordering is greater for the Δ(5) than the Δ(4) sterols, whereas the opposite is the case for the steroid pair. All of these results indicate that the typical effects of sterols/steroids in increasing the packing density and thermal stability of fluid lipid bilayers are optimal when an OH group rather than C=O group is present at C3, and that this OH group is more effective in the equatorial rather than the axial orientation. We can explain all of our sterol results by noting that the shift of the double bond from Δ(5) to Δ(4) introduces of a bend in ring A, which in turn destroys the coplanarity of the steroid fused ring system and reduces the goodness of sterol packing in the host DPPC bilayer. However, this conformational change should also occur in the ketosteroid pair, yet our experimental results indicate that the presence of the Δ(4) double bond is less disruptive than a double bond at Δ(5). We suggest that the presence of keto-enol tautomerism in the conjugated Δ(4) ketosteroid, but not in the nonconjugated Δ(5) compound, may provide additional H-bonding opportunities to adjacent DPPC molecules in the bilayer, which can overcome the unfavourable conformational change in ring A induced by the Δ(4) double bond. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Shear bond strength of a new one-bottle dentin adhesive.

PubMed

Swift, E J; Bayne, S C

1997-08-01

To test the shear bond strength of a new adhesive, 3M Single Bond, to dentin surfaces containing different degrees of moisture. Two commercially available one-bottle adhesives (Prime & Bond, One-Step) and a conventional three-step system (Scotchbond Multi-Purpose Plus) were included for comparison. 120 bovine teeth were embedded in acrylic and the labial surfaces were polished to 600 grit to create standardized dentin surfaces for testing. Resin composite was bonded to dentin using a gelatin capsule technique. Four adhesive systems were evaluated with three different degrees of surface moisture (moist, wet, and overwet). Shear bond strengths of adhesives to dentin were determined using a universal testing machine and analyzed by ANOVA and Tukey's post hoc tests. Single Bond had mean shear bond strengths of 19.2, 23.2 and 20.3 MPa to moist, wet, and overwet dentin, respectively. Bond strengths of the three-component system Scotchbond Multi-Purpose Plus ranged from 23.1 to 25.3 MPa, but were not significantly higher than the values for Single Bond. Prime & Bond had bond strengths similar to those of Single Bond, but One-Step had significantly lower bond strengths (P < 0.05) in the wet and overwet conditions.

Synthetic study on the relationship between structure and sweet taste properties of steviol glycosides.

PubMed

Upreti, Mani; Dubois, Grant; Prakash, Indra

2012-04-05

The structure activity relationship between the C₁₆-C₁₇ methylene double bond on the aglycone of steviol glycosides and the corresponding impact on their sweet taste has been reported here for the first time. It has been observed that converting stevioside and rebaudioside A to their corresponding ketones by switching the doubly bonded methylene on C-17 for a ketone group actually removes the sweet taste properties of these molecules completely. Regenerating the original molecules tends to restore the sweet taste of both the steviol glycosides. Thus this C₁₆-C₁₇ methylene double bond in rebaudioside A and stevioside can be regarded as a pharmacophore essential for the sweetness property of these molecules.

Can nature's design be improved upon? High strength, transparent nacre-like nanocomposites with double network of sacrificial cross links.

PubMed

Podsiadlo, Paul; Kaushik, Amit K; Shim, Bong Sup; Agarwal, Ashish; Tang, Zhiyong; Waas, Anthony M; Arruda, Ellen M; Kotov, Nicholas A

2008-11-20

The preparation of a high-strength and highly transparent nacre-like nanocomposite via layer-by-layer assembly technique from poly(vinyl alcohol) (PVA) and Na+-montmorillonite clay nanosheets is reported in this article. We show that a high density of weak bonding interactions between the polymer and the clay particles: hydrogen, dipole-induced dipole, and van der Waals undergoing break-reform deformations, can lead to high strength nanocomposites: sigmaUTS approximately 150 MPa and E' approximately 13 GPa. Further introduction of ionic bonds into the polymeric matrix creates a double network of sacrificial bonds which dramatically increases the mechanical properties: sigmaUTS approximately 320 MPa and E' approximately 60 GPa.

Raman spectroscopy for the characterization of the polymerization rate in an acrylamide-based photopolymer

NASA Astrophysics Data System (ADS)

Jallapuram, Raghavendra; Naydenova, Izabela; Byrne, Hugh J.; Martin, Suzanne; Howard, Robert; Toal, Vincent

2008-01-01

Investigations of polymerization rates in an acrylamide-based photopolymer are presented. The polymerization rate for acrylamide and methylenebisacrylamide was determined by monitoring the changes in the characteristic vibrational peaks at 1284 and 1607 cm-1 corresponding to the bending mode of the CH bond and CC double bonds of acrylamide and in the characteristic peak at 1629 cm-1 corresponding to the carbon-carbon double bond of methylenebisacrylamide using Raman spectroscopy. To study the dependence of the polymerization rate on intensity and to find the dependence parameter, the polymerization rate constant is measured at different intensities. A comparison with a commercially available photopolymer shows that the polymerization rate in this photopolymer is much faster.

Integrated packaging of multiple double sided cooling planar bond power modules

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

Liang, Zhenxian

An integrated double sided cooled power module has one or multiple phase legs configuration including one or more planar power packages, each planar power package having an upper power switch unit and a lower power switch unit directly bonded and interconnected between two insulated power substrates, and further sandwiched between two heat exchangers via direct bonds. A segmented coolant manifold is interposed with the one or more planar power packages and creates a sealed enclosure that defines a coolant inlet, a coolant outlet and a coolant flow path between the inlet and the outlet. A coolant circulates along the flowmore » path to remove heat and increase the power density of the power module.« less

X-ray scattering and spectroscopy studies on diesel soot from oxygenated fuel under various engine load conditions

USGS Publications Warehouse

Braun, Andreas; Shah, N.; Huggins, Frank E.; Kelly, K.E.; Sarofim, A.; Jacobsen, C.; Wirick, S.; Francis, H.; Ilavsky, J.; Thomas, G.E.; Huffman, G.P.

2005-01-01

Diesel soot from reference diesel fuel and oxygenated fuel under idle and load engine conditions was investigated with X-ray scattering and X-ray carbon K-edge absorption spectroscopy. Up to five characteristic size ranges were found. Idle soot was generally found to have larger primary particles and aggregates but smaller crystallites, than load soot. Load soot has a higher degree of crystallinity than idle soot. Adding oxygenates to diesel fuel enhanced differences in the characteristics of diesel soot, or even reversed them. Aromaticity of idle soot from oxygenated diesel fuel was significantly larger than from the corresponding load soot. Carbon near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was applied to gather information about the presence of relative amounts of carbon double bonds (CC, CO) and carbon single bonds (C-H, C-OH, COOH). Using scanning X-ray transmission microspectroscopy (STXM), the relative amounts of these carbon bond states were shown to vary spatially over distances approximately 50 to 100 nm. The results from the X-ray techniques are supported by thermo-gravimetry analysis and high-resolution transmission electron microscopy. ?? 2005 Elsevier Ltd. All rights reserved.

Detection of subsurface core-level shifts in Si 2p core-level photoemission from Si(111)-(1x1):As

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

Paggel, J.J.; Hasselblatt, M.; Horn, K.

1997-04-01

The (7 x 7) reconstruction of the Si(111) surface arises from a lowering energy through the reduction of the number of dangling bonds. This reconstruction can be removed by the adsorption of atoms such as hydrogen which saturate the dangling bonds, or by the incorporation of atoms, such as arsenic which, because of the additional electron it possesses, can form three bonds and a nonreactive lone pair orbital from the remaining two electrons. Core and valence level photoemission and ion scattering data have shown that the As atoms replace the top silicon atoms. Previous core level spectra were interpreted inmore » terms of a bulk and a single surface doublet. The authors present results demonstrate that the core level spectrum contains two more lines. The authors assign these to subsurface silicon layers which also experience changes in the charge distribution when a silicon atom is replaced by an arsenic atom. Subsurface core level shifts are not unexpected since the modifications of the electronic structure and/or of photohole screening are likely to decay into the bulk and not just to affect the top-most substrate atoms. The detection of subsurface components suggests that the adsorption of arsenic leads to charge flow also in the second double layer of the Si(111) surface. In view of the difference in atomic radius between As and Si, it was suggested that the (1 x 1): As surface is strained. The presence of charge rearrangement up to the second double layer implies that the atomic coordinates also exhibit deviations from their ideal Si(111) counterparts, which might be detected through a LEED I/V or photoelectron diffraction analysis.« less

Structures, chemotaxonomic significance, cytotoxic and Na(+),K(+)-ATPase inhibitory activities of new cardenolides from Asclepias curassavica.

PubMed

Zhang, Rong-Rong; Tian, Hai-Yan; Tan, Ya-Fang; Chung, Tse-Yu; Sun, Xiao-Hui; Xia, Xue; Ye, Wen-Cai; Middleton, David A; Fedosova, Natalya; Esmann, Mikael; Tzen, Jason T C; Jiang, Ren-Wang

2014-11-28

Five new cardenolide lactates (1–5) and one new dioxane double linked cardenolide glycoside (17) along with 15 known compounds (6–16 and 18–21) were isolated from the ornamental milkweed Asclepias curassavica. Their structures were elucidated by extensive spectroscopic methods (IR, UV, MS, 1D- and 2D-NMR). The molecular structures and absolute configurations of 1–3 and 17 were further confirmed by single-crystal X-ray diffraction analysis. Simultaneous isolation of dioxane double linked cardenolide glycosides (17–21) and cardenolide lactates (1–5) provided unique chemotaxonomic markers for this genus. Compounds 1–21 were evaluated for the inhibitory activities against DU145 prostate cancer cells. The dioxane double linked cardenolide glycosides showed the most potent cytotoxic effect followed by normal cardenolides and cardenolide lactates, while the C21 steroids were non-cytotoxic. Enzymatic assay established a correlation between the cytotoxic effects in DU145 cancer cells and the Ki for the inhibition of Na(+),K(+)-ATPase. Molecular docking analysis revealed relatively strong H-bond interactions between the bottom of the binding cavity and compounds 18 or 20, and explained why the dioxane double linked cardenolide glycosides possessed higher inhibitory potency on Na(+),K(+)-ATPase than the cardenolide lactate.

A Zn(2+)-responsive highly sensitive fluorescent probe and 1D coordination polymer based on a coumarin platform.

PubMed

Kumar, Virendra; Kumar, Ajit; Diwan, Uzra; Upadhyay, K K

2013-09-28

A coumarin-based Schiff base (receptor 1) exhibited fluorescence enhancement selectively with Zn(2+) at a nanomolar level in near-aqueous medium (EtOH-H2O; 1:1, v/v). The response was instantaneous with a detection limit of 3.26 × 10(-9) M. The sensing event is supposed to incorporate a combinational effect of intramolecular charge transfer (ICT), chelation-enhanced fluorescence (CHEF) and C[double bond, length as m-dash]N isomerization mechanisms. Various spectroscopic methods, viz. IR, UV-visible, fluorescence and NMR in association with single crystal XRD studies, were used for thorough investigation of the structure of receptor 1 as well as of the sensing event. The Zn(2+) complex of receptor 1 exhibited a very nice 1D chain coordination polymeric framework in its single crystal XRD.

Structures, Bonding, and Energetics of Potential Triatomic Circumstellar Molecules Containing Group 15 and 16 Elements.

PubMed

Turner, Walter E; Agarwal, Jay; Schaefer, Henry F

2015-12-03

The recent discovery of PN in the oxygen-rich shell of the supergiant star VY Canis Majoris points to the formation of several triatomic molecules involving oxygen, nitrogen, and phosphorus; these are also intriguing targets for main-group synthetic inorganic chemistry. In this research, high-level ab initio electronic structure computations were conducted on the potential circumstellar molecule OPN and several of its heavier group 15 and 16 congeners (SPN, SePN, TePN, OPP, OPAs, and OPSb). For each congener, four isomers were examined. Optimized geometries were obtained with coupled cluster theory [CCSD(T)] using large Dunning basis sets [aug-cc-pVQZ, aug-cc-pV(Q+d)Z, and aug-cc-pVQZ-PP], and relative energies were determined at the complete basis set limit of CCSDT(Q) from focal point analyses. The linear phosphorus-centered molecules were consistently the lowest in energy of the group 15 congeners by at least 6 kcal mol(-1), resulting from double-triple and single-double bond resonances within the molecule. The linear nitrogen-centered molecules were consistently the lowest in energy of the group 16 congeners by at least 5 kcal mol(-1), due to the electronegative central nitrogen atom encouraging electron delocalization throughout the molecule. For OPN, OPP, and SPN, anharmonic vibrational frequencies and vibrationally corrected rotational constants are predicted; good agreement with available experimental data is observed.

Accumulation of specific sterol precursors targets a MAP kinase cascade mediating cell-cell recognition and fusion.

PubMed

Weichert, Martin; Lichius, Alexander; Priegnitz, Bert-Ewald; Brandt, Ulrike; Gottschalk, Johannes; Nawrath, Thorben; Groenhagen, Ulrike; Read, Nick D; Schulz, Stefan; Fleißner, André

2016-10-18

Sterols are vital components of eukaryotic cell membranes. Defects in sterol biosynthesis, which result in the accumulation of precursor molecules, are commonly associated with cellular disorders and disease. However, the effects of these sterol precursors on the metabolism, signaling, and behavior of cells are only poorly understood. In this study, we show that the accumulation of only ergosterol precursors with a conjugated double bond in their aliphatic side chain specifically disrupts cell-cell communication and fusion in the fungus Neurospora crassa Genetically identical germinating spores of this fungus undergo cell-cell fusion, thereby forming a highly interconnected supracellular network during colony initiation. Before fusion, the cells use an unusual signaling mechanism that involves the coordinated and alternating switching between signal sending and receiving states of the two fusion partners. Accumulation of only ergosterol precursors with a conjugated double bond in their aliphatic side chain disrupts this coordinated cell-cell communication and suppresses cell fusion. These specific sterol precursors target a single ERK-like mitogen-activated protein (MAP) kinase (MAK-1)-signaling cascade, whereas a second MAP kinase pathway (MAK-2), which is also involved in cell fusion, is unaffected. These observations indicate that a minor specific change in sterol structure can exert a strong detrimental effect on a key signaling pathway of the cell, resulting in the absence of cell fusion.

Accumulation of specific sterol precursors targets a MAP kinase cascade mediating cell–cell recognition and fusion

PubMed Central

Weichert, Martin; Lichius, Alexander; Priegnitz, Bert-Ewald; Brandt, Ulrike; Gottschalk, Johannes; Nawrath, Thorben; Groenhagen, Ulrike; Read, Nick D.; Schulz, Stefan; Fleißner, André

2016-01-01

Sterols are vital components of eukaryotic cell membranes. Defects in sterol biosynthesis, which result in the accumulation of precursor molecules, are commonly associated with cellular disorders and disease. However, the effects of these sterol precursors on the metabolism, signaling, and behavior of cells are only poorly understood. In this study, we show that the accumulation of only ergosterol precursors with a conjugated double bond in their aliphatic side chain specifically disrupts cell–cell communication and fusion in the fungus Neurospora crassa. Genetically identical germinating spores of this fungus undergo cell–cell fusion, thereby forming a highly interconnected supracellular network during colony initiation. Before fusion, the cells use an unusual signaling mechanism that involves the coordinated and alternating switching between signal sending and receiving states of the two fusion partners. Accumulation of only ergosterol precursors with a conjugated double bond in their aliphatic side chain disrupts this coordinated cell–cell communication and suppresses cell fusion. These specific sterol precursors target a single ERK-like mitogen-activated protein (MAP) kinase (MAK-1)-signaling cascade, whereas a second MAP kinase pathway (MAK-2), which is also involved in cell fusion, is unaffected. These observations indicate that a minor specific change in sterol structure can exert a strong detrimental effect on a key signaling pathway of the cell, resulting in the absence of cell fusion. PMID:27708165

Chemical Kinetic Influences of Alkyl Chain Structure on the High Pressure and Temperature Oxidation of a Representative Unsaturated Biodiesel: Methyl Nonenoate.

PubMed

Fridlyand, Aleksandr; Goldsborough, S Scott; Brezinsky, Kenneth

2015-07-16

The high pressure and temperature oxidation of methyl trans-2-nonenoate, methyl trans-3-nonenoate, 1-octene, and trans-2-octene are investigated experimentally to probe the influence of the double bond position on the chemical kinetics of long esters and alkenes. Single pulse shock tube experiments are performed in the ranges p = 3.8-6.2 MPa and T = 850-1500 K, with an average reaction time of 2 ms. Gas chromatographic measurements indicate increased reactivity for trans-2-octene compared to 1-octene, whereas both methyl nonenoate isomers have reactivities similar to that of 1-octene. A difference in the yield of stable intermediates is observed for the octenes when compared to the methyl nonenoates. Chemical kinetic models are developed with the aid of the Reaction Mechanism Generator to interpret the experimental results. The models are created using two different base chemistry submodels to investigate the influence of the foundational chemistry (i.e., C0-C4), whereas Monte Carlo simulations are performed to examine the quality of agreement with the experimental results. Significant uncertainties are found in the chemistry of unsaturated esters with the double bonds located close to the ester groups. This work highlights the importance of the foundational chemistry in predictive chemical kinetics of biodiesel combustion at engine relevant conditions.

Metal-metal bond lengths in complexes of transition metals*

PubMed Central

Pauling, Linus

1976-01-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

Estimation of strength in different extra Watson-Crick hydrogen bonds in DNA double helices through quantum chemical studies.

PubMed

Bandyopadhyay, D; Bhattacharyya, D

2006-10-15

It was shown earlier, from database analysis, model building studies, and molecular dynamics simulations that formation of cross-strand bifurcated or Extra Watson-Crick hydrogen (EWC) bonds between successive base pairs may lead to extra rigidity to DNA double helices of certain sequences. The strengths of these hydrogen bonds are debatable, however, as they do not have standard linear geometry criterion. We have therefore carried out detailed ab initio quantum chemical studies using RHF/6-31G(2d,2p) and B3LYP/6-31G(2p,2d) basis sets to determine strengths of several bent hydrogen bonds with different donor and acceptors. Interaction energy calculations, corrected for the basis set superposition errors, suggest that N-H...O type bent EWC hydrogen bonds are possible along same strands or across the strands between successive base pairs, leading to significant stability (ca. 4-9 kcal/mol). The N-H...N and C-H...O type interactions, however, are not so stabilizing. Hence, consideration of EWC N-H...O H-bonds can lead to a better understanding of DNA sequence directed structural features. Copyright (c) 2006 Wiley Periodicals, Inc.

Characterization of the interdependency between residues that bind the substrate in a beta-glycosidase.

PubMed

Tomassi, M H; Rozenfeld, J H K; Gonçalves, L M; Marana, S R

2010-01-01

The manner by which effects of simultaneous mutations combine to change enzymatic activity is not easily predictable because these effects are not always additive in a linear manner. Hence, the characterization of the effects of simultaneous mutations of amino acid residues that bind the substrate can make a significant contribution to the understanding of the substrate specificity of enzymes. In the beta-glycosidase from Spodoptera frugiperda (Sfbetagly), both residues Q39 and E451 interact with the substrate and this is essential for defining substrate specificity. Double mutants of Sfbetagly (A451E39, S451E39 and S451N39) were prepared by site-directed mutagenesis, expressed in bacteria and purified using affinity chromatography. These enzymes were characterized using p-nitrophenyl beta-galactoside and p-nitrophenyl beta-fucoside as substrates. The k cat/Km ratio for single and double mutants of Sfbetagly containing site-directed mutations at positions Q39 and E451 was used to demonstrate that the effect on the free energy of ESdouble dagger (enzyme-transition state complex) of the double mutations (Gdouble daggerxy) is not the sum of the effects resulting from the single mutations (Gdouble daggerx and Gdouble daggery). This difference in Gdouble dagger indicates that the effects of the single mutations partially overlap. Hence, this common effect counts only once in Gdouble daggerxy. Crystallographic data on beta-glycosidases reveal the presence of a bidentate hydrogen bond involving residues Q39 and E451 and the same hydroxyl group of the substrate. Therefore, both thermodynamic and crystallographic data suggest that residues Q39 and E451 exert a mutual influence on their respective interactions with the substrate.

Average bond energies between boron and elements of the fourth, fifth, sixth, and seventh groups of the periodic table

NASA Technical Reports Server (NTRS)

Altshuller, Aubrey P

1955-01-01

The average bond energies D(gm)(B-Z) for boron-containing molecules have been calculated by the Pauling geometric-mean equation. These calculated bond energies are compared with the average bond energies D(exp)(B-Z) obtained from experimental data. The higher values of D(exp)(B-Z) in comparison with D(gm)(B-Z) when Z is an element in the fifth, sixth, or seventh periodic group may be attributed to resonance stabilization or double-bond character.

Theoretical investigation of HNgNH{sub 3}{sup +} ions (Ng = He, Ne, Ar, Kr, and Xe)

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

Gao, Kunqi; Sheng, Li, E-mail: shengli@hit.edu.cn

2015-04-14

The equilibrium geometries, harmonic frequencies, and dissociation energies of HNgNH{sub 3}{sup +} ions (Ng = He, Ne, Ar, Kr, and Xe) were investigated using the following method: Becke-3-parameter-Lee-Yang-Parr (B3LYP), Boese-Matrin for Kinetics (BMK), second-order Møller-Plesset perturbation theory (MP2), and coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)). The results indicate that HHeNH{sub 3}{sup +}, HArNH{sub 3}{sup +}, HKrNH{sub 3}{sup +}, and HXeNH{sub 3}{sup +} ions are metastable species that are protected from decomposition by high energy barriers, whereas the HNeNH{sub 3}{sup +} ion is unstable because of its relatively small energy barrier for decomposition.more » The bonding nature of noble-gas atoms in HNgNH{sub 3}{sup +} was also analyzed using the atoms in molecules approach, natural energy decomposition analysis, and natural bond orbital analysis.« less

Low doping concentration studies of doped PVA-Coumarin nanocomposite films

NASA Astrophysics Data System (ADS)

Tripathi, J.; Tripathi, S.; Bisen, R.; Sharma, A.; Choudhary, A.; Shripathi, T.

2016-05-01

The observations of combination of Poly (vinyl) alcohol and Coumarin properties in nanocmposite films are reported. The X-ray diffraction measurements reveal nanocrystalline nature of PVA film, which remains nanocrystalline after doping Coumarin but along with PVA peaks, additional peak due to dopant crystallinity is seen. The absorption edge shows a double edge feature, where distinct bandgaps for PVA host and dopant Coumarin are obtained. However at a higher doping wt % of 1 and 2, the absorption is mainly dominated by Coumarin and single absorption edge is observed giving a bandgap equal to that of bulk Coumarin (3.3 eV). The composite formation affects the bonding of host drastically and is seen through the bond modification in FTIR spectra. The results suggest that doping below 2 wt% is advantageous as combination of PVA and Coumarin properties are obtained but at 2 wt %, the properties are dominated by mainly Coumarin and the signature of PVA from optical properties is completely lost.

Low doping concentration studies of doped PVA-Coumarin nanocomposite films

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

Tripathi, J., E-mail: jtripathi00@rediffmail.com; Bisen, R.; Choudhary, A.

2016-05-23

The observations of combination of Poly (vinyl) alcohol and Coumarin properties in nanocmposite films are reported. The X-ray diffraction measurements reveal nanocrystalline nature of PVA film, which remains nanocrystalline after doping Coumarin but along with PVA peaks, additional peak due to dopant crystallinity is seen. The absorption edge shows a double edge feature, where distinct bandgaps for PVA host and dopant Coumarin are obtained. However at a higher doping wt % of 1 and 2, the absorption is mainly dominated by Coumarin and single absorption edge is observed giving a bandgap equal to that of bulk Coumarin (3.3 eV). Themore » composite formation affects the bonding of host drastically and is seen through the bond modification in FTIR spectra. The results suggest that doping below 2 wt% is advantageous as combination of PVA and Coumarin properties are obtained but at 2 wt %, the properties are dominated by mainly Coumarin and the signature of PVA from optical properties is completely lost.« less

Lithium-decorated oxidized graphyne for hydrogen storage by first principles study

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

Yan, Zeyu; Wang, Lang; Cheng, Julong

2014-11-07

The geometric stability and hydrogen storage capacity of Li decorated oxidized γ-graphyne are studied based on the first-principles calculations. It is found that oxygen atoms trend to bond with acetylenic carbons and form C=O double bonds on both sides of graphyne. The binding energy of single Li atom on oxidized graphyne is 3.29 eV, owning to the strong interaction between Li atom and O atom. Meanwhile, the dispersion of Li is stable even under a relatively high density. One attached Li atom can at least adsorb six hydrogen molecules around. Benefitting from the porous structure of graphyne and the high attachedmore » Li density, a maximum hydrogen storage density 12.03 wt. % is achieved with four Li atoms in graphyne cell. The corresponding average binding energy is 0.24 eV/H{sub 2}, which is suitable for reversible storage. These results indicate that Li decorated graphyne can serve as a promising hydrogen storage material.« less

Double salt crystal structure of hexa-sodium hemiundeca-hydrogen α-hexa-molybdoplatinate(IV) heminona-hydrogen α-hexa-molybdoplatinate(IV) nona-cosa-hydrate: di-hydrogen disordered-mixture double salt.

PubMed

Joo, Hea-Chung; Park, Ki-Min; Lee, Uk

2015-10-01

The title double salt containing two distinct, differently protonated hexa-molybdoplatinate(IV) polyanions, Na6[H5.5 α-PtMo6O24][H4.5 α-PtMo6O24]·29H2O, has been synthesized by a hydro-thermal reaction at ca pH 1.80. The positions of the H atoms in the polyanions were established from difference Fourier maps and confirmed by the inter-polyanion hydrogen bonds, bond-distance elongation, and bond-valence sum (BVS) calculations. The fractional numbers of H atoms in each polyanion are required for charge balance and in order to avoid unrealistically short H⋯H distances in the inter-polyanion hydrogen bonds. Considering the disorder, the refined formula of the title polyanion, {[H5.5 α-PtMo6O24]; polyanion (A) and [H4.5 α-PtMo6O24]; polyanion (B)}(6-), can be rewritten as a set of real formula, viz. {[H6 α-PtMo6O24]; polyanion (A). [H4 α-PtMo6O24]; polyanion (B)}(6-) and {[H5 α-PtMo6O24]; polyanion (A). [H5 α-PtMo6O24]; polyanion (B)}(6-). The polyanion pairs both form dimers of the same formula, viz. {[H10 α-Pt2Mo12O48]}(6-) connected by seven inter-polyanion O-H⋯O hydrogen bonds.

Anharmonicity in a double hydrogen transfer reaction studied in a single porphycene molecule on a Cu(110) surface.

PubMed

Liu, S; Baugh, D; Motobayashi, K; Zhao, X; Levchenko, S V; Gawinkowski, S; Waluk, J; Grill, L; Persson, M; Kumagai, T

2018-05-07

Anharmonicity plays a crucial role in hydrogen transfer reactions in hydrogen-bonding systems, which leads to a peculiar spectral line shape of the hydrogen stretching mode as well as highly complex intra/intermolecular vibrational energy relaxation. Single-molecule study with a well-defined model is necessary to elucidate a fundamental mechanism. Recent low-temperature scanning tunnelling microscopy (STM) experiments revealed that the cis↔cis tautomerization in a single porphycene molecule on Cu(110) at 5 K can be induced by vibrational excitation via an inelastic electron tunnelling process and the N-H(D) stretching mode couples with the tautomerization coordinate [Kumagai et al. Phys. Rev. Lett. 2013, 111, 246101]. Here we discuss a pronounced anharmonicity of the N-H stretching mode observed in the STM action spectra and the conductance spectra. Density functional theory calculations find a strong intermode coupling of the N-H stretching with an in-plane bending mode within porphycene on Cu(110).

The spatial configuration of ordered polynucleotide chains. II. The poly(rA) helix.

PubMed Central

Olson, W K

1975-01-01

Approximate details of the spatial configuration of the ordered single-stranded poly(rA) molecule in dilute solution have been obtained in a combined theoretical analysis of base stacking and chain flexibility. Only those regularly repeating structures which fulfill the criterion of conformational flexibility (based upon all available experimental and theoretical evidence of preferred bond rotations) and which also exhibit the right-handed base stacking pattern observed in nmr investigations of poly(rA) are deemed suitable single-stranded helices. In addition, the helical geometry of the stacked structures is required to be consistent with the experimentally observed dimensions of both completely ordered and partially ordered poly(rA) chains. Only a single category of poly(rA) helices (very similar in all conformational details to the individual chains of the poly(rA) double-stranded X-ray structure) is thus obtained. Other conformationally feasible polynucleotide helices characterized simply by a parallel and overlapping base stacking arrangement are also discussed. PMID:1052529

Influence of laboratory degradation methods and bonding application parameters on microTBS of self-etch adhesives to dentin.

PubMed

Erhardt, Maria Carolina G; Pisani-Proença, Jatyr; Osorio, Estrella; Aguilera, Fátima S; Toledano, Manuel; Osorio, Raquel

2011-04-01

To evaluate the laboratory resistance to degradation and the use of different bonding treatments on resin-dentin bonds formed with three self-etching adhesive systems. Flat, mid-coronal dentin surfaces from extracted human molars were bonded according to manufacturer's directions and submitted to two challenging regimens: (A) chemical degradation with 10% NaOC1 immersion for 5 hours; and (B) fatigue loading at 90 N using 50,000 cycles at 3.0 Hz. Additional dentin surfaces were bonded following four different bonding application protocols: (1) according to manufacturer's directions; (2) acid-etched with 36% phosphoric acid (H3PO4) for 15 seconds; (3) 10% sodium hypochlorite (NaOClaq) treated for 2 minutes, after H3PO4-etching; and (4) doubling the application time of the adhesives. Two one-step self-etch adhesives (an acetone-based: Futurabond/FUT and an ethanol-based: Futurabond NR/FNR) and a two-step self-etch primer system (Clearfil SE Bond/CSE) were examined. Specimens were sectioned into beams and tested for microtensile bond strength (microTBS). Selected debonded specimens were observed under scanning electron microscopy (SEM). Data (MPa) were analyzed by ANOVA and multiple comparisons tests (alpha= 0.05). microTBS significantly decreased after chemical and mechanical challenges (P< 0.05). CSE showed higher microTBS than the other adhesive systems, regardless the bonding protocol. FUT attained the highest microTBS after doubling the application time. H3PO4 and H3PO4 + NaOCl pretreatments significantly decreased bonding efficacy of the adhesives.

26 CFR 1.6165-1 - Bonds where time to pay the tax or deficiency has been extended.

Code of Federal Regulations, 2010 CFR

2010-04-01

... exceeding double the amount of the tax with respect to which the extension is granted. Such bond shall be... 26 Internal Revenue 13 2010-04-01 2010-04-01 false Bonds where time to pay the tax or deficiency... THE TREASURY (CONTINUED) INCOME TAX (CONTINUED) INCOME TAXES Extensions of Time for Payment § 1.6165-1...

Atomic and molecular analysis highlights the biophysics of unprotonated and protonated retinal in UV and scotopic vision.

PubMed

Kubli-Garfias, Carlos; Vázquez-Ramírez, Ricardo; Cabrera-Vivas, Blanca M; Gómez-Reyes, Baldomero; Ramírez, Juan Carlos

2015-09-26

During the photoreaction of rhodopsin, retinal isomerizes, rotating the C11[double bond, length as m-dash]C12 π-bond from cis to an all-trans configuration. Unprotonated (UR) or protonated (PR) retinal in the Schiff's base (SB) is related to UV and light vision. Because the UR and PR have important differences in their physicochemical reactivities, we compared the atomic and molecular properties of these molecules using DFT calculations. The C10-C11[double bond, length as m-dash]C12-C13 dihedral angle was rotated from 0° to 180° in 45° steps, giving five conformers, and the following were calculated from them: atomic orbital (AO) contributions to the HOMO and LUMO, atomic charges, bond length, bond order, HOMO, LUMO, hardness, electronegativity, polarizability, electrostatic potential, UV-vis spectra and dipole moment (DM). Similarly, the following were analyzed: the energy profile, hybridization, pyramidalization and the hydrogen-out-of-plane (HOOP) wagging from the H11-C11[double bond, length as m-dash]C12-H12 dihedral angle. In addition, retinal with a water H-bond (HR) in the SB was included for comparison. Interestingly, in the PR, C11 and C12 are totally the LUMO and the HOMO, respectively, and have a large electronegativity difference, which predicts an electron jump in these atoms during photoexcitation. At the same time, the PR showed a longer bond length and lower bond order, with a larger DM, lower HOMO-LUMO gap, lower hardness and higher electronegativity. In addition, the AOs of -45° and -90° conformers changed significantly, from pz to py, during the rotation concomitantly with marked hybridization, smooth pyramidalization and lower HOOP activity. Clearly, the atomic and molecular differences between the UR and PR are overwhelming, including the rotational energy profile and light absorption spectra, which indicates that light absorption of UR and PR is already determined by the retinal characteristics of the SB protonation. The HR-model compared with UR shows a lower energy barrier and a discreet bathochromic effect in the UV region.

Photoelectron spectroscopy of B{sub 4}O{sub 4}{sup −}: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

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

Tian, Wen-Juan; Chen, Qiang; Ou, Ting

2015-04-07

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B{sub 4}O{sub 4}{sup 0/−} clusters. The measured PES spectra of B{sub 4}O{sub 4}{sup −} exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDEmore » of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of C{sub s} B{sub 4}O{sub 4}{sup −} ({sup 2}A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D{sub 2h} B{sub 4}O{sub 4}{sup −} ({sup 2}B{sub 2g}) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B{sub 2}O{sub 2} core bonded with terminal BO and/or BO{sub 2} groups. The same Y-shaped and rhombic structures are also located for the B{sub 4}O{sub 4} neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B{sub 4}O{sub 4}{sup 0/−} clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B{sub 4}O{sub 4}{sup 0/−} clusters. This work is the first experimental study on a molecular system with an o-bond.« less

Synthesis, X-ray Single Crystal Structure, Molecular Docking and DFT Computations on N-[(1E)-1-(2H-1,3-Benzodioxol-5-yl)-3-(1H-imidazol-1-yl)propylidene]-hydroxylamine: A New Potential Antifungal Agent Precursor.

PubMed

Al-Wabli, Reem I; Al-Ghamdi, Alwah R; Ghabbour, Hazem A; Al-Agamy, Mohamed H; Monicka, James Clemy; Joe, Issac Hubert; Attia, Mohamed I

2017-02-28

Mycoses are serious health problem, especially in immunocompromised individuals. A new imidazole-bearing compound containing an oxime functionality was synthesized and characterized with different spectroscopic techniques to be used for the preparation of new antifungal agents. The stereochemistry of the oxime double bond was unequivocally determined via the single crystal X-ray technique. The title compound 4 , C 13 H 13 N₃O₃·C₃H₈O, crystallizes in the monoclinic space group P 2₁with a = 9.0963(3) Å, b = 14.7244(6) Å, c = 10.7035(4) Å, β = 94.298 (3)°, V = 1429.57(9) ų, Z = 2. The molecules were packed in the crystal structure by eight intermolecular hydrogen bond interactions. A comprehensive spectral analysis of the title molecule 4 has been performed based on the scaled quantum mechanical (SQM) force field obtained by density-functional theory (DFT) calculations. A molecular docking study illustrated the binding mode of the title compound 4 into its target protein. The preliminary antifungal activity of the title compound 4 was determined using a broth microdilution assay.

Silicon carbide at nanoscale: Finite single-walled to "infinite" multi-walled tubes

NASA Astrophysics Data System (ADS)

Adhikari, Kapil

A systematic ab initio study of silicon carbide (SiC) nanostructures, especially finite single-walled, infinite double- and multi-walled nanotubes and nanocones is presented. Electronic and structural properties of all these nanostructures have been calculated using hybrid density functionals (B3LYP and PBE0) as implemented in the GAUSSIAN 03/09 suite of software. The unusual dependence of band gap of silicon carbide nanotubes (SiCNT) has been explained as a direct consequence of curvature effect on the ionicity of the bonds. The study of fullerene hemisphere capped, finite SiC nanotubes indicates that the carbon-capped SiC nanotubes are energetically more preferred than silicon-capped finite or hydrogen terminated infinite nanotubes. Capping a nanotube by fullerene hemisphere reduces its band gap. SiC nanocones have also been investigated as possible cap structures of nanotubes. Electronic properties of the nanocones are found to be strongly dependent upon their tip and edge structures, with possible interesting applications in surface science. Three types of double-walled SiCNTs (n, n)@(m, m) (3 ≤ n ≤ 6 ; 7 ≤ m ≤ 12) have been studied using the finite cluster approximation. The stabilities of these nanotubes are of the same order as those of the single-walled SiC nanotubes and it should be experimentally possible to synthesize both single-walled and double-walled SiC nanotubes. The binding energy per atom or the cohesive energy of the double-walled nanotubes depends not only on the number of atoms but also on the coupling of the constituent single-walled nanotubes and their types. A study of binding energies, Mulliken charges, density of states and HOMO-LUMO gaps has been performed for all nanotubes from (n, n)@(n+3,n+3) to (n, n)@(n+6, n+6) (n=3-6). Evolution of band gaps of the SiCNTs with increase in the number of walls has also been investigated. The nature of interaction between transition metal atoms and silicon carbide nanotubes with different curvature has also been investigated. The curvature of the nanotubes affects the nature of the interaction between the nanotubes and the transition teal atoms. Our study of functionalized SiCNTs by 3d transition metal atoms indicates that these nanostructures can have possible applications in spintronics and nano-magnetic storage.

Phosphoric acid activation of sugarcane bagasse for removal of o-toluidine and benzidine

NASA Astrophysics Data System (ADS)

Adib, M. R. M.; Attahirah, M. H. M. N.; Amirza, A. R. M.

2018-04-01

In the effort to find alternatives for low cost adsorbent, activated carbon using sugarcane bagasse (SBAC) has been introduced in this study that has undergo chemical treatment using phosphoric acid to determine the effectiveness of adsorption process in removing o-toluidine and benzidine. Throughout this study, 92.9% of o-toluidine has been successfully removed by SBAC at optimum value of 1.1 g of dosage with contact time of 10 minutes and concentration of 10 mg/L. While benzidine was remove by 83.1% at optimum dosage of 1.1 g with 60 minutes of contact time and at 20 mg/L concentrations. Testing of SEM proves that SBAC has high porosity and comparable to CAC. In FTIR results, shows that CAC has high number of double bond while SBAC shows no double bond at all. Presence of double bond in CAC lead to increase in percentage of removal of adsorbate. After considering other factor such as cost, energy and environmental friendly, it shows that SBAC was considerable to replaced CAC.

n-Nonacosadienes from the marine haptophytes Emiliania huxleyi and Gephyrocapsa oceanica.

PubMed

Nakamura, Hideto; Sawada, Ken; Araie, Hiroya; Suzuki, Iwane; Shiraiwa, Yoshihiro

2015-03-01

The hydrocarbons in cultures of marine haptophytes Emiliania huxleyi NIES837 and Gephyrocapsa oceanica NIES1315 were analyzed, and nonacosadienes and hentriacontadienes were detected as the major compounds in both strains. C29 and C31 monoenes and di-, tri- and tetra-unsaturated C33 alkenes were also detected as minor compounds but not C37 and C38 alkenes. The positions of the double bonds in the C29 and C31 alkenes were determined by mass spectrometry of their dimethyl disulfide (DMDS) adducts. Among the four C29 alkenes identified, the most abundant isomer was 2,20-nonacosadiene, and the other three compounds were 1,20-nonacosadiene, 3,20-nonacosadiene and 9-nonacosene, respectively. Hitherto, 2,20-nonacosadiene and 3,20-nonacosadiene were unknown to be natural products. The double bond at the n-9 (ω9) position in these C29 alkenes is hypothesized to be derived from precursors of unsaturated fatty acids possessing an n-9 double bond, such as (9Z)-9-octadecenoic acid. Nonacosadienes have the potential for being used as distinct haptophyte biomarkers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effects of surface preparation on the long-term durability of adhesively bonded composite joints

NASA Astrophysics Data System (ADS)

Bardis, Jason Dante

The long-term durability of adhesively bonded composite joints is critical to modern aircraft structures, which are increasingly adopting bonding as an alternative option to mechanical fastening. The effects of the surface preparation of the adherends are critical, affecting initial strength, long-term durability, fracture toughness, and failure modes of bonded joints. In this study, several potential factors are evaluated, with focus on the following: (1) Effects of possible chemical contamination from release fabrics, release films, and peel plies during adherend cure. (2) Chemical and mechanical effects of abrasion on the fracture toughness and failure mode. (3) Characterization of paste and film adhesives. There are several standard test methods used to evaluate specimen fracture, but the majority concentrate on bonded metals and interlaminar composite fracture. Testing concentrated on mode I tests; a custom double cantilever beam specimen was devised and utilized, and two forms of a wedge crack test (traveling and static) were also used. Additionally, single lap shear tests were run to contrast the mode I tests. Non-destructive testing included X-ray photography of crack fronts, energy dispersive spectroscopy and X-ray photoelectron spectroscopy surface chemistry analyses, and scanning electron microscope imaging of prepared surfaces. All mode I test methods tended to be in agreement in the ranking of different surface preparation methods. Test results revealed that release agents deposited on adherend surfaces during their cure cycle prevented proper adhesion. While mechanical abrasion did improve their fracture toughness and lower their contamination greatly, the test values did not reach the levels of samples that were not contaminated before bonding, and the interfacial modes of failure did not always change to desirable modes.

[Bonding strength of resin and tooth enamel after teeth bleaching with cold plasma].

PubMed

Zhu, Meng-meng; Wang, Guo-min; Sun, Ke; Li, Ying-long; Pan, Jie

2016-02-18

To investigate the immediate bond strength and surface structure of resin and the tooth enamel which treated by cold plasma. In the study, 40 bovine incisors were divided into two equal parts. In this sense, all enamel adhesive samples were prepared and then randomly divided into 4 groups (n =20). group 1: acid + single bond 2+resin composite (control group); group 2:beyond bleaching+ acid+single bond 2+resin composite; group 3: treated by cold plasma for 5 minutes+ acid+single bond 2+resin composite; group 4: treated by cold plasma for 5 minutes+single bond 2+resin composite. Single bond 2 bonding system and Filtek Z250 resin were used in this experiment. The shear bond strength was tested by universal testing machine. The surface of the enamel in different processes was observed by scanning electron microscope (SEM). Statistical analyses by the single factor analysis of variance and multiple pairwise comparisons were performed with SPSS 17.0 . The shear bond strength of group 4 (8.60 MPa) was significantly lower than that of the other three groups (P<0.05). The shear bond strength of group 2 (17.89 MPa) was higher than that of group 4, but lower than group 1 and group 3 (P<0.05).There was no significant difference between group 1 (34.82 MPa) and group 3 (34.69 MPa). Scanning electron microscope indicated that the enamel treated by cold plasma had slight molten form, which was different from etched enamel surface.The fractured surface of group 3 was mix fracture, which was similar to the control group (group 1). Compared with the conventional clinic bleaching, immediate bond strength of resin-enamel that treated by cold plasma has not been affected.

A revised set of values of single-bond radii derived from the observed interatomic distances in metals by correction for bond number and resonance energy

PubMed Central

Pauling, Linus; Kamb, Barclay

1986-01-01

An earlier discussion [Pauling, L. (1947) J. Am. Chem. Soc. 69, 542] of observed bond lengths in elemental metals with correction for bond number and resonance energy led to a set of single-bond metallic radii with values usually somewhat less than the corresponding values obtained from molecules and complex ions. A theory of resonating covalent bonds has now been developed that permits calculation of the number of resonance structures per atom and of the effective resonance energy per bond. With this refined method of correcting the observed bond lengths for the effect of resonance energy, a new set of single-bond covalent radii, in better agreement with values from molecules and complex ions, has been constructed. PMID:16593698

Comparative evaluation of shear bond strength of metallic brackets bonded with two different bonding agents under dry conditions and with saliva contamination.

PubMed

Khanehmasjedi, Mashallah; Naseri, Mohammad Ali; Khanehmasjedi, Samaneh; Basir, Leila

2017-02-01

This study compared the shear bond strength of metallic brackets bonded with Single Bond and Assure bonding agents under dry and saliva-contamination conditions. Sixty sound premolar teeth were selected, and stainless-steel brackets were bonded on enamel surfaces with Single Bond and Assure bonding agents under dry condition or with saliva contamination. Shear bond strength values of brackets were measured in a universal testing machine. The adhesive remnant index scores were determined after debonding of the brackets under a stereomicroscope. One-way analysis of variance (ANOVA) was used to analyze bond strength. Two-by-two comparisons were made with post hoc Tukey tests (p<0.001). Frequencies of adhesive remnant index scores were analyzed by Kruskal-Wallis test. Bond strength values of brackets to tooth structure were 9.29±8.56 MPa and 21.25±8.93 MPa with the use of Assure resin bonding agent under saliva-contamination and dry conditions, respectively. These values were 10.13±6.69 MPa and 14.09±6.6 MPa, respectively, under the same conditions with the use of Single Bond adhesive. Contamination with saliva resulted in a significant decrease in the bond strength of brackets to tooth structure with the application of Assure adhesive resin (p<0.001). There were no significant differences in the adhesive remnant index scores between the study groups. Application of Single Bond and Assure bonding agents resulted in adequate bond strength of brackets to tooth structures. Contamination with saliva significantly decreased the bond strength of Assure bonding agent compared with dry conditions. Copyright © 2016. Published by Elsevier Taiwan LLC.

Hawaii Algal Biofuel

DTIC Science & Technology

2013-03-01

155 Figure 56. Ring heater. ....................................................................................................155 Figure 57...structure, the straight chain paraffins are first combined with high pressure hydrogen. The reaction converts them into a hydrogenated ring -like...bonds in the hydrogenated ring -like molecular structure to form many small olefinic double bonds of unsaturated hydrocarbons. The unsaturated

δ-Deuterium Isotope Effects as Probes for Transition-State Structures of Isoprenoid Substrates

PubMed Central

2015-01-01

The biosynthetic pathways to isoprenoid compounds involve transfer of the prenyl moiety in allylic diphosphates to electron-rich (nucleophilic) acceptors. The acceptors can be many types of nucleophiles, while the allylic diphosphates only differ in the number of isoprene units and stereochemistry of the double bonds in the hydrocarbon moieties. Because of the wide range of nucleophilicities of naturally occurring acceptors, the mechanism for prenyltransfer reactions may be dissociative or associative with early to late transition states. We have measured δ-secondary kinetic isotope effects operating through four bonds for substitution reactions with dimethylallyl derivatives bearing deuterated methyl groups at the distal (C3) carbon atom in the double bond under dissociative and associative conditions. Computational studies with density functional theory indicate that the magnitudes of the isotope effects correlate with the extent of bond formation between the allylic moiety and the electron-rich acceptor in the transition state for alkylation and provide insights into the structures of the transition states for associative and dissociative alkylation reactions. PMID:24665882

Synthesis of partially and fully fused polyaromatics by annulative chlorophenylene dimerization.

PubMed

Koga, Yoshito; Kaneda, Takeshi; Saito, Yutaro; Murakami, Kei; Itami, Kenichiro

2018-01-26

Since the discovery by Ullmann and Bielecki in 1901, reductive dimerization (or homocoupling) of aryl halides has been extensively exploited for the generation of a range of biaryl-based functional molecules. In contrast to the single-point connection in these products, edge-sharing fused aromatic systems have not generally been accessible from simple aryl halides via annulation cascades. Here we report a single-step synthesis of fused aromatics with a triphenylene core by the palladium-catalyzed annulative dimerization of structurally and functionally diverse chlorophenylenes through double carbon-hydrogen bond activation. The partially fused polyaromatics can be transformed into fully fused, small graphene nanoribbons, which are otherwise difficult to synthesize. This simple, yet powerful, method allows access to functional π-systems of interest in optoelectronics research. Copyright © 2018, The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

NASA Astrophysics Data System (ADS)

Wang, Se; Wang, Zhuang; Hao, Ce

2016-01-01

The time-dependent density functional theory (TDDFT) method was performed to investigate the excited-state intramolecular double proton transfer (ESIDPT) reaction of calix[4] arene (C4A) and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S1, S2 and T1) were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S2 and T1 states compared to those in the ground state. Interestingly, upon excitation to the S1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1···O2 and O2-H2···O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.

Hydrolysis of Ketene Catalyzed by Formic Acid: Modification of Reaction Mechanism, Energetics, and Kinetics with Organic Acid Catalysis

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

Louie, Matthew K.; Francisco, Joseph S.; Verdicchio, Marco

2015-05-14

The hydrolysis of ketene (H2C=C=O) to form acetic acid involving two water molecules and also separately in the presence of one to two water molecules and formic acid (FA) was investigated. Our results show that, while the currently accepted indirect mechanism, involving addition of water across the carbonyl C=O bond of ketene to form an ene-diol followed by tautomerization of the ene-diol to form acetic acid, is the preferred pathway when water alone is present, with formic acid as catalyst, addition of water across the ketene C=C double bond to directly produce acetic acid becomes the kinetically favored pathway formore » temperatures below 400 K. We find not only that the overall barrier for ketene hydrolysis involving one water molecule and formic acid (H2C2O + H2O + FA) is significantly lower than that involving two water molecules (H2C2O + 2H(2)O) but also that FA is able to reduce the barrier height for the direct path, involving addition of water across the C=C double bond, so that it is essentially identical with (6.4 kcal/mol) that for the indirect ene-diol formation path involving addition of water across the C=O bond. For the case of ketene hydrolysis involving two water molecules and formic acid (H2C2O + 2H(2)O + FA), the barrier for the direct addition of water across the C=C double bond is reduced even further and is 2.5 kcal/mol lower relative to the ene-diol path involving addition of water across the C=O bond. In fact, the hydrolysis barrier for the H2C2O + 2H(2)O + FA reaction through the direct path is sufficiently low (2.5 kcal/mol) for it to be an energetically accessible pathway for acetic acid formation under atmospheric conditions. Given the structural similarity between acetic and formic acid, our results also have potential implications for aqueous-phase chemistry. Thus, in an aqueous environment, even in the absence of formic acid, though the initial mechanism for ketene hydrolysis is expected to involve addition of water across the carbonyl bond as is currently accepted, the production and accumulation of acetic acid will likely alter the preferred pathway to one involving addition of water across the ketene C=C double bond as the reaction proceeds.« less

Urethane/Silicone Adhesives for Bonding Flexing Metal Parts

NASA Technical Reports Server (NTRS)

Edwards, Paul D.

2004-01-01

Adhesives that are blends of commercially available urethane and silicone adhesives have been found to be useful for bonding metal parts that flex somewhat during use. These urethane/silicone adhesives are formulated for the specific metal parts to be bonded. The bonds formed by these adhesives have peel and shear strengths greater than those of bonds formed by double-sided tapes and by other adhesives, including epoxies and neat silicones. In addition, unlike the bonds formed by epoxies, the bonds formed by these adhesives retain flexibility. In the initial application for which the urethane/silicone adhesives were devised, there was a need to bond spring rings, which provide longitudinal rigidity for inflatable satellite booms, with the blades that provide the booms axial strength. The problem was to make the bonds withstand the stresses, associated with differences in curvature between the bonded parts, that arose when the booms were deflated and the springs were compressed. In experiments using single adhesives (that is, not the urethane/ silicone blends), the bonds were broken and, in each experiment, it was found that the adhesive bonded well with either the ring or with the blade, but not both. After numerous experiments, the adhesive that bonded best with the rings and the adhesive that bonded best with the blades were identified. These adhesives were then blended and, as expected, the blend bonded well with both the rings and the blades. The two adhesives are Kalex (or equivalent) high-shear-strength urethane and Dow Corning 732 (or equivalent) silicone. The nominal mixture ratio is 5 volume parts of the urethane per 1 volume part of the silicone. Increasing the proportion of silicone makes the bond weaker but more flexible, and decreasing the proportion of silicone makes the bond stronger but more brittle. The urethane/silicone blend must be prepared and used quickly because of the limited working time of the urethane: The precursor of the urethane adhesive is supplied in a two-part form, comprising a resin and a hardener that must be mixed. The resulting urethane adhesive has a working time of 3 to 5 minutes. To prepare the urethane/silicone blend, one must quickly add the silicone to the urethane adhesive and mix it in thoroughly within the working time of the urethane. Once the urethane/silicone blend has been mixed and applied to the bond surfaces, it takes about 2 hours for the adhesive to cure under pressure. However, it takes about 24 hours for the adhesive to reach full strength.

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

PubMed

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

2012-01-27

Two series of DDD and AAA hydrogen-bond arrays were synthesized that form triply-hydrogen-bonded double-helical complexes when combined in CDCl(3) solution. Derivatization of the DDD arrays with electron-withdrawing groups increases the complex association constants by up to a factor of 30 in those arrays examined. Derivatization of the AAA arrays with electron donating substituents reveals a similar magnitude effect on the complex stabilities. The effect of substitution on both types of arrays are modeled quite satisfactorily (R(2) > 0.96 in all cases) as free energy relationships with respect to the sums of their Hammett substituent constants. In all, the complex stabilities can be manipulated over more than three orders of magnitude (>20 kJ mol(-1)) using this type of modification. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rupture of DNA aptamer: New insights from simulations

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

Mishra, Rakesh Kumar; Nath, Shesh; Kumar, Sanjay

2015-10-28

Base-pockets (non-complementary base-pairs) in a double-stranded DNA play a crucial role in biological processes. Because of thermal fluctuations, it can lower the stability of DNA, whereas, in case of DNA aptamer, small molecules, e.g., adenosinemonophosphate and adenosinetriphosphate, form additional hydrogen bonds with base-pockets termed as “binding-pockets,” which enhance the stability. Using the Langevin dynamics simulations of coarse grained model of DNA followed by atomistic simulations, we investigated the influence of base-pocket and binding-pocket on the stability of DNA aptamer. Striking differences have been reported here for the separation induced by temperature and force, which require further investigation by single moleculemore » experiments.« less

Theoretical study of the dipole moments of selected alkaline-earth halides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.; Ahlrichs, R.

1986-01-01

Ab initio calculations at the self-consistent-field (SCF), singles-plus-doubles configuration-interaction (SDCI), and coupled-pair functional (CPF) level, are reported for the dipole moments and dipole derivatives of the X2Sigma(+) ground states of BeF, BeCl, MgF, MgCl, CaF, CaCl, and SrF. For comparison, analogous calculations are performed for the X1Sigma(+) state of KCl. The CPF results are found to be in remarkably better agreement with experiment than are the SCF and SDCI results. Apparently higher excitations are required to properly describe the radial extent along the bond axis of the remaining valence electron on the alkaline-earth metal.

Dissociation and reconstruction of double-decker bis(phthalocyaninato) terbium(III) complex (TbPc2) on Pd(001): A theoretical investigation

NASA Astrophysics Data System (ADS)

Liu, Heng; Hu, Yujie; Wang, Hao; Jiang, Bo; Xu, Xuechun; Cai, Yingxiang

2017-01-01

The study of molecule dissociation is helpful to disclose the nature of chemical bonds and to extend molecular functions. The double-decker bis(phthalocyaninato) terbium(III) complex (TbPc2) is a promising single-molecule magnet (SMM) which exhibits potential applications in spin-devices. In this study, we investigate the dissociation and reconstruction of TbPc2 on Pd(001) surface. The results show that a single TbPc2 adsorbed on Pd(001) tends to split into Pc/Pd(001)+TbPc. However, the TbPc/Pd(001)+Pc might also be observed in an experimental study due to only a slight difference in their dissociation energy. The TbPc2 molecules on Pd(001) will form a (5×3) reconstruction which is different from the (3×4) reconstruction of PbPc on Pd(001). If the TbPc2 molecules with (5×3) reconstruction is dissociated, this reconstruction will be inherited by its daughter molecules due to strong molecule-substrate interaction. In addition, nudged elastic band (NEB) calculation shows that Tb-down is the stable state of TbPc/Pd(001) and Tb-up is a metastable state. The transition between two states might be utilized to realize TbPc's switch or storage functions.

Interlayer interaction in Ca-Fe layered double hydroxides intercalated with nitrate and chloride species

NASA Astrophysics Data System (ADS)

Al-Jaberi, Muayad; Naille, Sébastien; Dossot, Manuel; Ruby, Christian

2015-12-01

Ca-Fe layered double hydroxide (LDH) intercalated with chloride and nitrate ions has been synthesized with varying CaII:FeIII molar ratios of the initial solution. Phase pure LDH is observed with CaII:FeIII molar ratio of 2:1 and a mixture of LDH and Ca(OH)2 is formed for CaII:FeIII molar ratios higher than 2:1. Vibrational spectroscopies (Raman and IR) were used successfully to understand the interaction between the cationic and anionic sheets. The Raman bands positions at lower frequencies (150-600 cm-1) are intimately correlated to the nature of the divalent and trivalent ions but also to the nature of the anions. Indeed, a shift of ˜9 cm-1 is observed for the Raman double bands situated in the 300-400 cm-1 region when comparing Raman spectra of CaFe-LDH containing either nitrate or chloride ions. Two types of nitrate environments are observed namely free (non-hydrogen bonded) nitrate and nitrate hydrogen bonded to the interlayer water or to the 'brucite-like' hydroxyl surface. Multiple types of water structure are observed and would result from different hydrogen bond structures. Water bending modes are identified at 1645 cm-1 greater than the one observed for LDH intercalated with chloride anions (1618 cm-1), indicating that the water is strongly hydrogen bonded to the nitrate anions.

Spectrally edited 2D 13Csbnd 13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials

NASA Astrophysics Data System (ADS)

Johnson, Robert L.; Anderson, Jason M.; Shanks, Brent H.; Fang, Xiaowen; Hong, Mei; Schmidt-Rohr, Klaus

2013-09-01

Two robust combinations of spectral editing techniques with 2D 13Csbnd 13C NMR have been developed for characterizing the aromatic components of 13C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by 13C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, Csbnd H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and Cdbnd O carbons, which is particularly useful for identifying furan and arene rings. The Cdbnd O carbons, whose chemical shifts vary strongly (between 212 and 165 ppm) and systematically depend on their two bonding partners, show particularly informative cross peaks, given that one bonding partner is defined by the other frequency coordinate of the cross peak. The new techniques and the information content of the resulting spectra are validated on sulfuric-acid treated low-temperature carbon materials and on products of the Maillard reaction. The crucial need for spectral editing for correct peak assignment is demonstrated in an example.

Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy

2015-10-01

Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110-120 kHz), 1H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong 1H-1H homonuclear dipolar couplings and narrow 1H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) 1H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about 1H-1H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical information for a variety of solid systems that possess high proton density.

Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

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

Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2015-10-14

Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110–120 kHz), {sup 1}H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong {sup 1}H–{sup 1}H homonuclear dipolar couplings and narrow {sup 1}H chemical shift (CS) ranges, which rendermore » it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) {sup 1}H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about {sup 1}H–{sup 1}H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical information for a variety of solid systems that possess high proton density.« less

Avoided crossings, conical intersections, and low-lying excited states with a single reference method: the restricted active space spin-flip configuration interaction approach.

PubMed

Casanova, David

2012-08-28

The restricted active space spin-flip CI (RASCI-SF) performance is tested in the electronic structure computation of the ground and the lowest electronically excited states in the presence of near-degeneracies. The feasibility of the method is demonstrated by analyzing the avoided crossing between the ionic and neutral singlet states of LiF along the molecular dissociation. The two potential energy surfaces (PESs) are explored by means of the energies of computed adiabatic and approximated diabatic states, dipole moments, and natural orbital electronic occupancies of both states. The RASCI-SF methodology is also used to study the ground and first excited singlet surface crossing involved in the double bond isomerization of ethylene, as a model case. The two-dimensional PESs of the ground (S(0)) and excited (S(1)) states are calculated for the complete configuration space of torsion and pyramidalization molecular distortions. The parameters that define the state energetics in the vicinity of the S(0)/S(1) conical intersection region are compared to complete active space self-consistent field (CASSCF) results. These examples show that it is possible to describe strongly correlated electronic states using a single reference methodology without the need to expand the wavefunction to high levels of collective excitations. Finally, RASCI is also examined in the electronic structure characterization of the ground and 2(1)A(g)(-), 1(1)B(u)(+), 1(1)B(u)(-), and 1(3)B(u)(-) states of all-trans polyenes with two to seven double bonds and beyond. Transition energies are compared to configuration interaction singles, time-dependent density functional theory (TDDFT), CASSCF, and its second-order perturbation correction calculations, and to experimental data. The capability of RASCI-SF to describe the nature and properties of each electronic state is discussed in detail. This example is also used to expose the properties of different truncations of the RASCI wavefunction and to show the possibility to use an excitation operator with any number of α-to-β electronic promotions.

The Effect of Nylon and Polyester Peel Ply Surface Preparation on the Bond Quality of Composite Laminates

NASA Astrophysics Data System (ADS)

Moench, Molly K.

The preparation of the surfaces to be bonded is critical to the success of composite bonds. Peel ply surface preparation is attractive from a manufacturing and quality assurance standpoint, but is a well known example of the extremely system-specific nature of composite bonds. This study examined the role of the surface energy, morphology, and chemistry left by peel ply removal in resulting bond quality. It also evaluated the use of contact angle surface energy measurement techniques for predicting the resulting bond quality of a prepared surface. The surfaces created by preparing three aerospace fiber-reinforced composite prepregs were compared when prepared with a nylon vs a polyester peel ply. The prepared surfaces were characterized with contact angle measurements with multiple fluids, scanning electron microscopy (SEM), and x-ray electron spectroscopy. The laminates were bonded with aerospace grade film adhesives. Bond quality was assessed via double cantilever beam testing followed by optical and scanning electron microscopy of the fracture surfaces.The division was clear between strong bonds (GIC of 600- 1000J/m2 and failure in cohesion) and weak bonds (GIC of 80-400J/m2 and failure in adhesion). All prepared laminates showed the imprint of the peel ply texture and evidence of peel ply remnants after fabric removal, either through SEM or XPS. Within an adhesive system, large amounts of SEM-visible peel ply material transfer correlated with poor bond quality and cleaner surfaces with higher bond quality. The both sides of failed weak bonds showed evidence of peel ply remnants under XPS, showing that at least some failure is occurring through the remnants. The choice of adhesive was found to be significant. AF 555 adhesive was more tolerant of peel ply contamination than MB 1515-3. Although the bond quality results varied substantially between tested combinations, the total surface energies of all prepared surfaces were very similar. Single fluid contact angle measurements/water break tests were therefore not predictive of bond quality, and are recommended against. The multiple fluids used allowed the construction of wettability envelopes, a more detailed look at the surface energy profile. The envelopes of nylon and polyester prepared systems were noticeably different, but while potentially useful for detecting changes or errors in surface preparation of known systems, they were not valid for predicting bond quality in new systems. Ultimately, it was determined that wetting is a necessary but not sufficient condition for bonding.

Alchemical and structural distribution based representation for universal quantum machine learning

NASA Astrophysics Data System (ADS)

Faber, Felix A.; Christensen, Anders S.; Huang, Bing; von Lilienfeld, O. Anatole

2018-06-01

We introduce a representation of any atom in any chemical environment for the automatized generation of universal kernel ridge regression-based quantum machine learning (QML) models of electronic properties, trained throughout chemical compound space. The representation is based on Gaussian distribution functions, scaled by power laws and explicitly accounting for structural as well as elemental degrees of freedom. The elemental components help us to lower the QML model's learning curve, and, through interpolation across the periodic table, even enable "alchemical extrapolation" to covalent bonding between elements not part of training. This point is demonstrated for the prediction of covalent binding in single, double, and triple bonds among main-group elements as well as for atomization energies in organic molecules. We present numerical evidence that resulting QML energy models, after training on a few thousand random training instances, reach chemical accuracy for out-of-sample compounds. Compound datasets studied include thousands of structurally and compositionally diverse organic molecules, non-covalently bonded protein side-chains, (H2O)40-clusters, and crystalline solids. Learning curves for QML models also indicate competitive predictive power for various other electronic ground state properties of organic molecules, calculated with hybrid density functional theory, including polarizability, heat-capacity, HOMO-LUMO eigenvalues and gap, zero point vibrational energy, dipole moment, and highest vibrational fundamental frequency.

DFT and ab initio study of the unimolecular decomposition of the lowest singlet and triplet states of nitromethane

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

Manaa, M.R.; Fried, L.E.

1998-11-26

The fully optimized potential energy curves for the unimolecular decomposition of the lowest singlet and triplet states of nitromethane through the C-NO{sub 2} bond dissociation pathway are calculated using various DFT and high-level ab initio electronic structure methods. The authors perform gradient corrected density functional theory (DFT) and multiconfiguration self-consistent field (MCSCF) to conclusively demonstrate that the triplet state of nitromethane is bound. The adiabatic curve of this state exhibits a 33 kcal/mol energy barrier as determined at the MCSCF level. DFT methods locate this barrier at a shorter C-N bond distance with 12--16 kcal/mol lower energy than does MCSCF.more » In addition to MCSCF and DFT, quadratic configuration interactions with single and double substitutions (QCISD) calculations are also performed for the singlet curve. The potential energy profiles of this state predicted by FT methods based on Becke`s 1988 exchange functional differ by as much as 17 kcal/mol from the predictions of MCSCF and QCISD in the vicinity of the equilibrium structure. The computational methods predict bond dissociation energies 5--9 kcal/mol lower than the experimental value. DFT techniques based on Becke`s 3-parameter exchange functional show the best overall agreement with the higher level methods.« less

Isomer-Specific Spectroscopy of Benzene-(H2O)n, n = 6,7: Benzene's Role in Reshaping Water's Three-Dimensional Networks.

PubMed

Tabor, Daniel P; Kusaka, Ryoji; Walsh, Patrick S; Sibert, Edwin L; Zwier, Timothy S

2015-05-21

The water hexamer and heptamer are the smallest sized water clusters that support three-dimensional hydrogen-bonded networks, with several competing structures that could be altered by interactions with a solute. Using infrared-ultraviolet double resonance spectroscopy, we record isomer-specific OH stretch infrared spectra of gas-phase benzene-(H2O)(6,7) clusters that demonstrate benzene's surprising role in reshaping (H2O)(6,7). The single observed isomer of benzene-(H2O)6 incorporates an inverted book structure rather than the cage or prism. The main conformer of benzene-(H2O)7 is an inserted-cubic structure in which benzene replaces one water molecule in the S4-symmetry cube of the water octamer, inserting itself into the water cluster by engaging as a π H-bond acceptor with one water and via C-H···O donor interactions with two others. The corresponding D(2d)-symmetry inserted-cube structure is not observed, consistent with the calculated energetic preference for the S4 over the D(2d) inserted cube. A reduced-dimension model that incorporates stretch-bend Fermi resonance accounts for the spectra in detail and sheds light on the hydrogen-bonding networks themselves and on the perturbations imposed on them by benzene.

Unveiling the mechanism of the promising two-dimensional photoswitch - Hemithioindigo

NASA Astrophysics Data System (ADS)

Li, Donglin; Yang, Yonggang; Li, Chaozheng; Liu, Yufang

2018-07-01

The control of internal molecular motions by outside stimuli is a decisive task in the construction of functional molecules and molecular machines. Light-induced intramolecular rotations of photoswitches have attracted increasing research interests because of the high stability and high reversibility of photoswitches. Recently, Henry et al. reported an unprecedented two-dimensional controlled photoswitch, the hemithioindigo (HTI) derivative Z1, whose single bond rotation in dimethyl sulphoxide (DMSO) solvent and double bond rotation in cyclohexane solvent can be induced by visible light (J. Am. Chem. Soc. 2016, 138, 12,219). Here we investigate the intramolecular rotations of the HTI and Z1 in different polar solvents by time-dependent density functional theory (TDDFT) and Nonadiabatic dynamic simulations. Due to the steric hindrance between methyl and thioindigo fragment, the rotations of Z1 in the excited state are obstructed. Interestingly, the HTI exhibits two distinct rotation paths in DMSO and cyclohexane solvents at about 50 fs. The intermolecular hydrogen bonds between HTI and DMSO play an important role in the rotation of HTI in DMSO solvent. Therefore, the HTI is a more promising two-dimensional photoswitch compared with the Z1. Our finding is thus of fundamental importance to understand the mechanisms of this class of photoswitches and design complex molecular behavior.

The effectiveness of an adhesively bonded composite patch repair as applied to a transport aircraft lower wing skin

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

Ruschau, J.J.; Coate, J.E.

1996-12-31

Specimens were machined from lower wing skin extrusions of a transport aircraft, precracked under fatigue loading, repaired with a boron/epoxy patch, and subsequently fatigue tested under simulated flight loading conditions to evaluate the effectiveness of an adhesively bonded repair patch. Testing was performed at RT and -54{degrees}C for two configurations: one with the crack running up the integral stiffener (riser), the other running down the riser towards the outer skin surface. Cracks were initiated from a single 6.35 mm diameter hole located in the riser portion of the 7075-T6 wing skin material. Ultrasonic inspections were performed during fatigue loading tomore » determine crack growth and damage underneath the patch. Limited results show the adhesively bonded patch was successful in stopping or greatly reducing any further crack growth. Under laboratory air conditions, no crack growth occurred following 30,000 equivalent flight hours, double the expected life of the patched structure. Similarly at -54{degrees}C, no crack growth was observed for a patched crack growing up the riser following 15,000 EFH. For the case of a crack growing down the riser at the lower test temperature, some crack growth was measured, though at a greatly reduced rate.« less

The fabrication of a double-layer atom chip with through silicon vias for an ultra-high-vacuum cell

NASA Astrophysics Data System (ADS)

Chuang, Ho-Chiao; Lin, Yun-Siang; Lin, Yu-Hsin; Huang, Chi-Sheng

2014-04-01

This study presents a double-layer atom chip that provides users with increased diversity in the design of the wire patterns and flexibility in the design of the magnetic field. It is more convenient for use in atomic physics experiments. A negative photoresist, SU-8, was used as the insulating layer between the upper and bottom copper wires. The electrical measurement results show that the upper and bottom wires with a width of 100 µm can sustain a 6 A current without burnout. Another focus of this study is the double-layer atom chips integrated with the through silicon via (TSV) technique, and anodically bonded to a Pyrex glass cell, which makes it a desired vacuum chamber for atomic physics experiments. Thus, the bonded glass cell not only significantly reduces the overall size of the ultra-high-vacuum (UHV) chamber but also conducts the high current from the backside to the front side of the atom chip via the TSV under UHV (9.5 × 10-10 Torr). The TSVs with a diameter of 70 µm were etched through by the inductively coupled plasma ion etching and filled by the bottom-up copper electroplating method. During the anodic bonding process, the electroplated copper wires and TSVs on atom chips also need to pass the examination of the required bonding temperature of 250 °C, under an applied voltage of 1000 V. Finally, the UHV test of the double-layer atom chips with TSVs at room temperature can be reached at 9.5 × 10-10 Torr, thus satisfying the requirements of atomic physics experiments under an UHV environment.

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2015-08-01

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

Two-Photon Study on the Electronic Interactions between the First Excited Singlet States in Carotenoid-Tetrapyrrole Dyads

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

Liao, Pen-Nan; Pillai, Smitha; Gust, Devens

Electronic interactions between the first excited states (S 1) of carotenoids (Car) of different conjugation lengths (8-11 double bonds) and phthalocyanines (Pc) in different Car-Pc dyad molecules were investigated by two-photon spectroscopy and compared with Car S 1-chlorophyll (Chl) interactions in photosynthetic light harvesting complexes (LHCs). The observation of Chl/Pc fluorescence after selective two-photon excitation of the Car S 1 state allowed sensitive monitoring of the flow of energy between Car S 1 and Pc or Chl. It is found that two-photon excitation excites to about 80% to 100% exclusively the carotenoid state Car S 1 and that only amore » small fraction of direct tetrapyrrole two-photon excitation occurs. Amide-linked Car-Pc dyads in tetrahydrofuran demonstrate a molecular gear shift mechanism in that effective Car S 1 → Pc energy transfer is observed in a dyad with 9 double bonds in the carotenoid, whereas in similar dyads with 11 double bonds in the carotenoid, the Pc fluorescence is strongly quenched by Pc → Car S 1 energy transfer. In phenylamino-linked Car-Pc dyads in toluene extremely large electronic interactions between the Car S 1 state and Pc were observed, particularly in the case of a dyad in which the carotenoid contained 10 double bonds. This observation together with previous findings in the same system provides strong evidence for excitonic Car S 1-Pc Q y interactions. Very similar results were observed with photosynthetic LHC II complexes in the past, supporting an important role of such interactions in photosynthetic down-regulation.« less

Different Roles of Endo- and Exo-cyclic Double Bonds in Limonene Ozonolysis System: Effect of Water and OH Radical Scavengers

NASA Astrophysics Data System (ADS)

Gong, Y.; Li, H.; Chen, Z.

2017-12-01

Limonene, as an important monoterpene, has a high emission rate both from biogenic and anthropogenic sources. Its doubly unsaturated structure leads to a high potential for secondary organic aerosol formation and a detailed understanding of roles of endo- and exo-cyclic double bonds in limonene ozonolysis is in urgent need. This study provided new insights into the mechanism and effect of both unsaturated bonds oxidation. A low and a high ratio set of [O3]/[limonene] experiments in the presence or absence of OH scavenger (2-butanol or cyclohexane) in the relative humidity (RH) range of 0-90% were conducted. Molar yields of hydrogen peroxide (H2O2) and hydromethyl hydroperoxide (HMHP) both increased rapidly as RH rose from 0 to 50%, then reached a plateau above 70% RH, while peroxyformic acid (PFA) and peroxyacetic acid (PAA) kept increasing with RH. The ozonolysis of exocyclic double bonds showed larger capacity for producing these peroxides than endocyclic ones, resulting in significantly higher yields of H2O2, HMHP, PFA and PAA in limonene ozonolysis than α-pinene when ozone was sufficient. The SOA mass fraction of total peroxides was 50% at high [O3]/[limonene] ratio, whereas only 12% at low ratio. The gas-particle partitioning coefficient of undetected peroxides rose up from (0.8-2.0)×10-3m3μg-1 at 0% RH to (4.0-5.2)×10-3m3μg-1 at 90% RH, indicating some water-dependent channels contributed low-volatility peroxides formation. A box model was employed to simulate the reaction system, and the results obviously underestimated the yield of H2O2, whilst overestimated the yield of undetected peroxides. It is interesting to note that SOA produced at high [O3]/[limonene] ratio could generate considerable amount of H2O2 in the aqueous phase, which may be another source of H2O2 in cloud drops. To elucidate the mechanism further, the yield of OH radicals formed from endocyclic double bonds was found to be about 3 times larger than that from exocyclic double bonds. The profile of OH radical formation as a function of RH demonstrated the existence of water-dependent OH formation pathways. Our results also revealed that different OH scavengers impacted yields of a series of products and their gas-particle partitioning, thus the secondary influence of OH scavengers should be taken into consideration in future studies.

Activation of a Carbon-Oxygen Bond of Benzofuran by Precoordination of Manganese to the Carbocyclic Ring: A Model for Hydrodeoxygenation.

PubMed

Zhang; Watson; Dullaghan; Gorun; Sweigart

1999-08-01

Stable unsaturated heterocycles such as benzofuran are difficult to remove from petroleum by conventional catalytic hydrotreating. However, in a model system, coordination of Mn(CO)(3)(+) to the aromatic ring of benzofuran activates the C-O bond towards insertion of [Pt(PPh(3))(2)] [Eq. (1)]. The insertion is preceded by precoordination to the furan C=C bond; thus, the 2,3-dihydro analogue of 1, which lacks this double bond, does not undergo insertion of the Pt moiety.

Halo and Pseudohalo Cu(I)-Pyridinato Double Chains with Tunable Physical Properties.

PubMed

Hassanein, K; Amo-Ochoa, P; Gómez-García, C J; Delgado, S; Castillo, O; Ocón, P; Martínez, J I; Perles, J; Zamora, F

2015-11-16

The properties recently reported on the Cu(I)-iodide pyrimidine nonporous 1D-coordination polymer [CuI(ANP)]n (ANP = 2-amino-5-nitropyridine) showing reversible physically and chemically driven electrical response have prompted us to carry a comparative study with the series of [CuX(ANP)]n (X = Cl (1), X = Br (2), X = CN (4), and X = SCN (5)) in order to understand the potential influence of the halide and pseudohalide bridging ligands on the physical properties and their electrical response to vapors of these materials. The structural characterization of the series shows a common feature, the presence of -X-Cu(ANP)-X- (X = Cl, Br, I, SCN) double chain structure. Complex [Cu(ANP)(CN)]n (4) presents a helical single chain. Additionally, the chains show supramolecular interlinked interactions via hydrogen bonding giving rise to the formation of extended networks. Their luminescent and electrical properties have been studied. The results obtained have been correlated with structural changes. Furthermore, the experimental and theoretical results have been compared using the density functional theory (DFT). The electrical response of the materials has been evaluated in the presence of vapors of diethyl ether, dimethyl methylphosphonate (DMMP), CH2Cl2, HAcO, MeOH, and EtOH, to build up simple prototype devices for gas detectors. Selectivity toward gases consisting of molecules with H-bonding donor or acceptor groups is clearly observed. This selective molecular recognition is likely due to the 2-amino-5-nitropyridine terminal ligand.

In vivo characterization of the liver fat 1H MR spectrum

PubMed Central

Hamilton, Gavin; Yokoo, Takeshi; Bydder, Mark; Cruite, Irene; Schroeder, Michael E.; Sirlin, Claude B.; Middleton, Michael S.

2013-01-01

A theoretical triglyceride model was developed for in vivo human liver fat 1H MRS characterization, using the number of double bonds (–CH=CH–), number of methylene-interrupted double bonds (–CH=CH–CH2–CH=CH–) and average fatty acid chain length. Five 3 T, single-voxel, stimulated echo acquisition mode spectra (STEAM) were acquired consecutively at progressively longer TEs in a fat–water emulsion phantom and in 121 human subjects with known or suspected nonalcoholic fatty liver disease. T2-corrected peak areas were calculated. Phantom data were used to validate the model. Human data were used in the model to determine the complete liver fat spectrum. In the fat–water emulsion phantom, the spectrum predicted by the model (based on known fatty acid chain distribution) agreed closely with spectroscopic measurement. In human subjects, areas of CH2 peaks at 2.1 and 1.3 ppm were linearly correlated (slope, 0.172; r = 0.991), as were the 0.9 ppm CH3 and 1.3 ppm CH2 peaks (slope, 0.125; r = 0.989). The 2.75 ppm CH2 peak represented 0.6% of the total fat signal in high-liver-fat subjects. These values predict that 8.6% ofm the total fat signal overlies the water peak. The triglyceride model can characterize human liver fat spectra. This allows more accurate determination of liver fat fraction from MRI and MRS. PMID:21834002

Emergent Ising degrees of freedom above a double-stripe magnetic ground state [Emergent Ising degrees of freedom above double-stripe magnetism

DOE PAGES

Zhang, Guanghua; Flint, Rebecca

2017-12-27

Here, double-stripe magnetism [Q=(π/2,π/2)] has been proposed as the magnetic ground state for both the iron-telluride and BaTi 2Sb 2O families of superconductors. Double-stripe order is captured within a J 1–J 2–J 3 Heisenberg model in the regime J 3 >> J 2 >> J 1. Intriguingly, besides breaking spin-rotational symmetry, the ground-state manifold has three additional Ising degrees of freedom associated with bond ordering. Via their coupling to the lattice, they give rise to an orthorhombic distortion and to two nonuniform lattice distortions with wave vector (π,π). Because the ground state is fourfold degenerate, modulo rotations in spin space,more » only two of these Ising bond order parameters are independent. Here, we introduce an effective field theory to treat all Ising order parameters, as well as magnetic order, and solve it within a large-N limit. All three transitions, corresponding to the condensations of two Ising bond order parameters and one magnetic order parameter are simultaneous and first order in three dimensions, but lower dimensionality, or equivalently weaker interlayer coupling, and weaker magnetoelastic coupling can split the three transitions, and in some cases allows for two separate Ising phase transitions above the magnetic one.« less

Emergent Ising degrees of freedom above a double-stripe magnetic ground state [Emergent Ising degrees of freedom above double-stripe magnetism

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

Zhang, Guanghua; Flint, Rebecca

Here, double-stripe magnetism [Q=(π/2,π/2)] has been proposed as the magnetic ground state for both the iron-telluride and BaTi 2Sb 2O families of superconductors. Double-stripe order is captured within a J 1–J 2–J 3 Heisenberg model in the regime J 3 >> J 2 >> J 1. Intriguingly, besides breaking spin-rotational symmetry, the ground-state manifold has three additional Ising degrees of freedom associated with bond ordering. Via their coupling to the lattice, they give rise to an orthorhombic distortion and to two nonuniform lattice distortions with wave vector (π,π). Because the ground state is fourfold degenerate, modulo rotations in spin space,more » only two of these Ising bond order parameters are independent. Here, we introduce an effective field theory to treat all Ising order parameters, as well as magnetic order, and solve it within a large-N limit. All three transitions, corresponding to the condensations of two Ising bond order parameters and one magnetic order parameter are simultaneous and first order in three dimensions, but lower dimensionality, or equivalently weaker interlayer coupling, and weaker magnetoelastic coupling can split the three transitions, and in some cases allows for two separate Ising phase transitions above the magnetic one.« less

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2014 CFR

2014-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2011 CFR

2011-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2010 CFR

2010-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2013 CFR

2013-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2012 CFR

2012-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

Is chlorhexidine-methacrylate as effective as chlorhexidine digluconate in preserving resin dentin interfaces?

PubMed

Abu Nawareg, Manar; Elkassas, Dina; Zidan, Ahmed; Abuelenain, Dalia; Abu Haimed, Tariq; Hassan, Ali H; Chiba, Ayaka; Bock, Thorsten; Agee, Kelli; Pashley, David H

2016-02-01

The aim of the current study was to evaluate the effect of 2% CHX and 2% CHX-methacrylate compared to the resin-dentin bonds created by a two-step etch-and-rinse adhesive system after 24h, 6min and 12min. Microtensile bond strengths and interfacial nanoleakage within resin-dentin interfaces created by Adper Single Bond 2, with or without CHX or CHX-methacrylate pre-treatment for 30s on acid-etched dentin surfaces, were evaluated after 24h, 6min and 12min of storage in distilled water at 37°C. Twelve months of storage resulted in a significant decrease in microtensile bond strength in the control group, and significant increases in silver nanoleakage. In contrast, Single Bond 2+CHX, and to a greater extent CHX-methacrylate, significantly reduced the rate of deterioration of resin-dentin interfaces over the 12min water storage period, in terms of bond strength. Similar to Single Bond 2+CHX, Single Bond+CHX-methacrylates reduced the degradation of resin-bonded interfaces over a 12 month storage period. Thus it can be concluded that Single Bond 2+CHX-methacrylate may be important to improve durability of bonded interfaces and therefore, prolong the life span of adhesive restorations. Although CHX primers have been shown to enhance the durability of etch-and-rinse adhesives, that protection is lost after 2h. The use of CHX-methacrylate should last much longer since it may copolymerize with adhesive monomers, unlike CHX. Copyright © 2015 Elsevier Ltd. All rights reserved.

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen.

PubMed

Andersen, J; Voute, A; Mihrin, D; Heimdal, J; Berg, R W; Torsson, M; Wugt Larsen, R

2017-06-28

The true global potential energy minimum configuration of the formaldehyde dimer (CH 2 O) 2 , including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of C s and C 2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar C s configuration of (CH 2 O) 2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol -1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol -1 for the dissociation energy D 0 of this global potential energy minimum.

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen

NASA Astrophysics Data System (ADS)

Andersen, J.; Voute, A.; Mihrin, D.; Heimdal, J.; Berg, R. W.; Torsson, M.; Wugt Larsen, R.

2017-06-01

The true global potential energy minimum configuration of the formaldehyde dimer (CH2O)2, including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of Cs and C2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar Cs configuration of (CH2O)2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol-1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol-1 for the dissociation energy D0 of this global potential energy minimum.

Cisplatin Radiosensitization of DNA Irradiated with 2-20 eV Electrons: Role of Transient Anions.

PubMed

Bao, Qianhong; Chen, Yunfeng; Zheng, Yi; Sanche, Léon

2014-06-20

Platinum chemotherapeutic agents, such as cisplatin ( cis -diamminedichloroplatinum(II)), can act as radiosensitizers when bound covalently to nuclear DNA in cancer cells. This radiosensitization is largely due to an increase in DNA damage induced by low-energy secondary electrons, produced in large quantities by high-energy radiation. We report the yields of single- and double-strand breaks (SSB and DSB) and interduplex cross-links (CL) induced by electrons of 1.6-19.6 eV (i.e., the yield functions) incident on 5 monolayer (ML) films of cisplatin-DNA complexes. These yield functions are compared with those previously recorded with 5 ML films of unmodified plasmid DNA. Binding of five cisplatin molecules to plasmid DNA (3197 base pairs) enhances SSB, DSB, and CL by factors varying, from 1.2 to 2.8, 1.4 to 3.5, and 1.2 to 2.7, respectively, depending on electron energy. All yield functions exhibit structures around 5 and 10 eV that can be attributed to enhancement of bond scission, via the initial formation of core-excited resonances associated with π → π * transitions of the bases. This increase in damage is interpreted as arising from a modification of the parameters of the corresponding transient anions already present in nonmodified DNA, particularly those influencing molecular dissociation. Two additional resonances, specific to cisplatin-modified DNA, are formed at 13.6 and 17.6 eV in the yield function of SSB. Furthermore, cisplatin binding causes the induction of DSB by electrons of 1.6-3.6 eV, i.e., in an energy region where a DSB cannot be produced by a single electron in pure DNA. Breaking two bonds with a subexcitation-energy electron is tentatively explained by a charge delocalization mechanism, where a single electron occupies simultaneously two σ * bonds linking the Pt atom to guanine bases on opposite strands.

Cisplatin Radiosensitization of DNA Irradiated with 2–20 eV Electrons: Role of Transient Anions

PubMed Central

Bao, Qianhong; Chen, Yunfeng; Zheng, Yi; Sanche, Léon

2015-01-01

Platinum chemotherapeutic agents, such as cisplatin (cis-diamminedichloroplatinum(II)), can act as radiosensitizers when bound covalently to nuclear DNA in cancer cells. This radiosensitization is largely due to an increase in DNA damage induced by low-energy secondary electrons, produced in large quantities by high-energy radiation. We report the yields of single- and double-strand breaks (SSB and DSB) and interduplex cross-links (CL) induced by electrons of 1.6–19.6 eV (i.e., the yield functions) incident on 5 monolayer (ML) films of cisplatin–DNA complexes. These yield functions are compared with those previously recorded with 5 ML films of unmodified plasmid DNA. Binding of five cisplatin molecules to plasmid DNA (3197 base pairs) enhances SSB, DSB, and CL by factors varying, from 1.2 to 2.8, 1.4 to 3.5, and 1.2 to 2.7, respectively, depending on electron energy. All yield functions exhibit structures around 5 and 10 eV that can be attributed to enhancement of bond scission, via the initial formation of core-excited resonances associated with π → π* transitions of the bases. This increase in damage is interpreted as arising from a modification of the parameters of the corresponding transient anions already present in nonmodified DNA, particularly those influencing molecular dissociation. Two additional resonances, specific to cisplatin-modified DNA, are formed at 13.6 and 17.6 eV in the yield function of SSB. Furthermore, cisplatin binding causes the induction of DSB by electrons of 1.6–3.6 eV, i.e., in an energy region where a DSB cannot be produced by a single electron in pure DNA. Breaking two bonds with a subexcitation-energy electron is tentatively explained by a charge delocalization mechanism, where a single electron occupies simultaneously two σ* bonds linking the Pt atom to guanine bases on opposite strands. PMID:26793285

"Anticlumping" and Other Combinatorial Effects on Clumped Isotopes: Implications for Tracing Biogeochemical Cycling

NASA Astrophysics Data System (ADS)

Yeung, L.

2015-12-01

I present a mode of isotopic ordering that has purely combinatorial origins. It can be important when identical rare isotopes are paired by coincidence (e.g., they are neighbors on the same molecule), or when extrinsic factors govern the isotopic composition of the two atoms that share a chemical bond. By itself, combinatorial isotope pairing yields products with isotopes either randomly distributed or with a deficit relative to a random distribution of isotopes. These systematics arise because of an unconventional coupling between the formation of singly- and multiply-substituted isotopic moieties. In a random distribution, rare isotopes are symmetrically distributed: Single isotopic substitutions (e.g., H‒D and D‒H in H2) occur with equal probability, and double isotopic substitutions (e.g., D2) occur according to random chance. The absence of symmetry in a bond-making complex can yield unequal numbers of singly-substituted molecules (e.g., more H‒D than D‒H in H2), which is recorded in the product molecule as a deficit in doubly-substituted moieties and an "anticlumped" isotope distribution (i.e., Δn < 0). Enzymatic isotope pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect. Chemical-kinetic isotope effects, which are related to the bond-forming transition state, arise independently and express second-order combinatorial effects. In general, both combinatorial and chemical factors are important for calculating and interpreting clumped-isotope signatures of individual reactions. In many reactions relevant to geochemical oxygen, carbon, and nitrogen cycling, combinatorial isotope pairing likely plays a strong role in the clumped isotope distribution of the products. These isotopic signatures, manifest as either directly bound isotope clumps or as features of a molecule's isotopic anatomy, could be exploited as tracers of biogeochemistry that can relate molecular mechanisms to signals observable at environmentally relevant spatial scales.

Switching bonds in a DNA gel: an all-DNA vitrimer.

PubMed

Romano, Flavio; Sciortino, Francesco

2015-02-20

We design an all-DNA system that behaves like vitrimers, innovative plastics with self-healing and stress-releasing properties. The DNA sequences are engineered to self-assemble first into tetra- and bifunctional units which, upon further cooling, bind to each other forming a fully bonded network gel. An innovative design of the binding regions of the DNA sequences, exploiting a double toehold-mediated strand displacement, generates a network gel which is able to reshuffle its bonds, retaining at all times full bonding. As in vitrimers, the rate of bond switching can be controlled via a thermally activated catalyst, which in the present design is very short DNA strands.

Replacement of the double bond of antitubulin chalcones with triazoles and tetrazoles: Synthesis and biological evaluation.

PubMed

Mesenzani, Ornella; Massarotti, Alberto; Giustiniano, Mariateresa; Pirali, Tracey; Bevilacqua, Valentina; Caldarelli, Antonio; Canonico, Pierluigi; Sorba, Giovanni; Novellino, Ettore; Genazzani, Armando A; Tron, Gian Cesare

2011-01-15

In the chalcone scaffold, it is thought that the double bond is an important structural linker but it is likely not essential for the interaction with tubulin. Yet, it may be a potential site of metabolic degradation and interaction with biological nucleophiles. In this letter, we have replaced this olefinic portion of chalcones with two metabolically stable and chemically inert heterocyclic rings, namely triazole or tetrazole. Yet, our biologic data suggest that, unlike in other antitubulinic structures, the olephinic ring might not be merely a structural linker. Copyright © 2010 Elsevier Ltd. All rights reserved.

Polymer system for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

2000-01-01

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

1998-11-17

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Resolution of concerted versus sequential mechanisms in photo-induced double-proton transfer reaction in 7-azaindole H-bonded dimer

PubMed Central

Catalán, Javier; del Valle, Juan Carlos; Kasha, Michael

1999-01-01

The experimental and theoretical bases for a synchronous or concerted double-proton transfer in centro-symmetric H-bonded electronically excited molecular dimers are presented. The prototype model is the 7-azaindole dimer. New research offers confirmation of a concerted mechanism for excited-state biprotonic transfer. Recent femtosecond photoionization and coulombic explosion techniques have given rise to time-of-flight MS observations suggesting sequential two-step biprotonic transfer for the same dimer. We interpret the overall species observed in the time-of-flight experiments as explicable without conflict with the concerted mechanism of proton transfer. PMID:10411876

Low-lying singlet states of carotenoids having 8-13 conjugated double bonds as determined by electronic absorption spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping

2005-07-01

Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.

Prediction of apatite lattice constants from their constituent elemental radii and artificial intelligence methods.

PubMed

Wu, P; Zeng, Y Z; Wang, C M

2004-03-01

Lattice constants (LCs) of all possible 96 apatite compounds, A(5)(BO(4))(3)C, constituted by A[double bond]Ba(2+), Ca(2+), Cd(2+), Pb(2+), Sr(2+), Mn(2+); B[double bond]As(5+), Cr(5+), P(5+), V(5+); and C[double bond]F(1-), Cl(1-), Br(1-), OH(1-), are predicted from their elemental ionic radii, using pattern recognition (PR) and artificial neural networks (ANN) techniques. In particular, by a PR study it is demonstrated that ionic radii predominantly govern the LCs of apatites. Furthermore, by using ANN techniques, prediction models of LCs a and c are developed, which reproduce well the measured LCs (R(2)=0.98). All the literature reported on 30 pure and 22 mixed apatite compounds are collected and used in the present work. LCs of all possible 66 new apatites (assuming they exist) are estimated by the developed ANN models. These proposed new apatites may be of interest to biomedical research especially in the design of new apatite biomaterials for bone remodeling. Similarly these techniques may also be applied in the study of interface growth behaviors involving other biomaterials.

The discovery and early structural studies of arachidonic acid

PubMed Central

Martin, Sarah A.; Brash, Alan R.; Murphy, Robert C.

2016-01-01

Arachidonic acid and esterified arachidonate are ubiquitous components of every mammalian cell. This polyunsaturated fatty acid serves very important biochemical roles, including being the direct precursor of bioactive lipid mediators such as prostaglandin and leukotrienes. This 20 carbon fatty acid with four double bonds was first isolated and identified from mammalian tissues in 1909 by Percival Hartley. This was accomplished prior to the advent of chromatography or any spectroscopic methodology (MS, infrared, UV, or NMR). The name, arachidonic, was suggested in 1913 based on its relationship to the well-known arachidic acid (C20:0). It took until 1940 before the positions of the four double bonds were defined at 5,8,11,14 of the 20-carbon chain. Total synthesis was reported in 1961 and, finally, the configuration of the double bonds was confirmed as all-cis-5,8,11,14. By the 1930s, the relationship of arachidonic acid within the family of essential fatty acids helped cue an understanding of its structure and the biosynthetic pathway. Herein, we review the findings leading up to the discovery of arachidonic acid and the progress toward its complete structural elucidation. PMID:27142391

Fabrication of (PPC/NCC)/PVA composites with inner-outer double constrained structure and improved glass transition temperature.

PubMed

Cui, Shaoying; Li, Li; Wang, Qi

2018-07-01

Improving glass transition temperature (T g ) and mechanical property of the environment-friendly poly(propylene carbonate) via intermacromolecular complexation through hydrogen bonding is attractive and of great importance. A novel and effective strategy to prepare (polypropylene carbonate/nanocrystalline cellulose)/polyvinyl alcohol ((PPC/NCC)/PVA) composites with inner-outer double constrained structure was reported in this work. Outside the PPC phase, PVA, as a strong skeleton at microscale, could constrain the movement of PPC molecular chains by forming hydrogen bonding with PPC at the interface of PPC and PVA phases; inside the PPC phase, the rod-like NCC could restrain the flexible molecular chains of PPC at nanoscale by forming multi-hydrogen bonding with PPC. Under the synergistic effect of this novel inner-outer double constrained structure, T g , mechanical properties and thermal stability of (PPC/NCC)/PVA composite were significantly increased, e.g. T g of the composite researched the maximum value of 49.6 °C, respectively 15.6 °C, 5.7 °C and 4.2 °C higher than that of PPC, PPC/NCC and PPC/PVA composite. Copyright © 2018 Elsevier Ltd. All rights reserved.

Myosin-cross-reactive antigen (MCRA) protein from Bifidobacterium breve is a FAD-dependent fatty acid hydratase which has a function in stress protection.

PubMed

Rosberg-Cody, Eva; Liavonchanka, Alena; Göbel, Cornelia; Ross, R Paul; O'Sullivan, Orla; Fitzgerald, Gerald F; Feussner, Ivo; Stanton, Catherine

2011-02-17

The aim of this study was to determine the catalytic activity and physiological role of myosin-cross-reactive antigen (MCRA) from Bifidobacterium breve NCIMB 702258. MCRA from B. breve NCIMB 702258 was cloned, sequenced and expressed in heterologous hosts (Lactococcus and Corynebacterium) and the recombinant proteins assessed for enzymatic activity against fatty acid substrates. MCRA catalysed the conversion of palmitoleic, oleic and linoleic acids to the corresponding 10-hydroxy fatty acids, but shorter chain fatty acids were not used as substrates, while the presence of trans-double bonds and double bonds beyond the position C12 abolished hydratase activity. The hydroxy fatty acids produced were not metabolised further. We also found that heterologous Lactococcus and Corynebacterium expressing MCRA accumulated increasing amounts of 10-HOA and 10-HOE in the culture medium. Furthermore, the heterologous cultures exhibited less sensitivity to heat and solvent stresses compared to corresponding controls. MCRA protein in B. breve can be classified as a FAD-containing double bond hydratase, within the carbon-oxygen lyase family, which may be catalysing the first step in conjugated linoleic acid (CLA) production, and this protein has an additional function in bacterial stress protection.

Composite bonding to stainless steel crowns using a new universal bonding and single-bottle systems.

PubMed

Hattan, Mohammad Ali; Pani, Sharat Chandra; Alomari, Mohammad

2013-01-01

Aim. The aim of this study is to evaluate the shear bond strength of nanocomposite to stainless steel crowns using a new universal bonding system. Material and Methods. Eighty (80) stainless steel crowns (SSCs) were divided into four groups (20 each). Packable nanocomposite was bonded to the lingual surface of the crowns in the following methods: Group A without adhesive (control group), Group B using a new universal adhesive system (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany), and Group C and Group D using two different brands of single-bottle adhesive systems. Shear bond strengths were calculated and the types of failure also were recorded. Results. The shear strength of Group B was significantly greater than that of other groups. No significant differences were found between the shear bond strengths of Groups C and D. The control group had significantly lower shear bond strength (P < 0.05) to composite than the groups that utilized bonding agents. Conclusion. Composites bonding to stainless steel crowns using the new universal bonding agent (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany) show significantly greater shear bond strengths and fewer adhesive failures when compared to traditional single-bottle systems.

Covalent bond force profile and cleavage in a single polymer chain

NASA Astrophysics Data System (ADS)

Garnier, Lionel; Gauthier-Manuel, Bernard; van der Vegte, Eric W.; Snijders, Jaap; Hadziioannou, Georges

2000-08-01

We present here the measurement of the single-polymer entropic elasticity and the single covalent bond force profile, probed with two types of atomic force microscopes (AFM) on a synthetic polymer molecule: polymethacrylic acid in water. The conventional AFM allowed us to distinguish two types of interactions present in this system when doing force spectroscopic measurements: the first interaction is associated with adsorption sites of the polymer chains onto a bare gold surface, the second interaction is directly correlated to the rupture process of a single covalent bond. All these bridging interactions allowed us to stretch the single polymer chain and to determine the various factors playing a role in the elasticity of these molecules. To obtain a closer insight into the bond rupture process, we moved to a force sensor stable in position when measuring attractive forces. By optimizing the polymer length so as to fulfill the elastic stability conditions, we were able for the first time to map out the entire force profile associated with the cleavage of a single covalent bond. Experimental data coupled with molecular quantum mechanical calculations strongly suggest that the breaking bond is located at one end of the polymer chain.

2-[3-Furyl(hydroxy)methyl]-2,3-dimethylcyclohexanone.

PubMed

García, Esther; Mendoza, Virgilio; Guzmán, José Agustín; Maldonado Graniel, Luis Angel; Hernández-Ortega, Simón

2002-06-01

Contribution No. 1750 of the Instituto de Quimica, UNAM, Mexico. In the molecule of the title compound, C(13)H(18)O(3), there is a syn relationship between the two vicinal methyl groups. The six-membered ring adopts a chair conformation, with one equatorial and two axial groups, and the furyl group is almost parallel to the ketone group. Intermolecular hydrogen bonds [O[bond]H...O[double bond]C 2.814 (3) A] form chains along [100].

A remarkable enhancement of selectivity towards versatile analytes by a strategically integrated H-bonding site containing phase.

PubMed

Mallik, Abul K; Qiu, Hongdeng; Kuwahara, Yutaka; Takafuji, Makoto; Ihara, Hirotaka

2015-09-28

A double β-alanylated L-glutamide-derived organic phase has been newly designed and synthesized in such a way that integrated H-bonding (interaction) sites make it very suitable for the separation of versatile analytes, including shape-constrained isomers, and nonpolar, polar and basic compounds. The β-alanine residues introduced into two long-chain alkyl group moieties provide ordered polar groups through H-bonding among the amide groups.

The Synthesis, Structures, and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays

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

Clearfield, Abraham

2014-11-01

In this part of the proposal we have concentrated on the surface functionalization of α-zirconium phosphate of composition Zr(O3POH)2•H2O. It is a layered compound that can be prepared as particles as small as 30 nm to single crystals in the range of cm. This compound is an ion exchanger with a capacity of 6.64 meq per gram. It finds use as a catalyst, proton conductor, sensors, biosensors, in kidney dialysis and drug delivery. By functionalizing the surface additional uses are contemplated as will be described. The layers consist of the metal, with 4+ charge, that is positioned slightly above andmore » below the mean layer plane and bridged by three of the four phosphate oxygens. The remaining POH groups point into the interlayer space creating double rows of POH groups but single arrays on the surface layers. The surface groups are reactive and we were able to bond silanes, isocyanates, epoxides, acrylates ` and phosphates to the surface POH groups. The layers are easily exfoliated or filled with ions by ion exchange or molecules by intercalation reactions. Highlights of our work include, in addition to direct functionalization of the surfaces, replacement of the protons on the surface with ions of different charge. This allows us to bond phosphates, biophosphates, phosphonic acids and alcohols to the surface. By variation of the ion charge of the ions that replace the surface protons, different surface structures are obtained. We have already shown that polymer fillers, catalysts and Janus particles may be prepared. The combination of surface functionalization with the ability to insert molecules and ions between the layers allow for a rich development of numerous useful other applications as well as nano-surface chemistry.« less

Intramolecular Nuclear Flux Densities

NASA Astrophysics Data System (ADS)

Barth, I.; Daniel, C.; Gindensperger, E.; Manz, J.; PéRez-Torres, J. F.; Schild, A.; Stemmle, C.; Sulzer, D.; Yang, Y.

The topic of this survey article has seen a renaissance during the past couple of years. Here we present and extend the results for various phenomena which we have published from 2012-2014, with gratitude to our coauthors. The new phenomena include (a) the first reduced nuclear flux densities in vibrating diatomic molecules or ions which have been deduced from experimental pump-probe spectra; these "experimental" nuclear flux densities reveal several quantum effects including (b) the "quantum accordion", i.e., during the turn from bond stretch to bond compression, the diatomic system never stands still — instead, various parts of it with different bond lengths flow into opposite directions. (c) Wavepacket interferometry has been extended from nuclear densities to flux densities, again revealing new phenomena: For example, (d) a vibrating nuclear wave function with compact initial shape may split into two partial waves which run into opposite directions, thus causing interfering flux densities. (e) Tunneling in symmetric 1-dimensional double-well systems yields maximum values of the associated nuclear flux density just below the potential barrier; this is in marked contrast with negligible values of the nuclear density just below the barrier. (f) Nuclear flux densities of pseudorotating nuclei may induce huge magnetic fields. A common methodologic theme of all topics is the continuity equation which connects the time derivative of the nuclear density to the divergence of the flux density, subject to the proper boundary conditions. (g) Nearly identical nuclear densities with different boundary conditions may be related to entirely different flux densities, e.g., during tunneling in cyclic versus non-cyclic systems. The original continuity equation, density and flux density of all nuclei, or of all nuclear degrees of freedom, may be reduced to the corresponding quantities for just a single nucleus, or just a single degree of freedom.

Identification of a Disulfide Bridge in Sodium-Coupled Neutral Amino Acid Transporter 2(SNAT2) by Chemical Modification.

PubMed

Chen, Chen; Wang, Jiahong; Cai, Ruiping; Yuan, Yanmeng; Guo, Zhanyun; Grewer, Christof; Zhang, Zhou

2016-01-01

Sodium-coupled neutral amino acid transporter 2 (SNAT2) belongs to solute carrier 38 (SLC38) family of transporters, which is ubiquitously expressed in mammalian tissues and mediates transport of small, neutral amino acids, exemplified by alanine(Ala, A). Yet structural data on SNAT2, including the relevance of intrinsic cysteine residues on structure and function, is scarce, in spite of its essential roles in many tissues. To better define the potential of intrinsic cysteines to form disulfide bonds in SNAT2, mutagenesis experiments and thiol-specific chemical modifications by N-ethylmaleimide (NEM) and methoxy-polyethylene glycol maleimide (mPEG-Mal, MW 5000) were performed, with or without the reducing regent dithiothreitol (DTT) treatment. Seven single mutant transporters with various cysteine (Cys, C) to alanine (Ala, A) substitutions, and a C245,279A double mutant were introduced to SNAT2 with a hemagglutinin (HA) tag at the C-terminus. The results showed that the cells expressing C245A or C279A were labeled by one equivalent of mPEG-Mal in the presence of DTT, while wild-type or all the other single Cys to Ala mutants were modified by two equivalents of mPEG-Mal. Furthermore, the molecular weight of C245,279A was not changed in the presence or absence of DTT treatment. The results suggest a disulfide bond between Cys245 and Cys279 in SNAT2 which has no effect on cell surface trafficking, as well as transporter function. The proposed disulfide bond may be important to delineate proximity in the extracellular domain of SNAT2 and related proteins.

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

Window Glazing Types | Efficient Windows Collaborative

Science.gov Websites

of glass. Single Clear Single Tint Double Glazing The following sections on high-performance double fills. Double Clear Double Tint Double High-Solar-Gain Low-E Double Medium-Solar-Gain Low-E Double Low -Solar-Gain Low-E Double High-Solar-Gain Low-E with Roomside (4th surface) Low-E Double Medium-Solar-Gain

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

Liu, Gang; Kong, Lingping; Gong, Jue

Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead-based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead-based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single-junction solar cells in lead-based perovskites, formore » the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH 2) 2PbI 3) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double-prolonged carrier lifetime. With First-principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials-by-design.« less

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

Liu, Gang; Kong, Lingping; Gong, Jue

Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead-based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead-based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single-junction solar cells in lead-based perovskites, formore » the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH2)2PbI3) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double-prolonged carrier lifetime. With First-principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials-by-design.« less

Structural requirements of cholesterol for binding to Vibrio cholerae hemolysin.

PubMed

Ikigai, Hajime; Otsuru, Hiroshi; Yamamoto, Koichiro; Shimamura, Tadakatsu

2006-01-01

Cholesterol is necessary for the conversion of Vibrio cholerae hemolysin (VCH) monomers into oligomers in liposome membranes. Using different sterols, we determined the stereochemical structures of the VCH-binding active groups present in cholesterol. The VCH monomers are bound to cholesterol, diosgenin, campesterol, and ergosterol, which have a hydroxyl group at position C-3 (3betaOH) in the A ring and a C-C double bond between positions C-5 and C-6 (C-C Delta(5)) in the B ring. They are not bound to epicholesterol and dihydrocholesterol, which form a covalent link with a 3alphaOH group and a C-C single bond between positions C-5 and C-6, respectively. This result suggests that the 3betaOH group and the C-CDelta(5) bond in cholesterol are required for VCH monomer binding. We further examined VCH oligomer binding to cholesterol. However, this oligomer did not bind to cholesterol, suggesting that the disappearance of the cholesterol-binding potential of the VCH oligomer might be a result of the conformational change caused by the conversion of the monomer into the oligomer. VCH oligomer formation was observed in liposomes containing sterols with the 3betaOH group and the C-C Delta(5) bond, and it correlated with the binding affinity of the monomer to each sterol. Therefore, it seems likely that monomer binding to membrane sterol leads to the assembly of the monomer. However, since oligomer formation was induced by liposomes containing either epicholesterol or dihydrocholesterol, the 3betaOH group and the C-C Delta(5) bond were not essential for conversion into the oligomer.

A comparison of angle-beam shear wave scattering from hidden defects in single-and double-layer plates

NASA Astrophysics Data System (ADS)

Maki, Carson T.; Michaels, Jennifer E.; Weng, Yu

2018-04-01

Quantification of shear wave scattering from hidden defects is challenging because it is difficult to separate defect-scattered waves from waves that are scattered from benign structural features such as interfaces and fastener holes. It is even more difficult for the case of a crack emanating from a through-hole because there is complicated scattering from both the hole and the crack. This present work reports the results of a study that considers measurements from several far-surface notches emanating from through-holes in an aluminum plate both before and after a second plate is bonded to the back surface of the first plate. Measurements are also made of scattering from just a through-hole in both the single and bonded plates as a basis for comparison. The presence of the second layer provides a path for energy to leak out of the first plate, which can reduce the scattered energy. The recorded data show that notch scattering is clearly visible in the wavefield data for all of the notched holes. This scattering is quantified by first applying frequency-wavenumber filtering to extract shear waves of interest, and then computing scattered energy as a function of direction. Results for the different specimens are reported and compared to show the differences in scattering caused by the presence of the second layer.

Proline Substitution of Dimer Interface β-strand Residues as a Strategy for the Design of Functional Monomeric Proteins

PubMed Central

Joseph, Prem Raj B.; Poluri, Krishna Mohan; Gangavarapu, Pavani; Rajagopalan, Lavanya; Raghuwanshi, Sandeep; Richardson, Ricardo M.; Garofalo, Roberto P.; Rajarathnam, Krishna

2013-01-01

Proteins that exist in monomer-dimer equilibrium can be found in all organisms ranging from bacteria to humans; this facilitates fine-tuning of activities from signaling to catalysis. However, studying the structural basis of monomer function that naturally exists in monomer-dimer equilibrium is challenging, and most studies to date on designing monomers have focused on disrupting packing or electrostatic interactions that stabilize the dimer interface. In this study, we show that disrupting backbone H-bonding interactions by substituting dimer interface β-strand residues with proline (Pro) results in fully folded and functional monomers, by exploiting proline’s unique feature, the lack of a backbone amide proton. In interleukin-8, we substituted Pro for each of the three residues that form H-bonds across the dimer interface β-strands. We characterized the structures, dynamics, stability, dimerization state, and activity using NMR, molecular dynamics simulations, fluorescence, and functional assays. Our studies show that a single Pro substitution at the middle of the dimer interface β-strand is sufficient to generate a fully functional monomer. Interestingly, double Pro substitutions, compared to single Pro substitution, resulted in higher stability without compromising native monomer fold or function. We propose that Pro substitution of interface β-strand residues is a viable strategy for generating functional monomers of dimeric, and potentially tetrameric and higher-order oligomeric proteins. PMID:24048001

Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

USGS Publications Warehouse

Luehrs, Dean C.; Hickey, James P.; Nilsen, Peter E.; Godbole, K.A.; Rogers, Tony N.

1995-01-01

A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals:  log K = −0.37 + 0.0341Vi − 1.07β + D + 0.65P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where Vi is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of Vi is used as a measure of the surface area in place of the volume term:  log K = −1.75 + 0.227V2/3 − 1.10β + D + 0.60P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

Raman and FTIR spectroscopic studies on two hydroxylated tung oils (HTO) bearing conjugated double bonds

NASA Astrophysics Data System (ADS)

Zhuang, Yuwei; Ren, Zhiyong; Jiang, Lei; Zhang, Jiaxiang; Wang, Huafen; Zhang, Guobao

2018-06-01

Tung oil (TO) was used as a model compound to study two hydroxylated tung oils (HTO), prepared from TO by either aminolysis (HTO-am) or alcoholysis (HTO-al). Main bands in Raman and FTIR spectra were initially assigned based on the detailed analysis of the compound spectra before and after exposure to elevated temperature (200 °C). The effect of heat treatment in air on spectral bands, and especially on the changes associated with double bonds, were then investigated. In the present work, changes in spectral bands due to heat treatment were compared with those revealed in the previous work of others. The results show that the conjugated triene structure of TO has been retained during alcoholysis and aminolysis, to yield the HTOs studied; yet the change of the triene structure caused by heating is different among the three samples; the H-bonding strength between OH and Cdbnd O in HTO-am is higher than that in HTO-al; the changes in HTO vOH and vCdbnd O bands in FTIR caused by the present heat treatment were significant; for TO, there is a big difference between changes in spectra as caused by thermal exposure, compared to those caused by ageing under UV light or exposure to a catalyst. The present work has laid additional groundwork for further study of the reactions of such triply conjugated double bond structures under different ageing conditions.

Reductive amination of aldehyde 2,4-dinitorophenylhydrazones using 2-picoline borane and high-performance liquid chromatographic analysis.

PubMed

Uchiyama, Shigehisa; Inaba, Yohei; Matsumoto, Mariko; Suzuki, Gen

2009-01-01

A new method for the determination of carbonyls in air using 2,4-dinitrophenylhydrazine (DNPH) has been developed. The traditional method for the measurement of carbonyl compounds, using DNPH to form the corresponding 2,4-dinitrophenylhydrazone (DNPhydrazone) derivatives, is subject to analytical errors because DNPhydrazones form both E- and Z-geometrical isomers as a result of the C=N double bond. To overcome this issue, a method for transforming the C=N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been developed. Reductive amination of aldehyde DNPhydrazones was carried out by adding 2-picoline borane acetonitrile solution in eluate through the DNPH-cartridge. The amination reactions of C(1)-C(10) aldehyde DNPhydrazones were completely converted into the reduced forms within 40 min in the presence of 1 mmol/L 2-picoline borane and 20 mmol/L of phosphoric acid. These reduced forms were very stable and did not change when stored for 2 weeks at room temperature. The absorption maximum wavelengths of the reduced forms from C(1)-C(10) aldehyde DNPhydrazones were 351-352 nm and shifted 6-7 nm toward shorter wavelengths when compared to the corresponding DNPhydrazones, and the molar absorption coefficients were 1.5 x 10(4) (C(1)) to 2.2 x 10(4) L/mol/cm (C(10)). Complete separation between C(1)-C(10) aldehyde DNPhydrazones and the corresponding reduced forms can be achieved by operating the HPLC in gradient mode using an Ascentis RP-Amide column (150 mm x 4.6 mm i.d.). The RSDs of DNPhydrazone (Z + E) peak areas ranged from 0.40-0.66 and those of the corresponding reduced forms ranged from 0.26-0.41. It was shown that the reductive amination method gave improved HPLC analytical precision because of the absence of isomers.

Insilico modeling and molecular dynamic simulation of claudin-1 point mutations in HCV infection.

PubMed

Vipperla, Bhavaniprasad; Dass, J Febin Prabhu; Jayanthi, S

2014-01-01

Claudin-1 (CLDN1) in association with envelope glycoprotein (CD81) mediates the fusion of HCV into the cytosol. Recent studies have indicated that point mutations in CLDN1 are important for the entry of hepatitis C virus (HCV). To validate these findings, we employed a computational platform to investigate the structural effect of two point mutations (I32M and E48K). Initially, three-dimensional co-ordinates for CLDN1 receptor sequence were generated. Then, three mutant models were built using the point mutation including a double mutant (I32M/E48K) model from the native model structure. Finally, all the four model structures including the native and three mutant models were subjected to molecular dynamics (MD) simulation for a period of 25 ns to appreciate their dynamic behavior. The MD trajectory files were analyzed using cluster and principal component method. The analysis suggested that either of the single mutation has negligible effect on the overall structure of CLDN1 compared to the double mutant form. However, the double mutant model of CLDN1 shows significant negative impact through the impairment of H-bonds and the simultaneous increase in solvent accessible surface area. Our simulation results are visibly consistent with the experimental report suggesting that the CLDN1 receptor distortion is prominent due to the double mutation with large surface accessibility. This increase in accessible surface area due to the coexistence of double mutation may be presumed as one of the key factor that results in permissive action of HCV attachment and infection.

Ballistic Phonon Penetration Depth in Amorphous Silicon Dioxide.

PubMed

Yang, Lin; Zhang, Qian; Cui, Zhiguang; Gerboth, Matthew; Zhao, Yang; Xu, Terry T; Walker, D Greg; Li, Deyu

2017-12-13

Thermal transport in amorphous silicon dioxide (a-SiO 2 ) is traditionally treated as random walks of vibrations owing to its greatly disordered structure, which results in a mean free path (MFP) approximately the same as the interatomic distance. However, this picture has been debated constantly and in view of the ubiquitous existence of thin a-SiO 2 layers in nanoelectronic devices, it is imperative to better understand this issue for precise thermal management of electronic devices. Different from the commonly used cross-plane measurement approaches, here we report on a study that explores the in-plane thermal conductivity of double silicon nanoribbons with a layer of a-SiO 2 sandwiched in-between. Through comparing the thermal conductivity of the double ribbon samples with that of corresponding single ribbons, we show that thermal phonons can ballistically penetrate through a-SiO 2 of up to 5 nm thick even at room temperature. Comprehensive examination of double ribbon samples with various oxide layer thicknesses and van der Waals bonding strengths allows for extraction of the average ballistic phonon penetration depth in a-SiO 2 . With solid experimental data demonstrating ballistic phonon transport through a-SiO 2 , this work should provide important insight into thermal management of electronic devices.

Gecko-inspired bidirectional double-sided adhesives.

PubMed

Wang, Zhengzhi; Gu, Ping; Wu, Xiaoping

2014-05-14

A new concept of gecko-inspired double-sided adhesives (DSAs) is presented. The DSAs, constructed by dual-angled (i.e. angled base and angled tip) micro-pillars on both sides of the backplane substrate, are fabricated by combinations of angled etching, mould replication, tip modification, and curing bonding. Two types of DSA, symmetric and antisymmetric (i.e. pillars are patterned symmetrically or antisymmetrically relative to the backplane), are fabricated and studied in comparison with the single-sided adhesive (SSA) counterparts through both non-conformal and conformal tests. Results indicate that the DSAs show controllable and bidirectional adhesion. Combination of the two pillar-layers can either amplify (for the antisymmetric DSA, providing a remarkable and durable adhesion capacity of 25.8 ± 2.8 N cm⁻² and a high anisotropy ratio of ∼8) or counteract (for the symmetric DSA, generating almost isotropic adhesion) the adhesion capacity and anisotropic level of one SSA (capacity of 16.2 ± 1.7 N cm⁻² and anisotropy ratio of ∼6). We demonstrate that these two DSAs can be utilized as a facile fastener for two individual objects and a small-scale delivery setup, respectively, complementing the functionality of the commonly studied SSA. As such, the double-sided patterning is believed to be a new branch in the further development of biomimetic dry adhesives.

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.

Supramolecular Nanocomposites Under Confinement: Chiral Optically Active Nanoparticle Assemblies and Beyond

NASA Astrophysics Data System (ADS)

Bai, Peter; Yang, Sui; Bao, Wei; Salmeron, Miquel; Zhang, Xiang; Xu, Ting

2015-03-01

Block copolymer-based supramolecules provide a versatile platform to direct the self-assembly of nanoparticles (NPs) into precisely controlled nanostructures in bulk and thin film geometries. A supramolecule, PS-b-P4VP(PDP), composed of the small molecule 3-pentadecylphenol (PDP) hydrogen bonded to a diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), was subjected to 2-D volume confinement in cylindrical anodic aluminum oxide (AAO) membrane pores. TEM and 3-D TEM tomography reveal that the morphologies accessible by the supramolecule and supramolecule/NP composites, such as NP clusters, arrays, stacked rings, and single and double helical ribbons, are significantly different from those in the bulk or thin film. Furthermore, single molecule dark field scattering measurements demonstrate strong chiral optical response of single helical Au NP ribbon nanostructures in the near infrared wavelength regime. These studies demonstrate 2-D confinement to be an effective means to tailor self-assembled NP structure within supramolecule nanocomposites and pave the way for this assembly approach to be applied towards next generation chiral metamaterials and optoelectronic devices.

Transition-metal-free synthesis of imidazo[2,1-b]thiazoles and thiazolo[3,2-a]benzimidazoles via an S-propargylation/5-exo-dig cyclization/isomerization sequence using propargyl tosylates as substrates.

PubMed

Omar, Mohamed A; Frey, Wolfgang; Conrad, Jürgen; Beifuss, Uwe

2014-11-07

A transition-metal-free route for the synthesis of several N-fused heterocycles, including thiazolo[3,2-a]benzimidazoles and imidazo[2,1-b]thiazoles, is reported. The reaction between propargyl tosylates and 2-mercaptobenzimidazoles under basic conditions results in 3-substituted thiazolo[3,2-a]benzimidazoles, in yields up to 92% in a single synthesis step. With 2-mercaptoimidazoles as the substrate, the corresponding imidazo[2,1-b]thiazoles were exclusively obtained. The transformation is considered to proceed as an intermolecular S-propargylation that is followed by 5-exo-dig ring closure and double-bond isomerization.

Theoretical Study of Fe(CO)n-

NASA Technical Reports Server (NTRS)

Ricca, Alessandra; Baushlicher, Charles W., Jr.

1995-01-01

The structures and CO binding energies are computed for Fe(CO)n- using a hybrid density functional theory (DFT) approach. The structures and ground states can be explained in terms of maximizing the Fe to CO 2pi* donation and minimizing Fe-CO 5 sigma repulsion. The trends in the CO binding energies for Fe(CO)n- and the differences between the trends for Fe(CO)n- and Fe(CO)n are also explained. For Fe(CO)n-, the second, third, and fourth CO bonding energies are in good agreement with experiment, while the first is too small. The first CO binding is also too small using the coupled cluster singles and doubles approach including a perturbation estimate of the connected triple excitations.

Trilinolein identified as a sex-specific component of tergal glands in alates of Coptotermes formosanus.

PubMed

Bland, John M; Park, Yong Ihl; Raina, Ashok K; Dickens, Joseph C; Hollister, Benedict

2004-04-01

Hexane extracts of the tergal glands from female alates of the Formosan subterranean termite Coptotermes formosanus were analyzed by high performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry with collision-induced dissociation. Double bond configuration was determined by chemical modifications with gas chromatography-mass spectrometry. A single component, identified as the triacylglycerol, trilinolein, was unique to the female tergal glands. This compound was not found in other areas of the female alate abdomen or in the corresponding area of male alates. Neither gland extract nor trilinolein caused a behavioral response from male alates. However, significant differences were found between males and females for responses from neurons within sensilla of the maxillary palps.

Collisional excitation of interstellar PO(X2Π) by He: new ab initio potential energy surfaces and scattering calculations

NASA Astrophysics Data System (ADS)

Lique, François; Jiménez-Serra, Izaskun; Viti, Serena; Marinakis, Sarantos

2018-01-01

We present the first ab initio potential energy surfaces (PESs) for the PO(X2Π)-He van der Waals system. The PESs were obtained using the open-shell partially spin-restricted coupled cluster approach with single, double and perturbative triple excitations [UCCSD(T)]. The augmented correlation-consistent polarized valence triple-zeta (aug-cc-pVTZ) basis set was employed supplemented by mid-bond functions. Integral and differential cross sections for the rotational excitation in PO-He collisions were calculated using the new PES and compared with results in similar systems. Finally, our work presents the first hyperfine-resolved cross sections for this system that are needed for accurate modelling in astrophysical environments.

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

AlKhaldi, Mashaal Q.; Wehlitz, Ralf, E-mail: rwehlitz@gmail.com

We have experimentally investigated the double-photoionization process in C{sub 6}BrF{sub 5} using monochromatized synchrotron radiation. We compare our results with previously published data for partially deuterated benzene (C{sub 6}H{sub 3}D{sub 3}) over a wide range of photon energies from threshold to 270 eV. A broad resonance in the ratio of doubly to singly charged parent ions at about 65 eV appears shifted in energy compared to benzene data. This shift is due to the difference in the bond lengths in two molecules. A simple model can explain the shape of this resonance. At higher photon energies, we observe another broadmore » resonance that can be explained as a second harmonic of the first resonance.« less

Practical applications of nondestructive materials characterization

NASA Astrophysics Data System (ADS)

Green, Robert E., Jr.

1992-10-01

Nondestructive evaluation (NDE) techniques are reviewed for applications to the industrial production of materials including microstructural, physical, and chemical analyses. NDE techniques addressed include: (1) double-pulse holographic interferometry for sealed-package leak testing; (2) process controls for noncontact metals fabrication; (3) ultrasonic detections of oxygen contamination in titanium welds; and (4) scanning acoustic microscopy for the evaluation of solder bonds. The use of embedded sensors and emerging NDE concepts provides the means for controlling the manufacturing and quality of quartz crystal resonators, nickel single-crystal turbine blades, and integrated circuits. Advances in sensor technology and artificial intelligence algorithms and the use of embedded sensors combine to make NDE technology highly effective in controlling industrial materials manufacturing and the quality of the products.

Modeling single molecule junction mechanics as a probe of interface bonding

NASA Astrophysics Data System (ADS)

Hybertsen, Mark S.

2017-03-01

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. A set of exemplary model junction structures has been analyzed using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond to the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N-Au and S-Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. The results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.

Modeling single molecule junction mechanics as a probe of interface bonding

DOE PAGES

Hybertsen, Mark S.

2017-03-07

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. We analyzed a set of exemplary model junction structures using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond tomore » the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N–Au and S–Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This, then, allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. Our results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.« less

Modeling single molecule junction mechanics as a probe of interface bonding

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

Hybertsen, Mark S.

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. We analyzed a set of exemplary model junction structures using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond tomore » the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N–Au and S–Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This, then, allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. Our results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.« less

Intrinsic bond strength of metal films on polymer substrates

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Osaki, Hiroyuki

1990-01-01

A semiquantitative method for the measurement of the intrinsic bond strength between elastic substrates and elastic films that fail by brittle fracture is described. Measurements on a polyethylene terephthalate (PET)-Ni couple were used to verify the essential features of the analysis. It was found that the interfacial shear strength of Ni on PET doubled after ion etching.

Cost-Effectiveness of Double Reading versus Single Reading of Mammograms in a Breast Cancer Screening Programme

PubMed Central

Posso, Margarita; Carles, Misericòrdia; Rué, Montserrat; Puig, Teresa; Bonfill, Xavier

2016-01-01

Objectives The usual practice in breast cancer screening programmes for mammogram interpretation is to perform double reading. However, little is known about its cost-effectiveness in the context of digital mammography. Our purpose was to evaluate the cost-effectiveness of double reading versus single reading of digital mammograms in a population-based breast cancer screening programme. Methods Data from 28,636 screened women was used to establish a decision-tree model and to compare three strategies: 1) double reading; 2) double reading for women in their first participation and single reading for women in their subsequent participations; and 3) single reading. We calculated the incremental cost-effectiveness ratio (ICER), which was defined as the expected cost per one additionally detected cancer. We performed a deterministic sensitivity analysis to test the robustness of the ICER. Results The detection rate of double reading (5.17‰) was similar to that of single reading (4.78‰; P = .768). The mean cost of each detected cancer was €8,912 for double reading and €8,287 for single reading. The ICER of double reading versus single reading was €16,684. The sensitivity analysis showed variations in the ICER according to the sensitivity of reading strategies. The strategy that combines double reading in first participation with single reading in subsequent participations was ruled out due to extended dominance. Conclusions From our results, double reading appears not to be a cost-effective strategy in the context of digital mammography. Double reading would eventually be challenged in screening programmes, as single reading might entail important net savings without significantly changing the cancer detection rate. These results are not conclusive and should be confirmed in prospective studies that investigate long-term outcomes like quality adjusted life years (QALYs). PMID:27459663

Repair Strength in Simulated Restorations of Methacrylate- or Silorane-Based Composite Resins.

PubMed

Consani, Rafael Leonardo Xediek; Marinho, Tatiane; Bacchi, Atais; Caldas, Ricardo Armini; Feitosa, Victor Pinheiro; Pfeifer, Carmem Silvia

2016-01-01

The study verified the bond strength in simulated dental restorations of silorane- or methacrylate-based composites repaired with methacrylate-based composite. Methacrylate- (P60) or silorane-based (P90) composites were used associated with adhesive (Adper Single Bond 2). Twenty-four hemi-hourglass-shaped samples were repaired with each composite (n=12). Samples were divided according to groups: G1= P60 + Adper Single Bond 2+ P60; G2= P60 + Adper Single Bond 2 + P60 + thermocycling; G3= P90 + Adper Single Bond 2 + P60; and G4= P90 + Adper Single Bond 2 + P60 + thermocycling. G1 and G3 were submitted to tensile test 24 h after repair procedure, and G2 and G4 after submitted to 5,000 thermocycles at 5 and 55 ?#61616;C for 30 s in each bath. Tensile bond strength test was accomplished in an universal testing machine at crosshead speed of 0.5 mm/min. Data (MPa) were analyzed by two-way ANOVA and Tukey's test (5%). Sample failure pattern (adhesive, cohesive in resin or mixed) was evaluated by stereomicroscope at 30?#61655; and images were obtained in SEM. Bond strength values of methacrylate-based composite samples repaired with methacrylate-based composite (G1 and G2) were greater than for silorane-based samples (G3 and G4). Thermocycling decreased the bond strength values for both composites. All groups showed predominance of adhesive failures and no cohesive failure in composite resin was observed. In conclusion, higher bond strength values were observed in methacrylate-based resin samples and greater percentage of adhesive failures in silorane-based resin samples, both composites repaired with methacrylate-based resin.

Double Negative Materials (DNM), Phenomena and Applications

DTIC Science & Technology

2009-07-01

Nanoparticles Formed by Pairs Of Concentric Double-Negative (DNG), Single-Negative ( SNG ) and/or Double-Positive (DPS) Metamaterial Layers.” J. Appl...material RRL Rapid Research Letters SHG second-harmonic generation SNG single-negative SSR split-ring resonator A-1 Appendix A. October 2008...Pairs of Concentric Double-Negative (DNG), Single-Negative ( SNG ), and/or Double-Positive (DPS) Metamaterial Layers.” J. Appl. Phys. 97, no. 9 (May

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, T.J.; Whinnery, L.L.

1998-11-17

A novel composition is described comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen. 1 fig.

Tetra­kis(2,3,5,5-tetra­methyl­hexen-2-yl)silane

PubMed Central

Meyer-Wegner, Frank; Bolte, Michael; Lerner, Hans-Wolfram

2014-01-01

In the title compound, C40H76Si, the Si atom is located on a special position of site symmetry -4. Thus, there is just a quarter of a mol­ecule in the asymmetric unit. The C=C double bonds exhibit a trans configuration. The Si atom and the tert-butyl group are located on the same side of the plane formed by the C=C double bond and its four substituents. The crystal packing shows no short contacts between the mol­ecules and despite the low crystal density (0.980 Mg m−3), there are no significant voids in the structure. PMID:24765057

Synthesis of novel 2-cyano substituted glycyrrhetinic acid derivatives as inhibitors of cancer cells growth and NO production in LPS-activated J-774 cells.

PubMed

Salomatina, Oksana V; Markov, Andrey V; Logashenko, Evgeniya B; Korchagina, Dina V; Zenkova, Marina A; Salakhutdinov, Nariman F; Vlassov, Valentin V; Tolstikov, Genrikh A

2014-01-01

Here we report the synthesis and biological activity of new semi-synthetic derivatives of naturally occurring glycyrrhetinic acid bearing a 2-cyano-3-oxo-1-en moiety in the A-ring and double bonds and carbonyl groups in the C, D and E rings. Bioassays using murine macrophage-like and tumor cells show that compound 4, which differs from Soloxolone methyl by the absence of a 9(11)-double bond in the C-ring, displays anti-inflammatory and inhibitory activities with respect to tumor cells with a high selectivity index value. Copyright © 2013 Elsevier Ltd. All rights reserved.

Double-row vs single-row rotator cuff repair: a review of the biomechanical evidence.

PubMed

Wall, Lindley B; Keener, Jay D; Brophy, Robert H

2009-01-01

A review of the current literature will show a difference between the biomechanical properties of double-row and single-row rotator cuff repairs. Rotator cuff tears commonly necessitate surgical repair; however, the optimal technique for repair continues to be investigated. Recently, double-row repairs have been considered an alternative to single-row repair, allowing a greater coverage area for healing and a possibly stronger repair. We reviewed the literature of all biomechanical studies comparing double-row vs single-row repair techniques. Inclusion criteria included studies using cadaveric, animal, or human models that directly compared double-row vs single-row repair techniques, written in the English language, and published in peer reviewed journals. Identified articles were reviewed to provide a comprehensive conclusion of the biomechanical strength and integrity of the repair techniques. Fifteen studies were identified and reviewed. Nine studies showed a statistically significant advantage to a double-row repair with regards to biomechanical strength, failure, and gap formation. Three studies produced results that did not show any statistical advantage. Five studies that directly compared footprint reconstruction all demonstrated that the double-row repair was superior to a single-row repair in restoring anatomy. The current literature reveals that the biomechanical properties of a double-row rotator cuff repair are superior to a single-row repair. Basic Science Study, SRH = Single vs. Double Row RCR.

Biomechanical Comparison of Single- Versus Double-Row Capsulolabral Repair for Shoulder Instability: A Review.

PubMed

Yousif, Matthew John; Bicos, James

2017-12-01

The glenohumeral joint is the most commonly dislocated joint in the body. Failure rates of capsulolabral repair have been reported to be approximately 8%. Recent focus has been on restoration of the capsulolabral complex by a double-row capsulolabral repair technique in an effort to decrease redislocation rates after arthroscopic capsulolabral repair. To present a review of the biomechanical literature comparing single- versus double-row capsulolabral repairs and discuss the previous case series of double-row fixation. Narrative review. A simple review of the literature was performed by PubMed search. Only biomechanical studies comparing single- versus double-row capsulolabral repair were included for review. Only those case series and descriptive techniques with clinical results for double-row repair were included in the discussion. Biomechanical comparisons evaluating the native footprint of the labrum demonstrated significantly superior restoration of the footprint through double-row capsulolabral repair compared with single-row repair. Biomechanical comparisons of contact pressure at the repair interface, fracture displacement in bony Bankart lesion, load to failure, and decreased external rotation (suggestive of increased load to failure) were also significantly in favor of double- versus single-row repair. Recent descriptive techniques and case series of double-row fixation have demonstrated good clinical outcomes; however, no comparative clinical studies between single- and double-row repair have assessed functional outcomes. The superiority of double-row capsulolabral repair versus single-row repair remains uncertain because comparative studies assessing clinical outcomes have yet to be performed.

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

PubMed

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 < δ < 0.5) by carefully monitoring the resistance changes under a switching flow of oxidizing gas (O2) and reducing gas (H2) in the temperature range of 250 ~ 800 °C. A giant resistance change ΔR by three to four orders of magnitude in less than 0.1 s was found with a fast oscillation behavior in the resistance change rates in the ΔR vs. t plots, suggesting that the oxygen vacancy exchange diffusion with oxygen/hydrogen atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

A -Site Ordered Double Perovskite CaMnTi 2 O 6 as a Multifunctional Piezoelectric and Ferroelectric–Photovoltaic Material

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

Gou, Gaoyang; Charles, Nenian; Shi, Jing

2017-09-11

The double perovskite CaMnTi2O6, is a rare A site ordered perovskite oxide that exhibits a sizable ferroelectric polarization and relatively high Curie temperature. Using first-principles calculations combined with detailed symmetry analyses, we identify the origin of the ferroelectricity in CaMnTi2O6. We further explore the material properties of CaMnTi2O6, including its ferroelectric polarization, dielectric and piezoelectric responses, magnetic order, electronic structure, and optical absorption coefficient. It is found that CaMnTi2O6 exhibits room-temperature-stable ferroelectricity and moderate piezoelectric responses. Moreover, CaMnTi2O6 is predicted to have a semiconducting energy band gap similar to that of BiFeO3, and its band gap can further be tuned-viamore » distortions of the planar Mn-O bond lengths. CaMnTi2O6 exemplifies a new class of single-phase semiconducting ferroelectric perovskites for potential applications in ferroelectric photovoltaic solar cells.« less

Predictive Models for the Free Energy of Hydrogen Bonded Complexes with Single and Cooperative Hydrogen Bonds.

PubMed

Glavatskikh, Marta; Madzhidov, Timur; Solov'ev, Vitaly; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

2016-12-01

In this work, we report QSPR modeling of the free energy ΔG of 1 : 1 hydrogen bond complexes of different H-bond acceptors and donors. The modeling was performed on a large and structurally diverse set of 3373 complexes featuring a single hydrogen bond, for which ΔG was measured at 298 K in CCl 4 . The models were prepared using Support Vector Machine and Multiple Linear Regression, with ISIDA fragment descriptors. The marked atoms strategy was applied at fragmentation stage, in order to capture the location of H-bond donor and acceptor centers. Different strategies of model validation have been suggested, including the targeted omission of individual H-bond acceptors and donors from the training set, in order to check whether the predictive ability of the model is not limited to the interpolation of H-bond strength between two already encountered partners. Successfully cross-validating individual models were combined into a consensus model, and challenged to predict external test sets of 629 and 12 complexes, in which donor and acceptor formed single and cooperative H-bonds, respectively. In all cases, SVM models outperform MLR. The SVM consensus model performs well both in 3-fold cross-validation (RMSE=1.50 kJ/mol), and on the external test sets containing complexes with single (RMSE=3.20 kJ/mol) and cooperative H-bonds (RMSE=1.63 kJ/mol). © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Different Radiation Doses on the Bond Strengths of Two Different Adhesive Systems to Enamel and Dentin.

PubMed

da Cunha, Sandra Ribeiro de Barros; Ramos, Pedro Augusto Minorin Mendes; Haddad, Cecília Maria Kalil; da Silva, João Luis Fernandes; Fregnani, Eduardo Rodrigues; Aranha, Ana Cecília Corrêa

2016-01-01

To evaluate the effects of three different radiation doses on the bond strengths of two different adhesive systems to enamel and dentin. Eighty human third molars were randomly divided into four groups (n = 20) according to the radiation dose (control/no radiation, 20 Gy, 40 Gy, and 70 Gy). The teeth were sagittally sectioned into three slices: one mesial and one distal section containing enamel and one middle section containing dentin. The sections were then placed in the enamel and dentin groups, which were further divided into two subgroups (n = 10) according to the adhesive used. Three restorations were performed in each tooth (one per section) using Adper Single Bond 2 (3M ESPE) or Universal Single Bond (3M ESPE) adhesive system and Filtek Z350 XT (3M ESPE) resin composite and subjected to the microshear bond test. Data were analyzed using a two-way ANOVA followed by Tukey's test. Failure modes were examined under a stereoscopic loupe. Radiotherapy did not affect the bond strengths of the adhesives to either enamel or dentin. In dentin, the Universal Single Bond adhesive system showed higher bond strength values when compared with the Adper Single Bond adhesive system. More adhesive failures were observed in the enamel for all radiation doses and adhesives. Radiotherapy did not influence the bond strength to enamel or dentin, irrespective of the adhesive or radiation dose used.

Studies with Laser Cooled Atoms and Single Molecules

DTIC Science & Technology

2007-09-01

between soda lime glass slides. The bond-setting time can be tailored to allow time for precision optical alignment. We also extended our previous single...This method achieves 100% successful bonding rates between soda lime glass slides. The bond-setting time and be can tailored to allow time for...simple method to bond optical components using silica nanoparticle sol-gel chemistry. The silica nanoparticles polymerize into highly branched

Correlation among electronegativity, cation polarizability, optical basicity and single bond strength of simple oxides

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

Dimitrov, Vesselin, E-mail: vesselin@uctm.edu; Komatsu, Takayuki, E-mail: komatsu@mst.nagaokaut.ac.jp

2012-12-15

A suitable relationship between free-cation polarizability and electronegativity of elements in different valence states and with the most common coordination numbers has been searched on the basis of the similarity in physical nature of both quantities. In general, the cation polarizability increases with decreasing element electronegativity. A systematic periodic change in the polarizability against the electronegativity has been observed in the isoelectronic series. It has been found that generally the optical basicity increases and the single bond strength of simple oxides decreases with decreasing the electronegativity. The observed trends have been discussed on the basis of electron donation ability ofmore » the oxide ions and type of chemical bonding in simple oxides. - Graphical abstract: This figure shows the single bond strength of simple oxides as a function of element electronegativity. A remarkable correlation exists between these independently obtained quantities. High values of electronegativity correspond to high values of single bond strength and vice versa. It is obvious that the observed trend in this figure is closely related to the type of chemical bonding in corresponding oxide. Highlights: Black-Right-Pointing-Pointer A suitable relationship between free-cation polarizability and electronegativity of elements was searched. Black-Right-Pointing-Pointer The cation polarizability increases with decreasing element electronegativity. Black-Right-Pointing-Pointer The single bond strength of simple oxides decreases with decreasing the electronegativity. Black-Right-Pointing-Pointer The observed trends were discussed on the basis of type of chemical bonding in simple oxides.« less

Pyrene-nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies.

PubMed

Jabłoński, Artur; Fritz, Yannic; Wagenknecht, Hans-Achim; Czerwieniec, Rafał; Bernaś, Tytus; Trzybiński, Damian; Woźniak, Krzysztof; Kowalski, Konrad

2017-01-01

Fluorescent pyrene-linker-nucleobase (nucleobase = thymine, adenine) conjugates with carbonyl and hydroxy functionalities in the linker were synthesized and characterized. X-ray single-crystal structure analysis performed for the pyrene-C(O)CH 2 CH 2 -thymine ( 2 ) conjugate reveals dimers of molecules 2 stabilized by hydrogen bonds between the thymine moieties. The photochemical characterization showed structure-dependent fluorescence properties of the investigated compounds. The conjugates bearing a carbonyl function represent weak emitters as compared to compounds with a hydroxy function in the linker. The self-assembly properties of pyrene nucleobases were investigated in respect to their binding to single and double strand oligonucleotides in water and in buffer solution. In respect to the complementary oligothymidine T 10 template in water, compounds 3 and 5 both show a self-assembling behavior according to canonical base-base pairing. However, in buffer solution, derivative 5 was much more effective than 3 in binding to the T 10 template. Furthermore the adenine derivative 5 binds to the double-stranded (dA) 10 -T 10 template with a self-assembly ratio of 112%. Such a high value of a self-assembly ratio can be rationalized by a triple-helix-like binding, intercalation, or a mixture of both. Remarkably, compound 5 also shows dual staining pattern in living HeLa cells. Confocal microscopy confirmed that 5 predominantly stains mitochondria but it also accumulates in the nucleoli of the cells.

Transfer in motion discrimination learning was no greater in double training than in single training.

PubMed

Huang, Jinfeng; Liang, Ju; Zhou, Yifeng; Liu, Zili

2017-06-01

We investigated the controversy regarding double training in motion discrimination learning. We collected data from 43 participants in a motion direction discrimination learning task with either double training (i.e., training plus exposure) or single training (i.e., no exposure). By pooling these data with those in the literature, we had data in double training from 28 participants and in single training from 36 participants. We found that, in double training, the transfer along the exposed direction was less than that along the trained direction, indicating incomplete transfer. Importantly, the transfer in double training was not reliably greater than that in single training.

Single Versus Double Lung Retransplantation Does Not Affect Survival Based on Previous Transplant Type.

PubMed

Schumer, Erin M; Rice, Jonathan D; Kistler, Amanda M; Trivedi, Jaimin R; Black, Matthew C; Bousamra, Michael; van Berkel, Victor

2017-01-01

Survival following retransplantation with a single lung is worse than after double lung transplant. We sought to characterize survival of patients who underwent lung retransplantation based on the type of their initial transplant, single or double. The United Network for Organ Sharing database was queried for adult patients who underwent lung retransplantation from 2005 onward. Patients were excluded if they underwent more than one retransplantation. The patient population was divided into 4 groups based on first followed by second transplant type, respectively: single then single, double then single, double then double, and single then double. Descriptive analysis and Kaplan-Meier survival analysis were performed. A p value less than 0.05 was considered significant. A total of 410 patients underwent retransplantation in the study time period. Overall mean survival for all patients who underwent retransplantation was 1,213 days. Kaplan-Meier survival analysis demonstrated no difference in graft survival between the 4 study groups (p = 0.146). There was no significant difference in graft survival between recipients of retransplant with single or double lungs when stratified by previous transplant type. These results suggest that when retransplantation is performed, single lung retransplantation should be considered, regardless of previous transplant type, in an effort to maximize organ resources. Copyright © 2017 The Society of Thoracic Surgeons. Published by Elsevier Inc. All rights reserved.

Leg tendon glands in male bumblebees ( Bombus terrestris): structure, secretion chemistry, and possible functions

NASA Astrophysics Data System (ADS)

Jarau, Stefan; Žáček, Petr; Šobotník, Jan; Vrkoslav, Vladimír; Hadravová, Romana; Coppée, Audrey; Vašíčková, Soňa; Jiroš, Pavel; Valterová, Irena

2012-12-01

Among the large number of exocrine glands described in bees, the tarsal glands were thought to be the source of footprint scent marks. However, recent studies showed that the compounds used for marking by stingless bees are secreted by leg tendon instead of tarsal glands. Here, we report on the structure of leg tendon glands in males of Bombus terrestris, together with a description of the chemical composition of their secretions and respective changes of both during the males' lives. The ultrastructure of leg tendon glands shows that the secretory cells are located in three independent regions, separated from each other by unmodified epidermal cells: in the femur, tibia, and basitarsus. Due to the common site of secretion release, the organ is considered a single secretory gland. The secretion of the leg tendon glands of B. terrestris males differs in its composition from those of workers and queens, in particular by (1) having larger proportions of compounds with longer chain lengths, which we identified as wax esters; and (2) by the lack of certain hydrocarbons (especially long chain dienes). Other differences consist in the distribution of double bond positions in the unsaturated hydrocarbons that are predominantly located at position 9 in males but distributed at seven to nine different positions in the female castes. Double bond positions may change chemical and physical properties of a molecule, which can be recognized by the insects and, thus, may serve to convey specific information. The function of male-specific compounds identified from their tendon glands remains elusive, but several possibilities are discussed.

Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

PubMed

Dau, Thuy Minh; Asamoah, Benjamin Darko; Belyaev, Andrey; Chakkaradhari, Gomathy; Hirva, Pipsa; Jänis, Janne; Grachova, Elena V; Tunik, Sergey P; Koshevoy, Igor O

2016-09-28

A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength.

Single-Crystal Material on Non-Single-Crystalline Substrate

DTIC Science & Technology

1999-02-01

point frit or solder glass can be deposited on a surface and bonded to a second surface using pressure and temperature. A sodium silicate material...interface. A metal or silicide at the bonding interface may be advantageous fQr electrical current conduction across the interface. 10 Applications...substrate, or a silicide or metal to aid bonding and vertical electrical current conduction. In some cases, it is difficult to polish the non- single

Screening Adhesively Bonded Single-Lap-Joint Testing Results Using Nonlinear Calculation Parameters

DTIC Science & Technology

2012-03-01

versus displacement response for single-lap-joints bonded with damage-tolerant adhe- sives, such the polyurea adhesive plotted in Figure 2, is much...displacement response for a single-lap-joint bonded with a polyurea adhesive. Complex x-y plots are commonly fitted using the Levenberg-Marquardt...expected decrease in maximum strength for the polyurea in compar- ison to the epoxy, which could have been obtained using a traditional analysis approach

Improvement of single domain antibody stability by disulfide bond introduction.

PubMed

Hagihara, Yoshihisa; Saerens, Dirk

2012-01-01

The successful medical application of single domain antibodies largely depends on their functionality. This feature is partly determined by the intrinsic stability of the single domain. Therefore a lot of research has gone into the elucidation of rules to uniformly increase stability of antibodies. Recently, a novel intra-domain disulfide bond was independently discovered by two research groups, after either rational design or careful investigation of the naturally occurring camelid antibody repertoire. By introducing this particular disulfide bond within a single domain antibody, the conformational stability can be increased in general. In this chapter it is described how to introduce this extra intra-domain disulfide bond and how to estimate the biophysical and biochemical impact of this cystine on the domain.

The Heat of Formation of HNO

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

1995-01-01

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO rev. reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X=H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate(DELTA)H(sup o)(sub f) value for HNO using state of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Tetrel Bonding as a Vehicle for Strong and Selective Anion Binding.

PubMed

Scheiner, Steve

2018-05-11

Tetrel atoms T (T = Si, Ge, Sn, and Pb) can engage in very strong noncovalent interactions with nucleophiles, which are commonly referred to as tetrel bonds. The ability of such bonds to bind various anions is assessed with a goal of designing an optimal receptor. The Sn atom seems to form the strongest bonds within the tetrel family. It is most effective in the context of a -SnF₃ group and a further enhancement is observed when a positive charge is placed on the receptor. Connection of the -SnF₃ group to either an imidazolium or triazolium provides a strong halide receptor, which can be improved if its point of attachment is changed from the C to an N atom of either ring. Aromaticity of the ring offers no advantage nor is a cyclic system superior to a simple alkyl amine of any chain length. Placing a pair of -SnF₃ groups on a single molecule to form a bipodal dicationic receptor with two tetrel bonds enhances the binding, but falls short of a simple doubling. These two tetrel groups can be placed on opposite ends of an alkyl diamine chain of any length although SnF₃⁺NH₂(CH₂) n NH₂SnF₃⁺ with n between 2 and 4 seems to offer the strongest halide binding. Of the various anions tested, OH − binds most strongly: OH − > F − > Cl − > Br − > I − . The binding energy of the larger NO₃ − and HCO₃ − anions is more dependent upon the charge of the receptor. This pattern translates into very strong selectivity of binding one anion over another. The tetrel-bonding receptors bind far more strongly to each anion than an equivalent number of K⁺ counterions, which leads to equilibrium ratios in favor of the former of many orders of magnitude.

Ligand reprogramming in dinuclear helicate complexes: a consequence of allosteric or electrostatic effects?

PubMed

Jeffery, John C; Rice, Craig R; Harding, Lindsay P; Baylies, Christian J; Riis-Johannessen, Thomas

2007-01-01

The ditopic ligand 6,6'-bis(4-methylthiazol-2-yl)-3,3'-([18]crown-6)-2,2'-bipyridine (L(1)) contains both a potentially tetradentate pyridyl-thiazole (py-tz) N-donor chain and an additional "external" crown ether binding site which spans the central 2,2'-bipyridine unit. In polar solvents (MeCN, MeNO(2)) this ligand forms complexes with Zn(II), Cd(II), Hg(II) and Cu(I) ions via coordination of the N donors to the metal ion. Reaction with both Hg(II) and Cu(I) ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central py--py bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With Zn(II) ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with Cd(II) ions gives rise to an equilibrium between both the dinuclear double-stranded helicate and the mononuclear species. These complexes can further coordinate s-block metal cations via the remote crown ether O-donor domains; a consequence of which are some remarkable changes in the binding modes of the N-donor domains. Reaction of the Hg(II)- or Cd(II)-containing helicate with either Ba(2+) or Sr(2+) ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM'(L(1))](4+) (M=Hg(II), Cd(II); M'=Ba(2+), Sr(2+)), where the transition and s-block cations reside in the N- and O-donor sites, respectively. In contrast, the same ions have only a minor structural impact on the Zn(II) species, which already exists as a single-stranded mononuclear complex. Similar reactions with the Cd(II) system result in a shift in equilibrium towards the single-stranded species, the extent of which depends on the size and charge of the s-block cation in question. Reaction of the dicopper(I) double-stranded helicate with Ba(2+) shows that the dinuclear structure still remains intact but the pitch length is significantly increased.

Infrared study of matrix-isolated ethyl cyanide: simulation of the photochemistry in the atmosphere of Titan.

PubMed

Toumi, A; Piétri, N; Couturier-Tamburelli, I

2015-11-11

Low-temperature Ar matrix isolation has been carried out to investigate the infrared spectrum of ethyl cyanide (CH3CH2CN), a molecule present in the atmosphere of Titan. The λ > 120 nm and λ > 230 nm photolysis reactions of ethyl cyanide in an Ar matrix were also performed in order to compare the behaviour of this compound when it is submitted to high and low energetic radiations. These different wavelengths have been used with the aim to reproduce the radiation reaching the various parts of the atmosphere. Several photoproducts have been identified during photolysis such as vinyl cyanide (CH2[double bond, length as m-dash]CHCN), cyanoacetylene (HC3N), and ethylene/hydrogen cyanide (C2H4/HCN), ethylene/hydrogen isocyanide (C2H4/HNC), acetylene/hydrogen cyanide (C2H2/HCN), acetylene/hydrogen isocyanide (C2H2/HNC), and acetylene:methylenimine (C2H2:HNCH2) complexes. Ethyl isocyanide (CH3CH2NC) and a ketenimine form (CH3CH[double bond, length as m-dash]C[double bond, length as m-dash]NH) have been identified as well. Photoproduct identification and spectral assignments were done using previous studies and density functional theory (DFT) calculations with the B3LYP/cc-pVTZ basis set.

Ablation of Dihydroceramide Desaturase Confers Resistance to Etoposide-Induced Apoptosis In Vitro

PubMed Central

Siddique, Monowarul M.; Bikman, Benjamin T.; Wang, Liping; Ying, Li; Reinhardt, Erin; Shui, Guanghou; Wenk, Markus R.; Summers, Scott A.

2012-01-01

Sphingolipid biosynthesis is potently upregulated by factors associated with cellular stress, including numerous chemotherapeutics, inflammatory cytokines, and glucocorticoids. Dihydroceramide desaturase 1 (Des1), the third enzyme in the highly conserved pathway driving sphingolipid biosynthesis, introduces the 4,5-trans-double bond that typifies most higher-order sphingolipids. Surprisingly, recent studies have shown that certain chemotherapeutics and other drugs inhibit Des1, giving rise to a number of sphingolipids that lack the characteristic double bond. In order to assess the effect of an altered sphingolipid profile (via Des1 inhibition) on cell function, we generated isogenic mouse embryonic fibroblasts lacking both Des1 alleles. Lipidomic profiling revealed that these cells contained higher levels of dihydroceramide than wild-type fibroblasts and that complex sphingolipids were comprised predominantly of the saturated backbone (e.g. sphinganine vs. sphingosine, dihydrosphingomyelin vs. sphingomyelin, etc.). Des1 ablation activated pro-survival and anabolic signaling intermediates (e.g. Akt/PKB, mTOR, MAPK, etc.) and provided protection from apoptosis caused by etoposide, a chemotherapeutic that induces sphingolipid synthesis by upregulating several sphingolipid biosynthesizing enzymes. These data reveal that the double bond present in most sphingolipids has a profound impact on cell survival pathways, and that the manipulation of Des1 could have important effects on apoptosis. PMID:22984457

Emergent Ising degrees of freedom above a double-stripe magnetic ground state

NASA Astrophysics Data System (ADS)

Zhang, Guanghua; Flint, Rebecca

2017-12-01

Double-stripe magnetism [Q =(π /2 ,π /2 )] has been proposed as the magnetic ground state for both the iron-telluride and BaTi2Sb2O families of superconductors. Double-stripe order is captured within a J1-J2-J3 Heisenberg model in the regime J3≫J2≫J1 . Intriguingly, besides breaking spin-rotational symmetry, the ground-state manifold has three additional Ising degrees of freedom associated with bond ordering. Via their coupling to the lattice, they give rise to an orthorhombic distortion and to two nonuniform lattice distortions with wave vector (π ,π ) . Because the ground state is fourfold degenerate, modulo rotations in spin space, only two of these Ising bond order parameters are independent. Here, we introduce an effective field theory to treat all Ising order parameters, as well as magnetic order, and solve it within a large-N limit. All three transitions, corresponding to the condensations of two Ising bond order parameters and one magnetic order parameter are simultaneous and first order in three dimensions, but lower dimensionality, or equivalently weaker interlayer coupling, and weaker magnetoelastic coupling can split the three transitions, and in some cases allows for two separate Ising phase transitions above the magnetic one.

Crystal structure of the fluorescent protein from Dendronephthya sp. in both green and photoconverted red forms

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

Pletneva, Nadya V.; Pletnev, Sergei; Pakhomov, Alexey A.

The fluorescent protein fromDendronephthyasp. (DendFP) is a member of the Kaede-like group of photoconvertible fluorescent proteins with a His62-Tyr63-Gly64 chromophore-forming sequence. Upon irradiation with UV and blue light, the fluorescence of DendFP irreversibly changes from green (506 nm) to red (578 nm). The photoconversion is accompanied by cleavage of the peptide backbone at the C α—N bond of His62 and the formation of a terminal carboxamide group at the preceding Leu61. The resulting double C α=C βbond in His62 extends the conjugation of the chromophore π system to include imidazole, providing the red fluorescence. Here, the three-dimensional structures of nativemore » green and photoconverted red forms of DendFP determined at 1.81 and 2.14 Å resolution, respectively, are reported. This is the first structure of photoconverted red DendFP to be reported to date. The structure-based mutagenesis of DendFP revealed an important role of positions 142 and 193: replacement of the original Ser142 and His193 caused a moderate red shift in the fluorescence and a considerable increase in the photoconversion rate. It was demonstrated that hydrogen bonding of the chromophore to the Gln116 and Ser105 cluster is crucial for variation of the photoconversion rate. The single replacement Gln116Asn disrupts the hydrogen bonding of Gln116 to the chromophore, resulting in a 30-fold decrease in the photoconversion rate, which was partially restored by a further Ser105Asn replacement.« less

Structural analysis of two tetraketones and theoretical investigation of the reactions involved in their preparation

NASA Astrophysics Data System (ADS)

da Silva, Milene Lopes; Teixeira, Róbson Ricardo; de Azevedo Santos, Lucas; Martins, Felipe Terra; Ramalho, Teodorico Castro

2018-03-01

The 2,2'-((5-(4-bromophenyl)furan-2-yl)methylene) bis (5,5-dimethylcyclohexane-1,3-dione) (3) and 2,2'-((5-(4-chlorophenyl)furan-2-yl)methylene) bis (5,5-dimethylcyclohexane-1,3-dione) (4) were prepared in, respectively, 63% and 59% yield, via ZrOCl2ṡ8H2O catalyzed condensation reactions between dimedone and appropriate aldehydes. Their structures were investigated by IR, NMR, and X-ray spectroscopy techniques. The asymmetric unit of tetraketone 3 is composed of just one molecule, while two almost identical crystallographically independent molecules of compound 4 are present there. Compound 3 is conformationally similar to both molecules of 4. The diketone rings assume a half-chair conformation with the flaps oriented toward the same side of the substituent at C1. Each diketone ring is featured by an electronic delocalization path encompassed through the keto-enol moiety. All bond lengths inside this conjugated system are intermediate between those of pure double and single bonds. Furthermore, the furan plane of the substituent at C1 is almost parallel to the bond axes bridging the diketone rings as a consequence of steric hindrance effects between the heterocycle moiety and two hydrogen bonded oxygens. The enol forms of compounds 3 and 4 were noticed via IR and NMR spectroscopies. Furthermore, thermodynamics parameters were calculated in order to interpret the experimental results. In this line, theoretical findings reveal that electronic and solvent effects play an important role in the chemical reactions involved in the preparation of tetraketones.

A hybrid MD-kMC algorithm for folding proteins in explicit solvent.

PubMed

Peter, Emanuel Karl; Shea, Joan-Emma

2014-04-14

We present a novel hybrid MD-kMC algorithm that is capable of efficiently folding proteins in explicit solvent. We apply this algorithm to the folding of a small protein, Trp-Cage. Different kMC move sets that capture different possible rate limiting steps are implemented. The first uses secondary structure formation as a relevant rate event (a combination of dihedral rotations and hydrogen-bonding formation and breakage). The second uses tertiary structure formation events through formation of contacts via translational moves. Both methods fold the protein, but via different mechanisms and with different folding kinetics. The first method leads to folding via a structured helical state, with kinetics fit by a single exponential. The second method leads to folding via a collapsed loop, with kinetics poorly fit by single or double exponentials. In both cases, folding times are faster than experimentally reported values, The secondary and tertiary move sets are integrated in a third MD-kMC implementation, which now leads to folding of the protein via both pathways, with single and double-exponential fits to the rates, and to folding rates in good agreement with experimental values. The competition between secondary and tertiary structure leads to a longer search for the helix-rich intermediate in the case of the first pathway, and to the emergence of a kinetically trapped long-lived molten-globule collapsed state in the case of the second pathway. The algorithm presented not only captures experimentally observed folding intermediates and kinetics, but yields insights into the relative roles of local and global interactions in determining folding mechanisms and rates.

Alternative definition of excitation amplitudes in multi-reference state-specific coupled cluster

NASA Astrophysics Data System (ADS)

Garniron, Yann; Giner, Emmanuel; Malrieu, Jean-Paul; Scemama, Anthony

2017-04-01

A central difficulty of state-specific Multi-Reference Coupled Cluster (MR-CC) in the multi-exponential Jeziorski-Monkhorst formalism concerns the definition of the amplitudes of the single and double excitation operators appearing in the exponential wave operators. If the reference space is a complete active space (CAS), the number of these amplitudes is larger than the number of singly and doubly excited determinants on which one may project the eigenequation, and one must impose additional conditions. The present work first defines a state-specific reference-independent operator T˜ ^ m which acting on the CAS component of the wave function |Ψ0m⟩ maximizes the overlap between (1 +T˜ ^ m ) |Ψ0m⟩ and the eigenvector of the CAS-SD (Singles and Doubles) Configuration Interaction (CI) matrix |ΨCAS-SDm⟩ . This operator may be used to generate approximate coefficients of the triples and quadruples, and a dressing of the CAS-SD CI matrix, according to the intermediate Hamiltonian formalism. The process may be iterated to convergence. As a refinement towards a strict coupled cluster formalism, one may exploit reference-independent amplitudes provided by (1 +T˜ ^ m ) |Ψ0m⟩ to define a reference-dependent operator T^ m by fitting the eigenvector of the (dressed) CAS-SD CI matrix. The two variants, which are internally uncontracted, give rather similar results. The new MR-CC version has been tested on the ground state potential energy curves of 6 molecules (up to triple-bond breaking) and two excited states. The non-parallelism error with respect to the full-CI curves is of the order of 1 mEh.

Comparison of outcomes after single or DOUBLE-CUFF artificial urinary sphincter insertion.

PubMed

O'Connor, R Corey; Gerber, Glenn S; Avila, Desiderio; Chen, Andrew A; Bales, Gregory T

2003-10-01

To assess the effectiveness and complications associated with single and double-cuff artificial urinary sphincter (AUS) implantation for postprostatectomy stress urinary incontinence. A retrospective study of 56 men with postprostatectomy stress urinary incontinence who underwent either single (28 patients) or double (28 patients) cuff AUS placement was performed. Patients in each cohort were matched on the basis of preoperative pad use, risk factors for complications, and age. Patient selection was blinded relative to outcome. Continence, quality of life, and complications were assessed using the Incontinence Impact Questionnaire Short Form (IIQ-7), postoperative pad use, and chart review. The mean age was 67 years for each group. Daily pad use decreased from 7.7 to 1.1 in patients treated with a single-cuff AUS and from 7.8 to 0.7 in patients with a double-cuff AUS (P = 0.25). Complete continence (0 pads daily) was reported in 3 (11%) of 28 men with single-cuff and 12 (43%) of 28 men with double-cuff sphincters (P = 0.008). The IIQ-7 scores improved from 14.8 to 3.1 after single-cuff placement and from 16.3 to 2.5 after double-cuff placement (P = 0.03). With an average follow-up of 41.3 and 21.2 months for the single and double-cuff cohorts, respectively, five complications were reported in the single-cuff recipients and four in the double-cuff patients. A significantly greater rate of complete continence and improvement in the IIQ-7 were seen in men with double-cuff AUS compared with single-cuff devices. Additional study is needed to confirm the relative advantages of double-cuff insertion.

An unusual alkylidyne homologation.

PubMed

Han, Yong-Shen; Hill, Anthony F; Kong, Richard Y

2018-02-27

The reaction of [W([triple bond, length as m-dash]CH)Br(CO) 2 (dcpe)] (dcpe = 1,2-bis(dicyclohexylphosphino)ethane) with t BuLi and SiCl 4 affords the trichlorosilyl ligated neopentylidyne complex [W([triple bond, length as m-dash]C t Bu)(SiCl 3 )(CO) 2 (dcpe)]. This slowly reacts with H 2 O to afford [W([triple bond, length as m-dash]CCH 2 t Bu)Cl 3 (dcpe)] and ultimately H 2 C[double bond, length as m-dash]CH t Bu via an unprecedented alkylidyne homologation in which coordinated CO is the source of the additional carbon atom with potential relevance to the Fischer-Tropsch process.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Baumann, Robert

1999-01-01

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, R.R.; Baumann, R.

1999-03-30

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Baumann, Robert

2003-08-26

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Bauman, Robert

2006-11-14

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Self-assembly of 3,5-bis(ethoxycarbonyl)pyrazolate anions and ammonium cations of beta-phenylethylamine or homoveratrylamine into hetero-double-stranded helical structures.

PubMed

Reviriego, Felipe; Sanz, Ana; Navarro, Pilar; Latorre, Julio; García-España, Enrique; Liu-Gonzalez, Malva

2009-08-21

Hydrogen-bonded double-stranded hetero-helices are formed when reacting sodium 3,5-bis(ethoxycarbonyl)pyrazolate with beta-phenethylammonium or homoveratrylammonium chloride, in which one of the strands is defined by the ammonium cations and the other one by the pyrazolate anions.

Energy efficient engine high-pressure turbine single crystal vane and blade fabrication technology report

NASA Technical Reports Server (NTRS)

Giamei, A. F.; Salkeld, R. W.; Hayes, C. W.

1981-01-01

The objective of the High-Pressure Turbine Fabrication Program was to demonstrate the application and feasibility of Pratt & Whitney Aircraft-developed two-piece, single crystal casting and bonding technology on the turbine blade and vane configurations required for the high-pressure turbine in the Energy Efficient Engine. During the first phase of the program, casting feasibility was demonstrated. Several blade and vane halves were made for the bonding trials, plus solid blades and vanes were successfully cast for materials evaluation tests. Specimens exhibited the required microstructure and chemical composition. Bonding feasibility was demonstrated in the second phase of the effort. Bonding yields of 75 percent for the vane and 30 percent for the blade were achieved, and methods for improving these yield percentages were identified. A bond process was established for PWA 1480 single crystal material which incorporated a transient liquid phase interlayer. Bond properties were substantiated and sensitivities determined. Tooling die materials were identified, and an advanced differential thermal expansion tooling concept was incorporated into the bond process.

Regioselective cis-trans isomerization of arachidonic double bonds by thiyl radicals: the influence of phospholipid supramolecular organization.

PubMed

Ferreri, Carla; Samadi, Abdelouahid; Sassatelli, Fabio; Landi, Laura; Chatgilialoglu, Chryssostomos

2004-02-04

Trans unsaturated fatty acids in humans may be originated by two different contributions. The exogenous track is due to dietary supplementation of trans fats and the endogenous path deals with free-radical-catalyzed cis-trans isomerization of fatty acids. Arachidonic acid residue (5c,8c,11c,14c-20:4), which has only two out of the four double bonds deriving from the diet, was used to differentiate the two paths and to assess the importance of a radical reaction. A detailed study on the formation of trans phospholipids catalyzed by the HOCH2CH2S* radical was carried out on L-alpha-phosphatidylcholine from egg lecithin and 1-stearoyl-2-arachidonoyl-L-alpha-phosphatidylcholine (SAPC) in homogeneous solution or in large unilamellar vesicles (LUVET). Thiyl radicals were generated from the corresponding thiol by either gamma-irradiation or UV photolysis, and the reaction course was followed by GC, Ag/TLC, and 13C NMR analyses. The isomerization was found to be independent of cis double bond location (random process) in i-PrOH solution. In the case of vesicles, the supramolecular organization of lipids produced a dramatic change of the isomerization outcome: (i) in egg lecithin, the reactivity of arachidonate moieties is higher than that of oleate and linoleate residues, (ii) in the linoleate residues of egg lecithin, the 9t,12c-18:2 isomer prevailed on the 9c,12t-18:2 isomer (3:1 ratio), and (iii) a regioselective isomerization of SAPC arachidonate residues occurred in the 5 and 8 positions. This effect of "positional preference" indicates that thiyl radicals entering the hydrophobic region of the membrane bilayer start to isomerize polyunsaturated fatty acid residues having the double bonds nearest to the membrane surfaces. We propose that arachidonic acid and its trans isomers can function as biomarkers in membranes for distinguishing the two trans fatty acid-forming pathways.

Single-layer nanosheets with exceptionally high and anisotropic hydroxyl ion conductivity

PubMed Central

Sun, Pengzhan; Ma, Renzhi; Bai, Xueyin; Wang, Kunlin; Zhu, Hongwei; Sasaki, Takayoshi

2017-01-01

When the dimensionality of layered materials is reduced to the physical limit, an ultimate two-dimensional (2D) anisotropy and/or confinement effect may bring about extraordinary physical and chemical properties. Layered double hydroxides (LDHs), bearing abundant hydroxyl groups covalently bonded within 2D host layers, have been proposed as inorganic anion conductors. However, typical hydroxyl ion conductivities for bulk or lamellar LDHs, generally up to 10−3 S cm−1, are considered not high enough for practical applications. We show that single-layer LDH nanosheets exhibited exceptionally high in-plane conductivities approaching 10−1 S cm−1, which were the highest among anion conductors and comparable to proton conductivities in commercial proton exchange membranes (for example, Nafion). The in-plane conductivities were four to five orders of magnitude higher than the cross-plane or cross-membrane values of restacked LDH nanosheets. This 2D superionic transport characteristic might have great promises in a variety of applications including alkaline fuel cells and water electrolysis. PMID:28439551

Interfacial structure of two-dimensional epitaxial Er silicide on Si(111)

NASA Astrophysics Data System (ADS)

Tuilier, M. H.; Wetzel, P.; Pirri, C.; Bolmont, D.; Gewinner, G.

1994-07-01

Auger-electron diffraction (AED) and surface-extended x-ray-absorption fine structure (SEXAFS) have been used to obtain a complete description of the atomic structure of a two-dimensional epitaxial Er silicide layer on Si(111). AED reveals that a monolayer of Er is located underneath a buckled Si double layer. The relevant Er-Si interlayer spacings are determined by means of single scattering cluster simulations and a R-factor analysis to be 1.92+/-0.05 Å to the first and 2.70+/-0.05 Å to the second Si top layer. Er near-neighbor bond lengths and coordination numbers are obtained independently from polarization-dependent SEXAFS. The SEXAFS data, when combined with the Si top-layer geometry inferred from AED, permit the determination of the atomic positions at the silicide/Si(111) interface. The Er is found to reside in relaxed T4 sites of Si(111) with a single Er-Si distance of 3.09+/-0.04 Å to the first- and second-layer Si atoms of the substrate.

Integrated Multi-Color Light Emitting Device Made with Hybrid Crystal Structure

NASA Technical Reports Server (NTRS)

Park, Yeonjoon (Inventor); Choi, Sang Hyouk (Inventor)

2017-01-01

An integrated hybrid crystal Light Emitting Diode ("LED") display device that may emit red, green, and blue colors on a single wafer. The various embodiments may provide double-sided hetero crystal growth with hexagonal wurtzite III-Nitride compound semiconductor on one side of (0001) c-plane sapphire media and cubic zinc-blended III-V or II-VI compound semiconductor on the opposite side of c-plane sapphire media. The c-plane sapphire media may be a bulk single crystalline c-plane sapphire wafer, a thin free standing c-plane sapphire layer, or crack-and-bonded c-plane sapphire layer on any substrate. The bandgap energies and lattice constants of the compound semiconductor alloys may be changed by mixing different amounts of ingredients of the same group into the compound semiconductor. The bandgap energy and lattice constant may be engineered by changing the alloy composition within the cubic group IV, group III-V, and group II-VI semiconductors and within the hexagonal III-Nitrides.

Integrated Multi-Color Light Emitting Device Made with Hybrid Crystal Structure

NASA Technical Reports Server (NTRS)

Park, Yeonjoon (Inventor); Choi, Sang Hyouk (Inventor)

2016-01-01

An integrated hybrid crystal Light Emitting Diode ("LED") display device that may emit red, green, and blue colors on a single wafer. The various embodiments may provide double-sided hetero crystal growth with hexagonal wurtzite III-Nitride compound semiconductor on one side of (0001) c-plane sapphire media and cubic zinc-blended III-V or II-VI compound semiconductor on the opposite side of c-plane sapphire media. The c-plane sapphire media may be a bulk single crystalline c-plane sapphire wafer, a thin free standing c-plane sapphire layer, or crack-and-bonded c-plane sapphire layer on any substrate. The bandgap energies and lattice constants of the compound semiconductor alloys may be changed by mixing different amounts of ingredients of the same group into the compound semiconductor. The bandgap energy and lattice constant may be engineered by changing the alloy composition within the cubic group IV, group III-V, and group II-VI semiconductors and within the hexagonal III-Nitrides.

Outcomes of the modified Brostrom procedure using suture anchors for chronic lateral ankle instability--a prospective, randomized comparison between single and double suture anchors.

PubMed

Cho, Byung-Ki; Kim, Yong-Min; Kim, Dong-Soo; Choi, Eui-Sung; Shon, Hyun-Chul; Park, Kyoung-Jin

2013-01-01

The present prospective, randomized study was conducted to compare the clinical outcomes of the modified Brostrom procedure using single and double suture anchors for chronic lateral ankle instability. A total of 50 patients were followed up for more than 2 years after undergoing the modified Brostrom procedure. Of the 50 procedures, 25 each were performed using single and double suture anchors by 1 surgeon. The Karlsson scale had improved significantly to 89.8 points and 90.6 points in the single and double anchor groups, respectively. Using the Sefton grading system, 23 cases (92%) in the single anchor group and 22 (88%) in the double anchor group achieved satisfactory results. The talar tilt angle and anterior talar translation on stress radiographs using the Telos device had improved significantly to an average of 5.7° and 4.6 mm in the single anchor group and 4.5° and 4.3 mm in the double anchor group, respectively. The double anchor technique was superior with respect to the postoperative talar tilt. The single and double suture anchor techniques produced similar clinical and functional outcomes, with the exception of talar tilt as a reference of mechanical stability. The modified Brostrom procedure using both single and double suture anchors appears to be an effective treatment method for chronic lateral ankle instability. Copyright © 2013 American College of Foot and Ankle Surgeons. Published by Elsevier Inc. All rights reserved.

Biomechanical Comparison of Single- Versus Double-Row Capsulolabral Repair for Shoulder Instability: A Review

PubMed Central

Yousif, Matthew John; Bicos, James

2017-01-01

Background: The glenohumeral joint is the most commonly dislocated joint in the body. Failure rates of capsulolabral repair have been reported to be approximately 8%. Recent focus has been on restoration of the capsulolabral complex by a double-row capsulolabral repair technique in an effort to decrease redislocation rates after arthroscopic capsulolabral repair. Purpose: To present a review of the biomechanical literature comparing single- versus double-row capsulolabral repairs and discuss the previous case series of double-row fixation. Study Design: Narrative review. Methods: A simple review of the literature was performed by PubMed search. Only biomechanical studies comparing single- versus double-row capsulolabral repair were included for review. Only those case series and descriptive techniques with clinical results for double-row repair were included in the discussion. Results: Biomechanical comparisons evaluating the native footprint of the labrum demonstrated significantly superior restoration of the footprint through double-row capsulolabral repair compared with single-row repair. Biomechanical comparisons of contact pressure at the repair interface, fracture displacement in bony Bankart lesion, load to failure, and decreased external rotation (suggestive of increased load to failure) were also significantly in favor of double- versus single-row repair. Recent descriptive techniques and case series of double-row fixation have demonstrated good clinical outcomes; however, no comparative clinical studies between single- and double-row repair have assessed functional outcomes. Conclusion: The superiority of double-row capsulolabral repair versus single-row repair remains uncertain because comparative studies assessing clinical outcomes have yet to be performed. PMID:29230427

Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

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

Guan, Zhibin; Lu, Yixuan

A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact withmore » a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.« less

Adhesive-bonded scarf and stepped-lap joints

NASA Technical Reports Server (NTRS)

Hart-Smith, L. J.

1973-01-01

Continuum mechanics solutions are derived for the static load-carrying capacity of scarf and stepped-lap adhesive-bonded joints. The analyses account for adhesive plasticity and adherend stiffness imbalance and thermal mismatch. The scarf joint solutions include a simple algebraic formula which serves as a close lower bound, within a small fraction of a per cent of the true answer for most practical geometries and materials. Digital computer programs were developed and, for the stepped-lap joints, the critical adherend and adhesive stresses are computed for each step. The scarf joint solutions exhibit grossly different behavior from that for double-lap joints for long overlaps inasmuch as that the potential bond shear strength continues to increase with indefinitely long overlaps on the scarf joints. The stepped-lap joint solutions exhibit some characteristics of both the scarf and double-lap joints. The stepped-lap computer program handles arbitrary (different) step lengths and thickness and the solutions obtained have clarified potentially weak design details and the remedies. The program has been used effectively to optimize the joint proportions.

Sound transmission through double cylindrical shells lined with porous material under turbulent boundary layer excitation

NASA Astrophysics Data System (ADS)

Zhou, Jie; Bhaskar, Atul; Zhang, Xin

2015-11-01

This paper investigates sound transmission through double-walled cylindrical shell lined with poroelastic material in the core, excited by pressure fluctuations due to the exterior turbulent boundary layer (TBL). Biot's model is used to describe the sound wave propagating in the porous material. Three types of constructions, bonded-bonded, bonded-unbonded and unbonded-unbonded, are considered in this study. The power spectral density (PSD) of the inner shell kinetic energy is predicted for two turbulent boundary layer models, different air gap depths and three types of polyimide foams, respectively. The peaks of the inner shell kinetic energy due to shell resonance, hydrodynamic coincidence and acoustic coincidence are discussed. The results show that if the frequency band over the ring frequency is of interest, an air gap, even if very thin, should exist between the two elastic shells for better sound insulation. And if small density foam has a high flow resistance, a superior sound insulation can still be maintained.

Sound transmission through a double-panel construction lined with poroelastic material in the presence of mean flow

NASA Astrophysics Data System (ADS)

Zhou, Jie; Bhaskar, Atul; Zhang, Xin

2013-08-01

This paper investigates the sound transmission characteristics through a system of double-panel lined with poroelastic material in the core. The panels are surrounded by external and internal fluid media where a uniform external mean flow exists on one side. Biot's theory is used to model the porous material. Three types of constructions—bonded-bonded, bonded-unbonded and unbonded-unbonded—are considered. The effect of Mach number of the external flow on the sound transmission over a wide frequency range in a diffuse sound field is examined. External mean flow is shown to give a modest increase in transmission loss at low frequency, but a significant increase at high frequency. It is brought out that calculations based on static air on the incidence side provide a conservative estimate of sound transmission through the sandwich structure. The acoustic performance of the sandwich panel for different configurations is presented. The effect of curvature of the panel is also brought out by using shallow shell theory.

Grafting cavitands on the Si(100) surface.

PubMed

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Fragalà, Ignazio L; Busi, Marco; Menozzi, Edoardo; Dalcanale, Enrico; Cristofolini, Luigi

2006-12-19

Cavitand molecules having double bond terminated alkyl chains and different bridging groups at the upper rim have been grafted on H-terminated Si(100) surface via photochemical hydrosilylation of the double bonds. Pure and mixed monolayers have been obtained from mesitylene solutions of either pure cavitand or cavitand/1-octene mixtures. Angle resolved high-resolution X-ray photoelectron spectroscopy has been used as the main tool for the monolayer characterization. The cavitand decorated surface consists of Si-C bonded layers with the upper rim at the top of the layer. Grafting of pure cavitands leads to not-well-packed layers, which are not able to efficiently passivate the Si(100) surface. By contrast, monolayers obtained from cavitand/1-octene mixtures consist of well-packed layers since they prevent silicon oxidation after aging. AFM measurements showed that these monolayers have a structured topography, with objects protruding from the Si(100) surface with average heights compatible with the expected ones for cavitand molecules.

Do matrix metalloproteinase inhibitors improve the bond durability of universal dental adhesives?

PubMed

Tekçe, Neslihan; Tuncer, Safa; Demirci, Mustafa; Balci, Sibel

2016-11-01

The aim of this study was to evaluate the effects of matrix metalloproteinases (MMPs) inhibitors on the microtensile bond strength (μTBS) and the adhesive-dentin interface of two universal dentin bonding agents, Single Bond Universal and All Bond Universal, after 12 months of water storage. Seventy extracted, caries-free, human third molars were used in this study. Of these, 50 were used for μTBS testing and 20 were used for scanning electron microscopy. The two bonding agents were applied to flat dentin surfaces in five different ways: self-etch mode, etch-and-rinse mode with 37% phosphoric acid, etch-and-rinse mode with phosphoric acid containing 1% benzalkonium chloride, etch-and-rinse mode with phosphoric acid and 2% chlorhexidine, and etch-and-rinse mode with 0.5 M ethylenediaminetetraacetic acid (EDTA) (n = 5 for each bonding agent in each group; N = 50). Half the specimens were subjected to μTBS tests at 24 h, while half were subjected to the tests after 12 months of water storage. For each bonding agent, inhibition, storage, and their interaction effects were tested by two-way analysis of variance and Bonferroni tests. For Single Bond Universal, the benzalkonium chloride (p = 0.024) and chlorhexidine groups (p = 0.033) exhibited significantly higher μTBS values at 24 h compared with the self-etch group. For All Bond Universal, all groups displayed similar bond strengths at 24 h (p > 0.05). After 12 months of water storage, the μTBS values decreased significantly in the benzalkonium chloride group for Single Bond Universal (p = 0.001) and the self-etch (p = 0.029), chlorhexidine (p = 0.046), and EDTA (p = 0.032) groups for All Bond Universal. These results suggest that the immediate dentin bond strength increases when universal bonding systems are applied in the etch-and-rinse mode, although the durability decreases. The use of chlorhexidine and EDTA can increase the bond durability of mild adhesives such as Single Bond Universal. SCANNING 38:535-544, 2016. © 2016 Wiley Periodicals, Inc. © Wiley Periodicals, Inc.

Double stranded nucleic acid biochips

DOEpatents

Chernov, Boris; Golova, Julia

2006-05-23

This invention describes a new method of constructing double-stranded DNA (dsDNA) microarrays based on the use of pre-synthesized or natural DNA duplexes without a stem-loop structure. The complementary oligonucleotide chains are bonded together by a novel connector that includes a linker for immobilization on a matrix. A non-enzymatic method for synthesizing double-stranded nucleic acids with this novel connector enables the construction of inexpensive and robust dsDNA/dsRNA microarrays. DNA-DNA and DNA-protein interactions are investigated using the microarrays.

Cyclic loading of rotator cuff reconstructions: single-row repair with modified suture configurations versus double-row repair.

PubMed

Lorbach, Olaf; Bachelier, Felix; Vees, Jochen; Kohn, Dieter; Pape, Dietrich

2008-08-01

Double-row repair is suggested to have superior biomechanical properties in rotator cuff reconstruction compared with single-row repair. However, double-row rotator cuff repair is frequently compared with simple suture repair and not with modified suture configurations. Single-row rotator cuff repairs with modified suture configurations have similar failure loads and gap formations as double-row reconstructions. Controlled laboratory study. We created 1 x 2-cm defects in 48 porcine infraspinatus tendons. Reconstructions were then performed with 4 single-row repairs and 2 double-row repairs. The single-row repairs included transosseous simple sutures; double-loaded corkscrew anchors in either a double mattress or modified Mason-Allen suture repair; and the Magnum Knotless Fixation Implant with an inclined mattress. Double-row repairs were either with Bio-Corkscrew FT using modified Mason-Allen stitches or a combination of Bio-Corkscrew FT and PushLock anchors using the SutureBridge Technique. During cyclic load (10 N to 60-200 N), gap formation was measured, and finally, ultimate load to failure and type of failure were recorded. Double-row double-corkscrew anchor fixation had the highest ultimate tensile strength (398 +/- 98 N) compared to simple sutures (105 +/- 21 N; P < .0001), single-row corkscrews using a modified Mason-Allen stitch (256 +/- 73 N; P = .003) or double mattress repair (290 +/- 56 N; P = .043), the Magnum Implant (163 +/- 13 N; P < .0001), and double-row repair with PushLock and Bio-Corkscrew FT anchors (163 +/- 59 N; P < .0001). Single-row double mattress repair was superior to transosseous sutures (P < .0001), the Magnum Implant (P = .009), and double-row repair with PushLock and Bio-Corkscrew FT anchors (P = .009). Lowest gap formation was found for double-row double-corkscrew repair (3.1 +/- 0.1 mm) compared to simple sutures (8.7 +/- 0.2 mm; P < .0001), the Magnum Implant (6.2 +/- 2.2 mm; P = .002), double-row repair with PushLock and Bio-Corkscrew FT anchors (5.9 +/- 0.9 mm; P = .008), and corkscrews with modified Mason-Allen sutures (6.4 +/- 1.3 mm; P = .001). Double-row double-corkscrew anchor rotator cuff repair offered the highest failure load and smallest gap formation and provided the most secure fixation of all tested configurations. Double-loaded suture anchors using modified suture configurations achieved superior results in failure load and gap formation compared to simple suture repair and showed similar loads and gap formation with double-row repair using PushLock and Bio-Corkscrew FT anchors. Single-row repair with modified suture configurations may lead to results comparable to several double-row fixations. If double-row repair is used, modified stitches might further minimize gap formation and increase failure load.

Adsorption and Reaction of Acetone over CeOX(111) Thin Films

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

Mullins, David R; Senanayake, Sanjaya D; Gordon, Wesley O

2009-01-01

This study reports the interaction of acetone (CH3COCH3), the simplest ketone, with well ordered CeO2(111) thin film surfaces. The fully oxidized CeO2(111) surface shows a weak interaction with acetone with the sole desorption product (TPD) being acetone at 210 K. The chemisorbed molecule binds to the surface as the ?1-acetone species rather than through a bridge-bonded dioxy-configuration. Exposure of a CeO2(111) surface to acetone at 600K removes oxygen as CO and results in the conversion of Ce4+ to Ce3+. Acetone chemisorbs strongly on reduced CeO2-x(111) with molecular acetone desorbing near 500 K. Decomposition also occurs with H2 desorbing between 450more » and 600 K and C reacting with O in the ceria to desorb above 650 K. A stable species exists from 200 to 500 K on the reduced surface that has three unique types of C. High resolution C 1s XPS spectra indicate these are Ce-CH2, C-CH3 and C-O species. C k-edge NEXAFS indicates the presence of C{double_bond}C and C{double_bond}O bonds. It is postulated that the intermediate is a carbanion bonded through both O and C atoms to Ce cations.« less

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

ALAM,TODD M.

Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

Synthesis and Characterization of a Hyperbranched Hydrogen Bond Acidic Carbosilane Sorbent Polymer

DTIC Science & Technology

2010-01-01

double bond of HCSA2 (1) electrophilically attacks the ketone carbon of the HFA. The bonds are formed via a pericyclic mechanism which requires formation...val- ues for H, 3.1% and C, 35.4% compared with the theoretical weight percents of H, 2.2%, and C, 34.3%. Fluorine composi- tion numbers were...Srcic, S. Acta Chim Solv 2004, 51, 373–394. 43 Bhadury, P. S.; Dubey, V.; Singh, S.; Saxena, C. J. Fluorine Chem 2005, 126, 1252–1256. 44 Grate, J. W

Mechanism for Si–Si Bond Rupture in Single Molecule Junctions

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

Li, Haixing; Kim, Nathaniel T.; Su, Timothy A.

The stability of chemical bonds can be studied experimentally by rupturing single molecule junctions under applied voltage. Here, we compare voltage-induced bond rupture in two Si–Si backbones: one has no alternate conductive pathway whereas the other contains an additional naphthyl pathway in parallel to the Si–Si bond. We show that in contrast to the first system, the second can conduct through the naphthyl group when the Si–Si bond is ruptured using an applied voltage. We investigate this voltage induced Si–Si bond rupture by ab initio density functional theory calculations and molecular dynamics simulations that ultimately demonstrate that the excitation ofmore » molecular vibrational modes by tunneling electrons leads to homolytic Si–Si bond rupture.« less

Mechanism for Si-Si Bond Rupture in Single Molecule Junctions.

PubMed

Li, Haixing; Kim, Nathaniel T; Su, Timothy A; Steigerwald, Michael L; Nuckolls, Colin; Darancet, Pierre; Leighton, James L; Venkataraman, Latha

2016-12-14

The stability of chemical bonds can be studied experimentally by rupturing single molecule junctions under applied voltage. Here, we compare voltage-induced bond rupture in two Si-Si backbones: one has no alternate conductive pathway whereas the other contains an additional naphthyl pathway in parallel to the Si-Si bond. We show that in contrast to the first system, the second can conduct through the naphthyl group when the Si-Si bond is ruptured using an applied voltage. We investigate this voltage induced Si-Si bond rupture by ab initio density functional theory calculations and molecular dynamics simulations that ultimately demonstrate that the excitation of molecular vibrational modes by tunneling electrons leads to homolytic Si-Si bond rupture.

The effect of nitrogen incorporation on the bonding structure of hydrogenated carbon nitride films

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

Camero, M.; Buijnsters, J. G.; Gomez-Aleixandre, C.

2007-03-15

This work describes the composition and bonding structure of hydrogenated carbon nitride (a-CN{sub x}:H) films synthesized by electron cyclotron resonance chemical vapor deposition using as precursor gases argon, methane, and nitrogen. The composition of the films was derived from Rutherford backscattering and elastic recoil detection analysis and the bonding structure was examined by infrared (IR) spectroscopy and x-ray absorption near edge spectroscopy (XANES). By varying the nitrogen to methane ratio in the applied gas mixture, polymeric a-CN{sub x}:H films with N/C contents varying from 0.06 to 0.49 were obtained. Remarkably, the H content of the films ({approx}40 at. %) wasmore » rather unaffected by the nitrogenation process. The different bonding states as detected in the measured XANES C(1s) and N(1s) spectra have been correlated with those of a large number of reference samples. The XANES and IR spectroscopy results indicate that N atoms are efficiently incorporated into the amorphous carbon network and can be found in different bonding environments, such as pyridinelike, graphitelike, nitrilelike, and amino groups. The nitrogenation of the films results in the formation of N-H bonding environments at the cost of C-H structures. Also, the insertion of N induces a higher fraction of double bonds in the structure at the expense of the linear polymerlike chains, hence resulting in a more cross-linked solid. The formation of double bonds takes place through complex C=N structures and not by formation of graphitic aromatic rings. Also, the mechanical and tribological properties (hardness, friction, and wear) of the films have been studied as a function of the nitrogen content. Despite the major modifications in the bonding structure with nitrogen uptake, no significant changes in these properties are observed.« less

Q-Band Electron-Nuclear Double Resonance Reveals Out-of-Plane Hydrogen Bonds Stabilize an Anionic Ubisemiquinone in Cytochrome bo3 from Escherichia coli.

PubMed

Sun, Chang; Taguchi, Alexander T; Vermaas, Josh V; Beal, Nathan J; O'Malley, Patrick J; Tajkhorshid, Emad; Gennis, Robert B; Dikanov, Sergei A

2016-10-11

The respiratory cytochrome bo 3 ubiquinol oxidase from Escherichia coli has a high-affinity ubiquinone binding site that stabilizes the one-electron reduced ubisemiquinone (SQ H ), which is a transient intermediate during the electron-mediated reduction of O 2 to water. It is known that SQ H is stabilized by two strong hydrogen bonds from R71 and D75 to ubiquinone carbonyl oxygen O1 and weak hydrogen bonds from H98 and Q101 to O4. In this work, SQ H was investigated with orientation-selective Q-band (∼34 GHz) pulsed 1 H electron-nuclear double resonance (ENDOR) spectroscopy on fully deuterated cytochrome (cyt) bo 3 in a H 2 O solvent so that only exchangeable protons contribute to the observed ENDOR spectra. Simulations of the experimental ENDOR spectra provided the principal values and directions of the hyperfine (hfi) tensors for the two strongly coupled H-bond protons (H1 and H2). For H1, the largest principal component of the proton anisotropic hfi tensor T z' = 11.8 MHz, whereas for H2, T z' = 8.6 MHz. Remarkably, the data show that the direction of the H1 H-bond is nearly perpendicular to the quinone plane (∼70° out of plane). The orientation of the second strong hydrogen bond, H2, is out of plane by ∼25°. Equilibrium molecular dynamics simulations on a membrane-embedded model of the cyt bo 3 Q H site show that these H-bond orientations are plausible but do not distinguish which H-bond, from R71 or D75, is nearly perpendicular to the quinone ring. Density functional theory calculations support the idea that the distances and geometries of the H-bonds to the ubiquinone carbonyl oxygens, along with the measured proton anisotropic hfi couplings, are most compatible with an anionic (deprotonated) ubisemiquinone.

Does double-row rotator cuff repair improve functional outcome of patients compared with single-row technique? A systematic review.

PubMed

DeHaan, Alexander M; Axelrad, Thomas W; Kaye, Elizabeth; Silvestri, Lorenzo; Puskas, Brian; Foster, Timothy E

2012-05-01

The advantage of single-row versus double-row arthroscopic rotator cuff repair techniques has been a controversial issue in sports medicine and shoulder surgery. There is biomechanical evidence that double-row techniques are superior to single-row techniques; however, there is no clinical evidence that the double-row technique provides an improved functional outcome. When compared with single-row rotator cuff repair, double-row fixation, although biomechanically superior, has no clinical benefit with respect to retear rate or improved functional outcome. Systematic review. The authors reviewed prospective studies of level I or II clinical evidence that compared the efficacy of single- and double-row rotator cuff repairs. Functional outcome scores included the American Shoulder and Elbow Surgeons (ASES) shoulder scale, the Constant shoulder score, and the University of California, Los Angeles (UCLA) shoulder rating scale. Radiographic failures and complications were also analyzed. A test of heterogeneity for patient demographics was also performed to determine if there were differences in the patient profiles across the included studies. Seven studies fulfilled our inclusion criteria. The test of heterogeneity across these studies showed no differences. The functional ASES, Constant, and UCLA outcome scores revealed no difference between single- and double-row rotator cuff repairs. The total retear rate, which included both complete and partial retears, was 43.1% for the single-row repair and 27.2% for the double-row repair (P = .057), representing a trend toward higher failures in the single-row group. Through a comprehensive literature search and meta-analysis of current arthroscopic rotator cuff repairs, we found that the single-row repairs did not differ from the double-row repairs in functional outcome scores. The double-row repairs revealed a trend toward a lower radiographic proven retear rate, although the data did not reach statistical significance. There may be a concerning trend toward higher retear rates in patients undergoing a single-row repair, but further studies are required.

Permanganate ion oxidations. IX. Manganese intermediates (complexes) in the oxidation of 2,4(1H,3H)-pyrimidinediones.

PubMed

Freeman, F; Karchefski, E M

1976-10-04

Uniquely stable manganese intermediates (complexes) are formed from the permanganate ion oxidation of the 5,6-carbon-carbon double bond in several 2,4(1H,3H)-pyrimidinediones [uracil, (compound 7), 5-methyluracil (thymine, compound 5), and 6-methyluracil (compound 8)]. These manganese complexes, which represent some of the most stable intermediate manganese species observed thus far in the oxidation of carbon-carbon double bonds, show absorption maxima in the 285-296 nm region (epsilon max approximately 4500). The relative reactivities of 6-methyluracil: uracil: thymine are 1: 23 : 194 and the bimolecular oxidation process is characterized by relatively small deltaH++ values and large negative deltaS++ values.

Micro-shear bond strengths of adhesive resins to coronal dentin versus the floor of the pulp chamber.

PubMed

Toba, Shigemitsu; Veerapravati, Weeraporn; Shimada, Yasushi; Nikaido, Toru; Tagami, Junji

2003-09-01

To evaluate the micro-shear bond strengths to superficial coronal dentin and the floor of the pulp chamber using two dentin bonding systems and to compare the ultrastructure of the resin-dentin interface of the two regions. 30 non-carious molars were used to obtain 2 mm thick slabs of coronal dentin and dentin at the pulp chamber. The specimens in each region were divided into three sub-groups to be bonded as follows; Clearfil SE Bond was used according to the manufacturer's instructions, Single Bond was applied to either wet dentin (Blot dry Group) or air-dried dentin (Dry Group) after phosphoric acid etching. A resin composite cylinder 0.5 mm high and 0.75 mm in diameter formed using a vinyl tube was bonded to the dentin. Specimens were stored at 37 degrees C for 24 hours in water and then stressed in shear at a crosshead speed of 1 mm/minute. The data were analyzed with one-way ANOVA and Fisher's PLSD test at the 5% level of significance. In addition, the ultrastructure of cross-sectioned dentin surfaces, the conditioned dentin surface and the resin dentin interfaces were observed by SEM. The bond strengths of Clearfil SE Bond and the Single Bond Blot dry group were approximately 40 MPa in coronal dentin and 30 MPa in the dentin at the floor of the pulp chamber respectively. However, the bond strengths of Single Bond were significantly lower in the Dry condition (MPa) (P < 0.05). SEM observations revealed the thickness of the hybrid layer created by Clearfil SE Bond in coronal dentin and at the floor of the pulp chamber were less than 1.0 microm thick. For Single Bond, a 3-4 microm hybrid layer was created in coronal dentin, while a thinner hybrid layer was observed in the floor of the pulp chamber. Morphological and structural variations in dentin may have influenced the bond strengths of the bonding systems to the floor of the pulp chamber.

The Lower Extremity Biomechanics of Single- and Double-Leg Stop-Jump Tasks

PubMed Central

2011-01-01

The anterior cruciate ligament (ACL) injury is a common occurrence in sports requiring stop-jump tasks. Single- and double-leg stop-jump techniques are frequently executed in sports. The higher risk of ACL injury in single-leg drop landing task compared to a double-leg drop landing task has been identified. However the injury bias between single- and double-leg landing techniques has not been investigated for stop-jump tasks. The purpose of this study was to determine the differences between single- and double-leg stop-jump tasks in knee kinetics that were influenced by the lower extremity kinematics during the landing phase. Ground reaction force, lower extremity kinematics, and knee kinetics data during the landing phase were obtained from 10 subjects performing single- and double-leg stop-jump tasks, using motion-capture system and force palates. Greater peak posterior and vertical ground reaction forces, and peak proximal tibia anterior and lateral shear forces (p < 0.05) during landing phase were observed of single-leg stop-jump. Single-leg stop-jump exhibited smaller hip and knee flexion angle, and knee flexion angular velocity at initial foot contact with the ground (p < 0.05). We found smaller peak hip and knee flexion angles (p < 0.05) during the landing phase of single-leg stop-jump. These results indicate that single-leg landing may have higher ACL injury risk than double-leg landing in stop-jump tasks that may be influenced by the lower extremity kinematics during the landing phase. Key points Non-contact ACL injuries are more likely to occur during the single-leg stop-jump task than during the double-leg stop-jump task. Single-leg stop-jump exhibited greater peak proximal tibia anterior and lateral shear forces, and peak posterior and vertical ground reaction forces during the landing phase than the double-leg stop-jump task. Single-leg stop-jump exhibited smaller hip flexion angle, knee flexion angle, and knee flexion angular velocity at initial foot contact with the ground. Single-leg stop-jump exhibited greater peak knee extension and valgus moment during the landing phase than the double-leg stop-jump task. Single-leg stop-jump extended the hip joint at initial foot contact with the ground. PMID:24149308