Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties.

PubMed

Zhang, Z; Fenter, P; Cheng, L; Sturchio, N C; Bedzyk, M J; Predota, M; Bandura, A; Kubicki, J D; Lvov, S N; Cummings, P T; Chialvo, A A; Ridley, M K; Bénézeth, P; Anovitz, L; Palmer, D A; Machesky, M L; Wesolowski, D J

2004-06-08

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

Variations in enamel damage after debonding of two different bracket base designs: An in vitro study.

PubMed

Ahangar Atashi, Mohammad Hossein; Sadr Haghighi, Amir Hooman; Nastarin, Parastou; Ahangar Atashi, Sina

2018-01-01

Background. Bracket base design is a factor influencing shear bond strength. High shear bond strength leads to enamel crack formation during debonding. The aim of this study was to compare enamel damage variations, including the number and length of enamel cracks after debonding of two different base designs. Methods. Eighty-eight extracted human premolars were randomly divided into2 groups (n=44). The teeth in each group were bonded by two types of brackets with different base designs: 80-gauge mesh design versus anchor pylon design with pylons for adhesive retention. The number and length of enamel cracks before bonding and after debonding were evaluated under an optical stereomicroscope ×40 in both groups. Mann-Whitney U test was used to compare the number of cracks between the two groups. ANCOVA was used for comparison of crack lengths after and before debonding in each group and between the two groups. Results. There was a significant increase in enamel crack length and numbers in each group after debonding. There was no significant difference in enamel crack numbers after debonding between the two groups, whereas the length of enamel cracks was significantly greater in anchor pylon base design after debonding. Conclusion. Bracket bases with pylon design for adhesive retention caused more iatrogenic debonding damage to enamel surface.

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.

Surface Protonation at the Rutile (110) Interface: Explicit Incorporation of Solvation Structure within the Refined MUSIC Model Framework

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

Machesky, Michael L.; Predota, M.; Wesolowski, David J

The detailed solvation structure at the (110) surface of rutile ({alpha}-TiO{sub 2}) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming thatmore » the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 {angstrom} of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 C that agrees quantitatively with the experimentally determined value (5.4 {+-} 0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pH{sub znpc} values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pH{sub znpc} value of the rutile (110) surface at 25 C into quantitative agreement with the experimental value (4.8 {+-} 0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength. Additionally, the H-bond interactions between protolyzable surface oxygen groups and water were found to be stronger than those between bulk water molecules at all temperatures investigated in our CMD simulations (25, 150 and 250 C). Comparison with the protonation scheme previously determined for the (110) surface of isostructural cassiterite ({alpha}-SnO{sub 2}) reveals that the greater extent of H-bonding on the latter surface, and in particular between water and the terminal hydroxyl group (Sn-OH) results in the predicted protonation constant for that group being lower than for the bridged oxygen (Sn-O-Sn), while the reverse is true for the rutile (110) surface. These results demonstrate the importance of H-bond structure in dictating surface protonation behavior, and that explicit use of this solvation structure within the refined MUSIC model framework results in predicted surface protonation constants that are also consistent with a variety of other experimental and computational data.« less

Surface protonation at the rutile (110) interface: explicit incorporation of solvation structure within the refined MUSIC model framework.

PubMed

Machesky, Michael L; Predota, Milan; Wesolowski, David J; Vlcek, Lukas; Cummings, Peter T; Rosenqvist, Jörgen; Ridley, Moira K; Kubicki, James D; Bandura, Andrei V; Kumar, Nitin; Sofo, Jorge O

2008-11-04

The detailed solvation structure at the (110) surface of rutile (alpha-TiO2) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 A of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 degrees C that agrees quantitatively with the experimentally determined value (5.4+/-0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pHznpc values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 degrees C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pHznpcvalue of the rutile (110) surface at 25 degrees C into quantitative agreement with the experimental value (4.8+/-0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength. Additionally, the H-bond interactions between protolyzable surface oxygen groups and water were found to be stronger than those between bulk water molecules at all temperatures investigated in our CMD simulations (25, 150 and 250 degrees C). Comparison with the protonation scheme previously determined for the (110) surface of isostructural cassiterite (alpha-SnO2) reveals that the greater extent of H-bonding on the latter surface, and in particular between water and the terminal hydroxyl group (Sn-OH) results in the predicted protonation constant for that group being lower than for the bridged oxygen (Sn-O-Sn), while the reverse is true for the rutile (110) surface. These results demonstrate the importance of H-bond structure in dictating surface protonation behavior, and that explicit use of this solvation structure within the refined MUSIC model framework results in predicted surface protonation constants that are also consistent with a variety of other experimental and computational data.

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.

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

NASA Astrophysics Data System (ADS)

Jörg, H.; Rösch, N.

The cluster Ni 2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the Ni-Ni distance fixed at the bulk value. The minimum energy is found at a Ni-C distance of 1.72 Å and a C-O bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm -1) shows reasonable agreement with EELS data (1810, 1870 cm -1), whereas the (Ni 2)-C frequency of 495 cm -1 is remarkably higher than the experimental values (380, 400 cm -1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a 1 orbital manifold exhibits strong antibonding effects.

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

NASA Astrophysics Data System (ADS)

Jörg, H.; Rösch, N.

1985-11-01

The cluster Ni 2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm -1) shows reasonable agreement with EELS data (1810, 1870 cm -1), whereas the (Ni 2)C frequency of 495 cm -1 is remarkably higher than the experimental values (380, 400 cm -1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a 1orbital manifold exhibits strong antibonding effects.

Driving force for hydrophobic interaction at different length scales.

PubMed

Zangi, Ronen

2011-03-17

We study by molecular dynamics simulations the driving force for the hydrophobic interaction between graphene sheets of different sizes down to the atomic scale. Similar to the prediction by Lum, Chandler, and Weeks for hard-sphere solvation [J. Phys. Chem. B 1999, 103, 4570-4577], we find the driving force to be length-scale dependent, despite the fact that our model systems do not exhibit dewetting. For small hydrophobic solutes, the association is purely entropic, while enthalpy favors dissociation. The latter is demonstrated to arise from the enhancement of hydrogen bonding between the water molecules around small hydrophobes. On the other hand, the attraction between large graphene sheets is dominated by enthalpy which mainly originates from direct solute-solute interactions. The crossover length is found to be inside the range of 0.3-1.5 nm(2) of the surface area of the hydrophobe that is eliminated in the association process. In the large-scale regime, different thermodynamic properties are scalable with this change of surface area. In particular, upon dimerization, a total and a water-induced stabilization of approximately 65 and 12 kJ/mol/nm(2) are obtained, respectively, and on average around one hydrogen bond is gained per 1 nm(2) of graphene sheet association. Furthermore, the potential of mean force between the sheets is also scalable except for interplate distances smaller than 0.64 nm which corresponds to the region around the barrier for removing the last layer of water. It turns out that, as the surface area increases, the relative height of the barrier for association decreases and the range of attraction increases. It is also shown that, around small hydrophobic solutes, the lifetime of the hydrogen bonds is longer than in the bulk, while around large hydrophobes it is the same. Nevertheless, the rearrangement of the hydrogen-bond network for both length-scale regimes is slower than in bulk water. © 2011 American Chemical Society

Mean bond-length variations in crystals for ions bonded to oxygen

PubMed Central

2017-01-01

Variations in mean bond length are examined in oxide and oxysalt crystals for 55 cation configurations bonded to O2−. Stepwise multiple regression analysis shows that mean bond length is correlated to bond-length distortion in 42 ion configurations at the 95% confidence level, with a mean coefficient of determination (〈R 2〉) of 0.35. Previously published correlations between mean bond length and mean coordination number of the bonded anions are found not to be of general applicability to inorganic oxide and oxysalt structures. For two of 11 ions tested for the 95% confidence level, mean bond lengths predicted using a fixed radius for O2− are significantly more accurate as those predicted using an O2− radius dependent on coordination number, and are statistically identical otherwise. As a result, the currently accepted ionic radii for O2− in different coordinations are not justified by experimental data. Previously reported correlation between mean bond length and the mean electronegativity of the cations bonded to the oxygen atoms of the coordination polyhedron is shown to be statistically insignificant; similar results are obtained with regard to ionization energy. It is shown that a priori bond lengths calculated for many ion configurations in a single structure-type leads to a high correlation between a priori and observed mean bond lengths, but a priori bond lengths calculated for a single ion configuration in many different structure-types leads to negligible correlation between a priori and observed mean bond lengths. This indicates that structure type has a major effect on mean bond length, the magnitude of which goes beyond that of the other variables analyzed here.

Effect of Surface Treatment on Enamel Cracks After Orthodontic Bracket Debonding: Er,Cr:YSGG Laser-Etching Versus Acid-Etching

PubMed Central

Ghaffari, Hassanali; Mirhashemi, Amirhossein; Baherimoghadam, Tahereh; Azmi, Amir

2017-01-01

Objectives: This study sought to compare enamel cracks after orthodontic bracket debonding in the surfaces prepared with erbium, chromium: yttrium-scandium-galliumgarnet (Er,Cr:YSGG) laser and the conventional acid-etching technique. Materials and Methods: This in-vitro experimental study was conducted on 60 sound human premolars extracted for orthodontic purposes. The teeth were randomly divided into two groups (n=30). The teeth in group A were etched with 37% phosphoric acid gel, while the teeth in group B were subjected to Er,Cr:YSGG laser irradiation (gold handpiece, MZ8 tip, 50Hz, 4.5W, 60μs, 80% water and 60% air). Orthodontic brackets were bonded to the enamel surfaces and were then debonded in both groups. The samples were inspected under a stereomicroscope at ×38 magnification to assess the number and length of enamel cracks before bonding and after debonding. Independent-samples t-test was used to compare the frequency of enamel cracks in the two groups. Levene’s test was applied to assess the equality of variances. Results: No significant difference was noted in the frequency or length of enamel cracks between the two groups after debonding (P>0.05). Conclusions: Despite the same results of the frequency and length of enamel cracks in the two groups and by considering the side effects of acid-etching (demineralization and formation of white spot lesions), Er,Cr:YSGG laser may be used as an alternative to acid-etching for enamel surface preparation prior to bracket bonding. PMID:29296111

The origin of unequal bond lengths in the C 1B 2 state of SO 2: Signatures of high-lying potential energy surface crossings in the low-lying vibrational structure

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

Park, G. Barratt; Jiang, Jun; Field, Robert W.

Here the C 1B 2 state of SO 2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. The asymmetry in the potential energy surface is expressed as a staggering in the energy levels of the v' 3 progression. We have recently made the first observation of low-lying levels with odd quanta of v' 3, which allows us--in the current work--to characterize the origins of the level staggering. Our work demonstrates the usefulness of low-lying vibrational level structure, where the character of the wavefunctions can be relatively easily understood,more » to extract information about dynamically important potential energy surface crossings that occur at much higher energy. The measured staggering pattern is consistent with a vibronic coupling model for the double-minimum, which involves direct coupling to the bound 2 1A 1 state and indirect coupling with the repulsive 3 1A 1 state. The degree of staggering in the v' 3 levels increases with quanta of bending excitation, which is consistent with the approach along the C state potential energy surface to a conical intersection with the 2 1A 1 surface at a bond angle of ~145°.« less

The origin of unequal bond lengths in the C 1B 2 state of SO 2: Signatures of high-lying potential energy surface crossings in the low-lying vibrational structure

DOE PAGES

Park, G. Barratt; Jiang, Jun; Field, Robert W.

2016-04-14

Here the C 1B 2 state of SO 2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. The asymmetry in the potential energy surface is expressed as a staggering in the energy levels of the v' 3 progression. We have recently made the first observation of low-lying levels with odd quanta of v' 3, which allows us--in the current work--to characterize the origins of the level staggering. Our work demonstrates the usefulness of low-lying vibrational level structure, where the character of the wavefunctions can be relatively easily understood,more » to extract information about dynamically important potential energy surface crossings that occur at much higher energy. The measured staggering pattern is consistent with a vibronic coupling model for the double-minimum, which involves direct coupling to the bound 2 1A 1 state and indirect coupling with the repulsive 3 1A 1 state. The degree of staggering in the v' 3 levels increases with quanta of bending excitation, which is consistent with the approach along the C state potential energy surface to a conical intersection with the 2 1A 1 surface at a bond angle of ~145°.« less

Evaluation of the interfacial bond properties between carbon phenolic and glass phenolic composites

NASA Technical Reports Server (NTRS)

Jordan, K.; Clinton, R.; Jeelani, S.

1991-01-01

The effects of moisture and surface finish on the mechanical and physical properties of the interfacial bond between carbon/phenolic (C/P) and glass/phenolic (G/P) composite materials have been studied. Test results indicate that moisture substantially degrades the integrity of the interfacial bond between C/P and G/P materials. The apparent effect of the autoclave curing of the C/P material reduces the ultimate interlaminar shear length of the C/P material by 20 percent compared to the hydroclave curing of the C/P material. The variation in applied surface finishes is found to have no appreciable effect on the ultimate interlaminar shear strength of the interface in the wet laminate.

Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

NASA Astrophysics Data System (ADS)

Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.

2018-01-01

Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

The atomic geometries of GaP(110) and ZnS(110) revisited - A structural ambiguity and its resolution

NASA Technical Reports Server (NTRS)

Duke, C. B.; Paton, A.; Kahn, A.

1984-01-01

The atomic geometries of GaP(110) and ZnS(110) are reexamined using the R-factor minimization procedure, developed for GaAs(110) and previously applied to GaSb(110), ZnTe(110), InAs(110), and AlP(110), to analyze experimental elastic low-energy electron diffraction intensities. Unlike most of the earlier cases, both GaP(110) and ZnS(110) exhibit two distinct minimum-Rx structures which cannot be distinguished by analysis of the shapes of the intensity profiles alone. One region of best-fit structures exhibits top-layer displacements normal to the surface characterized by a small bond-length-conserving, top-layer rotation (omega aproximately 2-3 deg), a small relaxation of the top layer away from the surface, and a 10 percent expansion of the top-layer bond length. The other region of best-fit structures is the conventional one: nearly bond-length-conserving rotations of omega = 26-28 deg in the top layer and a small (approximately 0.1 A) contraction of the uppermost layer spacing. This ambiguity may be removed, however, by consideration of the integrated beam intensities. The conventional region of structural parameters provides a decisively better description of the relative magnitudes of the integrated beam intensities and hence is the preferred structure.

Effect of metal surface topography on mechanical bonding at simulated total hip stem-cement interfaces.

PubMed

Chen, C Q; Scott, W; Barker, T M

1999-01-01

Bonding and loosening mechanisms between bone cement and joint prostheses have not been well identified. In this study, the effects of simulated hip stem surface topography on the interfacial shear strength were examined. Six different surface topographies were used. They were described by several surface characterization parameters that may directly relate to the interfacial bonding strength: average surface roughness R(a), root mean square slope R(Deltaq), correlation length beta, and fluid retention index R(ri). The shear strengths between Palacos E bone cement and stainless steel rods were measured using an Instron materials testing machine. We found that cement can "flow" into the surface microtopography and establish good contact with the metal surface. The results show that the interfacial strength increases monotonically with the increase of R(Deltaq) instead of with R(a). The relationship between interfacial strength and surface parameters shows that a metal stem with an isotropic surface texture, higher R(Deltaq), and greater R(ri) gives a higher interfacial strength. Copyright 1999 John Wiley & Sons, Inc.

Chlorine adsorption on the InAs (001) surface

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

Bakulin, A. V.; Eremeev, S. V.; Tereshchenko, O. E.

2011-01-15

Chlorine adsorption on the In-stabilized InAs(001) surface with {zeta}-(4 Multiplication-Sign 2) and {beta}3 Prime -(4 Multiplication-Sign 2) reconstructions and on the Ga-stabilized GaAs (001)-{zeta}-(4 Multiplication-Sign 2) surface has been studied within the electron density functional theory. The equilibrium structural parameters of these reconstructions, surface atom positions, bond lengths in dimers, and their changes upon chlorine adsorption are determined. The electronic characteristics of the clean surface and the surface with adsorbed chlorine are calculated. It is shown that the most energetically favorable positions for chlorine adsorption are top positions over dimerized indium or gallium atoms. The mechanism of chlorine binding withmore » In(Ga)-stabilized surface is explained. The interaction of chlorine atoms with dimerized surface atoms weakens surface atom bonds and controls the initial stage of surface etching.« less

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.

Method of assembling a thermal expansion compensator

NASA Technical Reports Server (NTRS)

Matejczyk, Daniel Edward (Inventor); Determan, William (Inventor)

2012-01-01

A thermal expansion compensator is provided and includes a first electrode structure having a first surface, a second electrode structure having a second surface facing the first surface and an elastic element bonded to the first and second surfaces and including a conductive element by which the first and second electrode structures electrically and/or thermally communicate, the conductive element having a length that is not substantially longer than a distance between the first and second surfaces.

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.

Shear Bond Strengths and Morphological Evaluation of Filled and Unfilled Adhesive Interfaces to Enamel and Dentine

PubMed Central

Mortazavi, Vajihesadat; Fathi, Mohammadhosein; Ataei, Ebrahim; Khodaeian, Niloufar; Askari, Navid

2012-01-01

In this laboratory study shear bond strengths of three filled and one unfilled adhesive systems to enamel and dentine were compared. Forty-eight extracted intact noncarious human mandibular molars were randomly assigned to two groups of 24 one for bonding to enamel and the other for bonding to dentine. Buccal and lingual surfaces of each tooth were randomly assigned for application of each one of filled (Prime & Bond NT (PBNT), Optibond Solo Plus (OBSP), and Clearfil SE Bond (CSEB)) and unfilled (Single Bond (SB)) adhesive systems (n = 12). A universal resin composite was placed into the translucent plastic cylinders (3 mm in diameter and 2 mm in length) and seated against the enamel and dentine surfaces and polymerized for 40 seconds. Shear bond strength was determined using a universal testing machine, and the results were statistically analyzed using two-way ANOVA, one-way ANOVA, t-test, and Tukey HSD post hoc test with a 5% level of significance.There were no statistically significant differences in bond strength between the adhesive systems in enamel, but CSEB and SB exhibited significantly higher and lower bond strength to dentine, respectively, than the other tested adhesive systems while there were no statistically significant differences between PBNT and OBSP. PMID:23209471

A chromatographic estimate of the degree of surface heterogeneity of reversed-phase liquid chromatography packing materials II-Endcapped monomeric C18-bonded stationary phase

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

Gritti, Fabrice; Guiochon, Georges A

2006-01-01

In a previous report, the heterogeneity of a non-endcapped C{sub 30}-bonded stationary phase was investigated, based on the results of the measurements of the adsorption isotherms of two neutral compounds (phenol and caffeine) and two ionizable compounds (sodium naphthalene sulfonate and propranololium chloride) by frontal analysis (FA). The same method is applied here for the characterization of the surface heterogeneity of two new brands of endcapped C{sub 18}-bonded stationary phases (Gemini and Sunfire). The adsorption isotherms of the same four chemicals were measured by FA and the results confirmed by the independent calculation of the adsorption energy distribution (AED), usingmore » the expectation-maximization (EM) method. The effect of the length of the bonded alkyl chain was investigated. Shorter alkyl-bonded-chains (C{sub 18} versus C{sub 30}) and the end-capping of the silica surface contribute to decrease the surface heterogeneity under the same experimental conditions (30% methanol, 25 mM NaCl). The AEDs of phenol and caffeine are bimodal with the C{sub 18}-bonded columns while they are trimodal and quadrimodal, respectively, with a non-endcapped C{sub 30}-bonded column. The 'supersites' (adsorption energy >20 kJ/mol) found on the C{sub 30}-Prontosil column and attributed to a cation exchange mechanism completely disappear on the C{sub 18}-Gemini and C{sub 18}-Sunfire, probably because the end-capping of the silica surface eliminates most if not all the ionic interactions.« less

Tooth surface treatment strategies for adhesive cementation

PubMed Central

2017-01-01

PURPOSE The aim of this study was to evaluate the effect of tooth surface pre-treatment steps on shear bond strength, which is essential for understanding the adhesive cementation process. MATERIALS AND METHODS Shear bond strengths of different cements with various tooth surface treatments (none, etching, priming, or etching and priming) on enamel and dentin of human teeth were measured using the Swiss shear test design. Three adhesives (Permaflo DC, Panavia F 2.0, and Panavia V5) and one self-adhesive cement (Panavia SA plus) were included in this study. The interface of the cement and the tooth surface with the different pre-treatments was analyzed using SEM. pH values of the cements and primers were measured. RESULTS The highest bond strength values for all cements were achieved with etching and primer on enamel (25.6 ± 5.3 - 32.3 ± 10.4 MPa). On dentin, etching and priming produced the highest bond strength values for all cements (8.6 ± 2.9 - 11.7 ± 3.5 MPa) except for Panavia V5, which achieved significantly higher bond strengths when pre-treated with primer only (15.3 ± 4.1 MPa). Shear bond strength values were correlated with the micro-retentive surface topography of enamel and the tag length on dentin except for Panavia V5, which revealed the highest bond strength with primer application only without etching, resulting in short but sturdy tags. CONCLUSION The highest bond strength can be achieved for Panavia F 2.0, Permaflo DC, and Panavia SA plus when the tooth substrate is previously etched and the respective primer is applied. The new cement Panavia V5 displayed low technique-sensitivity and attained significantly higher adhesion of all tested cements to dentin when only primer was applied. PMID:28435616

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.

On the correlation between bond-length change and vibrational frequency shift in halogen-bonded complexes

NASA Astrophysics Data System (ADS)

Wang, Weizhou; Zhang, Yu; Ji, Baoming; Tian, Anmin

2011-06-01

The C-Hal (Hal = Cl, Br, or I) bond-length change and the corresponding vibrational frequency shift of the C-Hal stretch upon the C-Hal ⋯Y (Y is the electron donor) halogen bond formation have been determined by using density functional theory computations. Plots of the C-Hal bond-length change versus the corresponding vibrational frequency shift of the C-Hal stretch all give straight lines. The coefficients of determination range from 0.94366 to 0.99219, showing that the correlation between the C-Hal bond-length change and the corresponding frequency shift is very good in the halogen-bonded complexes. The possible effects of vibrational coupling, computational method, and anharmonicity on the bond-length change-frequency shift correlation are discussed in detail.

Efficient Transition State Optimization of Periodic Structures through Automated Relaxed Potential Energy Surface Scans.

PubMed

Plessow, Philipp N

2018-02-13

This work explores how constrained linear combinations of bond lengths can be used to optimize transition states in periodic structures. Scanning of constrained coordinates is a standard approach for molecular codes with localized basis functions, where a full set of internal coordinates is used for optimization. Common plane wave-codes for periodic boundary conditions almost exlusively rely on Cartesian coordinates. An implementation of constrained linear combinations of bond lengths with Cartesian coordinates is described. Along with an optimization of the value of the constrained coordinate toward the transition states, this allows transition optimization within a single calculation. The approach is suitable for transition states that can be well described in terms of broken and formed bonds. In particular, the implementation is shown to be effective and efficient in the optimization of transition states in zeolite-catalyzed reactions, which have high relevance in industrial processes.

Contact angles and wettability of ionic liquids on polar and non-polar surfaces.

PubMed

Pereira, Matheus M; Kurnia, Kiki A; Sousa, Filipa L; Silva, Nuno J O; Lopes-da-Silva, José A; Coutinho, João A P; Freire, Mara G

2015-12-21

Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation-anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation-anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application.

Surface correlation behaviors of metal-organic Langmuir-Blodgett films on differently passivated Si(001) surfaces

NASA Astrophysics Data System (ADS)

Bal, J. K.; Kundu, Sarathi

2013-03-01

Langmuir-Blodgett films of standard amphiphilic molecules like nickel arachidate and cadmium arachidate are grown on wet chemically passivated hydrophilic (OH-Si), hydrophobic (H-Si), and hydrophilic plus hydrophobic (Br-Si) Si(001) surfaces. Top surface morphologies and height-difference correlation functions g(r) with in-plane separation (r) are obtained from the atomic force microscopy studies. Our studies show that deposited bilayer and trilayer films have self-affine correlation behavior irrespective of different passivations and different types of amphiphilic molecules, however, liquid like correlation coexists only for a small part of r, which is located near the cutoff length (1/κ) or little below the correlation length ξ obtained from the liquid like and self-affine fitting, respectively. Thus, length scale dependent surface correlation behavior is observed for both types of Langmuir-Blodgett films. Metal ion specific interactions (ionic, covalent, etc.,) in the headgroup and the nature of the terminated bond (polar, nonpolar, etc.,) of Si surface are mainly responsible for having different correlation parameters.

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.

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

Bent Bonds and Multiple Bonds.

ERIC Educational Resources Information Center

Robinson, Edward A.; Gillespie, Ronald J.

1980-01-01

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

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes.

PubMed

Armitt, David J; Bruce, Michael I; Gaudio, Maryka; Zaitseva, Natasha N; Skelton, Brian W; White, Allan H; Le Guennic, Boris; Halet, Jean-François; Fox, Mark A; Roberts, Rachel L; Hartl, Frantisek; Low, Paul J

2008-12-21

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) and RuCl(dppe)Cp' [Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC(6)F(5))(dppe)Cp' [Cp' = Cp (); Cp* ()], which are related to the known compound Ru(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3))(2)Cp (). Treatment of Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) with Pt(2)(mu-dppm)(2)Cl(2) in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt(2)(mu-dppm)(2)(C[triple bond, length as m-dash]CC(6)F(5))(2) (). The Pd(0)/Cu(i)-catalysed reactions between Au(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3)) and Mo( identical withCBr)(CO)(2)Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co(3)(mu(3)-CBr)(mu-dppm)(CO)(7) or IC[triple bond, length as m-dash]CFc [Fc = (eta(5)-C(5)H(4))FeCp] afford Mo( identical withCC[triple bond, length as m-dash]CC(6)F(5))(CO)(2)Tp* (), Co(3)(mu(3)-CC[triple bond, length as m-dash]CC(6)F(5))(mu-dppm)(CO)(7) () and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC(6)F(5) (), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)F(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()] are prepared from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)F(4) in a manner similar to that described for the monoruthenium complexes -. The non-fluorinated complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)H(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()], prepared for comparison, are obtained from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)H(4). Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes - and -, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes , , , and .

A novel disulfide bond in the SH2 Domain of the C-terminal Src kinase controls catalytic activity.

PubMed

Mills, Jamie E; Whitford, Paul C; Shaffer, Jennifer; Onuchic, Jose N; Adams, Joseph A; Jennings, Patricia A

2007-02-02

The SH2 domain of the C-terminal Src kinase [Csk] contains a unique disulfide bond that is not present in other known SH2 domains. To investigate whether this unusual disulfide bond serves a novel function, the effects of disulfide bond formation on catalytic activity of the full-length protein and on the structure of the SH2 domain were investigated. The kinase activity of full-length Csk decreases by an order of magnitude upon formation of the disulfide bond in the distal SH2 domain. NMR spectra of the fully oxidized and fully reduced SH2 domains exhibit similar chemical shift patterns and are indicative of similar, well-defined tertiary structures. The solvent-accessible disulfide bond in the isolated SH2 domain is highly stable and far from the small lobe of the kinase domain. However, reduction of this bond results in chemical shift changes of resonances that map to a cluster of residues that extend from the disulfide bond across the molecule to a surface that is in direct contact with the small lobe of the kinase domain in the intact molecule. Normal mode analyses and molecular dynamics calculations suggest that disulfide bond formation has large effects on residues within the kinase domain, most notably within the active-site cleft. Overall, the data indicate that reversible cross-linking of two cysteine residues in the SH2 domain greatly impacts catalytic function and interdomain communication in Csk.

Contact angles and wettability of ionic liquids on polar and non-polar surfaces†

PubMed Central

Sousa, Filipa L.; Silva, Nuno J. O.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Freire, Mara G.

2016-01-01

Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation–anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation–anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application. PMID:26554705

Sulfide bonded atomic radii

NASA Astrophysics Data System (ADS)

Gibbs, G. V.; Ross, N. L.; Cox, D. F.

2017-09-01

The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

Origin of the X-Hal (Hal = Cl, Br) bond-length change in the halogen-bonded complexes.

PubMed

Wang, Weizhou; Hobza, Pavel

2008-05-01

The origin of the X-Hal bond-length change in the halogen bond of the X-Hal...Y type has been investigated at the MP2(full)/6-311++G(d,p) level of theory using a natural bond orbital analysis, atoms in molecules procedure, and electrostatic potential fitting methods. Our results have clearly shown that various theories explaining the nature of the hydrogen bond cannot be applied to explain the origin of the X-Hal bond-length change in the halogen bond. We provide a new explanation for this change. The elongation of the X-Hal bond length is caused by the electron-density transfer to the X-Hal sigma* antibonding orbital. For the blue-shifting halogen bond, the electron-density transfer to the X-Hal sigma* antibonding orbital is only of minor importance; it is the electrostatic attractive interaction that causes the X-Hal bond contraction.

Low-loss integrated electrical surface plasmon source with ultra-smooth metal film fabricated by polymethyl methacrylate 'bond and peel' method.

PubMed

Liu, Wenjie; Hu, Xiaolong; Zou, Qiushun; Wu, Shaoying; Jin, Chongjun

2018-06-15

External light sources are mostly employed to functionalize the plasmonic components, resulting in a bulky footprint. Electrically driven integrated plasmonic devices, combining ultra-compact critical feature sizes with extremely high transmission speeds and low power consumption, can link plasmonics with the present-day electronic world. In an effort to achieve this prospect, suppressing the losses in the plasmonic devices becomes a pressing issue. In this work, we developed a novel polymethyl methacrylate 'bond and peel' method to fabricate metal films with sub-nanometer smooth surfaces on semiconductor wafers. Based on this method, we further fabricated a compact plasmonic source containing a metal-insulator-metal (MIM) waveguide with an ultra-smooth metal surface on a GaAs-based light-emitting diode wafer. An increase in propagation length of the SPP mode by a factor of 2.95 was achieved as compared with the conventional device containing a relatively rough metal surface. Numerical calculations further confirmed that the propagation length is comparable to the theoretical prediction on the MIM waveguide with perfectly smooth metal surfaces. This method facilitates low-loss and high-integration of electrically driven plasmonic devices, thus provides an immediate opportunity for the practical application of on-chip integrated plasmonic circuits.

Low-loss integrated electrical surface plasmon source with ultra-smooth metal film fabricated by polymethyl methacrylate ‘bond and peel’ method

NASA Astrophysics Data System (ADS)

Liu, Wenjie; Hu, Xiaolong; Zou, Qiushun; Wu, Shaoying; Jin, Chongjun

2018-06-01

External light sources are mostly employed to functionalize the plasmonic components, resulting in a bulky footprint. Electrically driven integrated plasmonic devices, combining ultra-compact critical feature sizes with extremely high transmission speeds and low power consumption, can link plasmonics with the present-day electronic world. In an effort to achieve this prospect, suppressing the losses in the plasmonic devices becomes a pressing issue. In this work, we developed a novel polymethyl methacrylate ‘bond and peel’ method to fabricate metal films with sub-nanometer smooth surfaces on semiconductor wafers. Based on this method, we further fabricated a compact plasmonic source containing a metal-insulator-metal (MIM) waveguide with an ultra-smooth metal surface on a GaAs-based light-emitting diode wafer. An increase in propagation length of the SPP mode by a factor of 2.95 was achieved as compared with the conventional device containing a relatively rough metal surface. Numerical calculations further confirmed that the propagation length is comparable to the theoretical prediction on the MIM waveguide with perfectly smooth metal surfaces. This method facilitates low-loss and high-integration of electrically driven plasmonic devices, thus provides an immediate opportunity for the practical application of on-chip integrated plasmonic circuits.

Pi Bond Orders and Bond Lengths

ERIC Educational Resources Information Center

Herndon, William C.; Parkanyi, Cyril

1976-01-01

Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

A simplified model for dynamics of cell rolling and cell-surface adhesion

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

Cimrák, Ivan, E-mail: ivan.cimrak@fri.uniza.sk

2015-03-10

We propose a three dimensional model for the adhesion and rolling of biological cells on surfaces. We study cells moving in shear flow above a wall to which they can adhere via specific receptor-ligand bonds based on receptors from selectin as well as integrin family. The computational fluid dynamics are governed by the lattice-Boltzmann method. The movement and the deformation of the cells is described by the immersed boundary method. Both methods are fully coupled by implementing a two-way fluid-structure interaction. The adhesion mechanism is modelled by adhesive bonds including stochastic rules for their creation and rupture. We explore amore » simplified model with dissociation rate independent of the length of the bonds. We demonstrate that this model is able to resemble the mesoscopic properties, such as velocity of rolling cells.« less

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).

Energetic and entropic components of the Tolman length for mW and TIP4P/2005 water nanodroplets

NASA Astrophysics Data System (ADS)

Joswiak, Mark N.; Do, Ryan; Doherty, Michael F.; Peters, Baron

2016-11-01

The surface free energy of a droplet is approximately γ ( R ) = γ ( ∞ ) ( 1 - 2 δ / R ) , with R being the droplet radius and δ being the Tolman length. Here we use the mitosis method to compute δ = - 0.56 ± 0.1 Å at 300 K for mW water, indicating that γ ( R ) increases as the droplet size decreases. The computed Tolman length agrees quite well with a previous study of TIP4P/2005 water. We also decompose the size-dependent surface free energy into energetic and entropic contributions for the mW and TIP4P/2005 force fields. Despite having similar Tolman lengths, the energy-entropy decompositions are very different for the two force fields. We discuss critical assumptions which lead to these findings and their relation to experiments on the nucleation of water droplets. We also discuss surface broken bonds and structural correlations as possible explanations for the energetic and entropic contributions.

Nature and potency interactions of the hydrogen bond through the NBO analysis for charge transfer complex between 2-amino-4-hydroxy-6-methylpyrimidine and 2,3-pyrazinedicarboxylic acid

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Afroz, Ziya; Alam, Mohammad Jane; Bhat, Sheeraz Ahmad; Ahmad, Shabbir; Ahmad, Afaq

2018-05-01

The intermolecular interactions in complex formation between 2-amino-4-hydroxy-6-methylpyrimidine (AHMP) and 2,3-pyrazinedicarboxylicacid (PDCA) have been explored using density functional theory calculations. The isolated 1:1 molecular geometry of proton transfer (PT) complex between AHMP and PDCA has been optimized on a counterpoise corrected potential energy surface (PES) at DFT-B3LYP/6-31G(d,p) level of theory in the gaseous phase. Further, the formation of hydrogen bonded charge transfer (HBCT) complex between PDCA and AHMP has been also discussed. PT energy barrier between two extremes is calculated using potential energy surface (PES) scan by varying bond length. The intermolecular interactions have been analyzed from theoretical perspective of natural bond orbital (NBO) analysis. In addition, the interaction energy between molecular fragments involved in the complex formation has been also computed by counterpoise procedure at same level of theory.

Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

PubMed

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2016-08-01

Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in [4]- and [6]-coordination, Na(+) in [4]- and [6]-coordination. For alkali-metal and alkaline-earth-metal ions, there is a positive correlation between cation coordination number and the grand mean incident bond-valence sum at the central cation, the values varying from 0.84 v.u. for ([5])K(+) to 1.06 v.u. for ([8])Li(+), and from 1.76 v.u. for ([7])Ba(2+) to 2.10 v.u. for ([12])Sr(2+). Bond-valence arguments suggest coordination numbers higher than [12] for K(+), Rb(+), Cs(+) and Ba(2+).

Photovoltaic array mounting apparatus, systems, and methods

DOEpatents

West, John Raymond; Atchley, Brian; Hudson, Tyrus Hawkes; Johansen, Emil

2014-12-02

An apparatus for mounting a photovoltaic (PV) module on a surface, including a support with an upper surface, a lower surface, tabs, one or more openings, and a clip comprising an arm and a notch, where the apparatus resists wind forces and seismic forces and creates a grounding electrical bond between the PV module, support, and clip. The invention further includes a method for installing PV modules on a surface that includes arranging supports in rows along an X axis and in columns along a Y axis on a surface such that in each row the distance between two neighboring supports does not exceed the length of the longest side of a PV module and in each column the distance between two neighboring supports does not exceed the length of the shortest side of a PV module.

Conserved Cysteine Residues Provide a Protein-Protein Interaction Surface in Dual Oxidase (DUOX) Proteins*

PubMed Central

Meitzler, Jennifer L.; Hinde, Sara; Bánfi, Botond; Nauseef, William M.; Ortiz de Montellano, Paul R.

2013-01-01

Intramolecular disulfide bond formation is promoted in oxidizing extracellular and endoplasmic reticulum compartments and often contributes to protein stability and function. DUOX1 and DUOX2 are distinguished from other members of the NOX protein family by the presence of a unique extracellular N-terminal region. These peroxidase-like domains lack the conserved cysteines that confer structural stability to mammalian peroxidases. Sequence-based structure predictions suggest that the thiol groups present are solvent-exposed on a single protein surface and are too distant to support intramolecular disulfide bond formation. To investigate the role of these thiol residues, we introduced four individual cysteine to glycine mutations in the peroxidase-like domains of both human DUOXs and purified the recombinant proteins. The mutations caused little change in the stabilities of the monomeric proteins, supporting the hypothesis that the thiol residues are solvent-exposed and not involved in disulfide bonds that are critical for structural integrity. However, the ability of the isolated hDUOX1 peroxidase-like domain to dimerize was altered, suggesting a role for these cysteines in protein-protein interactions that could facilitate homodimerization of the peroxidase-like domain or, in the full-length protein, heterodimeric interactions with a maturation protein. When full-length hDUOX1 was expressed in HEK293 cells, the mutations resulted in decreased H2O2 production that correlated with a decreased amount of the enzyme localized to the membrane surface rather than with a loss of activity or with a failure to synthesize the mutant proteins. These results support a role for the cysteine residues in intermolecular disulfide bond formation with the DUOX maturation factor DUOXA1. PMID:23362256

Chemical and constitutional influences in the self-assembly of functional supramolecular hydrogen-bonded nanoscopic fibres.

PubMed

Puigmartí-Luis, Josep; Minoia, Andrea; Pérez Del Pino, Angel; Ujaque, Gregori; Rovira, Concepció; Lledós, Agustí; Lazzaroni, Roberto; Amabilino, David B

2006-12-13

A new series of secondary amides bearing long alkyl chains with pi-electron-donor cores has been synthesized and characterised, and their self-assembly upon casting at surfaces has been studied. The different supramolecular assemblies of the materials have been visualized by using atomic force microscopy (AFM) and transmission electron microscopy (TEM). It is possible to obtain well-defined fibres of these aromatic core molecules as a result of the hydrogen bonds between the amide groups. Indeed, by altering the alkyl-chain lengths, constitutions, concentrations and solvent, it is possible to form different rodlike aggregates on graphite. Aggregate sizes with a lower limit of 6-8 nm width have been reached for different amide derivatives, while others show larger aggregates with rodlike morphologies which are several micrometers in length. For one compound that forms nanofibres, doping was performed by using a chemical oxidant, and the resulting layer on graphite was shown to exhibit metallic-like spectroscopy curves when probed with current-sensing AFM. This technique also revealed current maps of the surface of the molecular material. Fibre formation not only takes place on the graphite surface: nanometre scale rods have been imaged by using TEM on a grid after evaporation of solutions of the compounds in chloroform. Molecular modelling proves the importance of the hydrogen bonds in the generation of the fibres, and indicates that the constitution of the molecules is vital for the formation of the desired columnar stacks, results that are consistent with the images obtained by microscopic techniques. The results show the power of noncovalent bonds in self-assembly processes that can lead to electrically conducting nanoscale supramolecular wires.

Anti-Caries Effects of Dental Adhesives Containing Quaternary Ammonium Methacrylates with Different Chain Lengths

PubMed Central

Han, Qi; Li, Bolei; Zhou, Xuedong; Ge, Yang; Wang, Suping; Li, Mingyun; Ren, Biao; Wang, Haohao; Zhang, Keke; Xu, Hockin H. K.; Peng, Xian; Feng, Mingye; Weir, Michael D.; Chen, Yu; Cheng, Lei

2017-01-01

The objectives of this study were to investigate the effects of dental adhesives containing quaternary ammonium methacrylates (QAMs) with different alkyl chain lengths (CL) on ecological caries prevention in vitro. Five QAMs were synthesized with a CL = 3, 6, 9, 12, and 16 and incorporated into adhesives. Micro-tensile bond strength and surface charge density were used to measure the physical properties of the adhesives. The proportion change in three-species biofilms consisting of Streptococcus mutans, Streptococcus sanguinis, and Streptococcus gordonii was tested using the TaqMan real-time polymerase chain reaction. Lactic acid assay, MTT [3-(4,5-dimethyl-thiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay, exopolysaccharide staining, live/dead staining, scanning electron microscopy (SEM), and transverse microradiography (TMR) were performed to study the anti-biofilm and anti-demineralization effects of the dental adhesives. The results showed that incorporating QAMs with different alkyl chain lengths into the adhesives had no obvious effect on the dentin bond strength. The adhesives containing QAMs with a longer alkyl chain developed healthier biofilms. The surface charge density, anti-biofilm, and anti-demineralization effects of the adhesives increased with a CL of the QAMs from 3 to 12, but decreased slightly with a CL from 12 to 16. In conclusion, adhesives containing QAMs with a tailored chain length are promising for preventing secondary caries in an “ecological way”. PMID:28773004

Correlation of the bond-length change and vibrational frequency shift in model hydrogen-bonded complexes of pyrrole

NASA Astrophysics Data System (ADS)

McDowell, Sean A. C.

2017-04-01

An MP2 computational study of model hydrogen-bonded pyrrole⋯YZ (YZ = NH3, NCH, BF, CO, N2, OC, FB) complexes was undertaken in order to examine the variation of the Nsbnd H bond length change and its associated vibrational frequency shift. The chemical hardness of Y, as well as the YZ dipole moment, were found to be important parameters in modifying the bond length change/frequency shift. The basis set effect on the computed properties was also assessed. A perturbative model, which accurately reproduced the ab initio Nsbnd H bond length changes and frequency shifts, was useful in rationalizing the observed trends.

Asp-Gly based peptides confined at the surface of cationic gemini surfactant aggregates.

PubMed

Brizard, Aurélie; Dolain, Christel; Huc, Ivan; Oda, Reiko

2006-04-11

Cationic gemini surfactants complexed with anionic oligoglycine-aspartate (called gemini peptides hereafter) were synthesized, and their aggregation behaviors were studied. The effects of the hydrophobic chain length (C10-C22) and the length of the oligoglycine (0-4) were investigated, and it was clearly shown by critical micellar concentration, Krafft temperature, and isothermal surface pressure measurements that the hydrophobic effect and interpeptidic interaction influence the aggregation behavior in a cooperative manner. Below their Krafft temperatures, some of them formed both hydro- and organogels with three-dimensional networks and the Fourier transform infrared measurements show the presence of interpeptidic hydrogen bonds.

Structural Insights and the Surprisingly Low Mechanical Stability of the Au-S Bond in the Gold-Specific Protein GolB.

PubMed

Wei, Wei; Sun, Yang; Zhu, Mingli; Liu, Xiangzhi; Sun, Peiqing; Wang, Feng; Gui, Qiu; Meng, Wuyi; Cao, Yi; Zhao, Jing

2015-12-16

The coordination bond between gold and sulfur (Au-S) has been widely studied and utilized in many fields. However, detailed investigations on the basic nature of this bond are still lacking. A gold-specific binding protein, GolB, was recently identified, providing a unique opportunity for the study of the Au-S bond at the molecular level. We probed the mechanical strength of the gold-sulfur bond in GolB using single-molecule force spectroscopy. We measured the rupture force of the Au-S bond to be 165 pN, much lower than Au-S bonds measured on different gold surfaces (∼1000 pN). We further solved the structures of apo-GolB and Au(I)-GolB complex using X-ray crystallography. These structures showed that the average Au-S bond length in GolB is much longer than the reported average value of Au-S bonds. Our results highlight the dramatic influence of the unique biological environment on the stability and strength of metal coordination bonds in proteins.

Effect of EDTA and phosphoric Acid pretreatment on the bonding effectiveness of self-etch adhesives to ground enamel.

PubMed

Ibrahim, Ihab M; Elkassas, Dina W; Yousry, Mai M

2010-10-01

This in vitro study determined the effect of enamel pretreatment with phosphoric acid and ethylenediaminetetraacetic acid (EDTA) on the bond strength of strong, intermediary strong, and mild self-etching adhesive systems. Ninety sound human premolars were used. Resin composite cylinders were bonded to flat ground enamel surfaces using three self-etching adhesive systems: strong Adper Prompt L-Pop (pH=0.9-1.0), intermediary strong AdheSE (pH=1.6-1.7), and mild Frog (pH=2). Adhesive systems were applied either according to manufacturer instructions (control) or after pretreatment with either phosphoric acid or EDTA (n=10). After 24 hours, shear bond strength was tested using a universal testing machine at a cross-head speed of 0.5 mm/minute. Ultra-morphological characterization of the surface topography and resin/enamel interfaces as well as representative fractured enamel specimens were examined using scanning electron microscopy (SEM). Neither surface pretreatment statistically increased the mean shear bond strength values of either the strong or the intermediary strong self-etching adhesive systems. However, phosphoric acid pretreatment significantly increased the mean shear bond strength values of the mild self-etching adhesive system. SEM examination of enamel surface topography showed that phosphoric acid pretreatment deepened the same etching pattern of the strong and intermediary strong adhesive systems but converted the irregular etching pattern of the mild self-etching adhesive system to a regular etching pattern. SEM examination of the resin/enamel interface revealed that deepening of the etching pattern was consistent with increase in the length of resin tags. EDTA pretreatment had a negligible effect on ultra-morphological features. Use of phosphoric acid pretreatment can be beneficial with mild self-etching adhesive systems for bonding to enamel.

Effect of EDTA and Phosphoric Acid Pretreatment on the Bonding Effectiveness of Self-Etch Adhesives to Ground Enamel

PubMed Central

Ibrahim, Ihab M.; Elkassas, Dina W.; Yousry, Mai M.

2010-01-01

Objectives: This in vitro study determined the effect of enamel pretreatment with phosphoric acid and ethylenediaminetetraacetic acid (EDTA) on the bond strength of strong, intermediary strong, and mild self-etching adhesive systems. Methods: Ninety sound human premolars were used. Resin composite cylinders were bonded to flat ground enamel surfaces using three self-etching adhesive systems: strong Adper Prompt L-Pop (pH=0.9–1.0), intermediary strong AdheSE (pH=1.6–1.7), and mild Frog (pH=2). Adhesive systems were applied either according to manufacturer instructions (control) or after pretreatment with either phosphoric acid or EDTA (n=10). After 24 hours, shear bond strength was tested using a universal testing machine at a cross-head speed of 0.5 mm/minute. Ultra-morphological characterization of the surface topography and resin/enamel interfaces as well as representative fractured enamel specimens were examined using scanning electron microscopy (SEM). Results: Neither surface pretreatment statistically increased the mean shear bond strength values of either the strong or the intermediary strong self-etching adhesive systems. However, phosphoric acid pretreatment significantly increased the mean shear bond strength values of the mild self-etching adhesive system. SEM examination of enamel surface topography showed that phosphoric acid pretreatment deepened the same etching pattern of the strong and intermediary strong adhesive systems but converted the irregular etching pattern of the mild self-etching adhesive system to a regular etching pattern. SEM examination of the resin/enamel interface revealed that deepening of the etching pattern was consistent with increase in the length of resin tags. EDTA pretreatment had a negligible effect on ultra-morphological features. Conclusions: Use of phosphoric acid pretreatment can be beneficial with mild self-etching adhesive systems for bonding to enamel. PMID:20922162

Theoretical investigations on the structure and properties of p-n-alkoxy benzoic acid based liquid crystals

NASA Astrophysics Data System (ADS)

Subhapriya, P.; Dhanapal, V.; Sadasivam, K.; Vijayanand, P. S.

2016-05-01

The present study focused on the structural conformations, alkoxy chain lengths and mesogenic properties of two mole of alkoxy benzoic acid(nOBA) and one mole of suberic acid (SA) hydrogen bonded (nOBASA) complexes (n=8 to 10) by density functional theory (DFT) calculations and the Fourier Transform Infrared (FT-IR) spectrum. The intermolecular hydrogen bond formation was confirmed by the optimized geometric bond lengths and bond angles obtained by computation. Using the natural bond orbital (NBO) analysis, the stability of the molecule arising from hyper conjugative interactions and charge delocalization has been analyzed. Results obtained shows that the charge in electron density (ED) in σ*and π* antibonding orbital and second order delocalization energies E(2) authorizes the occurrence of intermolecular charge transfer. The molecular electrostatic potential (MEP) surface map is plotted over the optimized geometry of the molecule to obtain the chemical reactivity of the molecule. From the local charge distributions, the mesomorphic behavior and the nematic phase stabilities for each of the molecule have been predicted. Finally the calculated result is applied to simulated infrared spectra of 8OBASA mesogens which shows good agreement with the observed spectra. The comparison of the theoretical results obtained with the experimental ones shows the reliability of this DFT method.

The series of carbon-chain complexes {Ru(dppe)Cp*}₂{μ-(C≡C )x} (x = 4–8, 11): Synthesis, structures, properties and some reactions

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

Bruce, Michael I.; Cole, Marcus L.; Ellis, Benjamin G.

The construction of a series of compounds {Ru(dppe)Cp*} 2(μ-C 2x) (Ru*-C2x-Ru*, x = 4–8, 11)) is described. A direct reaction between RuCl(dppe)Cp* and Me 3Si(Ctriple bond; length of mdashC) 4SiMe 3 afforded Ru*-C8-Ru* in 89% yield. The Pd(0)/Cu(I)-catalysed coupling of Ru{Ctriple bond; length of mdashCCtriple bond; length of mdashCAu(PPh 3)}(dppe)Cp*Ru*-C4-Au (2 equiv.) with diiodoethyne gave Ru*-C10-Ru* (64%), or of 1 equiv. with I(Ctriple bond; length of mdashC) 3I gave Ru*-C14-Ru* (36%); similarly, Ru{(Ctriple bond; length of mdashC) 4Au(PPh 3)}(dppe)Cp*Ru*-C8-Au and I(Ctriple bond; length of mdashC) 3I gave Ru*-C22-Ru* (12%). Desilylation (TBAF) of Ru{(Ctriple bond; length of mdashC)xSiMe 3}(dppe)Cp*Ru*-C2x-Si (x =more » 3, 4) followed by oxidative coupling [Cu(OAc) 2/py] gave Ru*-C12-Ru* (82%) and Ru*-C16-Ru* (58%), respectively. Similar oxidative coupling of Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCH)(dppe)Cp* was a second route to Ru*-C8-Ru* (82%). Appropriate precursors are already known, or obtained by coupling of Ru*-C2x-Si (x = 2, 4) with AuCl(PPh 3)/NaOMe [Ru*-C4-Au, 95%; Ru*-C8-Au, 74%] or from Pd(0)/Cu(I) catalysed coupling of Ru*-C2x-Au (x = 2, 3) with I(Ctriple bond; length of mdashC) 2SiMe 3 (Ru*-C8-Si, 64%; Ru*-C10-Si, 2%). Reactions between Ru*-C2x-Ru* (x = 3, 4) and Fe 2(CO) 9 gave {Fe 3(CO) 9}{μ 3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]} 2Fe(C 3-Ru*) 2 and {Fe 3(CO) 9}{μ 3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}{μ 3-C(Ctriple bond; length of mdashC) 2[Ru(dppe)Cp*]} Fe(C 3-Ru*)(C 5-Ru*), respectively. The redox properties of the series of complexes with 2x = 2–16 were measured and showed a diminution of the separation of the first two oxidation potentials, ΔE = E 2 - E 1, with increasing carbon chain length. The X-ray-determined molecular structures of Ru*-C8-Si, Ru*-C8-Ru*, Ru*-C14-Ru* (two C 6H 6 solvates), {Ru(PPh 3) 2Cp} 2{μ-(Ctriple bond; length of mdashC) 4}·4CHCl 3Ru-C 8-Ru·4CHCl 3 and of Fe(C 3-Ru*) 2 and Fe(C 3-Ru*)(C 5-Ru*) are reported.« less

Effects of structure of fatty acid collectors on the adsorption of fluorapatite (0 0 1) surface: A first-principles calculations

NASA Astrophysics Data System (ADS)

Xie, Jun; Li, Xianhai; Mao, Song; Li, Longjiang; Ke, Baolin; Zhang, Qin

2018-06-01

Effects of carbon chain length, carbon chain isomerism, Cdbnd C double bonds number on fatty acid adsorption on FAP (0 0 1) surface have been investigated based on DFT. The results revealed that fatty acid collector can form stable adsorption configuration at Ca1 (surf) site. Chemical adsorption was formed between O (mole) of fatty acid collector and the Ca1 (surf) of fluorapatite (0 0 1) surface; hydrogen bond adsorption was formed between the H (mole) of fatty acid and the O (surf) of-[PO4]- of FAP (0 0 1) surface. Fatty acid collectors and FAP (0 0 1) surface are bonding by means of the hybridization of O (mole) 2p and Ca (surf) 4d orbitals, H (mole) 1s and O (surf) 2p orbital. The analysis of adsorption energy, DOS, electron density, Mulliken charge population and Mulliken bond population revealed that with the carbon chain growing within certain limits, the absolute value of the adsorption energy and the overlapping area between the DOS curve of O (mole) and Ca (surf) was greater, while that of H (mole) 1s and O (surf) 2p basically remained unchanged. As Cdbnd C double bonds of fatty acids increased within certain limits, the adsorption energy and the overlapping area between the state density curve of O (mole) and Ca (surf), H (mole) and O (surf) basically remained unchanged. The substituent groups of fatty acid changed, the absolute value of the adsorption energy and the overlapping area between the state density curve had a major change. The influence of fatty acids adsorption on FAP (0 0 1) surface depends mainly on the interaction between O (mole) and Ca (surf).

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si-O-CH[double bond, length as m-dash]CH2 and Si-(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments.

PubMed

Bruña, Sonia; González-Vadillo, Ana Mª; Ferrández, Marta; Perles, Josefina; Montero-Campillo, M Merced; Mó, Otilia; Cuadrado, Isabel

2017-09-12

The formation of a family of silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc 2 (CH 3 ) 3 C(CH 2 ) 2 SiCH[double bond, length as m-dash]CH 2 (5), Fc 2 (CH 2 [double bond, length as m-dash]CH-O)SiCH[double bond, length as m-dash]CH 2 (6), Fc 2 (OH)SiCH[double bond, length as m-dash]CH 2 (7), Fc 2 (CH 2 [double bond, length as m-dash]CH-O)Si-O-Si(O-CH[double bond, length as m-dash]CH 2 )Fc 2 (8) and Fc 2 (CH 2 [double bond, length as m-dash]CH-O)Si-O-SiFc 3 (9) is described. Silyl vinyl ether molecules 6, 8 and 9 and the heteroleptic vinylsilane 5 resulted from the competing metathesis reaction of lithioferrocene (FcLi), CH 2 [double bond, length as m-dash]CH-OLi or (CH 3 ) 3 C(CH 2 ) 2 Li with the corresponding multifunctional chlorosilane, Cl 3 SiCH[double bond, length as m-dash]CH 2 or Cl 3 Si-O-SiCl 3 . The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent. Diferrocenylvinyloxyvinylsilane 6 is noteworthy since it represents a rare example of a redox-active silyl mononomer in which two different C[double bond, length as m-dash]C polymerisable groups are directly connected to silicon. The molecular structures of the silicon-containing multiferrocenyl species 5, 6, 8 and 9 have been investigated by single-crystal X-ray diffraction studies, demonstrating the capture and storage processes of two ring fragments resulting from the cleavage of cyclic THF in redox-active and stable crystalline organometallic compounds. From electrochemical studies we found that by changing the anion of the supporting electrolyte from [PF 6 ] - to [B(C 6 F 5 ) 4 ] - , the redox behaviour of tetrametallic disiloxane 8 can be switched from a poorly resolved multistep redox process to four consecutive well-separated one-electron oxidations, corresponding to the sequential oxidation of the four ferrocenyl moieties.

Ab initio Hartree-Fock investigation of 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid

NASA Astrophysics Data System (ADS)

Ramek, Michael; Tomić, Sanja

2001-09-01

The potential energy surface of 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid has been investigated via RIIF/6-31G* calculations. The stationary points and reaction paths for syn orientation of the COOH group were determined and are compared with those of the derivatives of 3-indole acetic acid, which act as plant growth hormones. 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid forms a kinetically stable conformer with a strong intramolecular hydrogen bond, in which the COOH group is in anti orientation. The influence of this hydrogen bond on bond lengths and vibration frequencies is described.

NDE of Space Shuttle Solid Rocket Motor field joint

NASA Technical Reports Server (NTRS)

Johnston, Patrick H.

1987-01-01

One of the most critical areas for inspection in the Space Shuttle Solid Rocket Motors is the bond between the steel case and rubber insulation in the region of the field joints. The tang-and-clevis geometry of the field joints is sufficiently complex to prohibit the use of resonance-based techniques. One approach we are investigating is to interrogate the steel-insulation bondline in the tang and clevis regions using surface-travelling waves. A low-frequency contact surface wave transmitting array transducer is under development at our laboratory for this purpose. The array is placed in acoustic contact with the steel and surface waves are launched on the inside surface or the clevis leg which propagate along the steel-insulation interface. As these surface waves propagate along the bonded surface, the magnitude of the ultrasonic energy leaking into the steel is monitored on the outer surface of the case. Our working hypothesis is that the magnitude of energy received at the outer surface of the case is dependent upon the integrity of the case-insulation bond, with less attenuation for propagation along a disbond due to imperfect acoustic coupling between the steel and rubber. Measurements on test specimens indicate a linear relationship between received signal amplitude and the length of good bend between the transmitter and receiver, suggesting the validity of this working hypothesis.

Thermal Strain Analysis of Optic Fiber Sensors

PubMed Central

Her, Shiuh-Chuan; Huang, Chih-Ying

2013-01-01

An optical fiber sensor surface bonded onto a host structure and subjected to a temperature change is analytically studied in this work. The analysis is developed in order to assess the thermal behavior of an optical fiber sensor designed for measuring the strain in the host structure. For a surface bonded optical fiber sensor, the measuring sensitivity is strongly dependent on the bonding characteristics which include the protective coating, adhesive layer and the bonding length. Thermal stresses can be generated due to a mismatch of thermal expansion coefficients between the optical fiber and host structure. The optical fiber thermal strain induced by the host structure is transferred via the adhesive layer and protective coating. In this investigation, an analytical expression of the thermal strain and stress in the optical fiber is presented. The theoretical predictions are validated using the finite element method. Numerical results show that the thermal strain and stress are linearly dependent on the difference in thermal expansion coefficients between the optical fiber and host structure and independent of the thermal expansion coefficients of the adhesive and coating. PMID:23385407

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Sensitivity of hydrogen bonds of DNA and RNA to hydration, as gauged by 1JNH measurements in ethanol-water mixtures.

PubMed

Manalo, Marlon N; Kong, Xiangming; LiWang, Andy

2007-04-01

Hydrogen-bond lengths of nucleic acids are (1) longer in DNA than in RNA, and (2) sequence dependent. The physicochemical basis for these variations in hydrogen-bond lengths is unknown, however. Here, the notion that hydration plays a significant role in nucleic acid hydrogen-bond lengths is tested. Watson-Crick N1...N3 hydrogen-bond lengths of several DNA and RNA duplexes are gauged using imino 1J(NH) measurements, and ethanol is used as a cosolvent to lower water activity. We find that 1J(NH) values of DNA and RNA become less negative with added ethanol, which suggests that mild dehydration reduces hydrogen-bond lengths even as the overall thermal stabilities of these duplexes decrease. The 1J(NH) of DNA are increased in 8 mol% ethanol to those of RNA in water, which suggests that the greater hydration of DNA plays a significant role in its longer hydrogen bonds. The data also suggest that ethanol-induced dehydration is greater for the more hydrated G:C base pairs and thereby results in greater hydrogen-bond shortening than for the less hydrated A:T/U base pairs of DNA and RNA.

Sacrificial bonds and hidden length in biomaterials -- a kinetic description of strength and toughness in bone

NASA Astrophysics Data System (ADS)

Lieou, Charles K. C.; Elbanna, Ahmed E.; Carlson, Jean M.

2013-03-01

Sacrificial bonds and hidden length in structural molecules account for the greatly increased fracture toughness of biological materials compared to synthetic materials without such structural features, by providing a molecular-scale mechanism of energy dissipation. One example of occurrence of sacrificial bonds and hidden length is in the polymeric glue connection between collagen fibrils in animal bone. In this talk, we propose a simple kinetic model that describes the breakage of sacrificial bonds and the revelation of hidden length, based on Bell's theory. We postulate a master equation governing the rates of bond breakage and formation, at the mean-field level, allowing for the number of bonds and hidden lengths to take up non-integer values between successive, discrete bond-breakage events. This enables us to predict the mechanical behavior of a quasi-one-dimensional ensemble of polymers at different stretching rates. We find that both the rupture peak heights and maximum stretching distance increase with the stretching rate. In addition, our theory naturally permits the possibility of self-healing in such biological structures.

Extra-thermodynamic study on surface diffusion in reversed-phase liquid chromatography using silica gels bonded with alkyl ligands of different chain lengths

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

Miyabe, Kanji; Guiochon, Georges A

2005-06-01

Surface diffusion on adsorbents made of silica gels bonded to C{sub 1}, C{sub 4}, C{sub 8}, and C{sub 18} alkyl ligands was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships: enthalpy-entropy compensation (EEC) and linear free-energy relationship (LFER). First, the values of the surface diffusion coefficient (D{sub s}), normalized by the density of the alkyl ligands, were analyzed with the modified Arrhenius equation, following the four approaches proposed in earlier research. This showed that an actual EEC resulting from substantial physicochemical effects occurs for surface diffusion and suggested a mechanistic similarity of molecular migration bymore » surface diffusion, irrespective of the alkyl chain length. Second, a new model based on EEC was derived to explain the LFER between the logarithms of D{sub s} measured under different RPLC conditions. This showed that the changes of free energy, enthalpy, and entropy of surface diffusion are linearly correlated with the carbon number in the alkyl ligands of the bonded phases and that the contribution of the C{sub 18} ligand to the changes of the thermodynamic parameters corresponds to that of the C{sub 10} ligand. The new LFER model correlates the slope and intercept of the LFER to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, the new model was used to estimate D{sub s} under various RPLC conditions. The values of D{sub s} that were estimated from only two original experimental D{sub s} data were in agreement with corresponding experimental D{sub s} values, with relative errors of {approx}20%, irrespective of some RPLC conditions.« less

The effect of redox-active cyanomanganese(I) ligands on intramolecular electron transfer to, and alkyne alignment in, M(CO)(RC[triple bond, length as m-dash]CR)Tp' (M = Mo or W) units.

PubMed

Adams, Christopher J; Connelly, Neil G; Onganusorn, Sriwipha

2009-04-28

The complexes [(eta-C(5)Me(5))(ON)LMn(micro-CN)M(CO)(RC[triple bond, length as m-dash]CR)Tp'](+) (L = CNXyl, M = Mo; L = CNBu(t), M = Mo or W, R = Ph or Me) and trans- or cis-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-CN)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+), and their linkage isomers [(eta-C(5)Me(5))(ON)LMn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) and trans- or cis-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+), undergo two one-electron oxidations. The complexes [(eta-C(5)Me(5))(ON)LMn(micro-XY)M(CO)(RC[triple bond, length as m-dash]CR)Tp'](+) (XY = CN or NC) are oxidised first at the N-bound metal centre and then at the C-bound centre. For [(dppm){(EtO)(3)P}(OC)(2)Mn(micro-XY)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+), the trans isomers are first oxidised at manganese whereas the cis isomers are first oxidised at M. Thus, the order of one-electron oxidation of the two series of binuclear monocations is influenced by linkage isomerisation of the cyanide bridge and cis-trans isomerisation of the Mn(CO)(2) group. IR spectroscopic changes on reaction of Ag(+) with [(eta-C(5)Me(5))(ON)(Bu(t)NC)Mn(micro-CN)W(CO)(MeC[triple bond, length as m-dash]CMe)Tp'](+) are consistent with one-electron at the N-bound tungsten centre. Likewise, trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) (M = Mo or W) give the stable dications [(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](2+). Significantly longer Mn-P bond distances in trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)Mo(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](2+) than in trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)Mo(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) are consistent with one-electron oxidation first at Mn(I); the alignment of the (CN)Mn(CO)(2){P(OEt)(3)}(dppm) fragment relative to the alkyne in trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)Mo(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) suggests it acts as a pi-acceptor, in contrast to related species such as trans-(NC)Mn(CO)(2){P(OEt)(3)}(dppm) and (NC)Mn(NO){P(OPh)(3)}(pi-C(5)H(4)Me) which behave as simple N-donors.

Efficacy of ceramic repair material on the bond strength of composite resin to zirconia ceramic.

PubMed

Kirmali, Omer; Kapdan, Alper; Harorli, Osman Tolga; Barutcugil, Cagatay; Ozarslan, Mehmet Mustafa

2015-01-01

The aim of this study was to evaluate the shear bond strength of composite resin in five different repair systems. Sixty specimens (7 mm in diameter and 3 mm in height) of zirconia ceramic were fabricated. All specimen surfaces were prepared with a 30 µm fine diamond rotary cutting instrument with water irrigation for 10 s and dried with oil-free air. Specimens were then randomly divided into six groups for the following different intra-oral repair systems (n = 10): Group 1, control group; Group 2, Cojet system (3M ESPE, Seefeld, Germany); Group 3, Cimara® System (Voco, Cuxhaven, Germany); Group 4, Z-Prime Plus System (Bisco Inc., Schaumburg, IL); Group 5, Clearfil™ System (Kuraray, Osaka, Japan); and Group 6, Z-Bond System (Danville, CA). After surface conditioning, a composite resin Grandio (Voco, Cuxhaven, Germany) was applied to the zirconia surface using a cylindrical mold (5 mm in diameter and 3 mm in length) and incrementally filled up, according to the manufacturer's instructions of each intra-oral system. Each specimen was subjected to a shear load at a crosshead speed of 1 mm/min until fracture. One-way analysis of variance (ANOVA) and Tukey post-hoc tests were used to analyze the bond strength values. There were significant differences between Groups 2-6 and Group 1. The highest bond strength values were obtained with Group 2 (17.26 ± 3.22) and Group 3 (17.31 ± 3.62), while the lowest values were observed with Group 1 (8.96 ± 1.62) and Group 6 (12.85 ± 3.95). All repair systems tested increased the bond strength values between zirconia and composite resin that used surface grinding with a diamond bur.

Bond length variation in Zn substituted NiO studied from extended X-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Singh, S. D.; Poswal, A. K.; Kamal, C.; Rajput, Parasmani; Chakrabarti, Aparna; Jha, S. N.; Ganguli, Tapas

2017-06-01

Bond length behavior for Zn substituted NiO is determined through extended x-ray absorption fine structure (EXAFS) measurements performed at ambient conditions. We report bond length value of 2.11±0.01 Å for Zn-O of rock salt (RS) symmetry, when Zn is doped in RS NiO. Bond length for Zn substituted NiO RS ternary solid solutions shows relaxed behavior for Zn-O bond, while it shows un-relaxed behavior for Ni-O bond. These observations are further supported by first-principles calculations. It is also inferred that Zn sublattice remains nearly unchanged with increase in lattice parameter. On the other hand, Ni sublattice dilates for Zn compositions up to 20% to accommodate increase in the lattice parameter. However, for Zn compositions more than 20%, it does not further dilate. It has been attributed to the large disorder that is incorporated in the system at and beyond 20% of Zn incorporation in the cubic RS lattice of ternary solid solutions. For these large percentages of Zn incorporation, the Ni and the Zn atoms re-arrange themselves microscopically about the same nominal bond length rather than systematically increase in magnitude to minimize the energy of the system. This results in an increase in the Debye-Waller factor with increase in the Zn concentration rather than a systematic increase in the bond lengths.

A vector-based representation of the chemical bond for the substituted torsion of biphenyl

NASA Astrophysics Data System (ADS)

Li, Jiahui; Huang, Weijie; Xu, Tianlv; Kirk, Steven R.; Jenkins, Samantha

2018-06-01

We use a new interpretation of the chemical bond within QTAIM, the bond-path framework set B = {p, q, r} with associated linkages with lengths H∗, H and the familiar bond-path length is used to describe a torsion θ, 0.0° ≤ θ < 22.0° of para-substituted biphenyl, C12H9-x, x = N(CH3)2, NH2, CH3, CHO, CN, NO2. We include consideration of the H--H bonding interactions and find that the lengths H > H∗ that we explain in terms of the most and least preferred directions of charge density accumulation. We also consider the fractional eigenvector-following path with lengths Hf and Hfθmin.

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.

The Role of Glottal Surface Adhesion on Vocal Folds Biomechanics

PubMed Central

Bhattacharya, Pinaki; Siegmund, Thomas

2014-01-01

The airway surface liquid (ASL) is a very thin mucus layer and covers the vocal fold (VF) surface. Adhesion mediated by the ASL occurs during phonation as the VFs separate after collision. Such adhesion is hypothesized to determine voice quality and health. However, biomechanical insights into the adhesive processes during VF oscillation are lacking. Here, a computational study is reported on self-sustained VF vibration involving contact and adhesion. The VF structural model and the glottal airflow are considered fully three-dimensional. The mechanical behavior of the ASL is described through a constitutive traction–separation law where mucosal cohesive strength, cohesive energy and rupture length enter. Cohesive energy values considered are bound below by the cohesive energy of water at standard temperature and pressure. Cohesive strength values considered are bound above by prior reported data on the adhesive strength of mucosal surface of rat small intestine. This model introduces a mechanical length scale into the analysis. The sensitivity of various aspects of VF dynamics such as flow-declination rate, VF separation under adhesive condition and formation of multiple local fluid bridges is determined in relation to specific ASL adhesive properties. It is found that for the ASL considered here, the characteristics of the VF separation process are of debond type. Instabilities lead to the breakup of the bond area into several smaller bond patches. Such finding is consistent with in-vivo observations. PMID:25034504

Nanomagnets La0.8Pb0.2(Fe0.8Co0.2)O3 assembled with a bonded surface graphene oxide: sensitive for sensing small gas molecules.

PubMed

Bhargav, K K; Ram, S; Majumder, S B

2012-04-01

Nanocrystallites La0.8Pb0.2(Fe0.8Co0.2)O3 (LPFC) when bonded through a surface layer (carbon) in small ensembles display surface sensitive magnetism useful for biological probes, electrodes, and toxic gas sensors. A simple dispersion and hydrolysis of the salts in ethylene glycol (EG) in water is explored to form ensembles of the nanocrystallites (NCs) by combustion of a liquid precursor gel slowly in microwave at 70-80 dgrees C (apparent) in a closed container in air. In a dilute sample, the EG molecules mediate hydrolyzed species to configure in small groups in process to form a gel. Proposed models describe how a residual carbon bridges a stable bonded layer of a graphene-oxide-like hybrid structure on the LPFC-NCs in attenuating the magnetic structure. SEM images, measured from a pelletized sample which was used to study the gas sensing features in terms of the electrical resistance, describe plate shaped NCs, typically 30-60 nm widths, 60-180 nm lengths and -50 m2/g surface area (after heating at -750 degrees C). These NCs are arranged in ensembles (200-900 nm size). As per the X-ray diffraction, the plates (a Pnma orthorhombic structure) bear only small strain -0.0023 N/m2 and oxygen vacancies. The phonon and electronic bands from a bonded surface layer disappear when it is etched out slowly by heating above 550 degrees C in air. The surface layer actively promotes selective H2 gas sensor properties.

Bond-length distributions for ions bonded to oxygen: results for the non-metals and discussion of lone-pair stereoactivity and the polymerization of PO4

PubMed Central

Gagné, Olivier Charles

2018-01-01

Bond-length distributions are examined for three configurations of the H+ ion, 16 configurations of the group 14–16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen, for 223 coordination polyhedra and 452 bond distances for the H+ ion, 5957 coordination polyhedra and 22 784 bond distances for the group 14–16 non-metal ions, and 248 coordination polyhedra and 1394 bond distances for the group 17 non-metal ions. H⋯O and O—H + H⋯O distances correlate with O⋯O distance (R 2 = 0.94 and 0.96): H⋯O = 1.273 × O⋯O – 1.717 Å; O—H + H⋯O = 1.068 × O⋯O – 0.170 Å. These equations may be used to locate the hydrogen atom more accurately in a structure refined by X-ray diffraction. For non-metal elements that occur with lone-pair electrons, the most observed state between the n versus n+2 oxidation state is that of highest oxidation state for period 3 cations, and lowest oxidation state for period 4 and 5 cations when bonded to O2−. Observed O—X—O bond angles indicate that the period 3 non-metal ions P3+, S4+, Cl3+ and Cl5+ are lone-pair seteroactive when bonded to O2−, even though they do not form secondary bonds. There is no strong correlation between the degree of lone-pair stereoactivity and coordination number when including secondary bonds. There is no correlation between lone-pair stereoactivity and bond-valence sum at the central cation. In synthetic compounds, PO4 polymerizes via one or two bridging oxygen atoms, but not by three. Partitioning our PO4 dataset shows that multi-modality in the distribution of bond lengths is caused by the different bond-valence constraints that arise for Obr = 0, 1 and 2. For strongly bonded cations, i.e. oxyanions, the most probable cause of mean bond length variation is the effect of structure type, i.e. stress induced by the inability of a structure to follow its a priori bond lengths. For ions with stereoactive lone-pair electrons, the most probable cause of variation is bond-length distortion.

Molecular Dynamics Simulation of the Titration of Polyoxocations in Aqueous Solution

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

Rustad, James R.

The aqueous complex ion Al30O8(OH)56(H2O)26 18+(Al30) has a variety of bridging and terminal amphoteric surface functional groups which deprotonate over a pH range of 4–7. Their relative degree of protonation is calculated here from a series of molecular dynamics simulations in what appear to be the first molecular dynamics simulations of an acidometric titration. In these simulations, a model M30O8(OH)56(H2O)26 18+ ion is embedded in aqueous solution and titrated with hydroxide ions in the presence of a charge-compensating background of perchlorate ions. Comparison with titration of a model M13O4(OH)24(H2O)12 7+ reveals that the M30 ion is more acidic than themore » M13 ion due to the presence of acidic nH2O functional groups. The higher acidities of the functional groups on the M30 ion appear to result from enhanced hydration. Metal–oxygen bond lengths are calculated for the ion in solution, an isolated ion in the gas phase, and in its crystalline hydrate sulfate salt. Gas-phase and crystalline bond lengths do not correlate well with those calculated in solution. The acidities do not relate in any simple way to the number of metals coordinating the surface functional group or the M-O bond length. Moreover, the calculated acidity in solution does not correlate with proton affinities calculated for the isolated ion in the absence of solvent. It is concluded that the search for simple indicators of structure–reactivity relationships at the level of individual reactive sites faces major limitations, unless specific information on the hydration states of the functional groups is available.« less

Effects of Diode Laser Debonding of Ceramic Brackets on Enamel Surface and Pulpal Temperature.

PubMed

Yassaei, Soghra; Soleimanian, Azadeh; Nik, Zahra Ebrahimi

2015-04-01

Debonding of ceramic brackets due to their high bond strength and low fracture toughness is one of the most challenging complications of orthodontic clinicians. Application of lasers might be effective in the debonding of ceramic brackets as they reduce bond strength of resins and, therefore, can eliminate the risk of enamel damage. However, the thermal effects of laser radiation on dental tissue can cause undesirable results. The aim of this study is to evaluate the enamel surface characteristics and pulpal temperature changes of teeth after debonding of ceramic brackets with or without laser light. Thirty polycrystalline brackets were bonded to 30 intact extracted premolars, and later debonded conventionally or through a diode laser (2.5 W, 980 nm). The laser was applied for 10 seconds with sweeping movement. After debonding, the adhesive remnant index (ARI), the lengths and frequency of enamel cracks were compared among the groups. The increase in intrapulpal temperature was also measured. The collected data were analyzed by Chi-squared test and paired t-test using Statistical Package for Social Sciences (SPSS) software. There was no case of enamel fracture in none of the groups. Laser debonding caused a significant decrease in the frequency and lengths of enamel cracks, compared to conventional debonding. In laser debonding group, the increase in intrapulpal temperature (1.46°C) was significantly below the benchmark of 5.5°C for all the specimens. No significant difference was observed in ARI scores among the groups. Laser-assisted debonding of ceramic brackets could reduce the risk of enamel damage, without causing thermal damage to the pulp. However, some increases in the length and frequency of enamel cracks should be expected with all debonding methods.

Extreme oxatriquinanes and a record C-O bond length

NASA Astrophysics Data System (ADS)

Gunbas, Gorkem; Hafezi, Nema; Sheppard, William L.; Olmstead, Marilyn M.; Stoyanova, Irini V.; Tham, Fook S.; Meyer, Matthew P.; Mascal, Mark

2012-12-01

Oxatriquinanes are fused, tricyclic oxonium ions that are known to have exceptional stability compared to simple alkyl oxonium salts. C-O bonds in ethers are generally ˜1.43 Å in length, but oxatriquinane has been found to have C-O bond lengths of 1.54 Å. A search of the Cambridge Structural Database turned up no bona fide C-O bond length exceeding this value. Computational modelling of oxatriquinane alongside other alkyl oxonium ions indicated that the electronic consequences of molecular strain were primarily responsible for the observed bond elongation. We also show that substitution of the oxatriquinane ring system with alkyl groups of increasing steric demand pushes the C-O bond to unheard of distances, culminating in a tert-butyl derivative at a predicted 1.60 Å. Chemical synthesis and an X-ray crystallographic study of these compounds validated the results of the modelling work and, finally, an extraordinary 1.622 Å C-O bond was observed in 1,4,7-tri-tert-butyloxatriquinane.

1 mil gold bond wire study.

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

Huff, Johnathon; McLean, Michael B.; Jenkins, Mark W.

2013-05-01

In microcircuit fabrication, the diameter and length of a bond wire have been shown to both affect the current versus fusing time ratio of a bond wire as well as the gap length of the fused wire. This study investigated the impact of current level on the time-to-open and gap length of 1 mil by 60 mil gold bond wires. During the experiments, constant current was provided for a control set of bond wires for 250ms, 410ms and until the wire fused; non-destructively pull-tested wires for 250ms; and notched wires. The key findings were that as the current increases, themore » gap length increases and 73% of the bond wires will fuse at 1.8A, and 100% of the wires fuse at 1.9A within 60ms. Due to the limited scope of experiments and limited data analyzed, further investigation is encouraged to confirm these observations.« less

Periodic density functional theory calculations of bulk and the (010) surface of goethite

PubMed Central

Kubicki, James D; Paul, Kristian W; Sparks, Donald L

2008-01-01

Background Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP). Results Calculations of the bulk mineral structure accurately reproduced the observed crystal structure and vibrational frequencies, suggesting that this computational methodology was suitable for modeling the goethite-water interface. Energy-minimized structures of bare, hydrated (one H2O layer) and solvated (three H2O layers) (010) surfaces were calculated for 1 × 1 and 3 × 3 unit cell slabs. A good correlation between the calculated and observed vibrational frequencies was found for the 1 × 1 solvated surface. However, differences between the 1 × 1 and 3 × 3 slab calculations indicated that larger models may be necessary to simulate the relaxation of water at the interface. Comparison of two hydrated surfaces with molecularly and dissociatively adsorbed H2O showed a significantly lower potential energy for the former. Conclusion Surface Fe-O and (Fe)O-H bond lengths are reported that may be useful in surface complexation models (SCM) of the goethite (010) surface. These bond lengths were found to change significantly as a function of solvation (i.e., addition of two extra H2O layers above the surface), indicating that this parameter should be carefully considered in future SCM studies of metal oxide-water interfaces. PMID:18477389

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.

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

NASA Astrophysics Data System (ADS)

Billinghurst, Brant E.; Gough, Kathleen M.

2003-03-01

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

Simultaneous muscle force and displacement transducer

NASA Technical Reports Server (NTRS)

Feldstein, C.; Lewis, G. W.; Culler, V. H. (Inventor)

1980-01-01

A myocardial transducer for simultaneously measuring force and displacement within a very small area of myocardium is disclosed. The transducer comprised of an elongated body forked at one end to form an inverted Y shaped beam with each branch of the beam constituting a low compliant tine for penetrating the myocardium to a predetermined depth. Bonded to one of the low compliance tines is a small piezoresistive element for converting a force acting on the beam into an electrical signal. A third high compliant tine of the transducer, which measures displacement of the myocardium in a direction in line with the two low compliant tines, is of a length that just pierces the surface membrane. A small piezoresistive element is bonded to the third tine at its upper end where its bending is greatest. Displacement of the myocardium causes a deformation in curvature of the third tine, and the second small piezoresistive element bonded to the surface of its curved end converts its deformation into an electrical signal.

Bulk and surface structural investigations of diesel engine soot and carbon black.

PubMed

Müller, J-O; Su, D S; Wild, U; Schlögl, R

2007-08-14

The microstructure and electronic structure of environmentally relevant carbons such as Euro IV heavy duty diesel engine soot, soot from a black smoking diesel engine, spark discharge soot as model aerosol, commercial furnace soot and lamp black are investigated by transmission electron microscopy, electron energy-loss spectroscopy and X-ray photoelectron spectroscopy. The materials exhibit differences in the predominant bonding, which influences microstructure as well as surface functionalization. These chemical and physical properties depend on the formation history of the investigated carbonaceous materials. In this work, a correlation of the microstructure of the samples to the predominant bonding and incorporation of oxygen into the carbons is obtained. It is shown that a high amount of defects and the deviation of the carbons from a perfect graphitic structure results in a increased incorporation of oxygen and hydrogen. A correlation between the length and curvature of graphene layers with the bonding state of carbon atoms and incorporation of oxygen and hydrogen is established.

Chemical intuition for high thermoelectric performance in monolayer black phosphorus, α-arsenene and aW-antimonene

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

Peng, Bo; Zhang, Hao; Shao, Hezhu

Identifying materials with intrinsically high thermoelectric performance remains a challenge even with the aid of a high-throughput search. Here, using a chemically intuitive approach based on the bond-orbital theory, three anisotropic 2D group-V materials (monolayer black phosphorus, α-arsenene, and aW-antimonene) are identified as candidates for high thermoelectric energy conversion efficiency. Concepts, such as bond length, bond angle, and bond strength, are used to explain the trends in their electronic properties, such as the band gap and the effective mass. Our first principles calculations confirm that high carrier mobilities and large Seebeck coefficients can be obtained at the same time inmore » these materials, due to complex Fermi surfaces originating from the anisotropic structures. An intuitive understanding of how the bonding character affects phonon transport is also provided with emphasis on the importance of bonding strength and bond anharmonicity. High thermoelectric performance is observed in these materials. In conclusion, our approach provides a powerful tool to identify new thermoelectric materials and evaluate their transport properties.« less

Chemical intuition for high thermoelectric performance in monolayer black phosphorus, α-arsenene and aW-antimonene

DOE PAGES

Peng, Bo; Zhang, Hao; Shao, Hezhu; ...

2017-11-21

Identifying materials with intrinsically high thermoelectric performance remains a challenge even with the aid of a high-throughput search. Here, using a chemically intuitive approach based on the bond-orbital theory, three anisotropic 2D group-V materials (monolayer black phosphorus, α-arsenene, and aW-antimonene) are identified as candidates for high thermoelectric energy conversion efficiency. Concepts, such as bond length, bond angle, and bond strength, are used to explain the trends in their electronic properties, such as the band gap and the effective mass. Our first principles calculations confirm that high carrier mobilities and large Seebeck coefficients can be obtained at the same time inmore » these materials, due to complex Fermi surfaces originating from the anisotropic structures. An intuitive understanding of how the bonding character affects phonon transport is also provided with emphasis on the importance of bonding strength and bond anharmonicity. High thermoelectric performance is observed in these materials. In conclusion, our approach provides a powerful tool to identify new thermoelectric materials and evaluate their transport properties.« less

Influence of metal bonding layer on strain transfer performance of FBG

NASA Astrophysics Data System (ADS)

Liu, Hao; Chen, Weimin; Zhang, Peng; Liu, Li; Shu, Yuejie; Wu, Jun

2013-01-01

Metal bonding layer seriously affects the strain transfer performance of Fiber Bragg Grating (FBG). Based on the mode of FBG strain transfer, the influence of the length, the thickness, Poisson's ratio, elasticity modulus of metal bonding layer on the strain transfer coefficient of FBG is analyzed by numerical simulation. FBG is packaged to steel wire using metal bonding technology of FBG. The tensile tests of different bonding lengths and elasticity modulus are carried out. The result shows the strain transfer coefficient of FBGs are 0.9848,0.962 and their average strain sensitivities are 1.076 pm/μɛ,1.099 pm/μɛ when the metal bonding layer is zinc, whose lengths are 15mm, 20mm, respectively. The strain transfer coefficient of FBG packaged by metal bonding layer raises 8.9 percent compared to epoxy glue package. The preliminary experimental results show that the strain transfer coefficient increases with the length of metal bonding layer, decreases with the thickness of metal bonding layer and the influence of Poisson's ratio can be ignored. The experiment result is general agreement with the analysis and provides guidance for metal package of FBG.

Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy.

PubMed

Stiopkin, Igor V; Weeraman, Champika; Pieniazek, Piotr A; Shalhout, Fadel Y; Skinner, James L; Benderskii, Alexander V

2011-06-08

The air-water interface is perhaps the most common liquid interface. It covers more than 70 per cent of the Earth's surface and strongly affects atmospheric, aerosol and environmental chemistry. The air-water interface has also attracted much interest as a model system that allows rigorous tests of theory, with one fundamental question being just how thin it is. Theoretical studies have suggested a surprisingly short 'healing length' of about 3 ångströms (1 Å = 0.1 nm), with the bulk-phase properties of water recovered within the top few monolayers. However, direct experimental evidence has been elusive owing to the difficulty of depth-profiling the liquid surface on the ångström scale. Most physical, chemical and biological properties of water, such as viscosity, solvation, wetting and the hydrophobic effect, are determined by its hydrogen-bond network. This can be probed by observing the lineshape of the OH-stretch mode, the frequency shift of which is related to the hydrogen-bond strength. Here we report a combined experimental and theoretical study of the air-water interface using surface-selective heterodyne-detected vibrational sum frequency spectroscopy to focus on the 'free OD' transition found only in the topmost water layer. By using deuterated water and isotopic dilution to reveal the vibrational coupling mechanism, we find that the free OD stretch is affected only by intramolecular coupling to the stretching of the other OD group on the same molecule. The other OD stretch frequency indicates the strength of one of the first hydrogen bonds encountered at the surface; this is the donor hydrogen bond of the water molecule straddling the interface, which we find to be only slightly weaker than bulk-phase water hydrogen bonds. We infer from this observation a remarkably fast onset of bulk-phase behaviour on crossing from the air into the water phase.

Size-induced changes of structural and ferromagnetic properties in La1-xSrxMnO3 nanoparticles

NASA Astrophysics Data System (ADS)

Hintze, Cornelia E.; Fuchs, Dirk; Merz, Michael; Amari, Houari; Kübel, Christian; Huang, Meng-Jie; Powell, Annie; v. Löhneysen, Hilbert

2017-06-01

La1-xSrxMnO3 nanocrystals were grown using a microemulsion approach with different water-to-surfactant ratios Rw resulting in diameters between 20 and 40 nm. The variation of Rw entails a variation in the Sr concentrations between x = 0.35 and 0.50. This technique allows the controlled growth of structurally well-defined nanoparticles using the same calcination conditions. With decreasing particle size, the unit-cell volume increases together with the Mn-O bond length, while the Mn-O-Mn bond angle was found to decrease. The size-dependent change of structural properties is possibly related to surface effects or disorder. With the decrease in particle size, the ferromagnetic ordering temperature TC decreases significantly by up to 20%. The reduction of TC can be well understood with respect to the structural changes: the increase of Mn-O bond length and the decrease of Mn-O-Mn bond angle weaken the double-exchange coupling and hence reduce T C . In addition the intrinsic finite-size effect reduces T C . The observed size-induced change of magnetic properties may allow for a controlled manipulation of magnetism in La1-xSrxMnO3 nanoparticles by varying the particle size.

Mimicking the Interfacial Dynamics of Flowing White Blood Cells

NASA Astrophysics Data System (ADS)

Santore, Maria

2015-03-01

The rolling of particles on surfaces, facilitated by hydrodynamic forces combined with localized surface interactions of the appropriate strengths, spatial arrangements, and ranges, is a technologically useful means of transporting and manipulating particles. One's intuition for the rolling of a marble or a car tire cannot be extrapolated down to microparticle length scales because the microparticle interactions are dominated by electrostatic, van der Waals, and hydrogen bonding interactions rather than a friction that depends on an imposed normal force. Indeed, our microparticle rolling systems are inspired by the rolling of white blood cells on the inner walls of venules as part of the innate immune response: Selectin molecules engage with their counterparts on the opposing surfaces to slow cell motion relative to that for freely flowing cells. In the resulting rolling signature, ligand-receptor binding and crack closing on the front of the cell are balanced with molecular dis-bonding and crack opening at the rear. The contact region is relatively static, allowing other interactions (for instance signaling) to occur for a finite duration. Thus, achieving particle rolling in synthetic systems is important because it facilitates particle-surface interactions in a continuous nonfouling fashion where the contact surface is continually renewed. In developing a synthetic model for this system, we employ polymers to modify flowing particles and /or planar collectors, producing heterogeneous interfaces which can support rolling or produce other motion signatures such as skipping, arrest, or free flow. We identify, in the synthetic system, combinations of variables that produce rolling and demonstrate how the distinction between rolling and arrest is not a simple matter of the adhesion strength between the particles and the collector. Rolling is a cooperative process and the coordination of binding in one location with dis-bonding in another requires appropriate length scales in the design of the interface and in the processing parameters as well.

Dopant activation mechanism of Bi wire-δ-doping into Si crystal, investigated with wavelength dispersive fluorescence x-ray absorption fine structure and density functional theory.

PubMed

Murata, Koichi; Kirkham, Christopher; Shimomura, Masaru; Nitta, Kiyofumi; Uruga, Tomoya; Terada, Yasuko; Nittoh, Koh-Ichi; Bowler, David R; Miki, Kazushi

2017-04-20

We successfully characterized the local structures of Bi atoms in a wire-δ-doped layer (1/8 ML) in a Si crystal, using wavelength dispersive fluorescence x-ray absorption fine structure at the beamline BL37XU, in SPring-8, with the help of density functional theory calculations. It was found that the burial of Bi nanolines on the Si(0 0 1) surface, via growth of Si capping layer at 400 °C by molecular beam epitaxy, reduced the Bi-Si bond length from [Formula: see text] to [Formula: see text] Å. We infer that following epitaxial growth the Bi-Bi dimers of the nanoline are broken, and the Bi atoms are located at substitutional sites within the Si crystal, leading to the shorter Bi-Si bond lengths.

Tensile bond strength of an adhesive resin cement to different alloys having various surface treatments.

PubMed

Abreu, Amara; Loza, Maria A; Elias, Augusto; Mukhopadhyay, Siuli; Looney, Stephen; Rueggeberg, Frederick A

2009-02-01

The ability of a resin cement to bond to a restorative alloy is critical for maximal crown retention to nonideal preparations. Surface treatment and metal type may have an important role in optimizing resin-to-metal strength. The purpose of this study was to examine the effect of surface pretreatment on the tensile strength of base and noble metals bonded using a conventional resin cement. Cylindrical plastic rods (9.5 mm in diameter), cast in base (Rexillium NBF) or noble metal (IPS d.SIGN 53), were divided into rods 10 mm in length (n=10-12). Specimens were heated in a porcelain furnace to create an oxide layer. Test specimens were further subjected to airborne-particle abrasion (50-microm Al(2)O(3) particles) alone or with the application of a metal primer (Alloy Primer). Similarly treated rod ends were joined using resin cement (RelyX ARC), thermocycled (x500, 5 degrees -55 degrees C) and stored (24 hours, 37 degrees C) before debonding using a universal testing machine. Debond strength and failure site were recorded. Rank-based ANOVA for unbalanced designs was used to test for significant interaction (alpha=.050). Each pair of treatments was compared separately for each metal (Bonferroni-adjusted significance level of .0083, overall error rate for comparisons, .05). The 2 metals were compared separately for each of the 3 treatments using an adjusted significance level of .017, maintaining an overall error rate of .05. A multinomial logit model was used to describe the effect of metal type and surface pretreatment on failure site location (alpha=.05). Interaction between metal type and surface pretreatment was significant for stress values (P=.019). Metal type did not significantly affect tensile bond strength for any of the compared surface pretreatments. Metal primer significantly improved tensile bond strength for each metal type. Most failures tended to occur as either adhesive or mixed in nature. Metal primer application significantly enhanced tensile bond strength to base and noble metal. No significant differences in tensile strength were found between alloys. Differences in failure site incidence were found to be related to metal type and surface pretreatment.

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.

Synthesis and fabrication of sized-controlled nanoparticles: Using surface self-assemblies as building blocks for developing supralattices on nanocomposite materials

NASA Astrophysics Data System (ADS)

Yee, Chanel Kitmon

2001-10-01

A general one-phase synthesis for self-assembling thiols onto gold, platinum, palladium and iridium nanoparticles using tetrahydrofuran (THF) as the solvent, and lithium triethylborohydride (superhydride) as the reducing agent, is presented. Using the same synthetic procedure gold nanoparticles functionalized with 11-hydroxyundecane-1-thiol and 4'-bromo-4-mercaptobiphenyl were prepared to show that the availability and reflexibility of this method could lead to surface fabrication with various type of facial moieties. Alkyl selenide- and alkyl thiolate-functionalized gold nanoparticles were also prepared by the same method at 6°C. The properties were compared to their counterparts made at 25°C. The formation of the Se-Au bond and S-Au bonds was investigated by transmission Fourier transform infrared spectroscopy (FTIR), while the bond nature in each case was examined by x-ray photoelectron spectroscopy (XPS). Particle size was determined by Transmission Electron Microscopy (TEM), and further confirmed by ultraviolet spectroscopy (UV). Superparamagnetic Fe and Fe2O3 nanoparticles were synthesized by ultrasound irradiation and post-fabricated with alkyl sulfonic acids of various chain lengths and octadecyl phosphonic acid. TEM reveals nanoparticles of 5--10 mn in diameter. FTIR spectra suggest that the alkyl chains are packed in a solid-like assembly with packing disorder increasing with the decreasing chain length. The octadecyl sulfonic acid coating displays the lowest magnetization within the sulfonic acid series, which may be explained by the high packing and ordering of the alkyl chains on the particle surface. The smallest value of magnetization in the OPA case suggests that the spin-state of surface Fe3+ ions is affected by the bonded surfactant, and that the phosphonate empty d-orbitals increase magnetic interactions between neighboring Fe3+ spins. To build superstructures beyond the monolayer level, a general route for the attachment of amino-terminated biomolecules to nanoparticles was proposed. Thiophene thiolate-functionalized platinum nanoparticles were prepared and reacted with nitrosonium tetrafluoroborate to provide the nitroso-functionalized nanoparticles. The reaction of the nitroso group with primary amines to yield strong N=N bonds might provide a general route for the attachment of amino-terminated biomolecules to nanoparticles. The attachment of two cytidine molecules to platinum nanoparticles was accomplished, and experimental data were provided to demonstrate the intended grafting reaction.

High-resolution ultrahigh-pressure long column reversed-phase liquid chromatography for top-down proteomics

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

Shen, Yufeng; Tolic, Nikola; Piehowski, Paul D.

We report development of an approach providing high-resolution RPLC of proteins and its utility for mass spectrometry-based top-down proteomics. A chromatographic peak capacity of ~450 was achieved for proteins and large polypeptides having MWs up to 43 kDa in the context of proteomics applications. RPLC column lengths from 20 to 200 cm, particle sizes from 1.5 to 5 m, bonding alkyl chains from C1 to C2, C4, C8, and C18, and particle surface structures that spanned porous, superficially porous (porous shell, core-shell), and nonporous were investigated at pressures up to14K psi. Column length was found as the most important factormore » for >20 kDa proteins in gradient RPLC, and shortening column length degraded RPLC resolution and sensitivity regardless of the size and surface structure of the packing particles used. The alkyl chains bonded to the silica particle surface significantly affected the RPLC recovery and efficiency, and short alkyl C1-C4 phases provided higher sensitivity and resolution than C8 and C18 phases. Long gradient separations (e.g., >10 hours) with long columns (e.g., 100 cm) were particularly effective in conjunction with use of high accuracy mass spectrometers (e.g., the Orbitrap Elite) for top-down proteomics with improved proteoform coverage by allowing multiple HCD, CID, and ETD dissociation modes. It was also found that HCD produced small fragments useful for proteoform identification, while low energy CID and ETD often complemented HCD by providing large fragments.« less

The role of differing probe and target strand lengths in DNA microarrays investigated via Monte Carlo molecular simulation

NASA Astrophysics Data System (ADS)

Rivard, Brea R.; Cooper, Sarah J.; Stubbs, John M.

2018-02-01

DNA duplexes consisting of a 25mer together with shorter complementary sequences were studied over a range of temperature and surface binding motifs using a coarse-grained two-site nucleotide model. Results were analyzed in terms of hydrogen bonding interactions and structural characteristics and indicate that hybridization is most stable when furthest from the surface binding site. Strand elongation and straightening near the bound end are found to be correlated to duplex destabilization.

Bond-Slip Relationship for CFRP Sheets Externally Bonded to Concrete under Cyclic Loading.

PubMed

Li, Ke; Cao, Shuangyin; Yang, Yue; Zhu, Juntao

2018-02-26

The objective of this paper was to explore the bond-slip relationship between carbon fiber-reinforced polymer (CFRP) sheets and concrete under cyclic loading through experimental and analytical approaches. Modified beam tests were performed in order to gain insight into the bond-slip relationship under static and cyclic loading. The test variables are the CFRP-to-concrete width ratio, and the bond length of the CFRP sheets. An analysis of the test results in this paper and existing test results indicated that the slope of the ascending segment of the bond-slip curve decreased with an increase in the number of load cycles, but the slip corresponding to the maximum shear stress was almost invariable as the number of load cycles increased. In addition, the rate of reduction in the slope of the ascending range of the bond-slip curve during cyclic loading decreased as the concrete strength increased, and increased as the load level or CFRP-to-concrete width ratio enhanced. However, these were not affected by variations in bond length if the residual bond length was longer than the effective bond length. A bilinear bond-slip model for CFRP sheets that are externally bonded to concrete under cyclic loading, which considered the effects of the cyclic load level, concrete strength, and CFRP-to-concrete ratio, was developed based on the existing static bond-slip model. The accuracy of this proposed model was verified by a comparison between this proposed model and test results.

Strain engineering of the elasticity and the Raman shift of nanostructured TiO2

NASA Astrophysics Data System (ADS)

Liu, X. J.; Pan, L. K.; Sun, Z.; Chen, Y. M.; Yang, X. X.; Yang, L. W.; Zhou, Z. F.; Sun, Chang Q.

2011-08-01

Correlation between the elastic modulus (B) and the Raman shift (Δω) of TiO2 and their responses to the variation of crystal size, applied pressure, and measuring temperature have been established as a function depending on the order, length, and energy of a representative bond for the entire specimen. In addition to the derived fundamental information of the atomic cohesive energy, binding energy density, Debye temperature and nonlinear compressibility, theoretical reproduction of the observations clarified that (i) the size effect arises from the under-coordination induced cohesive energy loss and the energy density gain in the surface up to skin depth; (ii) the thermally softened B and Δω results from bond expansion and bond weakening due to vibration; and, (iii) the mechanically stiffened B and Δω results from bond compression and bond strengthening due to mechanical work hardening. With the developed premise, one can predict the changing trends of the concerned properties with derivatives of quantitative information as such from any single measurement alone.

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.

Some general aspects of torsional sensitivity and the GG-effect

NASA Astrophysics Data System (ADS)

Yu, C.-H.; Schäfer, L.; Ramek, M.; Miller, D. M.; Teppen, B. J.

1999-08-01

The geometries of 28 compounds of type X-C1-C2-C3-Y, with X,Y=CH 3, F, Cl, OH, NH 2, COH, and COOH, were fully optimized by ab initio HF/4-21G calculations at 30° grid points in their respective φ(X-C1-C2-C3), ψ(C1-C2-C3-Y)-torsional spaces. The results make it possible to construct parameter surfaces and their gradients in φ, ψ-space. The magnitude of the gradient, |∇ P|=[( ∂P/ ∂φ) 2+( ∂P/ ∂ψ) 2] 1/2, of a structural parameter P (a bond length, bond angle, or non-bonded distance) in φ, ψ-torsional space is a measure of torsional sensitivity (TS); i.e. a measure of the extent to which bond lengths, bond angles, and non-bonded distances change at a point in φ, ψ-space with backbone torsional angles. It is found that TS is not constant throughout the conformational space of a molecule, but varies in a characteristic way. It seems that, regardless of the nature of X or Y, extended forms are typically in regions of low TS; puckered conformations, of high TS. Conformations with two sequential gauche torsional angles (GG sequences) are characterized by high TS of 1,5-non-bonded distances concomitant with relatively low TS of other internal coordinates. This property of GG sequences is the source of a stabilizing and cooperative energy increment that is not afforded by other torsional sequences, such as trans- trans or trans- gauche. A structural data base, consisting of thousands of HF/4-21G structures of X-C-C-Y and X-C-C-C-Y systems has been assembled and is available on a CD.

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V 2+ /V 3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V 2+ /V 3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Single-Molecule Tribology: Force Microscopy Manipulation of a Porphyrin Derivative on a Copper Surface.

PubMed

Pawlak, Rémy; Ouyang, Wengen; Filippov, Alexander E; Kalikhman-Razvozov, Lena; Kawai, Shigeki; Glatzel, Thilo; Gnecco, Enrico; Baratoff, Alexis; Zheng, Quanshui; Hod, Oded; Urbakh, Michael; Meyer, Ernst

2016-01-26

The low-temperature mechanical response of a single porphyrin molecule attached to the apex of an atomic force microscope (AFM) tip during vertical and lateral manipulations is studied. We find that approach-retraction cycles as well as surface scanning with the terminated tip result in atomic-scale friction patterns induced by the internal reorientations of the molecule. With a joint experimental and computational effort, we identify the dicyanophenyl side groups of the molecule interacting with the surface as the dominant factor determining the observed frictional behavior. To this end, we developed a generalized Prandtl-Tomlinson model parametrized using density functional theory calculations that includes the internal degrees of freedom of the side group with respect to the core and its interactions with the underlying surface. We demonstrate that the friction pattern results from the variations of the bond length and bond angles between the dicyanophenyl side group and the porphyrin backbone as well as those of the CN group facing the surface during the lateral and vertical motion of the AFM tip.

The Effective Potential Energy Surfaces of the Nonadiabatic Collision

DTIC Science & Technology

2009-03-01

effective PESs data was extracted for the equilibrium H2 bond length and used to calculate inelastic scattering matrix elements using the time ...very grateful not only for the time he devoted each week to discussing the status of the work, but also his infectious love of learning that is...33 Structure of the Asymptotic Representation ................................................................. 43 The Time -Dependent

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.

The hydration of amides in helices; a comprehensive picture from molecular dynamics, IR, and NMR

PubMed Central

Walsh, Scott T.R.; Cheng, Richard P.; Wright, Wayne W.; Alonso, Darwin O.V.; Daggett, Valerie; Vanderkooi, Jane M.; DeGrado, William F.

2003-01-01

We examined the hydration of amides of α3D, a simple, designed three-helix bundle protein. Molecular dynamics calculations show that the amide carbonyls on the surface of the protein tilt away from the helical axis to interact with solvent water, resulting in a lengthening of the hydrogen bonds on this face of the helix. Water molecules are bonded to these carbonyl groups with partial occupancy (∼50%–70%), and their interaction geometries show a large variation in their hydrogen bond lengths and angles on the nsec time scale. This heterogeneity is reflected in the carbonyl stretching vibration (amide I′ band) of a group of surface Ala residues. The surface-exposed amides are broad, and shift to lower frequency (reflecting strengthening of the hydrogen bonds) as the temperature is decreased. By contrast, the amide I′ bands of the buried 13C-labeled Leu residues are significantly sharper and their frequencies are consistent with the formation of strong hydrogen bonds, independent of temperature. The rates of hydrogen-deuterium exchange and the proton NMR chemical shifts of the helical amide groups also depend on environment. The partial occupancy of the hydration sites on the surface of helices suggests that the interaction is relatively weak, on the order of thermal energy at room temperature. One unexpected feature that emerged from the dynamics calculations was that a Thr side chain subtly disrupted the helical geometry 4–7 residues N-terminal in sequence, which was reflected in the proton chemical shifts and the rates of amide proton exchange for several amides that engage in a mixed 310/α/π-helical conformation. PMID:12592022

Competing Thermodynamic and Dynamic Factors Select Molecular Assemblies on a Gold Surface

NASA Astrophysics Data System (ADS)

Haxton, Thomas K.; Zhou, Hui; Tamblyn, Isaac; Eom, Daejin; Hu, Zonghai; Neaton, Jeffrey B.; Heinz, Tony F.; Whitelam, Stephen

2013-12-01

Controlling the self-assembly of surface-adsorbed molecules into nanostructures requires understanding physical mechanisms that act across multiple length and time scales. By combining scanning tunneling microscopy with hierarchical ab initio and statistical mechanical modeling of 1,4-substituted benzenediamine (BDA) molecules adsorbed on a gold (111) surface, we demonstrate that apparently simple nanostructures are selected by a subtle competition of thermodynamics and dynamics. Of the collection of possible BDA nanostructures mechanically stabilized by hydrogen bonding, the interplay of intermolecular forces, surface modulation, and assembly dynamics select at low temperature a particular subset: low free energy oriented linear chains of monomers and high free energy branched chains.

Rapid and Facile Microwave-Assisted Surface Chemistry for Functionalized Microarray Slides

PubMed Central

Lee, Jeong Heon; Hyun, Hoon; Cross, Conor J.; Henary, Maged; Nasr, Khaled A.; Oketokoun, Rafiou; Choi, Hak Soo; Frangioni, John V.

2011-01-01

We describe a rapid and facile method for surface functionalization and ligand patterning of glass slides based on microwave-assisted synthesis and a microarraying robot. Our optimized reaction enables surface modification 42-times faster than conventional techniques and includes a carboxylated self-assembled monolayer, polyethylene glycol linkers of varying length, and stable amide bonds to small molecule, peptide, or protein ligands to be screened for binding to living cells. We also describe customized slide racks that permit functionalization of 100 slides at a time to produce a cost-efficient, highly reproducible batch process. Ligand spots can be positioned on the glass slides precisely using a microarraying robot, and spot size adjusted for any desired application. Using this system, we demonstrate live cell binding to a variety of ligands and optimize PEG linker length. Taken together, the technology we describe should enable high-throughput screening of disease-specific ligands that bind to living cells. PMID:23467787

Photonic polymer-blend structures and method for making

DOEpatents

Barnes, Michael D.

2004-06-29

The present invention comprises the formation of photonic polymer-blend structures having tunable optical and mechanical properties. The photonic polymer-blend structures comprise monomer units of spherical microparticles of a polymer-blend material wherein the spherical microparticles have surfaces partially merged with one another in a robust inter-particle bond having a tunable inter-particle separation or bond length sequentially attached in a desired and programmable architecture. The photonic polymer-blend structures of the present invention can be linked by several hundred individual particles sequentially linked to form complex three-dimensional structures or highly ordered two-dimensional arrays of 3D columns with 2D spacing.

A Computational Study on the Ground and Excited States of Nickel Silicide.

PubMed

Schoendorff, George; Morris, Alexis R; Hu, Emily D; Wilson, Angela K

2015-09-17

Nickel silicide has been studied with a range of computational methods to determine the nature of the Ni-Si bond. Additionally, the physical effects that need to be addressed within calculations to predict the equilibrium bond length and bond dissociation energy within experimental error have been determined. The ground state is predicted to be a (1)Σ(+) state with a bond order of 2.41 corresponding to a triple bond with weak π bonds. It is shown that calculation of the ground state equilibrium geometry requires a polarized basis set and treatment of dynamic correlation including up to triple excitations with CR-CCSD(T)L resulting in an equilibrium bond length of only 0.012 Å shorter than the experimental bond length. Previous calculations of the bond dissociation energy resulted in energies that were only 34.8% to 76.5% of the experimental bond dissociation energy. It is shown here that use of polarized basis sets, treatment of triple excitations, correlation of the valence and subvalence electrons, and a Λ coupled cluster approach is required to obtain a bond dissociation energy that deviates as little as 1% from experiment.

The state diagram for cell adhesion under flow: leukocyte rolling and firm adhesion.

PubMed

Chang, K C; Tees, D F; Hammer, D A

2000-10-10

Leukocyte adhesion under flow in the microvasculature is mediated by binding between cell surface receptors and complementary ligands expressed on the surface of the endothelium. Leukocytes adhere to endothelium in a two-step mechanism: rolling (primarily mediated by selectins) followed by firm adhesion (primarily mediated by integrins). Using a computational method called "Adhesive Dynamics," we have simulated the adhesion of a cell to a surface in flow, and elucidated the relationship between receptor-ligand functional properties and the dynamics of adhesion. We express this relationship in a state diagram, a one-to-one map between the biophysical properties of adhesion molecules and various adhesive behaviors. Behaviors that are observed in simulations include firm adhesion, transient adhesion (rolling), and no adhesion. We varied the dissociative properties, association rate, bond elasticity, and shear rate and found that the unstressed dissociation rate, k(r)(o), and the bond interaction length, gamma, are the most important molecular properties controlling the dynamics of adhesion. Experimental k(r)(o) and gamma values from the literature for molecules that are known to mediate rolling adhesion fall within the rolling region of the state diagram. We explain why L-selectin-mediated rolling, which has faster k(r)(o) than other selectins, is accompanied by a smaller value for gamma. We also show how changes in association rate, shear rate, and bond elasticity alter the dynamics of adhesion. The state diagram (which must be mapped for each receptor-ligand system) presents a concise and comprehensive means of understanding the relationship between bond functional properties and the dynamics of adhesion mediated by receptor-ligand bonds.

Electric double layer at metal oxide surfaces:static properties of the cassiterite-water interface.

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

Vlcek, L.; Zhang, Z.; Machesky, M .L.

2007-03-24

The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively chargedmore » variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).« less

Electric double layer at metal oxide surfaces: Static properties of the cassiterite - Water Interface

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

Vlcek, Lukas; Zhang, Zhan; Machesky, Michael L.

2007-01-01

The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively chargedmore » variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).« less

Effect of the electrostatic surface potential on the oligomerization of full-length human recombinant prion protein at single-molecule level

NASA Astrophysics Data System (ADS)

Wang, Bin; Lou, Zhichao; Zhang, Haiqian; Xu, Bingqian

2016-03-01

The electrostatic surface potential (ESP) of prion oligomers has critical influences on the aggregating processes of the prion molecules. The atomic force microscopy (AFM) and structural simulation were combined to investigate the molecular basis of the full-length human recombinant prion oligomerization on mica surfaces. The high resolution non-intrusive AFM images showed that the prion oligomers formed different patterns on mica surfaces at different buffer pH values. The basic binding units for the large oligomers were determined to be prion momoners (Ms), dimers (Ds), and trimers (Ts). The forming of the D and T units happened through the binding of hydrophobic β-sheets of the M units. In contrast, the α-helices of these M, D, and T units were the binding areas for the formation of large oligomers. At pH 4.5, the binding units M, D, and T showed clear polarized ESP distributions on the surface domains, while at pH 7.0, they showed more evenly distributed ESPs. Based on the conformations of oligomers observed from AFM images, the D and T units were more abundantly on mica surface at pH 4.5 because the ESP re-distribution of M units helped to stabilize these larger oligomers. The amino acid side chains involved in the binding interfaces were stabilized by hydrogen bonds and electrostatic interactions. The detailed analysis of the charged side chains at pH 4.5 indicated that the polarized ESPs induced the aggregations among M, D, and T to form larger oligomers. Therefore, the hydrogen bonds and electrostatic interactions worked together to form the stabilized prion oligomers.

Effect of the electrostatic surface potential on the oligomerization of full-length human recombinant prion protein at single-molecule level

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

Wang, Bin; Xu, Bingqian, E-mail: bxu@engr.uga.edu; Lou, Zhichao

2016-03-21

The electrostatic surface potential (ESP) of prion oligomers has critical influences on the aggregating processes of the prion molecules. The atomic force microscopy (AFM) and structural simulation were combined to investigate the molecular basis of the full-length human recombinant prion oligomerization on mica surfaces. The high resolution non-intrusive AFM images showed that the prion oligomers formed different patterns on mica surfaces at different buffer pH values. The basic binding units for the large oligomers were determined to be prion momoners (Ms), dimers (Ds), and trimers (Ts). The forming of the D and T units happened through the binding of hydrophobicmore » β-sheets of the M units. In contrast, the α-helices of these M, D, and T units were the binding areas for the formation of large oligomers. At pH 4.5, the binding units M, D, and T showed clear polarized ESP distributions on the surface domains, while at pH 7.0, they showed more evenly distributed ESPs. Based on the conformations of oligomers observed from AFM images, the D and T units were more abundantly on mica surface at pH 4.5 because the ESP re-distribution of M units helped to stabilize these larger oligomers. The amino acid side chains involved in the binding interfaces were stabilized by hydrogen bonds and electrostatic interactions. The detailed analysis of the charged side chains at pH 4.5 indicated that the polarized ESPs induced the aggregations among M, D, and T to form larger oligomers. Therefore, the hydrogen bonds and electrostatic interactions worked together to form the stabilized prion oligomers.« less

One-step solvothermal deposition of ZnO nanorod arrays on a wood surface for robust superamphiphobic performance and superior ultraviolet resistance

PubMed Central

Yao, Qiufang; Wang, Chao; Fan, Bitao; Wang, Hanwei; Sun, Qingfeng; Jin, Chunde; Zhang, Hong

2016-01-01

In the present paper, uniformly large-scale wurtzite-structured ZnO nanorod arrays (ZNAs) were deposited onto a wood surface through a one-step solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), and differential thermal analysis (DTA). ZNAs with a diameter of approximately 85 nm and a length of approximately 1.5 μm were chemically bonded onto the wood surface through hydrogen bonds. The superamphiphobic performance and ultraviolet resistance were measured and evaluated by water or oil contact angles (WCA or OCA) and roll-off angles, sand abrasion tests and an artificially accelerated ageing test. The results show that the ZNA-treated wood demonstrates a robust superamphiphobic performance under mechanical impact, corrosive liquids, intermittent and transpositional temperatures, and water spray. Additionally, the as-prepared wood sample shows superior ultraviolet resistance. PMID:27775091

One-step solvothermal deposition of ZnO nanorod arrays on a wood surface for robust superamphiphobic performance and superior ultraviolet resistance

NASA Astrophysics Data System (ADS)

Yao, Qiufang; Wang, Chao; Fan, Bitao; Wang, Hanwei; Sun, Qingfeng; Jin, Chunde; Zhang, Hong

2016-10-01

In the present paper, uniformly large-scale wurtzite-structured ZnO nanorod arrays (ZNAs) were deposited onto a wood surface through a one-step solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), and differential thermal analysis (DTA). ZNAs with a diameter of approximately 85 nm and a length of approximately 1.5 μm were chemically bonded onto the wood surface through hydrogen bonds. The superamphiphobic performance and ultraviolet resistance were measured and evaluated by water or oil contact angles (WCA or OCA) and roll-off angles, sand abrasion tests and an artificially accelerated ageing test. The results show that the ZNA-treated wood demonstrates a robust superamphiphobic performance under mechanical impact, corrosive liquids, intermittent and transpositional temperatures, and water spray. Additionally, the as-prepared wood sample shows superior ultraviolet resistance.

Fixman compensating potential for general branched molecules

NASA Astrophysics Data System (ADS)

Jain, Abhinandan; Kandel, Saugat; Wagner, Jeffrey; Larsen, Adrien; Vaidehi, Nagarajan

2013-12-01

The technique of constraining high frequency modes of molecular motion is an effective way to increase simulation time scale and improve conformational sampling in molecular dynamics simulations. However, it has been shown that constraints on higher frequency modes such as bond lengths and bond angles stiffen the molecular model, thereby introducing systematic biases in the statistical behavior of the simulations. Fixman proposed a compensating potential to remove such biases in the thermodynamic and kinetic properties calculated from dynamics simulations. Previous implementations of the Fixman potential have been limited to only short serial chain systems. In this paper, we present a spatial operator algebra based algorithm to calculate the Fixman potential and its gradient within constrained dynamics simulations for branched topology molecules of any size. Our numerical studies on molecules of increasing complexity validate our algorithm by demonstrating recovery of the dihedral angle probability distribution function for systems that range in complexity from serial chains to protein molecules. We observe that the Fixman compensating potential recovers the free energy surface of a serial chain polymer, thus annulling the biases caused by constraining the bond lengths and bond angles. The inclusion of Fixman potential entails only a modest increase in the computational cost in these simulations. We believe that this work represents the first instance where the Fixman potential has been used for general branched systems, and establishes the viability for its use in constrained dynamics simulations of proteins and other macromolecules.

Pauling bond strength, bond length and electron density distribution

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

Gibbs, Gerald V.; Ross, Nancy L.; Cox, David F.

2014-01-18

A power law regression equation, = 1.46(/r)-0.19, connecting the average experimental bond lengths, , with the average accumulation of the electron density at the bond critical point, , between bonded metal M and oxygen atoms, determined at ambient conditions for oxide crystals, where r is the row number of the M atom, is similar to the regression equation R(M-O) = 1.39(ρ(rc)/r)-0.21 determined for three perovskite crystals for pressures as high as 80 GPa. The two equations are also comparable with those, = 1.43( /r)-0.21, determined for a large number of oxide crystals at ambient conditions and = 1.39(/r)-0.22, determined formore » geometry optimized hydroxyacid molecules, that connect the bond lengths to the average Pauling electrostatic bond strength, , for the M-O bonded interactions. On the basis of the correspondence between the two sets of equations connecting ρ(rc) and the Pauling bond strength s with bond length, it appears that Pauling’s simple definition of bond strength closely mimics the accumulation of the electron density between bonded pairs of atoms. The similarity of the expressions for the crystals and molecules is compelling evidence that the M-O bonded interactions for the crystals and molecules 2 containing the same bonded interactions are comparable. Similar expressions, connecting bond lengths and bond strength, have also been found to hold for fluoride, nitride and sulfide molecules and crystals. The Brown-Shannon bond valence, σ, power law expression σ = [R1/(R(M-O)]N that has found wide use in crystal chemistry, is shown to be connected to a more universal expression determined for oxides and the perovskites, = r[(1.41)/]4.76, demonstrating that the bond valence for a bonded interaction is likewise closely connected to the accumulation of the electron density between the bonded atoms. Unlike the Brown-Shannon expression, it is universal in that it holds for the M-O bonded interactions for a relatively wide range of M atoms of the periodic table. The power law equation determined for the oxide crystals at ambient conditions is similar to the power law expression = r[1.46/]5.26 determined for the perovskites at pressures as high as 80 GPa, indicating that the intrinsic connection between R(M-O) and ρ(rc) that holds at ambient conditions also holds, to a first approximation, at high pressures.« less

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.

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

DOE PAGES

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali; ...

2017-05-12

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

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

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Analisis parametrico de las variables que influyen en el comportamiento adherente de las armaduras pretesas en el hormigon

NASA Astrophysics Data System (ADS)

Arbelaez Jaramillo, Cesar Augusto

Prestressed concrete technique through the use of prestressed reinforcement is extended in the precast concrete industry. This technique consists on casting a concrete element over a previously prestressed reinforcement, proceeding to release once the concrete has reached a determined strength so the prestressed stress introduced to the reinforcement be transmitted, by bond, to concrete. The bond behaviour of prestressed reinforcement includes two phenomena: prestress transmission from the reinforcement to concrete and anchorage of the reinforcement. This bond behaviour is characterized by mean of two lengths: transmission length and anchorage length. The good design of these lengths is a basic and fundamental aspect in the project of precast prestressed concrete elements to guaranty the appropriate transmission of prestress and to allow the anchorage of the reinforcement along the structural element service life. The influence of the parameters related to the concrete dosage on the transmission and anchorage lengths of prestressing strands have been analyzed. The ECADA test method has been applied. With this method the operations of transmission of prestress and anchorage of the reinforcement are sequentially done. The transmission and anchorage lengths are determined from the force control supported by the reinforcement testing series of specimens with different embedment lengths. The differentiation of the concepts of anchorage length without slips and with slips has been proposed. The relationship of the parameters of dosage with the bond stress and the registered slips during the processes of transmission and anchorage has been studied. Expressions to value the slips distribution of the reinforcement in the transmission zone and in the anchorage zone have been proposed. A study on the determination of the transmission length from the free reinforcement slip end has been done and the viability to experimentally determine the transmission length from the slips sequence in the pull-out end as a function of the embedment length has been verified. The experimental results have been compared with results and predictions from other authors and standards, and an expression to calculate the transmission length have been proposed. Finally, the bond behaviour of self-compacting concretes has been compared with the bond behaviour of traditional concretes.

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

Peeling a polymer from a surface or from a line

NASA Astrophysics Data System (ADS)

Di Marzio, Edmund A.; Guttman, C. M.

1991-07-01

We calculate the force on a long linear polymer molecule whose one end is zippered down onto a surface or onto a line and whose other end is at a perpendicular distance R from the surface or line. Random coil statistics are used for the unattached portion of the chain. The method is extended to the case when the bonds within the zippered portion are breaking and reforming. We also consider the case where the attached portion is in the form of loops and trains. Although the energy equations of state for these various systems are different from each other, the force equation of state is always given by f=((6)1/2/l)(kTΔg)1/2, where l is the bond length between monomers and Δg is the free energy change in pulling one monomer off of the surface. The force is independent of R except for small R. Applications are discussed briefly. They include (1) self-healing systems of gels and rubbers where the cross links may be hydrogen bonds; (2) adhesion; (3) the degree of crystallinity in crystal-amorphous lamellar systems; (4) the packing of DNA into the head of a bacteriophage virus and pulling apart of double stranded DNA; (5) an insight into the theory of rubber elasticity; (6) understanding the critical force for flow in thixotropic systems.

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.

Viscous friction of hydrogen-bonded matter

NASA Astrophysics Data System (ADS)

Erbas, Aykut; Horinek, Dominik; Netz, Roland R.

2012-02-01

Amontons' law successfully describes friction between macroscopic solid bodies for a wide range of velocities and normal forces. For the diffusion and forced sliding of adhering or entangled macromolecules, proteins and biological complexes, temperature effects are invariably important and a similarly successful friction law at biological length and velocity scales is missing. Hydrogen bonds are key to the specific binding of bio-matter. Here we show that friction between hydrogen-bonded matter obeys in the biologically relevant low-velocity viscous regime a simple equations: the friction force is proportional to the number of hydrogen bonds, the sliding velocity, and a friction coefficient γHB. This law is deduced from atomistic molecular dynamics simulations for short peptide chains that are laterally pulled over hydroxylated substrates in the presence of water and holds for widely different peptides, surface polarities and applied normal forces. The value of γHB is extrapolated from simulations at sliding velocities in the range from v=10-2 m/s to 100 m/s by mapping on a simple stochastic model and turns out to be of the order of γHB˜10-8 kg/s. 3 hydrogen bonds act collectively.

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.

Fabrication of sophisticated two-dimensional organic nanoarchitectures thought hydrogen bond mediated molecular self assembly

NASA Astrophysics Data System (ADS)

Silly, Fabien

2012-02-01

Complex supramolecular two-dimensional (2D) networks are attracting considerable interest as highly ordered functional materials for applications in nanotechnology. The challenge consists in tailoring the ordering of one or more molecular species into specific architectures over an extended length scale with molecular precision. Highly organized supramolecular arrays can be obtained through self-assembly of complementary molecules which can interlock via intermolecular interactions. Molecules forming hydrogen bonds (H-bonds) are especially interesting building blocks for creating sophisticated organic architectures due to high selectivity and directionality of these bindings. We used scanning tunnelling microscopy to investigate at the atomic scale the formation of H-bonded 2D organic nanoarchitectures on surfaces. We mixed perylene derivatives having rectangular shape with melamine and DNA base having triangular and non symmetric shape respectively. We observe that molecule substituents play a key role in formation of the multicomponent H-bonded architectures. We show that the 2D self-assembly of these molecules can be tailored by adjusting the temperature and molecular ratio. We used these stimuli to successfully create numerous close-packed and porous 2D multicomponent structures.

Recrystallization texture in nickel heavily deformed by accumulative roll bonding

NASA Astrophysics Data System (ADS)

Mishin, O. V.; Zhang, Y. B.; Godfrey, A.

2017-07-01

The recrystallization behavior of Ni processed by accumulative roll bonding to a total accumulated von Mises strain of 4.8 has been examined, and analyzed with respect to heterogeneity in the deformation microstructure. The regions near the bonding interface are found to be more refined and contain particle deformation zones around fragments of the steel wire brush used to prepare the surface for bonding. Sample-scale gradients are also observed, manifested as differences between the subsurface, intermediate and central layers, where the distributions of texture components are different. These heterogeneities affect the progress of recrystallization. While the subsurface and near-interface regions typically contain lower frequencies of cube-oriented grains than anywhere else in the sample, a strong cube texture forms in the sample during recrystallization, attributed to both a high nucleation rate and fast growth rate of cube-oriented grains. The observations highlight the sensitivity of recrystallization to heterogeneity in the deformation microstructure and demonstrate the importance of characterizing this heterogeneity over several length scales.

Adsorbate-induced reconstruction in the phase 1 × 2-3H/Rh(110)

NASA Astrophysics Data System (ADS)

Michl, M.; Nichtl-Pecher, W.; Oed, W.; Landskron, H.; Heinz, K.; Müller, K.

1989-10-01

The 1 × 2-3H superstructure of hydrogen on Rh(110) at coverage θ = {3}/{2} is analysed by low energy electron diffraction at 90 K. The spectra of eight beams are recorded with a computer-controlled TV measurement technique which yields low noise data even for weak superstructure spots by multiple averaging. Comparison to full dynamical calculations shows that a kinematic treatment of the hydrogen layer diffraction coupled to the full dynamical diffraction of the substrate is a very good approximation. Spectra computed in this way are compared with experimental data by R-factor evaluation. The three non-equivalent hydrogen atoms are found to adsorb in quasi-three-fold coordinated adsorption sites with slightly different local configurations and with H-Rh bond lengths between 1.87 and 1.93 Å to the first-layer rhodium atoms. Interaction between the adatoms seems to weaken the bonding to the adjacent atom in the second layer, so that H-Rh bond lengths larger than 2.17 Å result. A slight reconstruction of the substrate is necessary to bring superstructure spot intensities near the experimentally observed level. Rhodium atoms bonded to two hydrogen atoms are moved out of the surface by 0.03 ± 0.02 Å relative to Rh atoms bonded to only a single H atom. The relaxation of the first Rh layer spacing is determined to be {d 12}/{d 0} = -3.8 ± 1% and {d 22}/{d 0} = 0 ± 1% . The best fit Pendry R-factor is 0.33.

Computational insights into crystal plane dependence of thermal activity of anion (C and N)-substituted titania.

PubMed

V, Sai Phani Kumar; Arya, Rahul; Deshpande, Parag A

2017-11-29

Geometry optimizations of anion (C and N) doped anatase TiO 2 were carried out by using DFT+U calculations. Various anion vacancy sites were examined to study the synergistic effects of anion doping accompanied with anion vacancy formation on lattice oxygen activation. Two non-identical crystal planes (0 0 1) and (1 0 0) were chosen for C and N substitutions. Energetically favoured N-vacancy pairs were identified on TiO 2 surfaces. Substitution of N along with anion vacancies at various sites was energetically more favoured than that of C-doping in bulk TiO 2 while the energies were comparable for surface substitutions. Bond length distributions due to the formation of differential bonds were determined. Net oxygen activation and accompanying reversible oxygen exchange capacities were compared for TiO 2-2x C x and TiO 2-3x N 2x . Substitution of C in the surface exposed (1 0 0) plane of TiO 2 resulted in 47.6% and 23.8% of bond elongation and compression, respectively, resulting in 23.8% of net oxygen activation which was higher when compared to N substitution in the (1 0 0) plane of TiO 2 resulting in a net oxygen activation of 17%.

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.

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).

Enhanced photocatalytic degradation of Amaranth dye on mesoporous anatase TiO2: evidence of C-N, N[double bond, length as m-dash]N bond cleavage and identification of new intermediates.

PubMed

Naik, Amarja P; Salkar, Akshay V; Majik, Mahesh S; Morajkar, Pranay P

2017-07-01

The photocatalytic degradation mechanism of Amaranth, a recalcitrant carcinogenic azo dye, was investigated using mesoporous anatase TiO 2 under sunlight. Mesoporous anatase TiO 2 of a high photocatalytic activity has been synthesized using a sol-gel method and its photocatalytic activity for the degradation of Amaranth dye has been evaluated with respect to Degussa P25. The effect of bi-dentate complexing agents like oxalic acid, ethylene glycol and urea on the surface properties of TiO 2 catalyst has been investigated using TG-DTA, FTIR, HR-TEM, SAED, PXRD, EDS, UV-DRS, PL, BET N 2 adsorption-desorption isotherm studies and BJH analysis. The influence of catalyst properties such as the mesoporous network, pore volume and surface area on the kinetics of degradation of Amaranth as a function of irradiation time under natural sunlight has been monitored using UV-Vis spectroscopy. The highest rate constant value of 0.069 min -1 was obtained for the photocatalytic degradation of Amaranth using TiO 2 synthesized via a urea assisted sol-gel synthesis method. The effect of the reaction conditions such as pH, TiO 2 concentration and Amaranth concentration on the photodegradation rate has been investigated. The enhanced photocatalytic activity of synthesized TiO 2 in comparison with P25 is attributed to the mesoporous nature of the catalyst leading to increased pore diameter, pore volume, surface area and enhanced charge carrier separation efficiency. New intermediates of photocatalytic degradation of Amaranth, namely, sodium-3-hydroxynaphthalene-2,7-disulphonate, 3-hydroxynaphthalene, sodium-4-aminonaphthalenesulphonate and sodium-4-aminobenzenesulphonate have been identified using LC-ESI-MS for the very first time, providing direct evidence for simultaneous bond cleavage pathways (-C-N-) and (-N[double bond, length as m-dash]N-). A new plausible mechanism of TiO 2 catalysed photodegradation of Amaranth along with the comparison of its toxicity to that of its degradation intermediates and products is proposed.

Quantum chemical calculations of glycine glutaric acid

NASA Astrophysics Data System (ADS)

Arioǧlu, ćaǧla; Tamer, Ömer; Avci, Davut; Atalay, Yusuf

2017-02-01

Density functional theory (DFT) calculations of glycine glutaric acid were performed by using B3LYP levels with 6-311++G(d,p) basis set. The theoretical structural parameters such as bond lengths and bond angles are in a good agreement with the experimental values of the title compound. HOMO and LUMO energies were calculated, and the obtained energy gap shows that charge transfer occurs in the title compound. Vibrational frequencies were calculated and compare with experimental ones. 3D molecular surfaces of the title compound were simulated using the same level and basis set. Finally, the 13C and 1H NMR chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method.

Bi-directional ultrasonic wave coupling to FBGs in continuously bonded optical fiber sensing.

PubMed

Wee, Junghyun; Hackney, Drew; Bradford, Philip; Peters, Kara

2017-09-01

Fiber Bragg grating (FBG) sensors are typically spot-bonded onto the surface of a structure to detect ultrasonic waves in laboratory demonstrations. However, to protect the rest of the optical fiber from any environmental damage during real applications, bonding the entire length of fiber, called continuous bonding, is commonly done. In this paper, we investigate the impact of continuously bonding FBGs on the measured Lamb wave signal. In theory, the ultrasonic wave signal can bi-directionally transfer between the optical fiber and the plate at any adhered location, which could potentially produce output signal distortion for the continuous bonding case. Therefore, an experiment is performed to investigate the plate-to-fiber and fiber-to-plate signal transfer, from which the signal coupling coefficient of each case is theoretically estimated based on the experimental data. We demonstrate that the two coupling coefficients are comparable, with the plate-to-fiber case approximately 19% larger than the fiber-to-plate case. Finally, the signal waveform and arrival time of the output FBG responses are compared between the continuous and spot bonding cases. The results indicate that the resulting Lamb wave signal output is only that directly detected at the FBG location; however, a slight difference in signal waveform is observed between the two bonding configurations. This paper demonstrates the practicality of using continuously bonded FBGs for ultrasonic wave detection in structural health monitoring (SHM) applications.

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.

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

Unraveling the complexity of the interactions of DNA nucleotides with gold by single molecule force spectroscopy

NASA Astrophysics Data System (ADS)

Bano, Fouzia; Sluysmans, Damien; Wislez, Arnaud; Duwez, Anne-Sophie

2015-11-01

Addressing the effect of different environmental factors on the adsorption of DNA to solid supports is critical for the development of robust miniaturized devices for applications ranging from biosensors to next generation molecular technology. Most of the time, thiol-based chemistry is used to anchor DNA on gold - a substrate commonly used in nanotechnology - and little is known about the direct interaction between DNA and gold. So far there have been no systematic studies on the direct adsorption behavior of the deoxyribonucleotides (i.e., a nitrogenous base, a deoxyribose sugar, and a phosphate group) and on the factors that govern the DNA-gold bond strength. Here, using single molecule force spectroscopy, we investigated the interaction of the four individual nucleotides, adenine, guanine, cytosine, and thymine, with gold. Experiments were performed in three salinity conditions and two surface dwell times to reveal the factors that influence nucleotide-Au bond strength. Force data show that, at physiological ionic strength, adenine-Au interactions are stronger, asymmetrical and independent of surface dwell time as compared to cytosine-Au and guanine-Au interactions. We suggest that in these conditions only adenine is able to chemisorb on gold. A decrease of the ionic strength significantly increases the bond strength for all nucleotides. We show that moderate ionic strength along with longer surface dwell period suggest weak chemisorption also for cytosine and guanine.Addressing the effect of different environmental factors on the adsorption of DNA to solid supports is critical for the development of robust miniaturized devices for applications ranging from biosensors to next generation molecular technology. Most of the time, thiol-based chemistry is used to anchor DNA on gold - a substrate commonly used in nanotechnology - and little is known about the direct interaction between DNA and gold. So far there have been no systematic studies on the direct adsorption behavior of the deoxyribonucleotides (i.e., a nitrogenous base, a deoxyribose sugar, and a phosphate group) and on the factors that govern the DNA-gold bond strength. Here, using single molecule force spectroscopy, we investigated the interaction of the four individual nucleotides, adenine, guanine, cytosine, and thymine, with gold. Experiments were performed in three salinity conditions and two surface dwell times to reveal the factors that influence nucleotide-Au bond strength. Force data show that, at physiological ionic strength, adenine-Au interactions are stronger, asymmetrical and independent of surface dwell time as compared to cytosine-Au and guanine-Au interactions. We suggest that in these conditions only adenine is able to chemisorb on gold. A decrease of the ionic strength significantly increases the bond strength for all nucleotides. We show that moderate ionic strength along with longer surface dwell period suggest weak chemisorption also for cytosine and guanine. Electronic supplementary information (ESI) available: Details of the data analysis; Fig. S1-S5 histograms of rupture lengths; histograms for Au-adenine and Au-amine interactions; Force-extension curve for MCH-Au interactions; normalized force-extension curves; theoretical length of the DNA oligomers. See DOI: 10.1039/c5nr05695k

The Changing Nature of the Chemical Bond

NASA Astrophysics Data System (ADS)

Angel, R. J.; Ross, N. L.; Zhao, J.

2006-12-01

It is commonly assumed that the relationship between bond strength and bond length for a particular pair of atoms is a simple and single-valued one for a given coordination environment; longer bonds are weaker. This is the basis of the concept of bond valence, for example. Indeed, in strongly-bonded oxide minerals, the range of bond lengths found for a given cation-anion polyhedron is so small that it was long thought that the polyhedral bulk moduli were essentially independent of structure type and thus the environment of the polyhedron. This view is incompatible with the discovery that the response of the perovskite structure to high pressures is controlled by the equipartition of bond-valence strain between the A and B cation sites within the structure [1]. The same appears to be true, within experimental uncertainties, for all framework structures with rigid-unit modes. In perovskites, this explicitly implies that the octahedral compressibility depends not only upon the octahedral cation, but also upon the compressibility of the cation-oxygen bonds of the extra-framework (nominally dodecahedral) site. Thus the octahedral compressibility of a B cation site must change as the A- site cation is changed, whether or not the B-O bond lengths change as a result of the substitution on the A site. The strength of bonds is thus dependent upon the crystal environment and not solely upon the bond length. The observation of a plateau effect in the variation of octahedral compressibilities in perovskite solid solutions suggests that the bond-valence matching principle is followed not just globally, but on a local scale as well. Such observations should allow the change with pressure of the excess thermodynamic properties of solid solutions to be directly related to the microscopic (atomic scale) evolution of the structure. [1] Zhao, Ross, & Angel (2004). Acta Cryst. B60:263

Bond-length relaxation in crystalline Si1-xGex alloys: An extended x-ray-absorption fine-structure study

NASA Astrophysics Data System (ADS)

Kajiyama, Hiroshi; Muramatsu, Shin-Ichi; Shimada, Toshikazu; Nishino, Yoichi

1992-06-01

Extended x-ray-absorption fine-structure spectra for crystalline Si1-xGex alloys, measured at the K edge of Ge at room temperature, are analyzed with a curve-fitting method based on the spherical-wave approximation. The Ge-Ge and Ge-Si bond lengths, coordination numbers of Ge and Si atoms around a Ge atom, and Debye-Waller factors of Ge and Si atoms are obtained. It is shown that Ge-Ge and Ge-Si bonds relax completely, for all Ge concentrations of their study, while the lattice constant varies monotonically, following Vegard's law. As noted by Bragg and later by Pauling and Huggins, the Ge-Ge and Ge-Si bond lengths are close to the sum of their constituent-element atomic radii: nearly 2.45 Å for Ge-Ge bonds and 2.40 Å for Ge-Si bonds. A study on the coordination around a Ge atom in the alloys revealed that Ge and Si atoms mix randomly throughout the compositional range studied.

Interaction of Benzimidazoles and Benzotriazole: Its Corrosion Protection Properties on Mild Steel in Hydrochloric Acid

NASA Astrophysics Data System (ADS)

Ramya, K.; Mohan, Revathi; Joseph, Abraham

2014-11-01

Synergistic hydrogen-bonded interaction of alkyl benzimidazoles and 1,2,3-benzotrizole and its corrosion protection properties on mild steel in hydrochloric acid at different temperatures have been studied using polarization, EIS, adsorption, surface studies, and computational methods. The extent of synergistic interaction increases with temperature. Quantum chemical approach is used to calculate some electronic properties of the molecules and to ascertain the synergistic interaction, inhibitive effect, and molecular structures. The corrosion inhibition efficiencies and the global chemical reactivity relate to some parameters, such as total energy, E HOMO, E LUMO, and gap energy (Δ E). 1,2,3-Benzotrizole interacts with benzimidazoles derivatives up to a bond length of approximately 1.99 Å. This interaction represents the formation of a hydrogen bond between the 1,2,3-benzotrizole and benzimidazoles. This synergistic interaction of 1,2,3-benzotrizole and benzimidazole derivatives offers extended inhibition efficiency toward mild steel in hydrochloric acid.

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.

Gel Electrophoresis of Gold-DNA Nanoconjugates

DOE PAGES

Pellegrino, T.; Sperling, R. A.; Alivisatos, A. P.; ...

2007-01-01

Gold-DNA conjugates were investigated in detail by a comprehensive gel electrophoresis study based on 1200 gels. A controlled number of single-stranded DNA of different length was attached specifically via thiol-Au bonds to phosphine-stabilized colloidal gold nanoparticles. Alternatively, the surface of the gold particles was saturated with single stranded DNA of different length either specifically via thiol-Au bonds or by nonspecific adsorption. From the experimentally determined electrophoretic mobilities, estimates for the effective diameters of the gold-DNA conjugates were derived by applying two different data treatment approaches. The first method is based on making a calibration curve for the relation between effectivemore » diameters and mobilities with gold nanoparticles of known diameter. The second method is based on Ferguson analysis which uses gold nanoparticles of known diameter as reference database. Our study shows that effective diameters derived from gel electrophoresis measurements are affected with a high error bar as the determined values strongly depend on the method of evaluation, though relative changes in size upon binding of molecules can be detected with high precision. Furthermore, in this study, the specific attachment of DNA via gold-thiol bonds to Au nanoparticles is compared to nonspecific adsorption of DNA. Also, the maximum number of DNA molecules that can be bound per particle was determined.« less

Tuning surface grafting density of CeO2 nanocrystals with near- and supercritical solvent characteristics.

PubMed

Giroire, B; Slostowski, C; Marre, S; Aymonier, C; Aida, T; Hojo, D; Aoki, N; Takami, S; Adschiri, T

2016-01-21

In this work, the solvent effect on the synthesis of CeO2 nanocrystals synthesized in near- and supercritical alcohols is discussed. The materials prepared displayed a unique morphology of small nanocrystals (<10 nm) aggregated into larger nanospheres (∼100-200 nm). In such syntheses, alcohol molecules directly interact with the nanocrystal surface through alkoxide and carboxylate bondings. The grafting density was quantified from the weight loss measured using thermogravimetric analysis. A direct correlation between the grafting density and the alcohol chain length can be established. It was demonstrated that the shorter the alcohol chain length (i.e. methanol), the higher the surface coverage is. This trend is independent of the synthesis mode (batch or continuous). Additionally, an influence of the grafting density on the resulting nanocrystal size was established. It is suggested that the surface coverage has a high influence on the early stages of the nucleation and growth. Indeed, when high surface coverages are reached, all surface active sites are blocked, limiting the growth step and therefore leading to smaller particles. This effect was noticed with the materials prepared in the continuous mode where shorter reaction time was performed.

Bond Strength and Interfacial Morphology of Different Dentin Adhesives in Primary Teeth

PubMed Central

Vashisth, Pallavi; Mittal, Mudit; Goswami, Mousumi; Chaudhary, Seema; Dwivedi, Swati

2014-01-01

Objective: To evaluate the interfacial morphology and the bond strength produced by the three-step, two-step and single-step bonding systems in primary teeth. Materials and Methods: Occlusal surfaces of 72 extracted human deciduous teeth were ground to expose the dentin. The teeth were divided into four groups: (a) Scotchbond Multipurpose (3M, ESPE), (b) Adh Se (Vivadent), (d) OptiBond All-in-One (Kerr) and (e)Futurabond NR (VOCO, Cuxhaven, Germany). The adhesives were applied to each group following the manufacturer’s instructions. Then, teeth from each group were divided into two groups: (A) For viewing interfacial morphology (32 teeth), with 8 teeth in each group, and (B) For measurement of bond strength (40 teeth), with 10 teeth in each group. All the samples were prepared for viewing under SEM. The statistical analysis was done using SPSS version 15.0 software. Results: Observational measurement of tag length in different adhesives revealed that Scotchbond had the most widely spread values with a range from 12.20 to 89.10μm while OptiBond AIO had the narrowest range (0 to 22.50). The bond strength of Scotchbond Multipurpose was significantly higher (7.4744±1.88763) (p<0.001) as compared to Futurabond NR (3.8070±1.61345), Adhe SE (4.4478 ± 1.3820) and OptiBond-all-in-one (4.4856±1.07925). Conclusion: The three-step bonding system showed better results as compared to simplified studied bonding systems PMID:24910694

Short Carboxylic Acid–Carboxylate Hydrogen Bonds Can Have Fully Localized Protons

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

Lin, Jiusheng; Pozharski, Edwin; Wilson, Mark A.

Short hydrogen bonds (H-bonds) have been proposed to play key functional roles in several proteins. The location of the proton in short H-bonds is of central importance, as proton delocalization is a defining feature of low-barrier hydrogen bonds (LBHBs). Experimentally determining proton location in H-bonds is challenging. Here, bond length analysis of atomic (1.15–0.98 Å) resolution X-ray crystal structures of the human protein DJ-1 and its bacterial homologue, YajL, was used to determine the protonation states of H-bonded carboxylic acids. DJ-1 contains a buried, dimer-spanning 2.49 Å H-bond between Glu15 and Asp24 that satisfies standard donor–acceptor distance criteria for amore » LBHB. Bond length analysis indicates that the proton is localized on Asp24, excluding a LBHB at this location. However, similar analysis of the Escherichia coli homologue YajL shows both residues may be protonated at the H-bonded oxygen atoms, potentially consistent with a LBHB. A Protein Data Bank-wide screen identifies candidate carboxylic acid H-bonds in approximately 14% of proteins, which are typically short [O–O> = 2.542(2) Å]. Chemically similar H-bonds between hydroxylated residues (Ser/Thr/Tyr) and carboxylates show a trend of lengthening O–O distance with increasing H-bond donor pK a. This trend suggests that conventional electronic effects provide an adequate explanation for short, charge-assisted carboxylic acid–carboxylate H-bonds in proteins, without the need to invoke LBHBs in general. This study demonstrates that bond length analysis of atomic resolution X-ray crystal structures provides a useful experimental test of certain candidate LBHBs.« less

Evaluation of enamel damages following orthodontic bracket debonding in fluorosed teeth bonded with adhesion promoter.

PubMed

Baherimoghadam, Tahreh; Akbarian, Sahar; Rasouli, Reza; Naseri, Navid

2016-01-01

To evaluate shear bond strength (SBS) of the orthodontic brackets bonded to fluorosed and nonfluorosed teeth using Light Bond with and without adhesion promoters and compare their enamel damages following debonding. In this study, 30 fluorosed (Thylstrup and Fejerskov Index = 4-5) and 30 nonfluorosed teeth were randomly distributed between two subgroups according to the bonding materials: Group 1, fluorosed teeth bonded with Light Bond; Group 2, fluorosed teeth bonded with adhesion promoters and Light Bond; Group 3, nonfluorosed teeth bonded with Light Bond; Group 4, nonfluorosed bonded with adhesion promoters and Light Bond. After bonding, the SBS of the brackets was tested with a universal testing machine. Stereomicroscopic evaluation was performed by unbiased stereology in all teeth to determine the amount of adhesive remnants and the number and length of enamel cracks before bonding and after debonding. The data were analyzed using two-way analysis of variance, Kruskal-Wallis, Wilcoxon Signed Rank, and Mann-Whitney test. While fluorosis reduced the SBS of orthodontic bracket (P = 0.017), Enhance Locus Ceruleus LC significantly increased the SBS of the orthodontic bracket in fluorosed and nonfluorosed teeth (P = 0.039). Significant increasing in the number and length of enamel crack after debonding was found in all four groups. There were no significant differences in the length of enamel crack increased after debonding among four groups (P = 0.768) while increasing in the number of enamel cracks after debonding was significantly different among the four groups (P = 0.023). Teeth in Group 2 showed the highest enamel damages among four groups following debonding. Adhesion promoters could improve the bond strength of orthodontic brackets, but conservative debonding methods for decreasing enamel damages would be necessary.

Short Carboxylic Acid-Carboxylate Hydrogen Bonds Can Have Fully Localized Protons.

PubMed

Lin, Jiusheng; Pozharski, Edwin; Wilson, Mark A

2017-01-17

Short hydrogen bonds (H-bonds) have been proposed to play key functional roles in several proteins. The location of the proton in short H-bonds is of central importance, as proton delocalization is a defining feature of low-barrier hydrogen bonds (LBHBs). Experimentally determining proton location in H-bonds is challenging. Here, bond length analysis of atomic (1.15-0.98 Å) resolution X-ray crystal structures of the human protein DJ-1 and its bacterial homologue, YajL, was used to determine the protonation states of H-bonded carboxylic acids. DJ-1 contains a buried, dimer-spanning 2.49 Å H-bond between Glu15 and Asp24 that satisfies standard donor-acceptor distance criteria for a LBHB. Bond length analysis indicates that the proton is localized on Asp24, excluding a LBHB at this location. However, similar analysis of the Escherichia coli homologue YajL shows both residues may be protonated at the H-bonded oxygen atoms, potentially consistent with a LBHB. A Protein Data Bank-wide screen identifies candidate carboxylic acid H-bonds in approximately 14% of proteins, which are typically short [⟨d O-O ⟩ = 2.542(2) Å]. Chemically similar H-bonds between hydroxylated residues (Ser/Thr/Tyr) and carboxylates show a trend of lengthening O-O distance with increasing H-bond donor pK a . This trend suggests that conventional electronic effects provide an adequate explanation for short, charge-assisted carboxylic acid-carboxylate H-bonds in proteins, without the need to invoke LBHBs in general. This study demonstrates that bond length analysis of atomic resolution X-ray crystal structures provides a useful experimental test of certain candidate LBHBs.

Core-level spectra and molecular deformation in adsorption: V-shaped pentacene on Al(001)

PubMed Central

Lin, He; Brivio, Gian Paolo; Floreano, Luca; Fratesi, Guido

2015-01-01

Summary By first-principle simulations we study the effects of molecular deformation on the electronic and spectroscopic properties as it occurs for pentacene adsorbed on the most stable site of Al(001). The rationale for the particular V-shaped deformed structure is discussed and understood. The molecule–surface bond is made evident by mapping the charge redistribution. Upon X-ray photoelectron spectroscopy (XPS) from the molecule, the bond with the surface is destabilized by the electron density rearrangement to screen the core hole. This destabilization depends on the ionized carbon atom, inducing a narrowing of the XPS spectrum with respect to the molecules adsorbed hypothetically undistorted, in full agreement to experiments. When looking instead at the near-edge X-ray absorption fine structure (NEXAFS) spectra, individual contributions from the non-equivalent C atoms provide evidence of the molecular orbital filling, hybridization, and interchange induced by distortion. The alteration of the C–C bond lengths due to the V-shaped bending decreases by a factor of two the azimuthal dichroism of NEXAFS spectra, i.e., the energy splitting of the sigma resonances measured along the two in-plane molecular axes. PMID:26734516

Analysis of the vibronic structure of the trans-stilbene fluorescence and excitation spectra: the S0 and S1 PES along the Ce[double bond, length as m-dash]Ce and Ce-Cph torsions.

PubMed

Orlandi, Giorgio; Garavelli, Marco; Zerbetto, Francesco

2017-09-20

We analyze the highly resolved vibronic structure of the low energy (≤200 cm -1 ) region of the fluorescence and fluorescence excitation spectra of trans-stilbene in supersonic beams. In this spectral region the vibronic structure is associated mainly with vibrational levels of the C e -C e torsion (τ) and the a u combination of the two C e -C ph bond twisting (ϕ). We base this analysis on the well-established S 0 (τ, ϕ) two-dimensional potential energy surface (PES) and on a newly refined S 1 (τ, ϕ) PES. We obtain vibrational eigenvalues and eigenvectors of the anharmonic S 0 (τ, ϕ) and S 1 (τ, ϕ) PES using a numerical procedure based on the Meyer's flexible model [R. Meyer, J. Mol. Spectrosc., 1979, 76, 266]. Then we derive Franck-Condon factors and therefore intensities of the relevant vibronic bands for the S 0 → S 1 excitation and S 1 → S 0 fluorescence spectra. Furthermore, we assess the role of the b g combination of the two C e -C ph bond twisting (ν 48 ) in the structure of the S 1 → S 0 fluorescence spectra. By the use of these results we are able to assign most of the low energy vibrational levels of the S 0 → S 1 excitation spectra and of the fluorescence spectra of the emission from several low energy S 1 vibronic levels. The good agreement between the observed and the computed vibrational structure of the S 0 → S 1 and S 1 → S 0 spectra suggests that the proposed picture of the E 1 (τ, ϕ) and E 0 (τ, ϕ) PES, in particular along the coordinate τ governing trans-cis photo-isomerization in S 1 , is accurate. In S 0 , the barriers for the C e [double bond, length as m-dash]C e torsion and for the a u type C e -C ph bond twisting are 16 080 cm -1 and 3125 cm -1 , respectively, while in S 1 , where the bond orders of the C e [double bond, length as m-dash]C e and C e -C ph bonds are reversed, the two barriers become 1350 cm -1 and 8780 cm -1 , respectively.

Protonation enthalpies of metal oxides from high temperature electrophoresis

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

Rodriguez-Santiago, V; Fedkin, Mark V.; Lvov, Serguei N.

2012-01-01

Surface protonation reactions play an important role in the behavior of mineral and colloidal systems, specifically in hydrothermal aqueous environments. However, studies addressing the reactions at the solid/liquid interface at temperatures above 100 C are scarce. In this study, newly and previously obtained high temperature electrophoresis data (up to 260 C) zeta potentials and isoelectric points for metal oxides, including SiO2, SnO2, ZrO2, TiO2, and Fe3O4, were used in thermodynamic analysis to derive the standard enthalpies of their surface protonation. Two different approaches were used for calculating the protonation enthalpy: one is based on thermodynamic description of the 1-pKa modelmore » for surface protonation, and another one on a combination of crystal chemistry and solvation theories which link the relative permittivity of the solid phase and the ratio of the Pauling bond strength and bond length to standard protonation enthalpy. From this analysis, two expressions relating the protonation enthalpy to the relative permittivity of the solid phase were obtained.« less

Protonation enthalpies of metal oxides from high temperature electrophoresis.

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

Rodriguez-Santiago, V; Fedkin, Mark V; Lvov, Serguei N.

2012-01-01

Surface protonation reactions play an important role in the behavior of mineral and colloidal systems, specifically in hydrothermal aqueous environments. However, studies addressing the reactions at the solid/liquid interface at temperatures above 100 C are scarce. In this study, newly and previously obtained high temperature electrophoresis data (up to 260 C) - zeta potentials and isoelectric points - for metal oxides, including SiO{sub 2}, SnO{sub 2}, ZrO{sub 2}, TiO{sub 2}, and Fe{sub 3}O{sub 4}, were used in thermodynamic analysis to derive the standard enthalpies of their surface protonation. Two different approaches were used for calculating the protonation enthalpy: one ismore » based on thermodynamic description of the 1-pKa model for surface protonation, and another one - on a combination of crystal chemistry and solvation theories which link the relative permittivity of the solid phase and the ratio of the Pauling bond strength and bond length to standard protonation enthalpy. From this analysis, two expressions relating the protonation enthalpy to the relative permittivity of the solid phase were obtained.« less

Supramolecular assembly of biphenyl dicarboxylic acid on Au(1 1 1)

NASA Astrophysics Data System (ADS)

Zhu, N.; Osada, T.; Komeda, T.

2007-04-01

We investigate the structure of submonolayer film of 4,4'-biphenyl dicarboxylic acid (BDA) molecules on Au(1 1 1)-22 × √3 reconstructed surface with the use of scanning tunneling microscopy (STM). The BDA molecules form ordered structures on Au(1 1 1) surface which are commensurate with the substrate. We have concluded that the molecule-molecule interaction is mainly through hydrogen bonding formed by a straight dimer of BDA molecules. The straight dimer can be expressed as 4 s + 2 t or its six crystallographic equivalents using the unit vectors of the gold substrate of s and t. The length of hydrogen bonding (O-H-O) is estimated to be 0.31 nm assuming nearest neighbor distance of gold atoms of 0.275 nm. The ordering shows a clear contrast with the case of BDA on Cu(1 0 0) surface [S. Stepanow, N. Lin, F. Vidal, A. Landa, M. Ruben, J.V. Barth, K. Kern, Nanoletters 5 (2005) 901] in which a square type of ordering of molecules is observed by the formation of hydrogen bonding between a carboxylate (COO) and a benzene ring. The clear difference of the ordered structure on Cu(1 0 0) and Au(1 1 1) surface demonstrates that the absence (presence) of deprotonation of carboxyl group of BDA molecule on Au(1 1 1) (Cu(1 0 0)) switches the straight and square type ordering of BDA molecules.

Structure of thin diamond films: A 1H and 13C nuclear-magnetic-resonance study

NASA Astrophysics Data System (ADS)

Pruski, M.; Lang, D. P.; Hwang, Son-Jong; Jia, H.; Shinar, J.

1994-04-01

The 1H and 13C nuclear magnetic resonance (NMR) of thin diamond films deposited from naturally abundant (1.1 at. %) as well as 50% and 100% 13enriched CH4 heavily diluted in H2 is described and discussed. Less than 0.6 at. % of hydrogen is found in the films which contain crystallites up to ~15 μm across. The 1H NMR consists of a broad 50-65-kHz-wide Gaussian line attributed to H atoms bonded to carbon and covering the crystallite surfaces. A narrow Lorentzian line was only occasionally observed and is found not to be intrinsic to the diamond structure. The 13C NMR demonstrates that >99.5% of the C atoms reside in a quaternary diamondlike configuration. 1-13C cross-polarization measurement indicates that, at the very least, the majority of 13C nuclei cross polarized by 1H, i.e., within three bond distances from a 1H at a crystallite surface, reside in sp3 diamondlike coordinated sites. The 13C relaxation rates of the films are four orders of magnitude faster than that of natural diamond and believed to be due to 13C spin diffusion to paramagnetic centers, presumably carbon dangling bonds. Analysis of the measured relaxation rates indicates that within the 13C spin-diffusion length of √DTc1 ~0.05 μm, these centers are uniformly distributed in the diamond crystallites. The possibility that the dangling bonds are located at internal nanovoid surfaces is discussed.

Negative hyperconjugation and red-, blue- or zero-shift in X-Z∙∙∙Y complexes.

PubMed

Joy, Jyothish; Jemmis, Eluvathingal D; Vidya, Kaipanchery

2015-01-01

A generalized explanation is provided for the existence of the red- and blue-shifting nature of X-Z bonds (Z=H, halogens, chalcogens, pnicogens, etc.) in X-Z∙∙∙Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z∙∙∙Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z σ* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z σ* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z σ* ABMO back to X leads to blue-shifting and the CT from the Y-group to the σ* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z∙∙∙Y complexes.

Bond between smooth prestressing wires and concrete : finite element model and transfer length analysis for pretensioned concrete crossties.

DOT National Transportation Integrated Search

2014-04-03

Pretensioned concrete ties are increasingly employed in railroad high speed : and heavy haul applications. The bond between prestressing wires or strands and : concrete plays an important role in determining the transfer length of pretensioned : conc...

Second-harmonic generation and theoretical studies of protonation at the water/α-TiO 2 (1 1 0) interface

NASA Astrophysics Data System (ADS)

Fitts, Jeffrey P.; Machesky, Michael L.; Wesolowski, David J.; Shang, Xiaoming; Kubicki, James D.; Flynn, George W.; Heinz, Tony F.; Eisenthal, Kenneth B.

2005-08-01

The pH of zero net surface charge (pH pzc) of the α-TiO 2 (1 1 0) surface was characterized using second-harmonic generation (SHG) spectroscopy. The SHG response was monitored during a series of pH titrations conducted at three NaNO 3 concentrations. The measured pH pzc is compared with a pH pzc value calculated using the revised MUltiSIte Complexation (MUSIC) model of surface oxygen protonation. MUSIC model input parameters were independently derived from ab initio calculations of relaxed surface bond lengths for a hydrated surface. Model (pH pzc 4.76) and experiment (pH pzc 4.8 ± 0.3) agreement establishes the incorporation of independently derived structural parameters into predictive models of oxide surface reactivity.

Stress relaxation at a gelatin hydrogel-glass interface in direct shear sliding

NASA Astrophysics Data System (ADS)

Gupta, Vinit; Singh, Arun K.

2018-01-01

In this paper, we study experimentally the stress relaxation behavior of soft solids such as gelatin hydrogels on a smooth glass surface in direct shear sliding. It is observed experimentally that irrespective of pulling velocity, the sliding block relaxes to the same level of nonzero residual stress. However, residual stress increases with increasing gelatin concentration in the hydrogels. We have also validated a friction model for strong bond formation during steady relaxation in light of the experimental observations. Our theoretical analysis establishes that population of dangling chains at the sliding interface significantly affects the relaxation process. As a result, residual stress increases with increasing gelatin concentration or decreasing mesh size of the three-dimensional structures in the hydrogels. It is also found that the transition time, at which a weak bond converts to strong bond, increases with increasing mesh size of the hydrogels. Moreover, relaxation time constant of a strong bond decreases with increasing mesh size. However, activation length of a strong bond increases with mesh size. Finally, this study signifies the role of residual strength in frictional shear sliding and it is believed that these results should be useful to understand the role of residual stress in stick-slip instability.

Paramagnetic Liquid Bridge in a Gravity-Compensating Magnetic Field

NASA Technical Reports Server (NTRS)

Mahajan, Milind P.; Tsige, Mesfin; Taylor, P. L.; Rosenblatt, Charles

1999-01-01

Magnetic levitation was used to stabilize cylindrical columns of a paramagnetic liquid in air between two solid supports. The maximum achievable length to diameter ratio R(sub max) was approx. (3.10 +/- 0.07), very close to the Rayleigh-Plateau limit of pi. For smaller R, the stability of the column was measured as a function of the Bond number, which could be continuously varied by adjusting the strength of the magnetic field. Liquid bridges supported by two solid surfaces have been attracting scientific attention since the time of Rayleigh and Plateau. For a cylindrical bridge of length L and diameter d, it was shown theoretically that in zero gravity the maximum slenderness ratio R (identically = L/d) is pi. The stability and ultimate collapse of such bridges is of interest because of their importance in a number of industrial processes and their potential for low gravity applications. In the presence of gravity, however, the cylindrical shape of an axisymmetric bridge tends to deform, limiting its stability and decreasing the maximum achievable value of R. Theoretical studies have discussed the stability and possible shapes of axisymmetric bridges. Experiments typically are performed in either a Plateau tank, in which the bridge is surrounded by a density-matched immiscible fluid, or in a space-borne microgravity environment. It has been shown, for example, that the stability limit R can be pushed beyond pi by using flow stabilization, by acoustic radiation pressure, or by forming columns in the presence of an axial electric field. In this work, magnetic levitation was used to simulate a low gravity environment and create quasi-cylindrical liquid columns in air. Use of a magnetic field permits us to continuously vary the Bond number B identically equal to (g)(rho)d(exp 2)/4(sigma), where g is the gravitational acceleration, rho is the density of the liquid, and sigma is the surface tension of the liquid in air. The dimensionless Bond number represents the relative importance of external forces acting on the liquid column to those due to surface tension. Our central result is that in a large magnetic field gradient we could create and stabilize columns of mixtures of water and paramagnetic manganese chloride tetrahydrate (MnCl2.4H2O), achieving a length to diameter ratio very close to pi.

Continuum in the X-Z---Y weak bonds: Z= main group elements.

PubMed

Joy, Jyothish; Jose, Anex; Jemmis, Eluvathingal D

2016-01-15

The Continuum in the variation of the X-Z bond length change from blue-shifting to red-shifting through zero- shifting in the X-Z---Y complex is inevitable. This has been analyzed by ab-initio molecular orbital calculations using Z= Hydrogen, Halogens, Chalcogens, and Pnicogens as prototypical examples. Our analysis revealed that, the competition between negative hyperconjugation within the donor (X-Z) molecule and Charge Transfer (CT) from the acceptor (Y) molecule is the primary reason for the X-Z bond length change. Here, we report that, the proper tuning of X- and Y-group for a particular Z- can change the blue-shifting nature of X-Z bond to zero-shifting and further to red-shifting. This observation led to the proposal of a continuum in the variation of the X-Z bond length during the formation of X-Z---Y complex. The varying number of orbitals and electrons available around the Z-atom differentiates various classes of weak interactions and leads to interactions dramatically different from the H-Bond. Our explanations based on the model of anti-bonding orbitals can be transferred from one class of weak interactions to another. We further take the idea of continuum to the nature of chemical bonding in general. © 2015 Wiley Periodicals, Inc.

Crystal structure of (eth­oxy­ethyl­idene)di­methyl­aza­nium ethyl sulfate

PubMed Central

Tiritiris, Ioannis; Saur, Stefan; Kantlehner, Willi

2015-01-01

In the title salt, C6H14NO+·C2H5SO4 −, the C—N bond lengths in the cation are 1.2981 (14), 1.4658 (14) and 1.4707 (15) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.3157 (13) Å shows double-bond character, indicating charge delocalization within the NCO plane of the iminium ion. In the crystal, C—H⋯O hydrogen bonds between H atoms of the cations and O atoms of neighbouring ethyl sulfate anions are present, generating a three-dimensional network. PMID:26870525

Spontaneous adsorption on a hydrophobic surface governed by hydrogen bonding.

PubMed

Dang, Fuquan; Hasegawa, Takeshi; Biju, Vasudevanpillai; Ishikawa, Mitsuru; Kaji, Noritada; Yasui, Takao; Baba, Yoshinobu

2009-08-18

Spontaneous adsorption from solution onto solid surface is a common phenomenon in nature, but the force that governs adsorption is still a matter of considerable debate. (1, 2) We found that surfactants and cellulose adsorb from solution onto a poly(methyl methacrylate) (PMMA) surface in an ordered and cooperative way governed by hydrogen bonding. The glucose rings of n-dodecyl-beta-D-maltoside (DDM) and hydroxyethylcellulose (HEC) stand perpendicular to the surface, H-bond to the surface COOMe groups with their C=O and Me-O bonds parallel to the surface, and form a tight monolayer. The non-H-bonded COOMe groups orient their C=O bonds perpendicular to the surface. In contrast, the glucose rings of hydrophobically modified hydroxyethylcellulose (HMHEC) lie flat with the side chains perpendicular to the surface and H-bond to the perpendicular-oriented C=O groups. The non-H-bonded COOMe groups orient their C=O bonds parallel but Me-O bonds near-perpendicular to the surface for stabilizing HMHEC. The current work provides a detailed picture of how surface-active molecules interact with a solid surface and self-assemble into greatly different architectures.

Surface Modification and Nanojunction Fabrication with Molecular Metal Wires

DTIC Science & Technology

2012-12-21

single - crystal X-ray diffraction studies of 2 and 3. Both the single - crystal structural data of 2 and 3 and the spectroscopic/voltammetric data...structure, magnetic properties, and single -molecule conductance of two new trinuclear metal string complexes, [Ni3(dzp)4(NCS)2] (2) and [ Co3 (dzp)4(NCS...modifying the crystallization conditions. The [s- Co3 (dpa)4(Cl)2] contains a symmetrical tricobalt framework with identical Co–Co bond lengths (2.34 Å

Polymer brushes in explicit poor solvents studied using a new variant of the bond fluctuation model

NASA Astrophysics Data System (ADS)

Jentzsch, Christoph; Sommer, Jens-Uwe

2014-09-01

Using a variant of the Bond Fluctuation Model which improves its parallel efficiency in particular running on graphic cards we perform large scale simulations of polymer brushes in poor explicit solvent. Grafting density, solvent quality, and chain length are varied. Different morphological structures in particular octopus micelles are observed for low grafting densities. We reconsider the theoretical model for octopus micelles proposed by Williams using scaling arguments with the relevant scaling variable being σ/σc, and with the characteristic grafting density given by σc ˜ N-4/3. We find that octopus micelles only grow laterally, but not in height and we propose an extension of the model by assuming a cylindrical shape instead of a spherical geometry for the micelle-core. We show that the scaling variable σ/σc can be applied to master plots for the averaged height of the brush, the size of the micelles, and the number of chains per micelle. The exponents in the corresponding power law relations for the grafting density and chain length are in agreement with the model for flat cylindrical micelles. We also investigate the surface roughness and find that polymer brushes in explicit poor solvent at grafting densities higher than the stretching transition are flat and surface rippling can only be observed close to the stretching transition.

Controlling the bond scission sequence of oxygenates for energy applications

NASA Astrophysics Data System (ADS)

Stottlemyer, Alan L.

The so called "Holy Grail" of heterogeneous catalysis is a fundamental understanding of catalyzed chemical transformations which span multidimensional scales of both length and time, enabling rational catalyst design. Such an undertaking is realizable only with an atomic level understanding of bond formation and destruction with respect to intrinsic properties of the metal catalyst. In this study, we investigate the bond scission sequence of small oxygenates (methanol, ethanol, ethylene glycol) on bimetallic transition metal catalysts and transition metal carbide catalysts. Oxygenates are of interest both as hydrogen carriers for reforming to H2 and CO and as fuels in direct alcohol fuel cells (DAFC). To address the so-called "materials gap" and "pressure gap" this work adopted three parallel research approaches: (1) ultra high vacuum (UHV) studies including temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) on polycrystalline surfaces; (2) DFT studies including thermodynamic and kinetic calculations; (3) electrochemical studies including cyclic voltammetry (CV) and chronoamperometry (CA). Recent studies have suggested that tungsten monocarbide (WC) may behave similarly to Pt for the electrooxidation of oxygenates. TPD was used to quantify the activity and selectivity of oxygenate decomposition for WC and Pt-modifiedWC (Pt/WC) as compared to Pt. While decomposition activity was generally higher on WC than on Pt, scission of the C-O bond resulted in alkane/alkene formation on WC, an undesired product for DAFC. When Pt was added to WC by physical vapor deposition C-O bond scission was limited, suggesting that Pt synergistically modifies WC to improve the selectivity toward C-H bond scission to produce H2 and CO. Additionally, TPD confirmed WC and Pt/WC to be more CO tolerant than Pt. HREELS results verified that surface intermediates were different on Pt/WC as compared to Pt or WC and evidence of aldehyde intermediates was observed on the Pt and Pt/WC surfaces. For CH3OH decomposition, DFT calculations suggested that the bond scission sequence could be controlled using monolayer coverage of Pt on WC. The Ni/Pt bimetallic system was studied as an example for using oxygenates as a hydrogen source. There are two well characterized surface structures for the Ni/Pt system: the surface configuration, in which the Ni atoms reside primarily on the surface of the Pt bulk, and the subsurface configuration, in which the second atomic layer is enriched in Ni atoms and the surface is enriched in Pt atoms. These configurations are denoted NiPtPt and PtNiPt, respectively. DFT results revealed that trends established for the Ni/Pt(111) system extend to the Ni/Pt(100) analogue. TPD studies revealed that the NiPtPt surface was more active for oxygenate reforming than the Pt or PtNiPt surfaces. HREELS confirmed the presence of strongly bound reaction intermediates, including aldehyde-like species, and suggested that the first decomposition step was likely O-H bond scission. Thus, the binding energies of the deprotonated reaction intermediates are important parameters in controlling the decomposition pathways of oxygenates. These studies have demonstrated that the bond scission sequence of oxygenate decomposition can be controlled using bimetallic and transition metal carbide catalysts. While this study has focused on oxygenate decomposition for energy applications, the principles and methodology applied herein are universally applicable to the development of novel and marketable value-added products. The value in such a methodology is in the combination of both calculations to predict catalytic and chemical properties, and experiments to fine-tune theoretical predictions.

The Effect of Limited Diffusion and Wet-Dry Cycling on Reversible Polymerization Reactions: Implications for Prebiotic Synthesis of Nucleic Acids.

PubMed

Higgs, Paul G

2016-06-08

A long-standing problem for the origins of life is that polymerization of many biopolymers, including nucleic acids and peptides, is thermodynamically unfavourable in aqueous solution. If bond making and breaking is reversible, monomers and very short oligomers predominate. Recent experiments have shown that wetting and drying cycles can overcome this problem and drive the formation of longer polymers. In the dry phase, bond formation is favourable, but diffusion is restricted, and bonds only form between monomers that are initially close together. In the wet phase, some of the bonds are hydrolyzed. However, repositioning of the molecules allows new bonds to form in the next dry phase, leading to an increase in mean polymer length. Here, we consider a simple theoretical model that explains the effect of cycling. There is an equilibrium length distribution with a high mean length that could be achieved if diffusion occurred freely in the dry phase. This equilibrium is inaccessible without diffusion. A single dry cycle without diffusion leads to mean lengths much shorter than this. Repeated cycling leads to a significant increase in polymerization relative to a single cycle. In the most favourable case, cycling leads to the same equilibrium length distribution as would be achieved if free diffusion were possible in the dry phase. These results support the RNA World scenario by explaining a potential route to synthesis of long RNAs; however, they also imply that cycling would be beneficial to the synthesis of other kinds of polymers, including peptides, where bond formation involves a condensation reaction.

The Effect of Limited Diffusion and Wet–Dry Cycling on Reversible Polymerization Reactions: Implications for Prebiotic Synthesis of Nucleic Acids

PubMed Central

Higgs, Paul G.

2016-01-01

A long-standing problem for the origins of life is that polymerization of many biopolymers, including nucleic acids and peptides, is thermodynamically unfavourable in aqueous solution. If bond making and breaking is reversible, monomers and very short oligomers predominate. Recent experiments have shown that wetting and drying cycles can overcome this problem and drive the formation of longer polymers. In the dry phase, bond formation is favourable, but diffusion is restricted, and bonds only form between monomers that are initially close together. In the wet phase, some of the bonds are hydrolyzed. However, repositioning of the molecules allows new bonds to form in the next dry phase, leading to an increase in mean polymer length. Here, we consider a simple theoretical model that explains the effect of cycling. There is an equilibrium length distribution with a high mean length that could be achieved if diffusion occurred freely in the dry phase. This equilibrium is inaccessible without diffusion. A single dry cycle without diffusion leads to mean lengths much shorter than this. Repeated cycling leads to a significant increase in polymerization relative to a single cycle. In the most favourable case, cycling leads to the same equilibrium length distribution as would be achieved if free diffusion were possible in the dry phase. These results support the RNA World scenario by explaining a potential route to synthesis of long RNAs; however, they also imply that cycling would be beneficial to the synthesis of other kinds of polymers, including peptides, where bond formation involves a condensation reaction. PMID:27338479

Symmetry and novelty in the electronic and geometric structure of nanoalloys:. the case of Ag27Cu7

NASA Astrophysics Data System (ADS)

Ortigoza, M. Alcántara; Rahman, T. S.

2008-04-01

Nanoparticles of bimetallic alloys have been shown to possess composition dependent characteristics which distinguish themselves from the corresponding bulk alloys. Taking the 34-atom nanoalloy of Ag and Cu (Ag27Cu7), we show using first principles electronic structure calculations that this core-shell alloy indeed has perfect D5h symmetry and consists of only 6 non-equivalent (2 Cu and 4 Ag) atoms. Analysis of the interatomic bond lengths and detailed electronic structure further reveal that the Cu atoms play a major role in controlling the characteristics of the nanoalloy. The higher cohesive energy, together with shorter bond length for Cu, compared to Ag, conspire to produce a hierarchy in the relative strengths of the Ag - Cu, Ag - Ag, and Cu - Cu bonds and corresponding interatomic bond lengths, point to the uniqueness in the characteristics of this nanoalloy. Charge density plots of Ag27Cu7 provide further insights into the relative strengths of the various interatomic bonds.

Sealant Microleakage After Using Nano-Filled Bonding Agents on Saliva-Contaminated Enamel

PubMed Central

Paryab, Mehrsa

2013-01-01

Objective: The efficacy of correctly applied fissure sealants has been revealed in the prevention of caries. Saliva and moisture contamination of the etched enamel surface before sealant placement can decrease the bonding strength of the sealant to the enamel. The aim of this study was to test the new bonding agents containing nano-fillers in order to reduce the negative effect of saliva contamination on the sealant micro leakage. Materials and Methods: Seventy five sound human premolars were randomly assigned to five equal groups as follows: Group A: etching, sealant; Group B: etching, saliva contamination, sealant; Group C: etching, saliva contamination, Single bond, sealant; Group D: etching, saliva contamination, Adper Single bond 2, sealant; Group E: etching, saliva contamination, N Bond, sealant. The samples were thermo-cycled and immersed in basic fuchsine 0.5% by weight. Then, the teeth were sectioned bucco-lingually and parallel to the long axis into two segments. Finally, the length of dye penetration at the sealant-tooth interface was scored according to a four-point scale. Results: Micro-leakage was higher in group B compared to the other groups, while there were no differences among the evaluated dentin adhesives. Conclusion: The use of nano-filled bonding agents as an intermediate layer between the etched enamel and the sealant can reduce sealant micro-leakage after saliva contamination at the level of the uncontaminated enamel. PMID:25512749

Evidence from bond lengths and bond angles for enneacovalence of cobalt, rhodium, iridium, iron, ruthenium, and osmium in compounds with elements of medium electronegativity.

PubMed

Pauling, L

1984-03-01

Enneacovalence of neutral atoms can be achieved for Co, Rh, and Ir by promoting some electrons from the nd orbital to the (n + 1)s and (n + 1)p orbitals and for Fe, Ru, and Os by a similar promotion together with the addition of an electron, which may be provided by an electron pair from a singly bonded carbonyl group or other group. The bond lengths and bond angles are predicted by the theory of enneacovalence to be significantly different for the different transition metals. Recently reported experimental values are shown to be in good agreement with the predicted values, providing support for the theory of enneacovalence and the theory of hybrid sp(3)d(5) bond orbitals.

Short-range structure of barium tellurite glasses and its correlation with stress-optic response

NASA Astrophysics Data System (ADS)

Kaur, Amarjot; Khanna, Atul; Fábián, Margit

2018-06-01

The atomic parameters of metal ion-oxygen speciation such as bond-lengths and nearest neighbor distances for Ba-O, Te-O and O-O pairs, co-ordination numbers and bond angle distributions for O-Ba-O, O-Te-O and O-O-O linkages are determined by neutron diffraction and Reverse Monte Carlo simulations on the series of xBaO-(100-x)TeO2 glasses containing 10, 15 and 20 mol% BaO. The glass network depolymerizes and the average Te-O co-ordination number decreases from 3.60 ± 0.02 to 3.48 ± 0.02 with increase in BaO concentration. Te-O bond lengths are in the range: 1.97 ± 0.01–1.92 ± 0.01 Å. Ba2+ is mostly in octahedral coordination and the Ba-O bond lengths are in the range: 2.73 ± 0.01 to 2.76 ± 0.03 Å. Te-O co-ordination number is also determined by Raman spectroscopy and it shows good agreement with the neutron data. The short-range structural properties i.e. metal ion coordination number (Nc) and bond lengths (d) were correlated with the stress-optic response. The bonding characteristic, Br values were determined from the structural data of xBaO-(100-x)TeO2 glasses and were used to predict the stress-induced birefringence properties.

Gas phase chemistry in gallium nitride CVD: Theoretical determination of the Arrhenius parameters for the first Ga-C bond homolysis of trimethylgallium.

PubMed

Schmid, Rochus; Basting, Daniel

2005-03-24

Experimental evidence suggests that the energy of activation for the first homolytic Ga-C bond fission of GaMe3 of Ea = 249 kJ/mol, measured by Jacko and Price in a hot-wall tube reactor, is affected by surface catalytic effects. In this contribution, the rate constant for this crucial step in the gas-phase pyrolysis of GaMe3 has been calculated by variational transition state theory. By a basis set extrapolation on the MP2/cc-pVXZ level and a correlation correction from CCSD(T)/cc-pVDZ level, a theoretical "best estimate" for the bond energy of Delta H(289K) = 327.2 kJ/mol was derived. For the VTST calculation on the B3LYP/cc-pVDZ level, the energies were corrected to reproduce this bond energy. Partition functions of the transitional modes were approximated by a hindered rotor approximation to be valid along the whole reaction coordinate defined by the Ga-C bond length. On the basis of the canonical transition state theory, reaction rates were determined using the maxima of the free energy Delta G++. An Arrhenius-type rate law was fitted to these rate constants, yielding an apparent energy of activation of Ea = 316.7 kJ/mol. The preexponential factor A = 3.13 x 10(16) 1/s is an order of magnitude larger than the experimental results because of a larger release of entropy at the transition state as compared to that of the unknown surface catalyzed mechanism.

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.

Observation of pendular butterfly Rydberg molecules

PubMed Central

Niederprüm, Thomas; Thomas, Oliver; Eichert, Tanita; Lippe, Carsten; Pérez-Ríos, Jesús; Greene, Chris H.; Ott, Herwig

2016-01-01

Engineering molecules with a tunable bond length and defined quantum states lies at the heart of quantum chemistry. The unconventional binding mechanism of Rydberg molecules makes them a promising candidate to implement such tunable molecules. A very peculiar type of Rydberg molecules are the so-called butterfly molecules, which are bound by a shape resonance in the electron–perturber scattering. Here we report the observation of these exotic molecules and employ their exceptional properties to engineer their bond length, vibrational state, angular momentum and orientation in a small electric field. Combining the variable bond length with their giant dipole moment of several hundred Debye, we observe counter-intuitive molecules which locate the average electron position beyond the internuclear distance. PMID:27703143

Surface-imprinted microspheres prepared by a template-oriented method for the chiral separation of amlodipine.

PubMed

Lai, Shenzhi; Ouyang, Xiaoli; Cai, Changqun; Xu, Wensheng; Chen, Chunyan; Chen, Xiaoming

2017-05-01

The surface imprinting technique has been developed to overcome the mass-transfer difficulty, but the utilization ratio of template molecules in the imprinting procedure still remains a challengeable task to be improved. In this work, specifically designed surface-imprinted microspheres were prepared by a template-oriented method for enantioseparation of amlodipine besylate. Submicron mesoporous silica microspheres were surface-modified with double bonds, followed by polymerizing methacrylic acid to generate carboxyl modified mesoporous silica microspheres (PMAA@SiO 2 ). Afterwards, PMAA@SiO 2 was densely adsorbed with (S)-amlodipine molecules to immobilize template molecules through multiple hydrogen bonding interactions. Then surface molecular imprinting was carried out by cross-linking the carboxyl group of PMAA@SiO 2 with ethylene glycol diglycidyl ether. The surface-imprinted microspheres showed fast binding kinetics of only 20 min for equilibrium adsorption, and the saturation adsorption capacity reached 137 mg/g. The imprinted materials displayed appreciable chiral separation ability when used as column chromatography for enantioseparation of amlodipine from amlodipine besylate, and the enantiomeric excess of (S)-amlodipine reached 13.8% with only 2.3 cm column length by no extra chiral additives. Besides, the imprinted materials exhibited excellent reusability, and this allows the potential application for amplification production of amlodipine enantiomer. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical study on the adsorption and relative stability of conformers of L-ascorbic acid on γ - alumina (100) surface

NASA Astrophysics Data System (ADS)

Mozaffari Majd, M.; Dabbagh, H. A.; Farrokhpour, H.; Najafi Chermahini, A.

2017-11-01

The adsorption energies (Eads) and relative stabilities of selected conformers of the most stable tautomer of L-ascorbic acid (vitamin C) on the dehydroxylated γ-alumina (100) surface were calculated in both gas phase and solvent (water) using the density functional theory (DFT) method. The selected conformers were related to the different rotational angles of OH groups of L-ascorbic acid. The conformational analysis of bare tautomer in both gas and water showed that the conformer No.20 (conf. 20) and 13 (conf. 13) with the dihedral angles of H15sbnd O10sbnd C11sbnd C9 (-73°) and H20sbnd O19sbnd C9sbnd C11 (-135°) were the most stable and unstable conformers, respectively. The performed calculations in the presence of surface showed that the interaction of the conformers with the surface changes their relative stabilities and structures in both gas phase and water. The Ead of each conformer was calculated and it was determined that conf. 8 and conf. 16 have the highest value of Ead in the gas phase (-62.56 kcal/mol) and water (-54.44 kcal/mol), respectively. The optimized structure of each conformer on the surface and the number of hydrogen bonds between it and surface along with their bond lengths were determined.

Laser Surface Preparation for Adhesive Bonding of Aerospace Structural Composites

NASA Technical Reports Server (NTRS)

Belcher, M. A.; Wohl, C. J.; Hopkins, J. W.; Connell, J. W.

2010-01-01

Adhesive bonds are critical to the integrity of built-up structures. Disbonds can often be detected but the strength of adhesion between surfaces in contact is not obtainable without destructive testing. Typically the number one problem in a bonded structure is surface contamination, and by extension, surface preparation. Standard surface preparation techniques, including grit blasting, manual abrasion, and peel ply, are not ideal because of variations in their application. Etching of carbon fiber reinforced plastic (CFRP) panels using a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser appears to be a highly precise and promising way to both clean a composite surface prior to bonding and provide a bond-promoting patterned surface akin to peel ply without the inherent drawbacks from the same (i.e., debris and curvature). CFRP surfaces prepared using laser patterns conducive to adhesive bonding were compared to typical pre-bonding surface treatments through optical microscopy, contact angle goniometry, and post-bonding mechanical testing.

Sacrificial bonds and hidden length in biomaterials: A kinetic constitutive description of strength and toughness in bone

NASA Astrophysics Data System (ADS)

Lieou, Charles K. C.; Elbanna, Ahmed E.; Carlson, Jean M.

2013-07-01

Sacrificial bonds and hidden length in structural molecules account for the greatly increased fracture toughness of biological materials compared to synthetic materials without such structural features by providing a molecular-scale mechanism for energy dissipation. One example is in the polymeric glue connection between collagen fibrils in animal bone. In this paper we propose a simple kinetic model that describes the breakage of sacrificial bonds and the release of hidden length, based on Bell's theory. We postulate a master equation governing the rates of bond breakage and formation. This enables us to predict the mechanical behavior of a quasi-one-dimensional ensemble of polymers at different stretching rates. We find that both the rupture peak heights and maximum stretching distance increase with the stretching rate. In addition, our theory naturally permits the possibility of self-healing in such biological structures.

Studies of EXAFSSpectra using Copper (II) Schiff Base complexes and Determination of Bond lengths Using Synchrotron Radiation

NASA Astrophysics Data System (ADS)

Mishra, A.; Vibhute, V.; Ninama, S.; Parsai, N.; Jha, S. N.; Sharma, P.

2016-10-01

X-ray absorption fine structure (XAFS) at the K-edge of copper has been studied in some copper (II) complexes with substituted anilines like (2Cl, 4Br, 2NO2, 4NO2 and pure aniline) with o-PDA (orthophenylenediamine) as ligand. The X-ray absorption measurements have been performed at the recently developed BL-8 dispersive EXAFS beam line at 2.5 GeV Indus-2 Synchrotron Source at RRCAT, Indore, India. The data obtained has been processed using EXAFS data analysis program Athena.The graphical method gives the useful information about bond length and also the environment of the absorbing atom. The theoretical bond lengths of the complexes were calculated by using interactive fitting of EXAFS using fast Fourier inverse transformation (IFEFFIT) method. This method is also called as Fourier transform method. The Lytle, Sayers and Stern method and Levy's method have been used for determination of bond lengths experimentally of the studied complexes. The results of both methods have been compared with theoretical IFEFFIT method.

Evidence from bond lengths and bond angles for enneacovalence of cobalt, rhodium, iridium, iron, ruthenium, and osmium in compounds with elements of medium electronegativity

PubMed Central

Pauling, Linus

1984-01-01

Enneacovalence of neutral atoms can be achieved for Co, Rh, and Ir by promoting some electrons from the nd orbital to the (n + 1)s and (n + 1)p orbitals and for Fe, Ru, and Os by a similar promotion together with the addition of an electron, which may be provided by an electron pair from a singly bonded carbonyl group or other group. The bond lengths and bond angles are predicted by the theory of enneacovalence to be significantly different for the different transition metals. Recently reported experimental values are shown to be in good agreement with the predicted values, providing support for the theory of enneacovalence and the theory of hybrid sp3d5 bond orbitals. PMID:16593439

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

NASA Astrophysics Data System (ADS)

Larsson, J. A.; Cremer, D.

1999-08-01

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

Raman spectroscopic determination of the length, strength, compressibility, Debye temperature, elasticity, and force constant of the C-C bond in graphene.

PubMed

Yang, X X; Li, J W; Zhou, Z F; Wang, Y; Yang, L W; Zheng, W T; Sun, Chang Q

2012-01-21

From the perspective of bond relaxation and bond vibration, we have formulated the Raman phonon relaxation of graphene, under the stimuli of the number-of-layers, the uni-axial strain, the pressure, and the temperature, in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of the Raman shifts, which are due to the number-of-layers reduction, of the G-peak shift and arises from the vibration of a pair of atoms, while the D- and the 2D-peak shifts involve the z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C(3v) bond geometry to the C(2v) uni-axial bond elongation; (iii) the thermal softening of the phonons originates from bond expansion and weakening; and (iv) the pressure stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift as well as the length, energy, force constant, Debye temperature, compressibility and elastic modulus of the C-C bond in graphene, which is of instrumental importance in the understanding of the unusual behavior of graphene.

Models for mean bonding length, melting point and lattice thermal expansion of nanoparticle materials

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

Omar, M.S., E-mail: dr_m_s_omar@yahoo.com

2012-11-15

Graphical abstract: Three models are derived to explain the nanoparticles size dependence of mean bonding length, melting temperature and lattice thermal expansion applied on Sn, Si and Au. The following figures are shown as an example for Sn nanoparticles indicates hilly applicable models for nanoparticles radius larger than 3 nm. Highlights: ► A model for a size dependent mean bonding length is derived. ► The size dependent melting point of nanoparticles is modified. ► The bulk model for lattice thermal expansion is successfully used on nanoparticles. -- Abstract: A model, based on the ratio number of surface atoms to thatmore » of its internal, is derived to calculate the size dependence of lattice volume of nanoscaled materials. The model is applied to Si, Sn and Au nanoparticles. For Si, that the lattice volume is increases from 20 Å{sup 3} for bulk to 57 Å{sup 3} for a 2 nm size nanocrystals. A model, for calculating melting point of nanoscaled materials, is modified by considering the effect of lattice volume. A good approach of calculating size-dependent melting point begins from the bulk state down to about 2 nm diameter nanoparticle. Both values of lattice volume and melting point obtained for nanosized materials are used to calculate lattice thermal expansion by using a formula applicable for tetrahedral semiconductors. Results for Si, change from 3.7 × 10{sup −6} K{sup −1} for a bulk crystal down to a minimum value of 0.1 × 10{sup −6} K{sup −1} for a 6 nm diameter nanoparticle.« less

Introducing Quantum Mechanics into General Chemistry

NASA Astrophysics Data System (ADS)

Popkowski, Iwona; Bascal, Hafed

2008-10-01

Periodicity has long been recognized as the tool that chemists can use to bring some order to investigating the chemistry of more than one hundred elements. Such studies provide useful tools for understanding a wide array of chemical principles. The advances in computational chemistry make it possible to study and teach such trends with hands on approach. In this study we utilize recently acquired software Spartan Pro to illustrate theoretical measurements of bond length, bond angle and dipole as compared to experimental data. We constructed a matrix of values obtained from the theoretical calculations and obtained trends in bond length, bond angle and dipoles for the several periodic groups.

A new potential for radiation studies of borosilicate glass

NASA Astrophysics Data System (ADS)

Alharbi, Amal F.; Jolley, Kenny; Smith, Roger; Archer, Andrew J.; Christie, Jamieson K.

2017-02-01

Borosilicate glass containing 70 mol% SiO2 and 30 mol% B2O3 is investigated theoretically using fixed charge potentials. An existing potential parameterisation for borosilicate glass is found to give good agreement for the bond angle and bond length distributions compared to experimental values but the optimal density is 30% higher than experiment. Therefore the potential parameters are refitted to give an optimal density of 2.1 g/cm3, in line with experiment. To determine the optimal density, a series of random initial structures are quenched at a rate of 5 × 1012 K/s using constant volume molecular dynamics. An average of 10 such quenches is carried out for each fixed volume. For each quenched structure, the bond angles, bond lengths, mechanical properties and melting points are determined. The new parameterisation is found to give the density, bond angles, bond lengths and Young's modulus comparable with experimental data, however, the melting points and Poisson's ratio are higher than the reported experimental values. The displacement energy thresholds are computed to be similar to those determined with the earlier parameterisation, which is lower than those for ionic crystalline materials.

X-ray absorption spectral studies of copper (II) mixed ligand complexes

NASA Astrophysics Data System (ADS)

Soni, B.; Dar, Davood Ah; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2014-09-01

X-ray absorption spectra at the K-edge of copper have been studied in two copper mixed ligand complexes, one having tetramethyethylenediamine (tmen) and the other having tetraethyethylenediamine (teen) as one of the ligands. The spectra have been recorded at BL-8 dispersive extended X-ray absorption fine structure (EXAFS) beamline at the 2.5 GeV INDUS- 2 synchrotron, RRCAT, Indore, India. The data obtained has been processed using the data analysis program Athena. The energy of the K-absorption edge, chemical shift, edge-width and shift of the principal absorption maximum in the complexes have been determined and discussed. The values of these parameters have been found to be approximately the same in both the complexes indicating that the two complexes possess similar chemical environment around the copper metal atom. The chemical shift has been utilized to estimate effective nuclear charge on the absorbing atom. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length, which is shorter than the actual bond length because of energy dependence of the phase factors in the sine function of the EXAFS equation. This distance is thus the phase- uncorrected bond length. Bond length has also been determined by Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The results obtained from LSS and the Fourier transformation methods are comparable with each other, since both are phase uncorrected bond lengths.

Friction pull plug welding: chamfered heat sink pull plug design

NASA Technical Reports Server (NTRS)

Coletta, Edmond R. (Inventor); Cantrell, Mark A. (Inventor)

2002-01-01

Friction Pull Plug Welding (FPPW) is a solid state repair process for defects up to one inch in length, only requiring single sided tooling (OSL) for usage on flight hardware. Experimental data has shown that the mass of plug heat sink remaining above the top of the plate surface after a weld is completed (the plug heat sink) affects the bonding at the plug top. A minimized heat sink ensures complete bonding of the plug to the plate at the plug top. However, with a minimal heat sink three major problems can arise, the entire plug could be pulled through the plate hole, the central portion of the plug could be separated along grain boundaries, or the plug top hat can be separated from the body. The Chamfered Heat Sink Pull Plug Design allows for complete bonding along the ISL interface through an outside diameter minimal mass heat sink, while maintaining enough central mass in the plug to prevent plug pull through, central separation, and plug top hat separation.

Synthesis, surface characterization, and biointeraction studies of low-surface energy side-chain polyetherurethanes

NASA Astrophysics Data System (ADS)

Porter, Stephen Christopher

1999-10-01

New segmented polyetherurethanes (PEUs) with low surface energy hydrocarbon and fluorocarbon side-chains attached to the polymer hard segments were synthesized. The surface chemistry of solvent cast polymer films was studied using X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and dynamic contact angle (DCA) measurements. Increases in the overall density and length of the alkyl side-chains within the PEUs resulted in greater side-chain concentrations at the polymer surface. PEUs bearing long alkyl (> C10 ) and perfluorocarbon side-chains were found to posses surfaces with highly enriched side-chain concentrations relative to the bulk polymer. In PEUs with significant side-chain surface enrichment, the relatively polar hard segment blocks were shown to reside in high concentrations just below the side-chain enriched surface layer. Furthermore, DCA measurements demonstrated that the surface of the alkyl side-chain PEUs did not undergo significant rearrangement when placed into an aqueous environment, whereas the surface of a hard segment model polymer bearing C18 sidechains (PEU-C18-HS) did. Hydrogen bonding within the PEUs was examined using FTIR and was shown to be disrupted by the addition of side-chains; an effect dependent on the density but not on the length of the side-chains. Heteropolymer blends comprised of mixtures of high side-chain density and side-chain free PEUs were compared with homopolymers having the same overall side-chain concentration as the blends. Significantly more surface enrichment of side-chains was found in the heteropolymer blends whereas hydrogen bonding nearly the same as in the homopolymers. Adsorption of native and delipidized human serum albumin (HSA) from pure solution and blood plasma; the elutabilty of adsorbed HSA; and static platelet adhesion to plasma preadsorbed surfaces, were all examined on alkyl side-chain PEUs. Several polymers with high C18 side-chain densities displayed increased affinity for albumin, and reduced elutability. Among these, PEU-C18-HS demonstrated a significant reduction in platelet adhesion at low plasma pre-adsorption concentrations. However, competitive binary adsorption of fibrinogen in the presence of HSA demonstrated lower relative albumin affinity for PEU-C18-HS than other PEUs. The observed effects are thought to be mainly a result of increased surface hydrophobicity of the alkyl-side chain modified PEU, and not high specificity albumin binding.

Ab initio conformational analysis of N-formyl ?-alanine amide including electron correlation

NASA Astrophysics Data System (ADS)

Yu, Ching-Hsing; Norman, Mya A.; Schäfer, Lothar; Ramek, Michael; Peeters, Anik; van Alsenoy, Christian

2001-06-01

The conformational properties of N-formyl L-alanine amide (ALA) were investigated using RMP2/6-311G∗∗ ab initio gradient geometry optimization. One hundred forty four structures of ALA were optimized at 30° grid points in its φ(N-C(α)), ψ(C(α)-C‧) conformational space. Using cubic spline functions, the grid structures were then used to construct analytical representations of complete surfaces, in φ,ψ-space, of bond lengths, bond angles, torsional sensitivity and electrostatic atomic charges. Analyses show that, in agreement with previous studies, the right-handed helical conformation, αR, is not a local energy minimum of the potential energy surface of ALA. Comparisons with protein crystallographic data show that the characteristic differences between geometrical trends in dipeptides and proteins, previously found for ab initio dipeptide structures obtained without electron correlation, are also found in the electron-correlated geometries. In contrast to generally accepted features of force fields used in empirical molecular modeling, partial atomic charges obtained by the CHELPG method are found to be not constant, but to vary significantly throughout the φ,ψ-space. By comparing RHF and MP2 structures, the effects of dispersion forces on ALA were studied, revealing molecular contractions for those conformations, in which small adjustments of torsional angles entail large changes in non-bonded distances.

Comparison of the structural basis for thermal stability between archaeal and bacterial proteins.

PubMed

Ding, Yanrui; Cai, Yujie; Han, Yonggang; Zhao, Bingqiang

2012-01-01

In this study, the structural basis for thermal stability in archaeal and bacterial proteins was investigated. There were many common factors that confer resistance to high temperature in both archaeal and bacterial proteins. These factors include increases in the Lys content, the bends and blanks of secondary structure, the Glu content of salt bridge; decreases in the number of main-side chain hydrogen bond and exposed surface area, and changes in the bends and blanks of amino acids. Certainly, the utilization of charged amino acids to form salt bridges is a primary factor. In both heat-resistant archaeal and bacterial proteins, most Glu and Asp participate in the formation of salt bridges. Other factors may influence either archaeal or bacterial protein thermostability, which includes the more frequent occurrence of shorter 3(10)-helices and increased hydrophobicity in heat-resistant archaeal proteins. However, there were increases in average helix length, the Glu content in salt bridges, temperature factors and decreases in the number of main-side chain hydrogen bonds, uncharged-uncharged hydrogen bonds, hydrophobicity, and buried and exposed polar surface area in heat-resistant bacterial proteins. Evidently, there are few similarities and many disparities between the heat-resistant mechanisms of archaeal and bacterial proteins.

Fracture of a composite reinforced by unidirectional fibers

NASA Astrophysics Data System (ADS)

Hasanov, F. F.

2014-11-01

An elastic medium weakened by a periodic system of circular holes filled with homogeneous elastic fibers whose surface is coated with a homogeneous film is considered. A fracture model for a medium with a periodic structure is proposed, which is based on an analysis of the fracture zone near the crack tip. It is assumed that the fracture zone is a layer of finite length containing a material with partially broken bonds between separate structural elements (end zone). The fracture zone is considered as part of the crack. The bonds between crack faces in the end zone are modeled by applying the cohesive forces caused by the presence of bonds to the crack surface. An analysis of the limit equilibrium of shear cracks in the end zone of the model is performed on the basis of a nonlocal fracture criterion together with a force condition for the motion of crack tip and a deformation condition for determining the motion of faces of end-zone cracks. In the analysis, relationships between the cohesive forces and the shear of crack faces are established, the stress state near the crack is assessed with account of external loading, cohesive forces, and fiber arrangement, and the critical external loads as functions of geometric parameters of the composite are determined.

Finite Element Bond Modeling for Indented Wires in Pretensioned Concrete Crossties

DOT National Transportation Integrated Search

2016-04-12

Indented wires have been increasingly employed by : concrete crosstie manufacturers to improve the bond between : prestressing steel reinforcements and concrete, as bond can : affect several critical performance measures, including transfer : length,...

The effects of dentin and intaglio indirect ceramic optimized polymer restoration surface treatment on the shear bond strength of resin cement

NASA Astrophysics Data System (ADS)

Puspitarini, A.; Suprastiwi, E.; Usman, M.

2017-08-01

Ceramic optimized polymer (ceromer) bonds to the tooth substrate through resin cements. The bond strength between dentin, resin cement, and ceromer depends on the applied surface treatment. To analyze the effects of dentin and intaglio ceromer surface treatment on the shear bond strength self-adhesive resin cement. Forty-five dentin premolar and ceromer specimens were bonded with resin cement and divided into three groups as follows: in group 1, no treatment was applied; in group 2, dentin surface treatment was carried out with acid etching and a bonding agent; and in group 3, dentin surface treatment was carried out with acid etching, a bonding agent, and intaglio ceromer surface treatment with etching and silane. All specimens were incubated at 37 °C for 24 hours, and the shear bond strength was measured using a universal testing machine. Group 3 showed the highest shear bond strength, followed by group 2. The surface treatment of dentin and intaglio ceromer showed significantly improved shear bond strength in the group comparison. Dentin and intaglio ceromer surface treatment can improved the shear bond strength self-adhesive resin cement.

Bond–Slip Relationship for CFRP Sheets Externally Bonded to Concrete under Cyclic Loading

PubMed Central

Li, Ke; Cao, Shuangyin; Yang, Yue; Zhu, Juntao

2018-01-01

The objective of this paper was to explore the bond–slip relationship between carbon fiber-reinforced polymer (CFRP) sheets and concrete under cyclic loading through experimental and analytical approaches. Modified beam tests were performed in order to gain insight into the bond–slip relationship under static and cyclic loading. The test variables are the CFRP-to-concrete width ratio, and the bond length of the CFRP sheets. An analysis of the test results in this paper and existing test results indicated that the slope of the ascending segment of the bond–slip curve decreased with an increase in the number of load cycles, but the slip corresponding to the maximum shear stress was almost invariable as the number of load cycles increased. In addition, the rate of reduction in the slope of the ascending range of the bond–slip curve during cyclic loading decreased as the concrete strength increased, and increased as the load level or CFRP-to-concrete width ratio enhanced. However, these were not affected by variations in bond length if the residual bond length was longer than the effective bond length. A bilinear bond–slip model for CFRP sheets that are externally bonded to concrete under cyclic loading, which considered the effects of the cyclic load level, concrete strength, and CFRP-to-concrete ratio, was developed based on the existing static bond–slip model. The accuracy of this proposed model was verified by a comparison between this proposed model and test results. PMID:29495383

Crystal structure of catena-poly[[aquadi-n-propyl­tin(IV)]-μ-oxalato

PubMed Central

Reichelt, Martin; Reuter, Hans

2014-01-01

The title compound, [Sn(C3H7)2(H2O)(C2O4)]n, represents the first diorganotin(IV) oxalate hydrate to be structurally characterized. The tin(IV) atom of the one-dimensional coordination polymer is located on a twofold rotation axis and is coordinated by two chelating oxalate ligands with two slightly different Sn—O bond lengths of 2.290 (2) and 2.365 (2) Å, two symmetry-related n-propyl groups with a Sn—C bond lengths of 2.127 (3) Å, and a water mol­ecule with a Sn—O bond length of 2.262 (2) Å. The coordination polyhedron around the SnIV atom is a slightly distorted penta­gonal bipyramid with a nearly linear axis between the trans-oriented n-propyl groups [C—Sn—C = 176.8 (1)°]. The bond angles between the oxygen atoms of the equatorial plane range from 70.48 (6)° to 76.12 (8)°. A one-dimensional coordination polymer results from the less asymmetric bilateral coordination of the centrosymmetric oxalate anion, inter­nally reflected by two slightly different C—O bond lengths of 1.248 (3) and 1.254 (3) Å. The chains of the polymer propagate parallel to [001] and are held together by hydrogen bonds between water mol­ecules and oxalate anions of neighboring chains, leading to a two-dimensional network parallel to (100). PMID:25249862

Compositional effects on Si–OH bond length in hydrous silicates with implications for trends in the SiOH acidity

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

Zarubin, Dmitri P., E-mail: dmitri.zarubin@mtu-net.ru

2014-04-01

Theoretical calculations of the structure and Brønsted acidity of SiOH groups in silica clusters have never addressed the question if these vary with the degree of SiOH deprotonation. In this connection, a statistical analysis is presented of Si–OH bond lengths in crystalline hydrogen silicates with well-determined structures with a special emphasis placed on effects of the silicate composition. It is found that among hydrogen silicates of large cations with low charges the Si–OH bonds are always longer than terminal Si–O bonds in the same anion and correlate in length with the anionic charge per tetrahedron. The findings are explained bymore » steric limitations on charge balancing at oxygen atoms by hydrogen bonds and/or cations. It is suggested that similar limitations and imbalances may underlie the well-known trends in the Brønsted acidity of silicic acids and silicas in aqueous media: decreased acidity with increased SiOH deprotonation and increased acidity with increased tetrahedra connectivity. - Graphical abstract: Si–OH bonds in crystalline silicates lengthen with the anionic charge per tetrahedron, which is in parallel with the well-known trend of decreased acidity of silicic acids and silicas in solution with increased degree of deprotonation. - Highlights: • Si–OH bonds in alkali hydrogen silicates are always longer than terminal Si–O bonds. • Si–OH bonds in silicates lengthen with the anionic charge per tetrahedron. • The Si–OH bond elongation results from inherent underbonding of terminal O atoms. • The longer the Si–OH bond, the less acidic the OH group is.« less

The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

PubMed

Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

2005-03-01

The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and substrate bands. Significant implications are described for density-functional calculations of through-molecule electron transport in molecular electronics.

Shock response of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX): The C-N bond scission studied by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Yuan, Jiao-Nan; Wei, Yong-Kai; Zhang, Xiu-Qing; Chen, Xiang-Rong; Ji, Guang-Fu; Kotni, Meena Kumari; Wei, Dong-Qing

2017-10-01

The shock response has a great influence on the design, synthesis, and application of energetic materials in both industrial and military areas. Therefore, the initial decomposition mechanism of bond scission at the atomistic level of condensed-phase α-RDX under shock loading has been studied based on quantum molecular dynamics simulations in combination with a multi-scale shock technique. First, based on the frontier molecular orbital theory, our calculated result shows that the N-NO2 bond is the weakest bond in the α-RDX molecule in the ground state, which may be the initial bond for pyrolysis. Second, the changes of bonds under shock loading are investigated by the changes of structures, kinetic bond lengths, and Laplacian bond orders during the simulation. Also, the variation of thermodynamic properties with time in shocked α-RDX at 10 km/s along the lattice vector a for a timescale of up to 3.5 ps is presented. By analyzing the detailed structural changes of RDX under shock loading, we find that the shocked RDX crystal undergoes a process of compression and rotation, which leads to the C-N bond initial rupture. The time variation of dynamic bond lengths in a shocked RDX crystal is calculated, and the result indicates that the C-N bond is easier to rupture than other bonds. The Laplacian bond orders are used to predict the molecular reactivity and stability. The values of the calculated bond orders show that the C-N bonds are more sensitive than other bonds under shock loading. In a word, the C-N bond scission has been validated as the initial decomposition in a RDX crystal shocked at 10 km/s. Finally, the bond-length criterion has been used to identify individual molecules in the simulation. The distance thresholds up to which two particles are considered direct neighbors and assigned to the same cluster have been tested. The species and density numbers of the initial decomposition products are collected according to the trajectory.

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

Lu, Y.; Xie, D.; Yan, G.

Accurate knowledge of the potential energy surface (PES) and the spectroscopic properties of carbon dioxide plays an important role in understanding the greenhouse effect. The potential energy surface for the electronic ground state of CO{sub 2} is refined by means of a two-step variational procedure using the exact rovibrational Hamiltonian in the bond length-bond angle coordinates. In the refinement, the observed rovibrational energy levels for J = 0-4 below 16,000 cm {sup -1}, obtained from the effective spectroscopic constants of CO{sub 2} given by Rothman et al. (J Quant Spectrosc Radiat Transfer 1992, 48, 537) in HITRAN data base, aremore » used as the input data points. The accurate ab initio force constants of Martin et al. (Chem Phys Lett 1993, 205, 535) are taken as the initial guess for the potential. The root-mean-square error of this fit to the 431 observed rovibrational energy levels is 0.05 cm{sup {minus}1}. With the optimized potential energy surface, the authors also calculate the rovibrational energy levels of {sup 13}C{sup 16}O{sub 2} and {sup 12}C{sup 18}O{sub 2}. The results are in good agreement with experimental data.« less

Polymorphisms in Fibronectin Binding Protein A of Staphylococcus Aureus are Associated with Infection of Cardiovascular Devices

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

Lower, Steven; Lamlertthon, Supaporn; Casillas-Ituarte, Nadia

Medical implants, like cardiovascular devices, improve the quality of life for countless individuals but may become infected with bacteria like Staphylococcus aureus. Such infections take the form of a bio-film, a structured community of bacterial cells adherent to the surface of a solid substrate. Every bio-film begins with an attractive force or bond between bacterium and substratum. We used atomic force microscopy to probe experimentally forces between a fibronectin-coated surface (i.e., proxy for an implanted cardiac device) and fibronectin-binding receptors on the surface of individual living bacteria from each of 80 clinical isolates of S. aureus. These isolates originated frommore » humans with infected cardiac devices (CDI; n = 26), uninfected cardiac devices (n = 20), and the anterior nares of asymptomatic subjects (n = 34). CDI isolates exhibited a distinct bindingforce signature and had speci!c single amino acid polymorphisms in fibronectin-binding protein A corresponding to E652D, H782Q, and K786N. In silico molecular dynamics simulations demonstrate that residues D652, Q782, and N786 in fibronectin-binding protein A form extra hydrogen bonds with fibronectin, complementing the higher binding force and energy measured by atomic force microscopy for the CDI isolates. This study is significant, because it links pathogenic bacteria biofilms from the length scale of bonds acting across a nanometer-scale space to the clinical presentation of disease at the human dimension.« less

Bond Length Dependence on Quantum States as Shown by Spectroscopy

ERIC Educational Resources Information Center

Lim, Kieran F.

2005-01-01

A discussion on how a spreadsheet simulation of linear-molecular spectra could be used to explore the dependence of rotational band spacing and contours on average bond lengths in the initial and final quantum states is presented. The simulation of hydrogen chloride IR, iodine UV-vis, and nitrogen UV-vis spectra clearly show whether the average…

Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

PubMed

Humphries, T D; Sheppard, D A; Buckley, C E

2015-06-30

For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

Micro-miniature gas chromatograph column disposed in silicon wafers

DOEpatents

Yu, Conrad M.

2000-01-01

A micro-miniature gas chromatograph column is fabricated by forming matching halves of a circular cross-section spiral microcapillary in two silicon wafers and then bonding the two wafers together using visual or physical alignment methods. Heating wires are deposited on the outside surfaces of each wafer in a spiral or serpentine pattern large enough in area to cover the whole microcapillary area inside the joined wafers. The visual alignment method includes etching through an alignment window in one wafer and a precision-matching alignment target in the other wafer. The two wafers are then bonded together using the window and target. The physical alignment methods include etching through vertical alignment holes in both wafers and then using pins or posts through corresponding vertical alignment holes to force precision alignment during bonding. The pins or posts may be withdrawn after curing of the bond. Once the wafers are bonded together, a solid phase of very pure silicone is injected in a solution of very pure chloroform into one end of the microcapillary. The chloroform lowers the viscosity of the silicone enough that a high pressure hypodermic needle with a thumbscrew plunger can force the solution into the whole length of the spiral microcapillary. The chloroform is then evaporated out slowly to leave the silicone behind in a deposit.

Dynamic Responses and Initial Decomposition under Shock Loading: A DFTB Calculation Combined with MSST Method for β-HMX with Molecular Vacancy.

PubMed

He, Zheng-Hua; Chen, Jun; Ji, Guang-Fu; Liu, Li-Min; Zhu, Wen-Jun; Wu, Qiang

2015-08-20

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of β-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction.

Thinking Like a Chemist: Intuition in Thermoelectric Materials.

PubMed

Zeier, Wolfgang G; Zevalkink, Alex; Gibbs, Zachary M; Hautier, Geoffroy; Kanatzidis, Mercouri G; Snyder, G Jeffrey

2016-06-06

The coupled transport properties required to create an efficient thermoelectric material necessitates a thorough understanding of the relationship between the chemistry and physics in a solid. We approach thermoelectric material design using the chemical intuition provided by molecular orbital diagrams, tight binding theory, and a classic understanding of bond strength. Concepts such as electronegativity, band width, orbital overlap, bond energy, and bond length are used to explain trends in electronic properties such as the magnitude and temperature dependence of band gap, carrier effective mass, and band degeneracy and convergence. The lattice thermal conductivity is discussed in relation to the crystal structure and bond strength, with emphasis on the importance of bond length. We provide an overview of how symmetry and bonding strength affect electron and phonon transport in solids, and how altering these properties may be used in strategies to improve thermoelectric performance. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser Surface Preparation and Bonding of Aerospace Structural Composites

NASA Technical Reports Server (NTRS)

Belcher, M. A.; Wohl, C. J.; Hopkins, J. W.; Connell, J. W.

2010-01-01

Adhesive bonds are critical to the integrity of built-up structures. Disbonds can often be detected but the strength of adhesion between surfaces in contact is not obtainable without destructive testing. Typically the number one problem in a bonded structure is surface contamination, and by extension, surface preparation. Standard surface preparation techniques, including grit blasting, manual abrasion, and peel ply, are not ideal because of variations in their application. Etching of carbon fiber reinforced plastic (CFRP) panels using a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser appears to be a highly precise and promising way to both clean a composite surface prior to bonding and provide a bond-promoting patterned surface akin to peel ply without the inherent drawbacks from the same (i.e., debris and curvature). CFRP surfaces prepared using laser patterns conducive to adhesive bonding were compared to typical prebonding surface treatments through optical microscopy, contact angle goniometry, and post-bonding mechanical testing.

Surface decoration of short-cut polyimide fibers with multi-walled carbon nanotubes and their application for reinforcement of lightweight PC/ABS composites

NASA Astrophysics Data System (ADS)

Zhang, Le; Han, Enlin; Wu, Yulun; Wang, Xiaodong; Wu, Dezhen

2018-06-01

The surface decoration of short-cut polyimide (PI) fibers with multi-walled carbon nanotubes (MWCNTs) was performed by fabricating a polydopamine (PDA) coating layer on the fiber surface and then immobilizing MWCNTs onto the coating layer via covalent bonding. This successful surface decoration was confirmed by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared microscopy and static water contact angle. The application of the surface-decorated PI fibers as reinforcing fibers for reinforcement of polycarbonate (PC)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy was investigated, which indicated that the MWCNTs-decorated PI fibers not only could effectively reinforce the PC/ABS alloy but also generated a significant lightweighting effect on the resulting composites. The maximum mechanical properties were achieved for the composites at a fiber content of 20 wt.% and a fiber length of 3 mm. This significant reinforcement effect is attributed to the enhancement of interaction bonding strength between the fibers and matrix as a result of the surface decoration of PI fibers with MWCNTs. The morphological investigation suggested that fiber rupture was the major energy dissipation mechanism in the tensile and impact failures, whereas fiber debonding and pullout were partly involved in the fracture energy dissipation. In addition, the presence of surface-decorated PI fibers slightly enhanced the thermal stability and load bearing capability of composites. This work can provide a type of high-performance lightweight composite material for automobile and aviation industries.

Ultra precision and reliable bonding method

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2001-01-01

The bonding of two materials through hydroxide-catalyzed hydration/dehydration is achieved at room temperature by applying hydroxide ions to at least one of the two bonding surfaces and by placing the surfaces sufficiently close to each other to form a chemical bond between them. The surfaces may be placed sufficiently close to each other by simply placing one surface on top of the other. A silicate material may also be used as a filling material to help fill gaps between the surfaces caused by surface figure mismatches. A powder of a silica-based or silica-containing material may also be used as an additional filling material. The hydroxide-catalyzed bonding method forms bonds which are not only as precise and transparent as optical contact bonds, but also as strong and reliable as high-temperature frit bonds. The hydroxide-catalyzed bonding method is also simple and inexpensive.

Pullout Performances of Grouted Rockbolt Systems with Bond Defects

NASA Astrophysics Data System (ADS)

Xu, Chang; Li, Zihan; Wang, Shanyong; Wang, Shuren; Fu, Lei; Tang, Chunan

2018-03-01

This paper presents a numerical study on the pullout behaviour of fully grouted rockbolts with bond defects. The cohesive zone model (CZM) is adopted to model the bond-slip behaviour between the rockbolt and grout material. Tensile tests were also conducted to validate the numerical model. The results indicate that the defect length can obviously influence the load and stress distributions along the rockbolt as well as the load-displacement response of the grouted system. Moreover, a plateau in the stress distribution forms due to the bond defect. The linear limit and peak load of the load-displacement response decrease as the defect length increases. A bond defect located closer to the loaded end leads to a longer nonlinear stage in the load-displacement response. However, the peak loads measured from the specimens made with various defect locations are almost approximately the same. The peak load for a specimen with the defects equally spaced along the bolt is higher than that for a specimen with defects concentrated in a certain zone, even with the same total defect length. Therefore, the dispersed pattern of bond defects would be much safer than the concentrated pattern. For the specimen with dispersed defects, the peak load increases with an increase in the defect spacing, even if the total defect length is the same. The peak load for a grouted rockbolt system with defects increases with an increases in the bolt diameter. This work leads to a better understanding of the load transfer mechanism for grouted rockbolt systems with bond defects, and paves the way towards developing a general evaluation method for damaged rockbolt grouted systems.

Ge K-Edge Extended X-Ray Absorption Fine Structure Study of the Local Structure of Amorphous GeTe and the Crystallization

NASA Astrophysics Data System (ADS)

Maeda, Yoshihito; Wakagi, Masatoshi

1991-01-01

The local structure and crystallization of amorphous GeTe (a-GeTe) were examined by means of Ge K-edge EXAFS. In a-GeTe, both Ge-Ge and Ge-Te bonds were observed to exist in nearest neighbors of Ge. The average coordination number around Ge is 3.7, which is close to the tetrahedral structure. A random covalent network (RCN) model seems to be suitable for the local Structure. After a-GeTe crystallizes at 129°C, the Ge-Ge bond disappears and the Ge-Te bond length increases considerably. As temperature rises, in a-GeTe the Debye-Waller factor of the Ge-Te bond increases greatly, while that of the Ge-Ge bond increases only slightly. At the crystallization, it is found that the fluctuation of the Ge-Te bond length plays a major role in the change of the local structure and bonding state around Ge.

Surface texturing of fluoropolymers

NASA Technical Reports Server (NTRS)

Banks, B. A.; Mirtich, M. J.; Sovey, J. S. (Inventor)

1982-01-01

A method is disclosed for improving surface texture for adhesive bonding, metal bonding, substrate plating, decal substrate preparation, and biomedical implant applications. The surface to be bonded is dusted in a controlled fashion to produce a disbursed layer of fine mesh particles which serve as masks. The surface texture is produced by impinging gas ions on the masked surface. The textured surface takes the form of pillars or cones. The bonding material, such as a liquid epoxy, flows between the pillars which results in a bond having increased strength. For bonding metals a thin film of metal is vapor or sputter deposited onto the textured surface. Electroplating or electroless plating is then used to increase the metal thickness in the desired amount.

A noncontacting scanning photoelectron emission technique for bonding surface cleanliness inspection

NASA Technical Reports Server (NTRS)

Gause, Raymond L.

1989-01-01

Molecular contamination of bonding surfaces can drastically affect the bond strength that can be achieved and therefore the structural integrity and reliability of the bonded part. The presence of thin contaminant films on bonding surfaces can result from inadequate or incomplete cleaning methods, from oxide growth during the time between cleaning (such as grit blasting) and bonding, or from failure to properly protect cleaned surfaces from oils, greases, fingerprints, release agents, or deposition of facility airborne molecules generated by adjacent manufacturing or processing operations. Required cleanliness levels for desired bond performance can be determined by testing to correlate bond strength with contaminant type and quantity, thereby establishing the degree of contamination that can be tolerated based on the strength that is needed. Once the maximum acceptable contaminant level is defined, a method is needed to quantitatively measure the contaminant level on the bonding surface prior to bonding to verify that the surface meets the established cleanliness requirement. A photoelectron emission technique for the nondestructive inspection of various bonding surfaces, both metallic and nonmetallic, to provide quantitative data on residual contaminant levels is described. The technique can be used to scan surfaces at speeds of at least 30 ft/min using a servo system to maintain required sensor to surface spacing. The fundamental operation of the photoelectron emission sensor system is explained and the automated scanning system and computer data acquisition hardware and software are described.

Anisotropy of atomic bonds formed by p-type dopants in bulk GaN crystals

NASA Astrophysics Data System (ADS)

Lawniczak-Jablonska, K.; Suski, T.; Gorczyca, I.; Christensen, N. E.; Libera, J.; Kachniarz, J.; Lagarde, P.; Cortes, R.; Grzegory, I.

The anisotropy of atomic bonds formed by acceptor dopants with nitrogen in bulk wurtzite GaN crystals was studied by means of linearly polarized synchrotron radiation used in measurements of X-ray-absorption spectra for the K-edgeof Mg and Zn dopants. These spectra correspond to i) a single acceptor N bond along the c-axis and ii) three bonds realized with N atoms occupying the ab-plane perpendicular to the c-axis. The Zn dopant formed resonant spectra similar to that characteristic for Ga cations. In the case of the Mg dopant, similarity to Ga cations was observed for triple bonds in the ab-plane, only. Practically no resonant structure for spectra detected along the c-axis was observed. The absorption spectra were compared with ab initio calculations using the full-potential linear muffin-tin-orbital method. These calculations were also used for determination of the bond length for Mg-N and Zn-N in wurtzite GaN crystals and show that introducing dopants causes an increase of the lengths of the bonds formed by both dopants. Extended X-ray-absorption fine-structure measurements performed for bulk GaN:Zn confirmed the prediction of the theory in the case of the Zn-N bond. Finally, it is suggested that the anisotropy in the length of the Mg-N bonds, related to their larger strength in the case of bonds in the ab-plane, can explain preferential formation of a superlattice consisting of Mg-rich layers arranged in ab-planes of several bulk GaN:Mg crystals observed by transmission electron microscopy. Within the sensitivity of the method used, no parasitic metallic clusters or oxide compounds formed by the considered acceptors in GaN crystals were found.

Two-dimensional electronic transport and surface electron accumulation in MoS2.

PubMed

Siao, M D; Shen, W C; Chen, R S; Chang, Z W; Shih, M C; Chiu, Y P; Cheng, C-M

2018-04-12

Because the surface-to-volume ratio of quasi-two-dimensional materials is extremely high, understanding their surface characteristics is crucial for practically controlling their intrinsic properties and fabricating p-type and n-type layered semiconductors. Van der Waals crystals are expected to have an inert surface because of the absence of dangling bonds. However, here we show that the surface of high-quality synthesized molybdenum disulfide (MoS 2 ) is a major n-doping source. The surface electron concentration of MoS 2 is nearly four orders of magnitude higher than that of its inner bulk. Substantial thickness-dependent conductivity in MoS 2 nanoflakes was observed. The transfer length method suggested the current transport in MoS 2 following a two-dimensional behavior rather than the conventional three-dimensional mode. Scanning tunneling microscopy and angle-resolved photoemission spectroscopy measurements confirmed the presence of surface electron accumulation in this layered material. Notably, the in situ-cleaved surface exhibited a nearly intrinsic state without electron accumulation.

Relationship between surface area for adhesion and tensile bond strength--evaluation of a micro-tensile bond test.

PubMed

Sano, H; Shono, T; Sonoda, H; Takatsu, T; Ciucchi, B; Carvalho, R; Pashley, D H

1994-07-01

The purpose of this study was to test the null hypothesis that there is no relationship between the bonded surface area of dentin and the tensile strength of adhesive materials. The enamel was removed from the occlusal surface of extracted human third molars, and the entire flat surface was covered with resin composite bonded to the dentin to form a flat resin composite crown. Twenty-four hours later, the bonded specimens were sectioned parallel to the long axis of the tooth into 10-20 thin sections whose upper part was composed of resin composite with the lower half being dentin. These small sections were trimmed using a high speed diamond bur into an hourglass shape with the narrowest portion at the bonded interface. Surface area was varied by altering the specimen thickness and width. Tensile bond strength was measured using custom-made grips in a universal testing machine. Tensile bond strength was inversely related to bonded surface area. At surface areas below 0.4 mm2, the tensile bond strengths were about 55 MPa for Clearfil Liner Bond 2 (Kuraray Co., Ltd.), 38 MPa for Scotchbond MP (3M Dental Products), and 20 MPa for Vitremer (3M Dental Products). At these small surface areas all of the bond failures were adhesive in nature. This new method permits measurement of high bond strengths without cohesive failure of dentin. It also permits multiple measurements to be made within a single tooth.

3-Axis Fully-Integrated Capacitive Tactile Sensor with Flip-Bonded CMOS on LTCC Interposer.

PubMed

Asano, Sho; Muroyama, Masanori; Nakayama, Takahiro; Hata, Yoshiyuki; Nonomura, Yutaka; Tanaka, Shuji

2017-10-25

This paper reports a 3-axis fully integrated differential capacitive tactile sensor surface-mountable on a bus line. The sensor integrates a flip-bonded complementary metal-oxide semiconductor (CMOS) with capacitive sensing circuits on a low temperature cofired ceramic (LTCC) interposer with Au through vias by Au-Au thermo-compression bonding. The CMOS circuit and bonding pads on the sensor backside were electrically connected through Au bumps and the LTCC interposer, and the differential capacitive gap was formed by an Au sealing frame. A diaphragm for sensing 3-axis force was formed in the CMOS substrate. The dimensions of the completed sensor are 2.5 mm in width, 2.5 mm in length, and 0.66 mm in thickness. The fabricated sensor output coded 3-axis capacitive sensing data according to applied 3-axis force by three-dimensional (3D)-printed pins. The measured sensitivity was as high as over 34 Count/mN for normal force and 14 to 15 Count/mN for shear force with small noise, which corresponds to less than 1 mN. The hysteresis and the average cross-sensitivity were also found to be less than 2% full scale and 11%, respectively.

3-Axis Fully-Integrated Capacitive Tactile Sensor with Flip-Bonded CMOS on LTCC Interposer †

PubMed Central

Asano, Sho; Nakayama, Takahiro; Hata, Yoshiyuki; Tanaka, Shuji

2017-01-01

This paper reports a 3-axis fully integrated differential capacitive tactile sensor surface-mountable on a bus line. The sensor integrates a flip-bonded complementary metal-oxide semiconductor (CMOS) with capacitive sensing circuits on a low temperature cofired ceramic (LTCC) interposer with Au through vias by Au-Au thermo-compression bonding. The CMOS circuit and bonding pads on the sensor backside were electrically connected through Au bumps and the LTCC interposer, and the differential capacitive gap was formed by an Au sealing frame. A diaphragm for sensing 3-axis force was formed in the CMOS substrate. The dimensions of the completed sensor are 2.5 mm in width, 2.5 mm in length, and 0.66 mm in thickness. The fabricated sensor output coded 3-axis capacitive sensing data according to applied 3-axis force by three-dimensional (3D)-printed pins. The measured sensitivity was as high as over 34 Count/mN for normal force and 14 to 15 Count/mN for shear force with small noise, which corresponds to less than 1 mN. The hysteresis and the average cross-sensitivity were also found to be less than 2% full scale and 11%, respectively. PMID:29068429

Size-depressed critical temperatures for the order-disorder transition of FePt, CoPt, FePb, Cu2S, and ZnS nanostructures

NASA Astrophysics Data System (ADS)

Jiang, R.; Zhou, Z. F.; Yang, X. X.; Guo, N. G.; Qi, W. H.; Sun, C. Q.

2013-01-01

The size dependency of the critical temperature (TC) for the order-disorder phase transitions of both the bimetallic and the chalcogenide nanoclusters is shown to follow the rule of bond order-length-strength correlation. The loss of the cohesive energy of the undercoordinated atoms in the surface skin dictates the structural stability. Theoretical reproduction of the size TC trends of FePt, CoPt, FePb, Cu2S, and ZnS nanostructures not only confirms our expectations without involving the concepts of surface energy or entropy used for continuum bulk materials but also provides guideline for engineering nanostructured alloys or compounds.

Investigation of non-corrin cobalt(II)-containing sites in protein structures of the Protein Data Bank.

PubMed

Abriata, Luciano Andres

2013-04-01

Protein X-ray structures with non-corrin cobalt(II)-containing sites, either natural or substituting another native ion, were downloaded from the Protein Data Bank and explored to (i) describe which amino acids are involved in their first ligand shells and (ii) analyze cobalt(II)-donor bond lengths in comparison with previously reported target distances, CSD data and EXAFS data. The set of amino acids involved in Co(II) binding is similar to that observed for catalytic Zn(II) sites, i.e. with a large fraction of carboxylate O atoms from aspartate and glutamate and aromatic N atoms from histidine. The computed Co(II)-donor bond lengths were found to depend strongly on structure resolution, an artifact previously detected for other metal-donor distances. Small corrections are suggested for the target bond lengths to the aromatic N atoms of histidines and the O atoms of water and hydroxide. The available target distance for cysteine (Scys) is confirmed; those for backbone O and other donors remain uncertain and should be handled with caution in refinement and modeling protocols. Finally, a relationship between both Co(II)-O bond lengths in bidentate carboxylates is quantified.

Structure determination of the ordered (2 × 1) phase of NiSi surface alloy on Ni(111) using low-energy electron diffraction

NASA Astrophysics Data System (ADS)

Sazzadur Rahman, Md.; Amirul Islam, Md.; Saha, Bidyut Baran; Nakagawa, Takeshi; Mizuno, Seigi

2015-12-01

The (2 × 1) structure of the two-dimensional nickel silicide surface alloy on Ni(111) was investigated using quantitative low-energy electron diffraction analysis. The unit cell of the determined silicide structure contains one Si and one Ni atom, corresponding to a chemical formula of NiSi. The Si atoms adopt substitutional face-centered cubic hollow sites on the Ni(111) substrate. The Ni-Si bond lengths were determined to be 2.37 and 2.34 Å. Both the alloy surface and the underlying first layers of Ni atoms exhibit slight corrugation. The Ni-Si interlayer distance is smaller than the Ni-Ni interlayer distance, which indicates that Si atoms and underlying Ni atoms strongly interact.

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.

Modeling Shear Induced Von Willebrand Factor Binding to Collagen

NASA Astrophysics Data System (ADS)

Dong, Chuqiao; Wei, Wei; Morabito, Michael; Webb, Edmund; Oztekin, Alparslan; Zhang, Xiaohui; Cheng, Xuanhong

2017-11-01

Von Willebrand factor (vWF) is a blood glycoprotein that binds with platelets and collagen on injured vessel surfaces to form clots. VWF bioactivity is shear flow induced: at low shear, binding between VWF and other biological entities is suppressed; for high shear rate conditions - as are found near arterial injury sites - VWF elongates, activating its binding with platelets and collagen. Based on parameters derived from single molecule force spectroscopy experiments, we developed a coarse-grain molecular model to simulate bond formation probability as a function of shear rate. By introducing a binding criterion that depends on the conformation of a sub-monomer molecular feature of our model, the model predicts shear-induced binding, even for conditions where binding is highly energetically favorable. We further investigate the influence of various model parameters on the ability to predict shear-induced binding (vWF length, collagen site density and distribution, binding energy landscape, and slip/catch bond length) and demonstrate parameter ranges where the model provides good agreement with existing experimental data. Our results may be important for understanding vWF activity and also for achieving targeted drug therapy via biomimetic synthetic molecules. National Science Foundation (NSF),Division of Mathematical Sciences (DMS).

Vector-based model of elastic bonds for simulation of granular solids.

PubMed

Kuzkin, Vitaly A; Asonov, Igor E

2012-11-01

A model (further referred to as the V model) for the simulation of granular solids, such as rocks, ceramics, concrete, nanocomposites, and agglomerates, composed of bonded particles (rigid bodies), is proposed. It is assumed that the bonds, usually representing some additional gluelike material connecting particles, cause both forces and torques acting on the particles. Vectors rigidly connected with the particles are used to describe the deformation of a single bond. The expression for potential energy of the bond and corresponding expressions for forces and torques are derived. Formulas connecting parameters of the model with longitudinal, shear, bending, and torsional stiffnesses of the bond are obtained. It is shown that the model makes it possible to describe any values of the bond stiffnesses exactly; that is, the model is applicable for the bonds with arbitrary length/thickness ratio. Two different calibration procedures depending on bond length/thickness ratio are proposed. It is shown that parameters of the model can be chosen so that under small deformations the bond is equivalent to either a Bernoulli-Euler beam or a Timoshenko beam or short cylinder connecting particles. Simple analytical expressions, relating parameters of the V model with geometrical and mechanical characteristics of the bond, are derived. Two simple examples of computer simulation of thin granular structures using the V model are given.

Contamination and Surface Preparation Effects on Composite Bonding

NASA Technical Reports Server (NTRS)

Kutscha, Eileen O.; Vahey, Paul G.; Belcher, Marcus A.; VanVoast, Peter J.; Grace, William B.; Blohowiak, Kay Y.; Palmieri, Frank L.; Connell, John W.

2017-01-01

Results presented here demonstrate the effect of several prebond surface contaminants (hydrocarbon, machining fluid, latex, silicone, peel ply residue, release film) on bond quality, as measured by fracture toughness and failure modes of carbon fiber reinforced epoxy substrates bonded in secondary and co-bond configurations with paste and film adhesives. Additionally, the capability of various prebond surface property measurement tools to detect contaminants and potentially predict subsequent bond performance of three different adhesives is also shown. Surface measurement methods included water contact angle, Dyne solution wettability, optically stimulated electron emission spectroscopy, surface free energy, inverse gas chromatography, and Fourier transform infrared spectroscopy with chemometrics analysis. Information will also be provided on the effectiveness of mechanical and energetic surface treatments to recover a bondable surface after contamination. The benefits and drawbacks of the various surface analysis tools to detect contaminants and evaluate prebond surfaces after surface treatment were assessed as well as their ability to correlate to bond performance. Surface analysis tools were also evaluated for their potential use as in-line quality control of adhesive bonding parameters in the manufacturing environment.

Equation of state of wet granular matter.

PubMed

Fingerle, A; Herminghaus, S

2008-01-01

An expression for the near-contact pair correlation function of D -dimensional weakly polydisperse hard spheres is presented, which arises from elementary free-volume arguments. Its derivative at contact agrees very well with our simulations for D=2 . For jammed states, the expression predicts that the number of exact contacts is equal to 2D, in agreement with established simulations. When the particles are wetted, they interact by the formation and rupture of liquid capillary bridges. Since formation and rupture events of capillary bonds are well separated in configuration space, the interaction is hysteretic with a characteristic energy loss Ecb. The pair correlation is strongly affected by this capillary interaction depending on the liquid-bond status of neighboring particles. A theory is derived for the nonequilibrium probability currents of the capillary interaction which determines the pair correlation function near contact. This finally yields an analytic expression for the equation of state, P=P(N/V,T), of wet granular matter for D=2, valid in the complete density range from gas to jamming. Driven wet granular matter exhibits a van der Waals-like unstable branch at granular temperatures TT, is of relevance for aggregation in general, simulations have been performed which show very good agreement with the theoretically predicted coordination K of capillary bonds as a function of the bond length scrit. This result implies that particles that stick at the surface, scrit=0, form isostatic clusters. An extension of the theory in which the bridge coordination number K plays the role of a self-consistent mean-field is proposed.

Equation of state of wet granular matter

NASA Astrophysics Data System (ADS)

Fingerle, A.; Herminghaus, S.

2008-01-01

An expression for the near-contact pair correlation function of D -dimensional weakly polydisperse hard spheres is presented, which arises from elementary free-volume arguments. Its derivative at contact agrees very well with our simulations for D=2 . For jammed states, the expression predicts that the number of exact contacts is equal to 2D, in agreement with established simulations. When the particles are wetted, they interact by the formation and rupture of liquid capillary bridges. Since formation and rupture events of capillary bonds are well separated in configuration space, the interaction is hysteretic with a characteristic energy loss Ecb . The pair correlation is strongly affected by this capillary interaction depending on the liquid-bond status of neighboring particles. A theory is derived for the nonequilibrium probability currents of the capillary interaction which determines the pair correlation function near contact. This finally yields an analytic expression for the equation of state, P=P(N/V,T) , of wet granular matter for D=2 , valid in the complete density range from gas to jamming. Driven wet granular matter exhibits a van der Waals-like unstable branch at granular temperatures T

On the Use of Quartic Force Fields in Variational Calculations

NASA Technical Reports Server (NTRS)

Fortenberry, Ryan C.; Huang, Xinchuan; Yachmenev, Andrey; Thiel, Walter; Lee, Timothy J.

2013-01-01

The use of quartic force fields (QFFs) has been shown to be one of the most effective ways to efficiently compute vibrational frequencies for small molecules. In this paper we outline and discuss how the simple-internal or bond-length bond-angle (BLBA) coordinates can be transformed into Morse-cosine(-sine) coordinates which produce potential energy surfaces from QFFs that possess proper limiting behavior and can effectively describe the vibrational (or rovibrational) energy levels of an arbitrary molecular system. We investigate parameter scaling in the Morse coordinate, symmetry considerations, and examples of transformed QFFs making use of the MULTIMODE, TROVE, and VTET variational vibrational methods. Cases are referenced where variational computations coupled with transformed QFFs produce accuracies compared to experiment for fundamental frequencies on the order of 5 cm(exp -1) and often as good as 1 cm(exp -1).

Turbine airfoil fabricated from tapered extrusions

DOEpatents

Marra, John J

2013-07-16

An airfoil (30) and fabrication process for turbine blades with cooling channels (26). Tapered tubes (32A-32D) are bonded together in a parallel sequence, forming a leading edge (21), a trailing edge (22), and pressure and suction side walls (23, 24) connected by internal ribs (25). The tapered tubes may be extruded without camber to simplify the extrusion process, then bonded along matching surfaces (34), forming a non-cambered airfoil (28), which may be cambered in a hot forming process and cut (48) to length. The tubes may have tapered walls that are thinner at the blade tip (T1) than at the base (T2), reducing mass. A cap (50) may be attached to the blade tip. A mounting lug (58) may be forged (60) on the airfoil base and then machined, completing the blade for mounting in a turbine rotor disk.

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.

Fluorinion transfer in silver-assisted chemical etching for silicon nanowires arrays

NASA Astrophysics Data System (ADS)

Feng, Tianyu; Xu, Youlong; Zhang, Zhengwei; Mao, Shengchun

2015-08-01

Uniform silicon nanowires arrays (SiNWAs) were fabricated on unpolished rough silicon wafers through KOH pretreatment followed by silver-assisted chemical etching (SACE). Density functional theory (DFT) calculations were used to investigate the function of silver (Ag) at atomic scale in the etching process. Among three adsorption sites of Ag atom on Si(1 0 0) surface, Ag(T4) above the fourth-layer surface Si atoms could transfer fluorinion (F-) to adjacent Si successfully due to its stronger electrostatic attraction force between Ag(T4) and F-, smaller azimuth angle of Fsbnd Ag(T4)sbnd Si, shorter bond length of Fsbnd Si compared with Fsbnd Ag. As F- was transferred to adjacent Si by Ag(T4) one by one, the Si got away from the wafer in the form of SiF4 when it bonded with enough F- while Ag(T4) was still attached onto the Si wafer ready for next transfer. Cyclic voltammetry tests confirmed that Ag can improve the etching rate by transferring F- to Si.

Gas-phase synthesis and structure of monomeric ZnOH: a model species for metalloenzymes and catalytic surfaces.

PubMed

Zack, Lindsay N; Sun, Ming; Bucchino, Matthew P; Clouthier, Dennis J; Ziurys, Lucy M

2012-02-16

Monomeric ZnOH has been studied for the first time using millimeter and microwave gas-phase spectroscopy. ZnOH is important in surface processes and at the active site of the enzyme carbonic anhydrase. In the millimeter-wave direct-absorption experiments, ZnOH was synthesized by reacting zinc vapor, produced in a Broida-type oven, with water. In the Fourier-transform microwave measurements, ZnOH was produced in a supersonic jet expansion of CH(3)OH and zinc vapor, created by laser ablation. Multiple rotational transitions of six ZnOH isotopologues in their X(2)A' ground states were measured over the frequency range of 22-482 GHz, and splittings due to fine and hyperfine structure were resolved. An asymmetric top pattern was observed in the spectra, showing that ZnOH is bent, indicative of covalent bonding. From these data, spectroscopic constants and an accurate structure were determined. The Zn-O bond length was found to be similar to that in carbonic anhydrase and other model enzyme systems.

Toward the detection of the triatomic negative ion SPN-: Spectroscopy and potential energy surfaces

NASA Astrophysics Data System (ADS)

Trabelsi, Tarek; Hochlaf, Majdi; Francisco, Joseph S.

2018-04-01

High level theoretical calculations using coupled-cluster theory were performed to provide an accurate description of the electronic structure, spectroscopic properties, and stability of the triatomic negative ion comprising S, N, and P. The adiabatic electron affinities (AEAs) and vertical detachment energies (VDEs) of PNS, SPN, PSN, and cyc-PSN were calculated. The predicted AEA and VDE of the linear SPN isomer are large: 2.24 and 3.04 eV, respectively. The potential energy surfaces (PESs) of the lowest-lying electronic states of the SPN- isomer along the PN and SP bond lengths and bond angle were mapped. A set of spectroscopic parameters for SPN-, PNS-, and PSN- in their electronic ground states is obtained from the 3D PESs to help detect these species in the gas phase. The electronic excited state SPN-(12A″) is predicted to be stable with a long lifetime calculated to be 189.7 μs. The formation of SPN- in its electronic ground state through the bimolecular collision between S- + PN and N + PS- is also discussed.

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.

Transitions of tethered chain molecules under tension.

PubMed

Luettmer-Strathmann, Jutta; Binder, Kurt

2014-09-21

An applied tension force changes the equilibrium conformations of a polymer chain tethered to a planar substrate and thus affects the adsorption transition as well as the coil-globule and crystallization transitions. Conversely, solvent quality and surface attraction are reflected in equilibrium force-extension curves that can be measured in experiments. To investigate these effects theoretically, we study tethered chains under tension with Wang-Landau simulations of a bond-fluctuation lattice model. Applying our model to pulling experiments on biological molecules we obtain a good description of experimental data in the intermediate force range, where universal features dominate and finite size effects are small. For tethered chains in poor solvent, we observe the predicted two-phase coexistence at transitions from the globule to stretched conformations and also discover direct transitions from crystalline to stretched conformations. A phase portrait for finite chains constructed by evaluating the density of states for a broad range of solvent conditions and tensions shows how increasing tension leads to a disappearance of the globular phase. For chains in good solvents tethered to hard and attractive surfaces we find the predicted scaling with the chain length in the low-force regime and show that our results are well described by an analytical, independent-bond approximation for the bond-fluctuation model for the highest tensions. Finally, for a hard or slightly attractive surface the stretching of a tethered chain is a conformational change that does not correspond to a phase transition. However, when the surface attraction is sufficient to adsorb a chain it will undergo a desorption transition at a critical value of the applied force. Our results for force-induced desorption show the transition to be discontinuous with partially desorbed conformations in the coexistence region.

Geometry, bonding and magnetism in planar triangulene graphene molecules with D3h symmetry: Zigzag Cm∗∗2+4m+1H3m+3 (m = 2, …, 15)

NASA Astrophysics Data System (ADS)

Philpott, Michael R.; Cimpoesu, Fanica; Kawazoe, Yoshiyuki

2008-12-01

Ab initio plane wave based all valence electron DFT calculations with geometry optimization are reported for the electronic structure of planar zigzag edged triangular shaped graphene molecules CH where the zigzag ring number m = 2, …, 15. The largest molecule C 286H 48 has a 3.8 nm side length and retains D3h symmetric geometry. The zone in the middle of the molecules, where the geometry and electronic properties resemble infinite single sheet graphite (graphene), expands with increasing ring number m, driving deviations in geometry, charge and spin to the perimeter. If a molecule is viewed as a set of nested triangular rings of carbon, then the zone where the lattice resembles an infinite sheet of graphene with CC = 142 pm, extends to the middle of the penultimate ring. The radial bonds joining the perimeter carbon atoms to the interior are long CC = 144 pm, except near the three apexes where the bonds are shorter. Isometric surfaces of the total charge density show that the two bonds joined at the apex have the highest valence charge. The perimeter CC bonds establish a simple pattern as the zigzag number increases, which shares some features with the zigzag edges in the D2h linear acenes C 4m+2H 2m+4 and the D6h hexangulenes CH6m but not the D6h symmetric annulenes (CH). The two CC bonds forming each apex are short (≈139 pm), next comes one long bond CC ≈ 142 pm and a middle region where all the CC bonds have length ≈141 pm. The homo-lumo gap declines from 0.53 eV at m = 2 to approximately 0.29 V at m = 15, the latter being larger than found for linear or hexagonal shaped graphenes with comparable edge lengths. Across the molecule the charge on the carbon atoms undergoes a small oscillation following the bipartite lattice. The magnitude of the charge in the same nested triangle decreases monotonically with the distance of the row from the center of the molecule. These systems are predicted to have spin polarized ground states with S = ½( m - 1), in accord with the theorems of Lieb for a bipartite lattice with unequal numbers of sub-lattice carbon atoms. The magnitude of the spin on the atoms increases monotonically from the center to the edges, this effect being greatest on the majority A-sub lattice atoms. The spins are delocalized, not confined to specific atoms as might result in geometries stabilized by islands of aromatic resonance. In the largest systems the magnetic non-bonding levels (NBL) occur as a narrowly distributed set of homos close to the Fermi level, separated from the lower lying valence bond manifold by a gap of about 1 eV. The NBL are a set of disjoint radical orbitals having charge only on atoms belonging to the A-lattice and this charge is concentrated on the perimeter and penultimate row atoms.

Adsorption and dissociation of molecular oxygen on α-Pu (0 2 0) surface: A density functional study

NASA Astrophysics Data System (ADS)

Wang, Jianguang; Ray, Asok K.

2011-09-01

Molecular and dissociative oxygen adsorptions on the α-Pu (0 2 0) surface have been systematically studied using the full-potential linearized augmented-plane-wave plus local orbitals (FP-LAPW+lo) basis method and the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. Chemisorption energies have been optimized for the distance of the admolecule from the Pu surface and the bond length of O-O atoms for four adsorption sites and three approaches of O 2 admolecule to the (0 2 0) surface. Chemisorption energies have been calculated at the scalar relativistic level with no spin-orbit coupling (NSOC) and at the fully relativistic level with spin-orbit coupling (SOC). Dissociative adsorptions are found at the two horizontal approaches (O 2 is parallel to the surface and perpendicular/parallel to a lattice vector). Hor2 (O 2 is parallel to the surface and perpendicular to a lattice vector) approach at the one-fold top site is the most stable adsorption site, with chemisorption energies of 8.048 and 8.415 eV for the NSOC and SOC cases, respectively, and an OO separation of 3.70 Å. Molecular adsorption occurs at the Vert (O 2 is vertical to the surface) approach of each adsorption site. The calculated work functions and net spin magnetic moments, respectively, increase and decrease in all cases upon chemisorption compared to the clean surface. The partial charges inside the muffin-tins, the difference charge density distributions, and the local density of states have been used to investigate the Pu-admolecule electronic structures and bonding mechanisms.

Method for fabricating boron carbide articles

DOEpatents

Ardary, Zane L.; Reynolds, Carl D.

1980-01-01

The present invention is directed to the fabrication of boron carbide articles having length-to-diameter or width ratios greater than 2 to 1. The process of the present invention is practiced by the steps comprising hot pressing boron carbide powder into article segments or portions in which the segments have a length-to-diameter or width ratio less than 1.5, aligning a plurality of the initially hot-pressed segments in a hot-pressing die with the end surfaces of the segments placed in intimate contact with one another, and then hot pressing the aligned segments into an article of the desired configuration. The resulting article exhibits essentially uniform density throughout the structure with the bonds between the segments being equivalent in hardness, strength, and density to the remainder of the article.

Effect of Boric Acid Versus Conventional Irrigation Solutions on the Bond Strength Between Fiber Post 
and Root Dentin.

PubMed

Culhaoglu, Ahmet Kursad; Özcan, Erdal; Kilicarslan, Mehmet Ali; Seker, Emre

2017-01-01

To compare the effect of boric acid solutions of different percentages to conventional irrigation solutions on the adhesive bond strength between fiber posts and radicular dentin surface with different cement types. One hundred fifteen extracted human incisors were endodontically instrumented to a length of 14-15 mm, and 12-mm post spaces were prepared with specific drills. Cylindrical fiber posts (Panavia Post) were luted with two different composite cements (Panavia F 2.0, Panavia SA) and cut into 1-mm-thick slices. These specimens were randomly allocated to 5 groups according to the irrigant applied: 1. control, no irrigant; 2. 10 ml of 2% chlorhexidine; 3. 10 ml of 5.25% NaOCl for 5 min and 10 ml of 17% EDTA for 3 min; 4. 10 ml of 5% boric acid solution at a temperature of 55°C for 60 s; 5. 10% boric acid solution, conditions as in group 4. Bond strength was determined using the push-out test. Microscopic assessment and SEM evaluations were performed in combination with push-out tests. The push-out bond strengths of cervical segments were significantly higher than for the middle and apical segments in all groups. The type of irrigation solution used significantly affected the bond strengths of the posts. The 10% boric acid solution and EDTA + NaOCl irrigation solutions provided the highest bond strengths (p < 0.005). SEM analysis showed that the dentin tubules were open and the smear layer was completely removed when EDTA/NaOCl and 10% boric acid were used as irrigation agents. Boric acid solutions, especially at a concentration of 10%, can be a viable alternative to the conventional irrigants used during endodontic treatment. The extent to which the 10% boric acid solution successfully removed the smear layer and the ease of rinsing boric acid from the root surface are advantageous.

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.

Research on Anchorage Performance of Grouting Anchor Connection of Precast Concrete Structure

NASA Astrophysics Data System (ADS)

Wang, Donghui; Liu, Xudong; Wang, Sheng; Cao, Xixi

2018-03-01

The bonding of grouted anchor bars is one of the vertical connection forms of steel bars in fabricated concrete structures. The performance of grouted connection is mainly affected by the anchorage length and lap length of steel bars. The mechanisms of bond and anchorage between steel bar and concrete are analyzed, and the factors that influence the anchorage performance of steel bar are systematically summarized. Results show that the bond and anchorage performance of steel and concrete have been studied widely, but there are still shortcomings, and the connection forms need to be further improved.

Medical implants and methods of making medical implants

DOEpatents

Shaw, Wendy J; Yonker, Clement R; Fulton, John L; Tarasevich, Barbara J; McClain, James B; Taylor, Doug

2014-09-16

A medical implant device having a substrate with an oxidized surface and a silane derivative coating covalently bonded to the oxidized surface. A bioactive agent is covalently bonded to the silane derivative coating. An implantable stent device including a stent core having an oxidized surface with a layer of silane derivative covalently bonded thereto. A spacer layer comprising polyethylene glycol (PEG) is covalently bonded to the layer of silane derivative and a protein is covalently bonded to the PEG. A method of making a medical implant device including providing a substrate having a surface, oxidizing the surface and reacting with derivitized silane to form a silane coating covalently bonded to the surface. A bioactive agent is then covalently bonded to the silane coating. In particular instances, an additional coating of bio-absorbable polymer and/or pharmaceutical agent is deposited over the bioactive agent.

Heparin-bonded, expanded polytetrafluoroethylene-lined stent graft in the treatment of femoropopliteal artery disease: 1-year results of the VIPER (Viabahn Endoprosthesis with Heparin Bioactive Surface in the Treatment of Superficial Femoral Artery Obstructive Disease) trial.

PubMed

Saxon, Richard R; Chervu, Arun; Jones, Paul A; Bajwa, Tanvir K; Gable, Dennis R; Soukas, Peter A; Begg, Richard J; Adams, John G; Ansel, Gary M; Schneider, Darren B; Eichler, Charles M; Rush, Michael J

2013-02-01

To evaluate the performance of a heparin-bonded, expanded polytetrafluoroethylene (ePTFE)-lined nitinol endoprosthesis in the treatment of long-segment occlusive disease of the femoropopliteal artery (FPA) and to identify factors associated with loss of patency. In a single-arm, prospective, 11-center study (VIPER [Gore Viabahn Endoprosthesis with Heparin Bioactive Surface in the Treatment of Superficial Femoral Artery Obstructive Disease] trial), 119 limbs (113 patients; 69 men; mean age, 67 y), including 88 with Rutherford category 3-5 disease and 72 with Inter-Society Consensus for the Management of Peripheral Arterial Disease (TASC II) C or D lesions of the FPA, underwent stent graft implantation. The mean lesion length was 19 cm; 56% of lesions were occlusions. Follow-up evaluations included color duplex ultrasonography in all patients, with patency defined as a peak systolic velocity ratio< 2.5. At 12 months, Rutherford category and ankle-brachial index (ABI) were significantly improved (mean category improvement, 2.4; ABI increased from 0.6±0.2 to 0.9±0.19; P<.0001). Primary and secondary patency rates were 73% and 92%. The primary patency for devices oversized<20% at the proximal landing zone was 88%, whereas the primary patency for devices oversized by>20% was 70% (P = .047). Primary patency was not significantly affected by device diameter (5 vs 6 vs 7 mm) or lesion length (≤20 cm vs>20 cm). The 30-day major adverse event rate was 0.8%. The heparin-bonded, ePTFE/nitinol stent graft provided clinical improvement and a primary patency rate of 73% at 1 year in the treatment of long-segment FPA disease. Careful sizing of the device relative to vessel landing zones is essential for achieving optimal outcomes. Copyright © 2013 SIR. Published by Elsevier Inc. All rights reserved.

pi-Turns: types, systematics and the context of their occurrence in protein structures

PubMed Central

Dasgupta, Bhaskar; Chakrabarti, Pinak

2008-01-01

Background For a proper understanding of protein structure and folding it is important to know if a polypeptide segment adopts a conformation inherent in the sequence or it depends on the context of its flanking secondary structures. Turns of various lengths have been studied and characterized starting from three-residue γ-turn to six-residue π-turn. The Schellman motif occurring at the C-terminal end of α-helices is a classical example of hydrogen bonded π-turn involving residues at (i) and (i+5) positions. Hydrogen bonded and non-hydrogen bonded β- and α-turns have been identified previously; likewise, a systematic characterization of π-turns would provide valuable insight into turn structures. Results An analysis of protein structures indicates that at least 20% of π-turns occur independent of the Schellman motif. The two categories of π-turns, designated as π-HB and SCH, have been further classified on the basis of backbone conformation and both have AAAa as the major class. They differ in the residue usage at position (i+1), the former having a large preference for Pro that is absent in the latter. As in the case of shorter length β- and α-turns, π-turns have also been identified not only on the basis of the existence of hydrogen bond, but also using the distance between terminal Cα-atoms, and this resulted in a comparable number of non-hydrogen-bonded π-turns (π-NHB). The presence of shorter β- and α-turns within all categories of π-turns, the subtle variations in backbone torsion angles along the turn residues, the location of the turns in the context of tertiary structures have been studied. Conclusion π-turns have been characterized, first using hydrogen bond and the distance between Cα atoms of the terminal residues, and then using backbone torsion angles. While the Schellman motif has a structural role in helix termination, many of the π-HB turns, being located on surface cavities, have functional role and there is also sequence conservation. PMID:18808671

pi-Turns: types, systematics and the context of their occurrence in protein structures.

PubMed

Dasgupta, Bhaskar; Chakrabarti, Pinak

2008-09-22

For a proper understanding of protein structure and folding it is important to know if a polypeptide segment adopts a conformation inherent in the sequence or it depends on the context of its flanking secondary structures. Turns of various lengths have been studied and characterized starting from three-residue gamma-turn to six-residue pi-turn. The Schellman motif occurring at the C-terminal end of alpha-helices is a classical example of hydrogen bonded pi-turn involving residues at (i) and (i+5) positions. Hydrogen bonded and non-hydrogen bonded beta- and alpha-turns have been identified previously; likewise, a systematic characterization of pi-turns would provide valuable insight into turn structures. An analysis of protein structures indicates that at least 20% of pi-turns occur independent of the Schellman motif. The two categories of pi-turns, designated as pi-HB and SCH, have been further classified on the basis of backbone conformation and both have AAAa as the major class. They differ in the residue usage at position (i+1), the former having a large preference for Pro that is absent in the latter. As in the case of shorter length beta- and alpha-turns, pi-turns have also been identified not only on the basis of the existence of hydrogen bond, but also using the distance between terminal C alpha-atoms, and this resulted in a comparable number of non-hydrogen-bonded pi-turns (pi-NHB). The presence of shorter beta- and alpha-turns within all categories of pi-turns, the subtle variations in backbone torsion angles along the turn residues, the location of the turns in the context of tertiary structures have been studied. pi-turns have been characterized, first using hydrogen bond and the distance between C alpha atoms of the terminal residues, and then using backbone torsion angles. While the Schellman motif has a structural role in helix termination, many of the pi-HB turns, being located on surface cavities, have functional role and there is also sequence conservation.

Low-temperature wafer direct bonding of silicon and quartz glass by a two-step wet chemical surface cleaning

NASA Astrophysics Data System (ADS)

Wang, Chenxi; Xu, Jikai; Zeng, Xiaorun; Tian, Yanhong; Wang, Chunqing; Suga, Tadatomo

2018-02-01

We demonstrate a facile bonding process for combining silicon and quartz glass wafers by a two-step wet chemical surface cleaning. After a post-annealing at 200 °C, strong bonding interfaces with no defects or microcracks were obtained. On the basis of the detailed surface and bonding interface characterizations, the bonding mechanism was explored and discussed. The amino groups terminated on the cleaned surfaces might contribute to the bonding strength enhancement during the annealing. This cost-effective bonding process has great potentials for silicon- and glass-based heterogeneous integrations without requiring a vacuum system.

XRD- and infrared-probed anisotropic thermal expansion properties of an organic semiconducting single crystal.

PubMed

Mohanraj, J; Capria, E; Benevoli, L; Perucchi, A; Demitri, N; Fraleoni-Morgera, A

2018-01-17

The anisotropic thermal expansion properties of an organic semiconducting single crystal constituted by 4-hydroxycyanobenzene (4HCB) have been probed by XRD in the range 120-300 K. The anisotropic thermal expansion coefficients for the three crystallographic axes and for the crystal volume have been determined. A careful analysis of the crystal structure revealed that the two different H-bonds stemming from the two independent, differently oriented 4HCB molecules composing the unit cell have different rearrangement patterns upon temperature variations, in terms of both bond length and bond angle. Linearly Polarized Mid InfraRed (LP-MIR) measurements carried out in the same temperature range, focused on the O-H bond spectral region, confirm this finding. The same LP-MIR measurements, on the basis of a semi-empirical relation and of geometrical considerations and assumptions, allowed calculation of the -CNH-O- hydrogen bond length along the a and b axes of the crystal. In turn, the so-calculated -CNH-O- bond lengths were used to derive the thermal expansion coefficients along the corresponding crystal axes, as well as the volumetric one, using just the LP-MIR data. Reasonable to good agreement with the same values obtained from XRD measurements was obtained. This proof-of-principle opens interesting perspectives about the possible development of a rapid, low cost and industry-friendly assessment of the thermal expansion properties of organic semiconducting single crystals (OSSCs) involving hydrogen bonds.

Bond strength of the porcelain repair system to all-ceramic copings and porcelain.

PubMed

Lee, Sang J; Cheong, Chan Wook; Wright, Robert F; Chang, Brian M

2014-02-01

The purpose of this study was to investigate the shear bond strength of the porcelain repair system on alumina and zirconia core ceramics, comparing this strength with that of veneering porcelain. Veneering ceramic (n = 12), alumina core (n = 24), and zirconia core (n = 24) blocks measuring 10 × 5 × 5 mm(3) were fabricated. Veneering ceramic blocks were used as the control. Alumina and zirconia core blocks were divided into 2 groups (n = 12 each), and a slot (2 × 2 × 4 mm(3)) filled with veneering ceramics was prepared into one of the alumina and zirconia core groups (n = 12). Followed by surface treatments of micro-abrasion with 30 μm alumina particles, etching with 35% phosphoric acid and silane primer and bond, composite resin blocks (2 × 2 × 2 mm(3)) were built up and light polymerized onto the treated surfaces by 3 configurations: (a) composite blocks bonded onto veneering ceramic surface alone, (b) composite blocks bonded onto alumina core or zirconia core surfaces, (c) a 50% surface area of the composite blocks bonded to veneering ceramics and the other 50% surface area of the composite blocks to alumina core or zirconia core surfaces. The shear bond strength of the composite to each specimen was tested by a universal testing machine at a 0.5 mm/min crosshead speed. The shear bond strength was analyzed by unpaired t-tests for within the configuration groups and ANOVA for among the different configuration groups. When the mean shear bond strength was compared within groups of the same configuration, there were no statistically significant differences. Comparison of the shear bond strength among groups of different configurations revealed statistically significant differences. The mean shear bond strength of composite onto 100% veneering ceramic surface and composite onto 50% veneering 50% all-ceramic cores was statistically higher than that of composite onto 100% all-ceramic cores; however, the differences of the shear bond strength of composite bonded only onto the veneering ceramic surface were not statistically significant from those of 50% surface area of composite bonded onto all-ceramic cores. No statistically significant differences in the bond strength of a porcelain repair system to alumina and zirconia copings were observed. Increasing the surface of veneering ceramics to a porcelain repair system improved the repair material's bond strength. © 2013 by the American College of Prosthodontists.

Investigation of field corrosion performance and bond/development length of galvanized reinforcing steel : [tech transfer summary].

DOT National Transportation Integrated Search

2014-12-01

In reinforced concrete systems, ensuring that a good bond between the : concrete and the embedded reinforcing steel is critical to long-term structural : performance. Without good bond between the two, the system simply cannot : behave as intended. :...

Investigation of field corrosion performance and bond/development length of galvanized reinforcing steel.

DOT National Transportation Integrated Search

2014-12-01

In reinforced concrete systems, ensuring that a good bond between the concrete and the embedded reinforcing steel is critical to : long-term structural performance. Without good bond between the two, the system simply cannot behave as intended. The b...

HYDROGEN BONDING IN THE METHANOL DIMER

USDA-ARS?s Scientific Manuscript database

In this work, two methanol molecules are placed in different arrangements to study hydrogen bonding in carbohydrate materials such as cellulose. Energy was calculated as a function of both hydrogen bond length and angle over wide ranges, using quantum mechanics (QM). The QM wavefunctions are analyze...

Stability and electronic structure of the low- Σ grain boundaries in CdTe: a density functional study

DOE PAGES

Park, Ji-Sang; Kang, Joongoo; Yang, Ji-Hui; ...

2015-01-15

Using first-principles density functional calculations, we investigate the relative stability and electronic structure of the grain boundaries (GBs) in zinc-blende CdTe. Among the low-Σ-value symmetric tilt Σ3 (111), Σ3 (112), Σ5 (120), and Σ5 (130) GBs, we show that the Σ3 (111)GB is always the most stable due to the absence of dangling bonds and wrong bonds. The Σ5 (120) GBs, however, are shown to be more stable than the Σ3 (112) GBs, even though the former has a higher Σ value, and the latter is often used as a model system to study GB effects in zinc-blende semiconductors. Furthermore,more » we find that although containing wrong bonds, the Σ5 (120) GBs are electrically benign due to the short wrong bond lengths, and thus are not as harmful as the Σ3 (112) GBs also having wrong bonds but with longer bond lengths.« less

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

Using Excel To Study The Relation Between Protein Dihedral Angle Omega And Backbone Length

NASA Astrophysics Data System (ADS)

Shew, Christopher; Evans, Samari; Tao, Xiuping

How to involve the uninitiated undergraduate students in computational biophysics research? We made use of Microsoft Excel to carry out calculations of bond lengths, bond angles and dihedral angles of proteins. Specifically, we studied protein backbone dihedral angle omega by examining how its distribution varies with the length of the backbone length. It turns out Excel is a respectable tool for this task. An ordinary current-day desktop or laptop can handle the calculations for midsized proteins in just seconds. Care has to be taken to enter the formulas for the spreadsheet column after column to minimize the computing load. Supported in part by NSF Grant #1238795.

Analyzing the Molecular Kinetics of Water Spreading on Hydrophobic Surfaces via Molecular Dynamics Simulation.

PubMed

Zhao, Lei; Cheng, Jiangtao

2017-09-07

In this paper, we report molecular kinetic analyses of water spreading on hydrophobic surfaces via molecular dynamics simulation. The hydrophobic surfaces are composed of amorphous polytetrafluoroethylene (PTFE) with a static contact angle of ~112.4° for water. On the basis of the molecular kinetic theory (MKT), the influences of both viscous damping and solid-liquid retarding were analyzed in evaluating contact line friction, which characterizes the frictional force on the contact line. The unit displacement length on PTFE was estimated to be ~0.621 nm and is ~4 times as long as the bond length of C-C backbone. The static friction coefficient was found to be ~[Formula: see text] Pa·s, which is on the same order of magnitude as the dynamic viscosity of water, and increases with the droplet size. A nondimensional number defined by the ratio of the standard deviation of wetting velocity to the characteristic wetting velocity was put forward to signify the strength of the inherent contact line fluctuation and unveil the mechanism of enhanced energy dissipation in nanoscale, whereas such effect would become insignificant in macroscale. Moreover, regarding a liquid droplet on hydrophobic or superhydrophobic surfaces, an approximate solution to the base radius development was derived by an asymptotic expansion approach.

Density functional theory analysis of the impact of steric interaction on the function of switchable polarity solvents

DOE PAGES

McNally, Joshua S.; Noll, Bruce; Orme, Christopher J.; ...

2015-05-04

Here, a density functional theory (DFT) analysis has been performed to explore the impact of steric interactions on the function of switchable polarity solvents (SPS) and their implications on a quantitative structure-activity relationship (QSAR) model previously proposed for SPS. An x-ray crystal structure of the N,N-dimethylcyclohexylammonium bicarbonate (Hdmcha) salt has been solved as an asymmetric unit containing two cation/anion pairs, with a hydrogen bonding interaction observed between the bicarbonate anions, as well as between the cation and anion in each pair. DFT calculations provide an optimized structure of Hdmcha that closely resembles experimental data and reproduces the cation/anion interaction withmore » the inclusion of a dielectric field. Relaxed potential energy surface (PES) scans have been performed on Hdmcha-based computational model compounds, differing in the size of functional group bonded to the nitrogen center, to assess the steric impact of the group on the relative energy and structural properties of the compound. Results suggest that both the length and amount of branching associated with the substituent impact the energetic limitations on rotation of the group along the N-R bond and NC-R bond, and disrupt the energy minimized position of the hydrogen bonded bicarbonate group. The largest interaction resulted from functional groups that featured five bonds between the ammonium proton and a proton on a functional group with the freedom of rotation to form a pseudo-six membered ring which included both protons.« less

CCSDT calculations of molecular equilibrium geometries

NASA Astrophysics Data System (ADS)

Halkier, Asger; Jørgensen, Poul; Gauss, Jürgen; Helgaker, Trygve

1997-08-01

CCSDT equilibrium geometries of CO, CH 2, F 2, HF, H 2O and N 2 have been calculated using the correlation-consistent cc-pVXZ basis sets. Similar calculations have been performed for SCF, CCSD and CCSD(T). In general, bond lengths decrease when improving the basis set and increase when improving the N-electron treatment. CCSD(T) provides an excellent approximation to CCSDT for bond lengths as the largest difference between CCSDT and CCSD(T) is 0.06 pm. At the CCSDT/cc-pVQZ level, basis set deficiencies, neglect of higher-order excitations, and incomplete treatment of core-correlation all give rise to errors of a few tenths of a pm, but to a large extent, these errors cancel. The CCSDT/cc-pVQZ bond lengths deviate on average only by 0.11 pm from experiment.

Dental plaque microcosm response to bonding agents containing quaternary ammonium methacrylates with different chain lengths and charge densities

PubMed Central

Zhou, Han; Li, Fang; Weir, Michael D.; Xu, Hockin H.K.

2013-01-01

Objectives Antibacterial bonding agents are promising to combat bacteria and caries at tooth-restoration margins. The objectives of this study were to incorporate new quaternary ammonium methacrylates (QAMs) to bonding agent and determine the effects of alkyl chain length (CL) and quaternary amine charge density on dental plaque microcosm bacteria response for the first time. Methods Six QAMs were synthesized with CL = 3, 6, 9, 12, 16, 18. Each QAM was incorporated into Scotchbond Multi-purpose (SBMP). To determine the charge density effect, dimethylaminododecyl methacrylate (DMAHDM, CL = 16) was mixed into SBMP at mass fraction = 0%, 2.5%, 5%, 7.5%, 10%. Charge density was measured using a fluorescein dye method. Dental plaque microcosm using saliva from ten donors was tested. Bacteria were inoculated on resins. Early-attachment was tested at 4 hours. Biofilm colony-forming units (CFU) were measured at 2 days. Results Incorporating QAMs into SBMP reduced bacteria early-attachment. Microcosm biofilm CFU for CL = 16 was 4 log lower than SBMP control. Charge density of bonding agent increased with DMAHDM content. Bacteria early-attachment decreased with increasing charge density. Biofilm CFU at 10% DMAHDM was reduced by 4 log. The killing effect was similarly-strong against total microorganisms, total streptococci, and mutans streptococci. Conclusions Increasing alkyl chain length and charge density of bonding agent was shown for the first time to decrease microcosm bacteria attachment and reduce biofilm CFU by 4 orders of magnitude. Novel antibacterial resins with tailored chain length and charge density are promising for wide applications in bonding, cements, sealants and composites to inhibit biofilms and caries. PMID:23948394

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.

Dental plaque microcosm response to bonding agents containing quaternary ammonium methacrylates with different chain lengths and charge densities.

PubMed

Zhou, Han; Li, Fang; Weir, Michael D; Xu, Hockin H K

2013-11-01

Antibacterial bonding agents are promising to combat bacteria and caries at tooth-restoration margins. The objectives of this study were to incorporate new quaternary ammonium methacrylates (QAMs) to bonding agent and determine the effects of alkyl chain length (CL) and quaternary amine charge density on dental plaque microcosm bacteria response for the first time. Six QAMs were synthesized with CL=3, 6, 9, 12, 16, 18. Each QAM was incorporated into Scotchbond multi-purpose (SBMP). To determine the charge density effect, dimethylaminododecyl methacrylate (DMAHDM, CL=16) was mixed into SBMP at mass fraction=0%, 2.5%, 5%, 7.5%, 10%. Charge density was measured using a fluorescein dye method. Dental plaque microcosm using saliva from ten donors was tested. Bacteria were inoculated on resins. Early-attachment was tested at 4h. Biofilm colony-forming units (CFU) were measured at 2 days. Incorporating QAMs into SBMP reduced bacteria early-attachment. Microcosm biofilm CFU for CL=16 was 4 log lower than SBMP control. Charge density of bonding agent increased with DMAHDM content. Bacteria early-attachment decreased with increasing charge density. Biofilm CFU at 10% DMAHDM was reduced by 4 log. The killing effect was similarly-strong against total microorganisms, total streptococci, and mutans streptococci. Increasing alkyl chain length and charge density of bonding agent was shown for the first time to decrease microcosm bacteria attachment and reduce biofilm CFU by 4 orders of magnitude. Novel antibacterial resins with tailored chain length and charge density are promising for wide applications in bonding, cements, sealants and composites to inhibit biofilms and caries. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

A comprehensive study of acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces was carried out by means of calculations based on periodic density functional theory, using the Perdew–Burke–Ernzerhof exchange–correlation functional. It was found that the bonding of acetylene was significantly affected by the electronic and structural properties of the carbide surfaces. The adsorbate interacted with metal and/or carbon sites of the carbide. The interaction of acetylene with the TiC(001) and ZrC(001) surfaces was strong (binding energies higher than $-$3.5 eV), while moderate acetylene adsorption energies were observed on δ-MoC(001) ($-$1.78 eV to –0.66 eV). Adsorption energies, charge density difference plotsmore » and Mulliken charges suggested that the binding of the hydrocarbon to the surface had both ionic and covalent contributions. According to the C–C bond lengths obtained, the adsorbed molecule was modified from acetylene-like into ethylene-like on the δ-MoC(001) surface (desired behavior for hydrogenation reactions) but into ethane-like on TiC(001) and ZrC(001). The obtained results suggest that the δ-MoC(001) surface is expected to have the best performance in selective hydrogenation reactions to convert alkynes into alkenes. Another advantage of δ-MoC(001) is that, after C 2H 2 adsorption, surface carbon sites remain available, which are necessary for H 2 dissociation. Furthermore, these sites were occupied when C 2H 2 was adsorbed on TiC(001) and ZrC(001), limiting their application in the hydrogenation of alkynes.« less

Maximally resolved anharmonic OH vibrational spectrum of the water/ZnO(101 \\xAF 0) interface from a high-dimensional neural network potential

NASA Astrophysics Data System (ADS)

Quaranta, Vanessa; Hellström, Matti; Behler, Jörg; Kullgren, Jolla; Mitev, Pavlin D.; Hermansson, Kersti

2018-06-01

Unraveling the atomistic details of solid/liquid interfaces, e.g., by means of vibrational spectroscopy, is of vital importance in numerous applications, from electrochemistry to heterogeneous catalysis. Water-oxide interfaces represent a formidable challenge because a large variety of molecular and dissociated water species are present at the surface. Here, we present a comprehensive theoretical analysis of the anharmonic OH stretching vibrations at the water/ZnO(101 ¯ 0) interface as a prototypical case. Molecular dynamics simulations employing a reactive high-dimensional neural network potential based on density functional theory calculations have been used to sample the interfacial structures. In the second step, one-dimensional potential energy curves have been generated for a large number of configurations to solve the nuclear Schrödinger equation. We find that (i) the ZnO surface gives rise to OH frequency shifts up to a distance of about 4 Å from the surface; (ii) the spectrum contains a number of overlapping signals arising from different chemical species, with the frequencies decreasing in the order ν(adsorbed hydroxide) > ν(non-adsorbed water) > ν(surface hydroxide) > ν(adsorbed water); (iii) stretching frequencies are strongly influenced by the hydrogen bond pattern of these interfacial species. Finally, we have been able to identify substantial correlations between the stretching frequencies and hydrogen bond lengths for all species.

Accurate characterization of wafer bond toughness with the double cantilever specimen

NASA Astrophysics Data System (ADS)

Turner, Kevin T.; Spearing, S. Mark

2008-01-01

The displacement loaded double cantilever test, also referred to as the "Maszara test" and the "crack opening method" by the wafer bonding community, is a common technique used to evaluate the interface toughness or surface energy of direct wafer bonds. While the specimen is widely used, there has been a persistent question as to the accuracy of the method since the actual specimen geometry differs from the ideal beam geometry assumed in the expression used for data reduction. The effect of conducting the test on whole wafer pairs, in which the arms of cantilevers are wide plates rather than slender beams, is examined in this work using finite element analysis. A model is developed to predict the equilibrium shape of the crack front and to develop a corrected expression for calculating interface toughness from crack length measurements obtained in tests conducted on whole wafer pairs. The finite element model, which is validated through comparison to experiments, demonstrates that using the traditional beam theory-based expressions for data reduction can lead to errors of up to 25%.

A theoretical perspective of the nature of hydrogen-bond types - the atoms in molecules approach

NASA Astrophysics Data System (ADS)

Vijaya Pandiyan, B.; Kolandaivel, P.; Deepa, P.

2014-06-01

Hydrogen bonds and their strength were analysed based on their X-H proton-donor bond properties and the parameters of the H-Y distance (Y proton acceptor). Strong, moderate and weak interactions in hydrogen-bond types were verified through the proton affinities of bases (PA), deprotanation enthalpies of acids (DPE) and the chemical shift (σ). The aromaticity and anti-aromaticity were analysed by means of the NICS (0) (nucleus-independent chemical shift), NICS (1) and ΔNICS (0), ΔNICS (1) of hydrogen-bonded molecules. The strength of a hydrogen bond depends on the capacity of hydrogen atom engrossing into the electronegative acceptor atom. The correlation between the above parameters and their relations were discussed through curve fitting. Bader's theory of atoms in molecules has been applied to estimate the occurrence of hydrogen bonds through eight criteria reported by Popelier et al. The lengths and potential energy shifts have been found to have a strong negative linear correlation, whereas the lengths and Laplacian shifts have a strong positive linear correlation. This study illustrates the common factors responsible for strong, moderate and weak interactions in hydrogen-bond types.

Relativistic Corrections to the Properties of the Alkali Fluorides

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Partridge, Harry

1993-01-01

Relativistic corrections to the bond lengths, dissociation energies and harmonic frequencies of KF, RbF and CsF have been obtained at the self-consistent field level by dissociating to ions. The relativistic corrections to the bond lengths, harmonic frequencies and dissociation energies to the ions are very small, due to the ionic nature of these molecules and the similarity of the relativistic and nonrelativistic ionic radii.

Optoelectronic tuning of organoborylazadipyrromethenes via effective electronegativity at the metalloid center.

PubMed

Berhe, Seare A; Rodriguez, Marco T; Park, Eunsol; Nesterov, Vladimir N; Pan, Hongjun; Youngblood, W Justin

2014-03-03

Organoborylazadipyrromethenes were synthesized from free base and fluoroborylazadipyrromethenes and characterized with regard to their structural and electronic properties. B-N bond lengths, along with photophysical and redox behavior, appear dependent on the effective electronegativity at the boron atom as tuned by its substituents, with stronger electronegativity correlating to a shorter B-N bond length, red-shifted absorbance, enhanced fluorescence lifetime and yield, and positively shifted redox potentials.

Molecular mechanism of gelation upon the addition of water to a solution of poly(acrylonitrile) in dimethylsulfoxide

NASA Astrophysics Data System (ADS)

Vettegren, V. I.; Kulik, V. B.; Savitskii, A. V.; Fetisov, O. I.; Usov, V. V.

2010-05-01

The solidification of a solution of poly(acrylonitrile) (PAN) in dimethylsulfoxide (DMSO) upon introduction of water into the solution is studied by Raman spectroscopy. In the absence of water, DMSO molecules are found to produce dipole-dipole bonds with PAN molecules. Upon the introduction of water, DMSO molecules produce hydrogen bonds with it and bands at 1005 and 1015 cm-1 appear in the Raman spectrum, which are assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. Simultaneously, water molecules produce hydrogen bonds with PAN molecules: R-C≡N...H-O-H...N≡C-R, where R is the carbon skeleton of a PAN molecule. Accordingly, a band at 2250 cm-1 arises in the Raman spectrum, which is assigned to the valence vibrations of C≡N bonds producing hydrogen bonds with a water molecule. When the water content is low and the DMSO concentration is high, the length of the hydrogen bonds varies in wide limits and the band at 2250 cm-1 is wide. As the water content rises, DMSO molecules come out of PAN, the variation of the hydrogen bond length in it decreases (the band at 2250 cm-1 narrows), and a high-viscosity system (gel) arises that consists of PAN molecules bonded to water molecules via “equally strong” hydrogen bonds.

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

Varanasi, S. R., E-mail: s.raovaranasi@uq.edu.au, E-mail: guskova@ipfdd.de; John, A.; Guskova, O. A., E-mail: s.raovaranasi@uq.edu.au, E-mail: guskova@ipfdd.de

Fullerene C{sub 60} sub-colloidal particle with diameter ∼1 nm represents a boundary case between small and large hydrophobic solutes on the length scale of hydrophobic hydration. In the present paper, a molecular dynamics simulation is performed to investigate this complex phenomenon for bare C{sub 60} fullerene and its amphiphilic/charged derivatives, so called shape amphiphiles. Since most of the unique properties of water originate from the pattern of hydrogen bond network and its dynamics, spatial, and orientational aspects of water in solvation shells around the solute surface having hydrophilic and hydrophobic regions are analyzed. Dynamical properties such as translational-rotational mobility, reorientationalmore » correlation and occupation time correlation functions of water molecules, and diffusion coefficients are also calculated. Slower dynamics of solvent molecules—water retardation—in the vicinity of the solutes is observed. Both the topological properties of hydrogen bond pattern and the “dangling” –OH groups that represent surface defects in water network are monitored. The fraction of such defect structures is increased near the hydrophobic cap of fullerenes. Some “dry” regions of C{sub 60} are observed which can be considered as signatures of surface dewetting. In an effort to provide molecular level insight into the thermodynamics of hydration, the free energy of solvation is determined for a family of fullerene particles using thermodynamic integration technique.« less

Proton Diffusion through Bilayer Pores

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2017-09-26

The transport of protons through channels in complex environments is important in biology and materials science. In this work, we use multistate empirical valence bond simulations to study proton transport within a well-defined bilayer pore in a lamellar L β phase lyotropic liquid crystal (LLC). The LLC is formed from the self-assembly of dicarboxylate gemini surfactants in water, and a bilayer-spanning pore of radius of approximately 3–5 Å results from the uneven partitioning of surfactants between the two leaflets of the lamella. Local proton diffusion within the pore is significantly faster than diffusion at the bilayer surface, which is duemore » to the greater hydrophobicity of the surfactant/water interface within the pore. Proton diffusion proceeds by surface transport along exposed hydrophobic pockets at the surfactant/water interface and depends on the continuity of hydronium–water hydrogen bond networks. At the bilayer surface, there is a reduced fraction of the “Zundel” intermediates that are central to the Grotthuss transport mechanism, whereas the fraction of these species within the bilayer pore is similar to that in bulk water. Our results demonstrate that the chemical nature of the confining interface, in addition to confinement length scale, is an important determiner of local proton transport in nanoconfined aqueous environments.« less

Laser Surface Preparation and Bonding of Aerospace Structural Composites

NASA Technical Reports Server (NTRS)

Belcher, Marcus A.; Wohl, Christopher J.; Connell, John W.

2009-01-01

A Nd:YAG laser was used to etch patterns conducive to adhesive bonding onto CFRP surfaces. These were compared to typical pre-bonding surface treatments including grit blasting, manual abrasion, and peel ply. Laser treated composites were then subjected to optical microscopy, contact angle measurements, and post-bonding mechanical testing.

Influence of air-powder polishing on bond strength and surface-free energy of universal adhesive systems.

PubMed

Tamura, Yukie; Takamizawa, Toshiki; Shimamura, Yutaka; Akiba, Shunsuke; Yabuki, Chiaki; Imai, Arisa; Tsujimoto, Akimasa; Kurokawa, Hiroyasu; Miyazaki, Masashi

2017-11-29

The influences of air-powder polishing with glycine or sodium bicarbonate powders on shear bond strengths (SBS) and surface-free energies of universal adhesives were examined. Scotchbond Universal Adhesive (SU, 3M ESPE), G-Premio Bond (GP, GC), Adhese Universal (AU, Ivoclar Vivadent), and All-Bond Universal (AB, Bisco) were used in this study. Bovine dentin surfaces were air polished with glycine or sodium bicarbonate powders prior to the bonding procedure, and resin pastes were bonded to the dentin surface using universal adhesives. SBSs were determined after 24-h storage in distilled water at 37°C. Surface-free energy was then determined by measuring contact angles using three test liquids on dentin surfaces. Significantly lower SBSs were observed for dentin that was air-powder polished and surface-free energies were concomitantly lowered. This study indicated that air-powder polishing influences SBSs and surface-free energies. However, glycine powder produced smaller changes in these surface parameters than sodium bicarbonate.

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

Effect of nanoscale surface roughness on the bonding energy of direct-bonded silicon wafers

NASA Astrophysics Data System (ADS)

Miki, N.; Spearing, S. M.

2003-11-01

Direct wafer bonding of silicon wafers is a promising technology for manufacturing three-dimensional complex microelectromechanical systems as well as silicon-on-insulator substrates. Previous work has reported that the bond quality declines with increasing surface roughness, however, this relationship has not been quantified. This article explicitly correlates the bond quality, which is quantified by the apparent bonding energy, and the surface morphology via the bearing ratio, which describes the area of surface lying above a given depth. The apparent bonding energy is considered to be proportional to the real area of contact. The effective area of contact is defined as the area sufficiently close to contribute to the attractive force between the two bonding wafers. Experiments were conducted with silicon wafers whose surfaces were roughened by a buffered oxide etch solution (BOE, HF:NH4F=1:7) and/or a potassium hydroxide solution. The surface roughness was measured by atomic force microscopy. The wafers were direct bonded to polished "monitor" wafers following a standard RCA cleaning and the resulting bonding energy was measured by the crack-opening method. The experimental results revealed a clear correlation between the bonding energy and the bearing ratio. A bearing depth of ˜1.4 nm was found to be appropriate for the characterization of direct-bonded silicon at room temperature, which is consistent with the thickness of the water layer at the interface responsible for the hydrogen bonds that link the mating wafers.

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).

Comparison of the effect of different surface treatments on the bond strength of different cements with nickel chromium metal alloy: An in vitro study

PubMed Central

Kapoor, Saumya; Balakrishnan, Dhanasekar

2017-01-01

Background For success of any indirect metal restoration, a strong bond between cement and the intaglio surface of metal is imperative. The aim of this study is to evaluate and compare the effect of different surface treatment on the tensile and shear bond strength of different cements with nickel–chromium alloy. Material and Methods 120 premolars were sectioned horizontally parallel to the occlusal surface to expose the dentin. Wax patterns were fabricated for individual tooth followed by casting them in nickel chromium alloy. 60 samples were tested for tensile bond strength, and the remaining 60 for shear bond strength. The samples were divided into three groups (of 20 samples each) as per the following surface treatment: oxidation only, oxidation and sandblasting, or oxidation, sandblasting followed by application of alloy primer. Each group was subdivided into 2 subgroups of 10 samples each, according to the bonding cement i.e RM-GIC and resin cement. Samples were subjected to thermocycling procedure followed by evaluation of bond strength. Results Two-way analyses of variance (ANOVA) was performed to compare the means of tensile and shear bond strength across type of surface treatment and cement, followed by post hoc parametric analysis. For all tests ‘p’ value of less than 0.05 was considered statistically significant. Conclusions The surface treatment of oxidation and sandblasting followed by application of alloy primer offered the maximum tensile and shear bond strength for both RM GIC and resin cement. Resin cement exhibited greater tensile and shear bond strength than RM-GIC for all the three surface treatment methods. Key words:Resin cement, resin modified glass ionomer cement, oxidation, sandblasting, alloy primer, tensile bond strength, shear bond strength, universal testing machine. PMID:28828160

[Influence of different porcelain surface treatment method on the bonding of metal brackets to porcelain].

PubMed

Fan, Cun-Hui; Chen, Jie; Liu, Xin-Qiang; Ma, Xin

2005-08-01

To investigate the influence of different porcelain surface treatment methods on the shear bond strength of metal brackets bonded to porcelain. 80 porcelain facets were divided randomly into two groups according to different adhesive material that was used to bond metal brackets. Adhesive material were Jing-Jin enamel adhesive and light-cured composite resin. Each group was further divided into 4 subgroups according to different surface treatment methods, which were acid etching with 37% phosphoric acid (H3PO4), acid etching with 9.6% hydrofluoric acid (HF), deglazing by grinding and silanating the porcelain surface. All specimens were stored in 37 degrees C water for 24 hours and then the shear bond strength and the porcelain fracture after debonding was determined. The porcelain surfaces after HF etching, H3PO4 etching and deglazing by grinding were examined by scanning electron microscopy respectively. The shear bond strengths in the HF etching groups, the deglazing groups and the silanating groups were much greater than that in the phosphoric etching groups (P < 0.01). Adequate orthodontic bonding strength was achieved both when bonded with light-cured composite resin after deglazing by grinding and when bonded with either of these adhesives after HF etching or surface silanating. There were no differences in the rates of porcelain fractures among groups (P > 0.05). HF etching, deglazing by grinding and silanating can all increase the shear bond strength between metal bracket and porcelain. Surface silanating of porcelain is a better surface treatment when metal brackets bonded to porcelain.

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

Production of large-scale, freestanding vanadium pentoxide nanobelt porous structures

NASA Astrophysics Data System (ADS)

Yun, Yong Ju; Kim, Byung Hoon; Hong, Won G.; Kim, Chang Hee; Kim, Yark Yeon; Jeong, Eun-Ju; Jang, Won Ick; Yu, Han Young

2012-02-01

Large-scale, freestanding, porous structures of vanadium pentoxide nanobelts (VPNs) were successfully prepared using the template-free freeze-drying method. The porous and multi-layered VPN macrostructures are composed of randomly oriented long nanobelts (over 100 μm) and their side length can be controlled up to a few tens of centimetres. Also, the bulk density and surface area of these macrostructures are 3-5 mg cm-3 and 40-80 m2 g-1, respectively, which are similar to those of the excellent adsorbents. In addition, the removal efficiency measurements of ammonia molecules revealed that the VPN porous structures can adsorb the ammonia molecules with the combinations of van der Waals forces and strong chemical bonding by functional groups on the VPN surface.

Production of large-scale, freestanding vanadium pentoxide nanobelt porous structures.

PubMed

Yun, Yong Ju; Kim, Byung Hoon; Hong, Won G; Kim, Chang Hee; Kim, Yark Yeon; Jeong, Eun-ju; Jang, Won Ick; Yu, Han Young

2012-03-07

Large-scale, freestanding, porous structures of vanadium pentoxide nanobelts (VPNs) were successfully prepared using the template-free freeze-drying method. The porous and multi-layered VPN macrostructures are composed of randomly oriented long nanobelts (over 100 μm) and their side length can be controlled up to a few tens of centimetres. Also, the bulk density and surface area of these macrostructures are 3-5 mg cm(-3) and 40-80 m(2) g(-1), respectively, which are similar to those of the excellent adsorbents. In addition, the removal efficiency measurements of ammonia molecules revealed that the VPN porous structures can adsorb the ammonia molecules with the combinations of van der Waals forces and strong chemical bonding by functional groups on the VPN surface.

Room temperature bonding and debonding of polyimide film and glass substrate based on surface activate bonding method

NASA Astrophysics Data System (ADS)

Takeuchi, Kai; Fujino, Masahisa; Matsumoto, Yoshiie; Suga, Tadatomo

2018-02-01

The temporary bonding of polyimide (PI) films and glass substrates is a key technology for realizing flexible devices with thin-film transistors (TFTs). In this paper, we report the surface activated bonding (SAB) method using Si intermediate layers and its bonding and debonding mechanisms after heating. The bonding interface composed of Si and Fe shows a higher bond strength than the interface of only Si, while the bond strengths of both interfaces decrease with post bonding heating. It is also clarified by composition analysis on the debonded surfaces and cross-sectional observation of the bonding interface that the bond strength depends on the toughness of the intermediated layers and PI. The SAB method using Si intermediate layers is found to be applicable to the bonding and debonding of PI and glass.

Repair Bond Strength of Aged Resin Composite after Different Surface and Bonding Treatments

PubMed Central

Wendler, Michael; Belli, Renan; Panzer, Reinhard; Skibbe, Daniel; Petschelt, Anselm; Lohbauer, Ulrich

2016-01-01

The aim of this study was to compare the effect of different mechanical surface treatments and chemical bonding protocols on the tensile bond strength (TBS) of aged composite. Bar specimens were produced using a nanohybrid resin composite and aged in distilled water for 30 days. Different surface treatments (diamond bur, phosphoric acid, silane, and sandblasting with Al2O3 or CoJet Sand), as well as bonding protocols (Primer/Adhesive) were used prior to application of the repair composite. TBS of the specimens was measured and the results were analyzed using analysis of variance (ANOVA) and the Student–Newman–Keuls test (α = 0.05). Mechanically treated surfaces were characterized under SEM and by profilometry. The effect of water aging on the degree of conversion was measured by means of FTIR-ATR spectroscopy. An important increase in the degree of conversion was observed after aging. No significant differences in TBS were observed among the mechanical surface treatments, despite variations in surface roughness profiles. Phosphoric acid etching significantly improved repair bond strength values. The cohesive TBS of the material was only reached using resin bonding agents. Application of an intermediate bonding system plays a key role in achieving reliable repair bond strengths, whereas the kind of mechanical surface treatment appears to play a secondary role. PMID:28773669

Active vibration control using a modal-domain fiber optic sensor

NASA Technical Reports Server (NTRS)

Cox, David E.

1992-01-01

A closed-loop control experiment is described in which vibrations of a cantilevered beam are suppressed using measurements from a modal-domain fiber optic sensor. Modal-domain sensors are interference between the modes of a few-mode optical waveguide to detect strain. The fiber is bonded along the length of the beam and provides a measurement related to the strain distribution on the surface of the beam. A model for the fiber optic sensor is derived, and this model is integrated with the dynamic model of the beam. A piezoelectric actuator is also bonded to the beam and used to provide control forces. Control forces are obtained through dynamic compensation of the signal from the fiber optic sensor. The compensator is implemented with a real-time digital controller. Analytical models are verified by comparing simulations to experimental results for both open-loop and closed-loop configurations.

Laser rods with undoped, flanged end-caps for end-pumped laser applications

DOEpatents

Meissner, Helmuth E.; Beach, Raymond J.; Bibeau, Camille; Sutton, Steven B.; Mitchell, Scott; Bass, Isaac; Honea, Eric

1999-01-01

A method and apparatus for achieving improved performance in a solid state laser is provided. A flanged, at least partially undoped end-cap is attached to at least one end of a laserable medium. Preferably flanged, undoped end-caps are attached to both ends of the laserable medium. Due to the low scatter requirements for the interface between the end-caps and the laser rod, a non-adhesive method of bonding is utilized such as optical contacting combined with a subsequent heat treatment of the optically contacted composite. The non-bonded end surfaces of the flanged end-caps are coated with laser cavity coatings appropriate for the lasing wavelength of the laser rod. A cooling jacket, sealably coupled to the flanged end-caps, surrounds the entire length of the laserable medium. Radiation from a pump source is focussed by a lens duct and passed through at least one flanged end-cap into the laser rod.

Electron transport in NH3/NO2 sensed buckled antimonene

NASA Astrophysics Data System (ADS)

Srivastava, Anurag; Khan, Md. Shahzad; Ahuja, Rajeev

2018-04-01

The structural and electronic properties of buckled antimonene have been analysed using density functional theory based ab-initio approach. Geometrical parameters in terms of bond length and bond angle are found close to the single ruffle mono-layer of rhombohedral antimony. Inter-frontier orbital analyses suggest localization of lone pair electrons at each atomic centre. Phonon dispersion along with high symmetry point of Brillouin zone does not signify any soft mode. With an electronic band gap of 1.8eV, the quasi-2D nano-surface has been further explored for NH3/NO2 molecules sensing and qualities of interaction between NH3/NO2 gas and antimonene scrutinized in terms of electronic charges transfer. A current-voltage characteristic has also been analysed, using Non Equilibrium Green's function (NEGF), for antimonene, in presence of incoming NH3/NO2 molecules.

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.

NDT evaluation of long-term bond durability of CFRP-structural systems applied to RC highway bridges

NASA Astrophysics Data System (ADS)

Crawford, Kenneth C.

2016-06-01

The long-term durability of CFRP structural systems applied to reinforced-concrete (RC) highway bridges is a function of the system bond behavior over time. The sustained structural load performance of strengthened bridges depends on the carbon fiber-reinforced polymer (CFRP) laminates remaining 100 % bonded to concrete bridge members. Periodic testing of the CFRP-concrete bond condition is necessary to sustain load performance. The objective of this paper is to present a non-destructive testing (NDT) method designed to evaluate the bond condition and long-term durability of CFRP laminate (plate) systems applied to RC highway bridges. Using the impact-echo principle, a mobile mechanical device using light impact hammers moving along the length of a bonded CFRP plate produces unique acoustic frequencies which are a function of existing CFRP plate-concrete bond conditions. The purpose of this method is to test and locate CFRP plates de-bonded from bridge structural members to identify associated deterioration in bridge load performance. Laboratory tests of this NDT device on a CFRP plate bonded to concrete with staged voids (de-laminations) produced different frequencies for bonded and de-bonded areas of the plate. The spectra (bands) of frequencies obtained in these tests show a correlation to the CFRP-concrete bond condition and identify bonded and de-bonded areas of the plate. The results of these tests indicate that this NDT impact machine, with design improvements, can potentially provide bridge engineers a means to rapidly evaluate long lengths of CFRP laminates applied to multiple highway bridges within a national transportation infrastructure.

Ab initio characterization of coupling strength for all types of dangling-bond pairs on the hydrogen-terminated Si(100)-2 × 1 surface

NASA Astrophysics Data System (ADS)

Shaterzadeh-Yazdi, Zahra; Sanders, Barry C.; DiLabio, Gino A.

2018-04-01

Recent work has suggested that coupled silicon dangling bonds sharing an excess electron may serve as building blocks for quantum-cellular-automata cells and quantum computing schemes when constructed on hydrogen-terminated silicon surfaces. In this work, we employ ab initio density-functional theory to examine the details associated with the coupling between two dangling bonds sharing one excess electron and arranged in various configurations on models of phosphorous-doped hydrogen-terminated silicon (100) surfaces. Our results show that the coupling strength depends strongly on the relative orientation of the dangling bonds on the surface and on the separation between them. The orientation of dangling bonds is determined by the anisotropy of the silicon (100) surface, so this feature of the surface is a significant contributing factor to variations in the strength of coupling between dangling bonds. The results demonstrate that simple models for approximating tunneling, such as the Wentzel-Kramer-Brillouin method, which do not incorporate the details of surface structure, are incapable of providing reasonable estimates of tunneling rates between dangling bonds. The results provide guidance to efforts related to the development of dangling-bond based computing elements.

Analytical energy gradient for the two-component normalized elimination of the small component method

NASA Astrophysics Data System (ADS)

Zou, Wenli; Filatov, Michael; Cremer, Dieter

2015-06-01

The analytical gradient for the two-component Normalized Elimination of the Small Component (2c-NESC) method is presented. The 2c-NESC is a Dirac-exact method that employs the exact two-component one-electron Hamiltonian and thus leads to exact Dirac spin-orbit (SO) splittings for one-electron atoms. For many-electron atoms and molecules, the effect of the two-electron SO interaction is modeled by a screened nucleus potential using effective nuclear charges as proposed by Boettger [Phys. Rev. B 62, 7809 (2000)]. The effect of spin-orbit coupling (SOC) on molecular geometries is analyzed utilizing the properties of the frontier orbitals and calculated SO couplings. It is shown that bond lengths can either be lengthened or shortened under the impact of SOC where in the first case the influence of low lying excited states with occupied antibonding orbitals plays a role and in the second case the jj-coupling between occupied antibonding and unoccupied bonding orbitals dominates. In general, the effect of SOC on bond lengths is relatively small (≤5% of the scalar relativistic changes in the bond length). However, large effects are found for van der Waals complexes Hg2 and Cn2, which are due to the admixture of more bonding character to the highest occupied spinors.

Effects of ultraviolet irradiation on bonding strength between Co-Cr alloy and citric acid-crosslinked gelatin matrix.

PubMed

Inoue, Motoki; Sasaki, Makoto; Katada, Yasuyuki; Taguchi, Tetsushi

2014-02-01

Novel techniques for creating a strong bond between polymeric matrices and biometals are required. We immobilized polymeric matrices on the surface of biometal for drug-eluting stents through covalent bond. We performed to improve the bonding strength between a cobalt-chromium alloy and a citric acid-crosslinked gelatin matrix by ultraviolet irradiation on the surface of cobalt-chromium alloy. The ultraviolet irradiation effectively generated hydroxyl groups on the surface of the alloy. The bonding strength between the gelatin matrix and the alloy before ultraviolet irradiation was 0.38 ± 0.02 MPa, whereas it increased to 0.48 ± 0.02 MPa after ultraviolet irradiation. Surface analysis showed that the citric acid derivatives occurred on the surface of the cobalt-chromium alloy through ester bond. Therefore, ester bond formation between the citric acid derivatives active esters and the hydroxyl groups on the cobalt-chromium alloy contributed to the enhanced bonding strength. Ultraviolet irradiation and subsequent immobilization of a gelatin matrix using citric acid derivatives is thus an effective way to functionalize biometal surfaces.

Influence of anatomical, physical, and mechanical properties of diffuse-porous hardwoods on moisture durability of bonded assemblies

Treesearch

Daniel J. Yelle; Ashley M. Stirgus

2016-01-01

Studying wood adhesive bond durability is challenging because wood is highly variable and heterogeneous at all length scales. In this study, three North American diffuse-porous hardwoods (hard maple, soft maple, and basswood) and their adhesively bonded as-semblies were exposed to wet and dry cyclic tests. Then, their den-sity differences were related to bond...

Bonded Radii and the Contraction of the Electron Density of the Oxygen Atom by Bonded Interactions

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

Gibbs, Gerald V.; Ross, Nancy L.; Cox, David F.

2013-02-21

The bonded radii for more than 550 bonded pairs of atoms, comprising more than 50 crystals, determined from experimental and theoretical electron density distributions, are compared with the effective ionic, ri(M), and crystal radii, rc(M), for metal atoms, M, bonded to O atoms. At odds with the fixed ionic radius of 1.40 Å, assumed for the O atom in the compilation of the ionic radii, the bonded radius for the atom, rb(O), is not fixed but displays a relatively wide range of values as the O atom is progressively polarized by the M-O bonded interactions: as such, rb(O) decreases systematicallymore » from 1.40 Å (the Pauling radius of the oxide anion) as bond lengths decrease when bonded to an electropositive atom like sodium, to 0.64 Å (Bragg’s atomic radius of the O atom) when bonded to an electronegative atom like nitrogen. Both rb(M) and rb(O) increase in tandum with the increasing coordination number of the M atom. The bonded radii of the M atoms are highly correlated with both ri(M) and rc(M), but they both depart systematically from rb(M) and become smaller as the electronegativity of the M atom increases and the M-O bond length decreases. The well-developed correlations between both sets of radii and rb(M) testifies to the relative precision of both sets of radii and the fact that both sets are highly correlated the M-O bond 1 lengths. On the other hand, the progressive departure of rb(O) from the fixed ionic radius of the O atom with the increasing electronegativity of the bonded M atom indicates that any compilation of sets of ionic radii, assuming that the radius for the oxygen atom is fixed in value, is problematical and impacts on the accuracy of the resulting sets of ionic and crystal radii thus compiled. The assumption of a fixed O atom radius not only results in a negative ionic radii for several atoms, but it also results in values of rb(M) that are much as ~ 0.6 Å larger than the ri(M) and rc(M) values, respectively, particularly for the more electronegative M atoms. On the other hand, the ionic radii are in closer agreement with rb(M) for the more electropositive atoms. Notwithstanding that ionic radii are typically smaller than bonded radii, particularly for the more electronegative atoms, they have been used with considerable success in understanding and rationalizing problems and properties in crystal chemistry primarily because both ionic and crystal radii are highly correlated on a one-to-one basis with both the bonded radii and the associated M-O bond lengths. The lack of agreement between the effective ionic and crystal radii and the bonded radii for the more shared bonded interactions is ascribed to the progressive increase in the polarization of the O atom by the bonded atoms with a concomitant decrease in its radius, a factor that was neglected in the compilation of ionic and crystal radii for fluorides, oxides, sulfides and nitrides. This accounts for ionic radii for these materials being smaller than the bonded radii for the more electronegative atoms.« less

Temperature and composition dependence of short-range order and entropy, and statistics of bond length: the semiconductor alloy (GaN)(1-x)(ZnO)(x).

PubMed

Liu, Jian; Pedroza, Luana S; Misch, Carissa; Fernández-Serra, Maria V; Allen, Philip B

2014-07-09

We present total energy and force calculations for the (GaN)1-x(ZnO)x alloy. Site-occupancy configurations are generated from Monte Carlo (MC) simulations, on the basis of a cluster expansion model proposed in a previous study. Local atomic coordinate relaxations of surprisingly large magnitude are found via density-functional calculations using a 432-atom periodic supercell, for three representative configurations at x = 0.5. These are used to generate bond-length distributions. The configurationally averaged composition- and temperature-dependent short-range order (SRO) parameters of the alloys are discussed. The entropy is approximated in terms of pair distribution statistics and thus related to SRO parameters. This approximate entropy is compared with accurate numerical values from MC simulations. An empirical model for the dependence of the bond length on the local chemical environments is proposed.

Quantitative structure activity relationships from optimised ab initio bond lengths: steroid binding affinity and antibacterial activity of nitrofuran derivatives

NASA Astrophysics Data System (ADS)

Smith, P. J.; Popelier, P. L. A.

2004-02-01

The present day abundance of cheap computing power enables the use of quantum chemical ab initio data in Quantitative Structure-Activity Relationships (QSARs). Optimised bond lengths are a new such class of descriptors, which we have successfully used previously in representing electronic effects in medicinal and ecological QSARs (enzyme inhibitory activity, hydrolysis rate constants and pKas). Here we use AM1 and HF/3-21G* bond lengths in conjunction with Partial Least Squares (PLS) and a Genetic Algorithm (GA) to predict the Corticosteroid-Binding Globulin (CBG) binding activity of the classic steroid data set, and the antibacterial activity of nitrofuran derivatives. The current procedure, which does not require molecular alignment, produces good r2 and q2 values. Moreover, it highlights regions in the common steroid skeleton deemed relevant to the active regions of the steroids and nitrofuran derivatives.

Investigation of heat transfer and material flow of P-FSSW: Experimental and numerical study

NASA Astrophysics Data System (ADS)

Rezazadeh, Niki; Mosavizadeh, Seyed Mostafa; Azizi, Hamed

2018-02-01

Friction stir spot welding (FSSW) is the joining process which utilizes a rotating tool consisting of a shoulder and/or a probe. In this study, the novel method of FSSW, which is called protrusion friction stir spot welding (P-FSSW), has been presented and effect of shoulder diameter parameter has been studied numerically and experimentally on the weld quality including temperature field, velocity contour, material flow, bonding length, and the depth of the stirred area. The results show that the numerical findings are in good agreement with experimental measurements. The present model could well predict the temperature distribution, velocity contour, depth of the stirred area, and the bonding length. As the shoulder diameter increases, the amount of temperature rises which leads to a rise in stirred area depth, bonding length and temperatures and velocities. Therefore, a weld of higher quality will be performed.

Linear free-energy relationships between a single gas-phase ab initio equilibrium bond length and experimental pKa values in aqueous solution.

PubMed

Alkorta, Ibon; Popelier, Paul L A

2015-02-02

Remarkably simple yet effective linear free energy relationships were discovered between a single ab initio computed bond length in the gas phase and experimental pKa values in aqueous solution. The formation of these relationships is driven by chemical features such as functional groups, meta/para substitution and tautomerism. The high structural content of the ab initio bond length makes a given data set essentially divide itself into high correlation subsets (HCSs). Surprisingly, all molecules in a given high correlation subset share the same conformation in the gas phase. Here we show that accurate pKa values can be predicted from such HCSs. This is achieved within an accuracy of 0.2 pKa units for 5 drug molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bone bonding at natural and biomaterial surfaces.

PubMed

Davies, John E

2007-12-01

Bone bonding is occurring in each of us and all other terrestrial vertebrates throughout life at bony remodeling sites. The surface created by the bone-resorbing osteoclast provides a three-dimensionally complex surface with which the cement line, the first matrix elaborated during de novo bone formation, interdigitates and is interlocked. The structure and composition of this interfacial bony matrix has been conserved during evolution across species; and we have known for over a decade that this interfacial matrix can be recapitulated at a biomaterial surface implanted in bone, given appropriate healing conditions. No evidence has emerged to suggest that bone bonding to artificial materials is any different from this natural biological process. Given this understanding it is now possible to explain why bone-bonding biomaterials are not restricted to the calcium-phosphate-based bioactive materials as was once thought. Indeed, in the absence of surface porosity, calcium phosphate biomaterials are not bone bonding. On the contrary, non-bonding materials can be rendered bone bonding by modifying their surface topography. This paper argues that the driving force for bone bonding is bone formation by contact osteogenesis, but that this has to occur on a sufficiently stable recipient surface which has micron-scale surface topography with undercuts in the sub-micron scale-range.

Vibrational studies of phosphoryl transfer enzymes: ras- p21(*)magnesium-GTP and Myosin S1(*)magnesium-ADP- vanadate

NASA Astrophysics Data System (ADS)

Wang, Jianghua

1999-07-01

We have measured the Raman spectra of monophosphate compounds in aqueous solution. The measured frequencies were correlated with P••O valence bond order by using a modification of the Hardcastle- Wachs procedure. The P••O bond order and bond length in phosphates can be determined from vibrational spectra by using the derived bond order/stretching frequency correlation and the bond length/bond order correlation of Brown and Wu. The Raman and infrared spectra of guanosine 5'-diphosphate (GDP) and guanosine 5'-triphosphate (GTP) in aqueous solution were also examined. Frequency shifts were observed as Mg2+ complexes with GDP and GTP in aqueous solution. These results suggested that Mg2+ binds to GDP in a bidentate manner to the α,β P••O bonds and in a tridentate manner to the α,β and γ P••O bonds of Mg•GTP . We have analyzed the previously obtained isotope edited Raman difference spectra of 1:1 complexes of Mg•GDP and Mg•GTP in ras-p21. Frequency changes of the phosphate groups were observed when Mg•GDP , Mg•GTP bind to the protein. Employing both the previous empirical relationships between bond orders/lengths and frequencies as well as vibrational analysis from ab initio calculations, the spectral changes can be explained by the change of the Mg2+ binding sites and hydrogen-bonding. Implications of these structural results for the reaction mechanism of GTP hydrolysis catalyzed by the GTPase are discussed. We have analyzed previously obtained isotope edited Raman difference spectra of the non-bridging V••O bonds of vanadates, both in solution, and when bound to the myosin S1•MgADP complex. By use of ab initio calculations on a model of the vanadate binding site in myosin, the angles between the non-bridging V••O bonds and between these bonds and the apical bonds in the myosin S1•MgADP -Vi complex were determined. The summed bond order of the two apical bonds between the attacking and leaving group oxygens with the central vanadium ion in the S1•MgADP -Vi complex was found to increase only slightly compared with the bond order of the ester V-O bond of a monoester vanadate model compound in solution, suggesting an SN2 like mechanism for the phosphoryl transfer reaction catalyzed by myosin.

Effect of surface contamination on adhesive bonding of cast pure titanium and Ti-6Al-4V alloy.

PubMed

Watanabe, I; Watanabe, E; Yoshida, K; Okabe, T

1999-03-01

There is little information regarding bond strengths of resin cements to cast titanium surfaces contaminated by investment material. This study examined the effect of surface contamination on the shear bond strength of resin cements to cast titanium and Ti-6Al-4V alloy. Two types of disks were cast from commercially pure titanium (CP-Ti) and Ti-6Al-4V alloy ingots using an argon-arc pressure casting unit and a phosphate-bonded Al2 O3 /LiAlSiO6 investment. After casting, disks were subjected to 3 surface treatments: (1) cast surface sandblasted (50 microm-sized Al2 O3 ) for 30 seconds; (2) metal surface sanded with silicon-carbide paper (600 grit) after grinding the contaminated cast surface (approximately 200 microm in thickness); and (3) metal surface sandblasted for 30 seconds after treatment 2. Surface structures were examined after each treatment with SEM and optical microscopy. Each type of disk was then bonded with 2 types of luting materials. Bonded specimens were subjected to thermocycling for up to 50,000 cycles, and shear bond strengths were determined after 0 (baseline) and 50,000 thermocycles. Results were statistically analyzed with 3-way ANOVA (P <.05). Microscopic observation of cast CP-Ti and Ti-6Al-4V exhibited noticeable structures on the cast surfaces apparently contaminated with investment material. However, there were no statistical differences (P >.05) in the bond strengths of both cements between contaminated (treatment 1) and uncontaminated surfaces (treatment 3) for both metals at baseline and after 50,000 thermocycles. The bond strength of specimens sanded with silicon-carbide paper (treatment 2) deteriorated dramatically after 50,000 thermocycles. Contamination of the cast metal surfaces by elements of the investment during casting did not affect bond strengths of the luting materials to CP-Ti and Ti-6Al-4V.

The effect of five kinds of surface treatment agents on the bond strength to various ceramics with thermocycle aging.

PubMed

Noda, Yukari; Nakajima, Masatoshi; Takahashi, Masahiro; Mamanee, Teerapong; Hosaka, Keiichi; Takagaki, Tomohiro; Ikeda, Masaomi; Foxton, Richard M; Tagami, Junji

2017-11-29

This study evaluated the effects of ceramic surface treatment agents on shear bond strengths to ceramic materials with and without thermocycling. Ceramic plates were prepared from feldspathic ceramic; AAA, lithium disilicate ceramic material; IPS e.max Press, zirconia ceramic; Lava. Ceramic surfaces were pretreated with one of five surface treatment agents (Clearfil PhotoBond mixed with Porcelainbond activator (PB), Clearfil SE One mixed with Porcelainbond activator (SO), Ceramic Primer (CP), Universal Primer (UP), Scotchbond Universal (SU)), and then a resin cement (Clapearl DC) was filled. After 0, 5,000, and 10,000 thermocycles, micro-shear bond strengths between ceramic-cement interfaces were determined. SU exhibited significantly lower initial bond strength to AAA and e.max than PB, SO, CP, and UP. For Lava, PB, SO, CP and SU exhibited higher initial bond strengths than UP. Thermocycles reduced bond strengths to all the ceramic materials with any surface treatment.

Acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces: A comprehensive periodic DFT study

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2016-12-06

A comprehensive study of acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces was carried out by means of calculations based on periodic density functional theory, using the Perdew–Burke–Ernzerhof exchange–correlation functional. It was found that the bonding of acetylene was significantly affected by the electronic and structural properties of the carbide surfaces. The adsorbate interacted with metal and/or carbon sites of the carbide. The interaction of acetylene with the TiC(001) and ZrC(001) surfaces was strong (binding energies higher than $-$3.5 eV), while moderate acetylene adsorption energies were observed on δ-MoC(001) ($-$1.78 eV to –0.66 eV). Adsorption energies, charge density difference plotsmore » and Mulliken charges suggested that the binding of the hydrocarbon to the surface had both ionic and covalent contributions. According to the C–C bond lengths obtained, the adsorbed molecule was modified from acetylene-like into ethylene-like on the δ-MoC(001) surface (desired behavior for hydrogenation reactions) but into ethane-like on TiC(001) and ZrC(001). The obtained results suggest that the δ-MoC(001) surface is expected to have the best performance in selective hydrogenation reactions to convert alkynes into alkenes. Another advantage of δ-MoC(001) is that, after C 2H 2 adsorption, surface carbon sites remain available, which are necessary for H 2 dissociation. Furthermore, these sites were occupied when C 2H 2 was adsorbed on TiC(001) and ZrC(001), limiting their application in the hydrogenation of alkynes.« less

Large scale atomistic simulation of single-layer graphene growth on Ni(111) surface: molecular dynamics simulation based on a new generation of carbon-metal potential

NASA Astrophysics Data System (ADS)

Xu, Ziwei; Yan, Tianying; Liu, Guiwu; Qiao, Guanjun; Ding, Feng

2015-12-01

To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results.To explore the mechanism of graphene chemical vapor deposition (CVD) growth on a catalyst surface, a molecular dynamics (MD) simulation of carbon atom self-assembly on a Ni(111) surface based on a well-designed empirical reactive bond order potential was performed. We simulated single layer graphene with recorded size (up to 300 atoms per super-cell) and reasonably good quality by MD trajectories up to 15 ns. Detailed processes of graphene CVD growth, such as carbon atom dissolution and precipitation, formation of carbon chains of various lengths, polygons and small graphene domains were observed during the initial process of the MD simulation. The atomistic processes of typical defect healing, such as the transformation from a pentagon into a hexagon and from a pentagon-heptagon pair (5|7) to two adjacent hexagons (6|6), were revealed as well. The study also showed that higher temperature and longer annealing time are essential to form high quality graphene layers, which is in agreement with experimental reports and previous theoretical results. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06016h

Experimental evidence and structural modeling of nonstoichiometric (010) surfaces coexisting in hydroxyapatite nano-crystals.

PubMed

Ospina, C A; Terra, J; Ramirez, A J; Farina, M; Ellis, D E; Rossi, A M

2012-01-01

High-resolution transmission electron microscopy (HRTEM) and ab initio quantum-mechanical calculations of electronic structure were combined to investigate the structure of the hydroxyapatite (HA) (010) surface, which plays an important role in HA interactions with biological media. HA was synthesized by in vitro precipitation at 37°C. HRTEM images revealed thin elongated rod nanoparticles with preferential growth along the [001] direction and terminations parallel to the (010) plane. The focal series reconstruction (FSR) technique was applied to develop an atomic-scale structural model of the high-resolution images. The HRTEM simulations identified the coexistence of two structurally distinct terminations for (010) surfaces: a rather flat Ca(II)-terminated surface and a zig-zag structure with open OH channels. Density functional theory (DFT) was applied in a periodic slab plane-wave pseudopotential approach to refine details of atomic coordination and bond lengths of Ca(I) and Ca(II) sites in hydrated HA (010) surfaces, starting from the HRTEM model. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of Er:YAG laser irradiation on bonding property of zirconia ceramics to resin cement.

PubMed

Lin, Yihua; Song, Xiaomeng; Chen, Yaming; Zhu, Qingping; Zhang, Wei

2013-12-01

This study aimed to investigate whether or not an erbium: yttrium-aluminum-garnet (Er:YAG) laser could improve the bonding property of zirconia ceramics to resin cement. Surface treatments can improve the bonding properties of dental ceramics. However, little is known about the effect of Er:YAG laser irradiated on zirconia ceramics. Specimens of zirconia ceramic pieces were made, and randomly divided into 11 groups according to surface treatments, including one control group (no treatment), one air abrasion group, and nine Er:YAG laser groups. The laser groups were subdivided by applying different energy intensities (100, 200, or 300 mJ) and irradiation times (5, 10, or 15 sec). After surface treatments, ceramic pieces had their surface morphology observed, and their surface roughness was measured. All specimens were bonded to resin cement. Shear bond strength was measured after the bonded specimens were stored in water for 24 h, and additionally aged by thermocycling. Statistical analyses were performed using one way analysis of variance (ANOVA) and Tukey's test for shear bond strength, and Dunnett's t test for surface roughness, with α=0.05. Er:YAG laser irradiation changed the morphological characteristics of zirconia ceramics. Higher energy intensities (200, 300 mJ) could roughen the ceramics, but also caused surface cracks. There were no significant differences in the bond strength between the control group and the laser groups treated with different energy intensities or irradiation times. Air abrasion with alumina particles induced highest surface roughness and shear bond strength. Er:YAG laser irradiation cannot improve the bonding property of zirconia ceramics to resin cement. Enhancing irradiation intensities and extending irradiation time have no benefit on the bond of the ceramics, and might cause material defect.

Insertion of terminal alkyne into Pt-N bond of the square planar [PtI2(Me2phen)] complex.

PubMed

Benedetti, Michele; De Castro, Federica; Lamacchia, Vincenza; Pacifico, Concetta; Natile, Giovanni; Fanizzi, Francesco P

2017-11-21

The reactivity of [PtX 2 (Me 2 phen)] complexes (X = Cl, Br, I; Me 2 phen = 2,9-dimethyl-1,10-phenanthroline) with terminal alkynes has been investigated. Although the dichlorido species [PtCl 2 (Me 2 phen)] exhibits negligible reactivity, the bromido and iodido derivatives lead in short time to the formation of five-coordinate Pt(ii) complexes of the type [PtX 2 (Me 2 phen)(η 2 -CH[triple bond, length as m-dash]CR)] (X = Br, I; R = Ph, n-Bu), in equilibrium with the starting reagents. Similar to analogous complexes with simple acetylene, the five coordinate species can also undergo dissociation of an halido ligand and formation of the transient square-planar cationic species [PtX(Me 2 phen)(η 2 -CH[triple bond, length as m-dash]CR)] + . This latter can further evolve to give an unusual, sparingly soluble square planar product where the former terminal alkyne is converted into a :C[double bond, length as m-dash]C(H)(R) moiety with the α-carbon bridging the Pt(ii) core with one of the two N-donors of coordinated Me 2 phen. The final product [PtX 2 {κ 2 -N,C-(Z)-N[combining low line]1-N10-C[combining low line][double bond, length as m-dash]C(H)(R)}] (N1-N10 = 2,9-dimethyl-1,10-phenanthroline; X = Br, I) contains a Pt-N-C-C-N-C six-membered chelate ring in a square planar Pt(ii) coordination environment.

Modeling of Interfacial Modification Effects on Thermal Conductivity of Carbon Nanotube Composites

NASA Technical Reports Server (NTRS)

Clancy, Thomas C.; Gates, Thomas S.

2006-01-01

The effect of functionalization of carbon nanotubes on the thermal conductivity of nanocomposites has been studied using a multi-scale modeling approach. These results predict that grafting linear hydrocarbon chains to the surface of a single wall carbon nanotube with covalent chemical bonds should result in a significant increase in the thermal conductivity of these nanocomposites. This is due to the decrease in the interfacial thermal (Kapitza) resistance between the single wall carbon nanotube and the surrounding polymer matrix upon chemical functionalization. The nanocomposites studied here consist of single wall carbon nanotubes in a bulk poly(ethylene vinyl acetate) matrix. The nanotubes are functionalized by end-grafting linear hydrocarbon chains of varying length to the surface of the nanotube. The effect which this functionalization has on the interfacial thermal resistance is studied by molecular dynamics simulation. Interfacial thermal resistance values are calculated for a range of chemical grafting densities and with several chain lengths. These results are subsequently used in an analytical model to predict the resulting effect on the bulk thermal conductivity of the nanocomposite.

Plasma combined self-assembled monolayer pretreatment on electroplated-Cu surface for low temperature Cu-Sn bonding in 3D integration

NASA Astrophysics Data System (ADS)

Wang, Junqiang; Wang, Qian; Wu, Zijian; Tan, Lin; Cai, Jian; Wang, Dejun

2017-05-01

A novel pretreatment of plasma combined self-assembled monolayer (PcSAM) was proposed to improve surface properties of electroplated Cu for low temperature Cu-Sn bonding in 3D integration. Measurement results revealed that self-assemble monolayer (SAM) would be easier absorbed on plasma-activated Cu surface and protect the clean surface from re-oxidation when storage. The absorbed SAM layer could be removed by thermal desorption during bonding process. With optimal PcSAM pretreatment, oxygen content of the Cu surface was reduced to as low as 1.39%. The followed Cu-Sn bonding was realized at low temperature of 200 °C. Finally, bonding interface exhibited a defect-free interconnection, and bonding strength has reached as high as 68.7 MPa.

Influence of handpiece maintenance sprays on resin bonding to dentin.

PubMed

Sugawara, Toyotarou; Kameyama, Atsushi; Haruyama, Akiko; Oishi, Takumi; Kukidome, Nobuyuki; Takase, Yasuaki; Tsunoda, Masatake

2010-01-01

To investigate the influence of maintenance spray on resin bonding to dentin. The crown of extracted, caries-free human molars was transversally sectioned with a model trimmer to prepare the dentin surfaces from mid-coronal sound dentin, and then uniformly abraded with #600 silicon carbide paper. The dentin surfaces were randomly divided into three groups: oil-free spray group where maintenance cleaner for air bearing handpieces was sprayed onto the dentin surface for 1 s and rinsed with water spray for 30 s; oil-containing spray group where maintenance cleaner for micro motor handpieces was sprayed onto the dentin surface for 1 s and rinsed with water spray for 30 s; and control group where the surface was rinsed with water spray for 30 s and then air-dried. These surfaces were then bonded with Clearfil SE Bond (Kuraray Medical), and resin composite (Clearfil AP-X, Kuraray Medical) build-up crowns were incrementally constructed on the bonded surfaces. After storage for 24 h in 37°C water, the bonded teeth were sectioned into hour-glass shaped slices (0.7-mm thick) perpendicular to the bonded surfaces. The specimens were then subjected to microtensile bond strength (μTBS) testing at a crosshead speed of 1.0 mm/min. Data were analyzed with one-way ANOVA and the Tukey-Kramer test. Maintenance spray-contaminated specimens (oil-free and oil-containing spray groups) showed significantly lower μTBS than control specimens (P < 0.05). However, there was no significant difference between the spray-contaminated groups (P > 0.05). Maintenance spray significantly reduces the bond strength of Clearfil SE Bond to dentin.

Locally measuring the adhesion of InP directly bonded on sub-100 nm patterned Si.

PubMed

Pantzas, K; Le Bourhis, E; Patriarche, G; Troadec, D; Beaudoin, G; Itawi, A; Sagnes, I; Talneau, A

2016-03-18

A nano-scale analogue to the double cantilever experiment that combines instrumented nano-indentation and atomic force microscopy is used to precisely and locally measure the adhesion of InP bonded on sub-100 nm patterned Si using oxide-free or oxide-mediated bonding. Surface-bonding energies of 0.548 and 0.628 J m(-2), respectively, are reported. These energies correspond in turn to 51% and 57% of the surface bonding energy measured in unpatterned regions on the same samples, i.e. the proportion of unetched Si surface in the patterned areas. The results show that bonding on patterned surfaces can be as robust as on unpatterned surfaces, provided care is taken with the post-patterning surface preparation process and, therefore, open the path towards innovative designs that include patterns embedded in the Si guiding layer of hybrid III-V/Si photonic integrated circuits.

Quadratic elongation: A quantitative measure of distortion in coordination polyhedra

USGS Publications Warehouse

Robinson, Kelly F.; Gibbs, G.V.; Ribbe, P.H.

1971-01-01

Quadratic elongation and the variance of bond angles are linearly correlated for distorted octahedral and tetrahedral coordination complexes, both of which show variations in bond length and bond angle. The quadratic elonga tion is dimensionless, giving a quantitative measure of polyhedral distortion which is independent of the effective size of the polyhedron.

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.

DFT study on the interaction of TiO2 (001) surface with HCHO molecules

NASA Astrophysics Data System (ADS)

Wu, Guofei; Zhao, Cuihua; Guo, Changqing; Chen, Jianhua; Zhang, Yibing; Li, Yuqiong

2018-01-01

The interactions of formaldehyde (HCHO) molecule with TiO2 (001) surface were studied using density functional theory calculations. HCHO molecules are dissociated by the cleavage of Csbnd H bonds after adsorption on TiO2 surface. The strong interactions between HCHO melecules and TiO2 surface are largely attributed to the bonding of hydrogen of HCHO and oxygen of TiO2 surface, which is mainly from the hybridization of the H 1s, O 2p and O 2s. The newly formed Hsbnd O bonds cause the structure changes of TiO2 surface, and lead to the cleavage of Osbnd Ti bond of TiO2 surface. The Csbnd O bond that the dissociated remains of HCHO and newly formed Hsbnd O bond can be oxidized to form carbon dioxide and water in subsequent action by oxygen from the atomosphere. The charges transfer from HCHO to TiO2 surface, and the sum amount of the charges transferred from four HCHO molecules to TiO2 surface is bigger than that from one HCHO molecule to TiO2 surface due to the combined interaction of four HCHO molecules with TiO2 surface.

Characterizing ceramics and the interfacial adhesion to resin: II- the relationship of surface treatment, bond strength, interfacial toughness and fractography.

PubMed

Della-Bona, Alvaro

2005-06-01

The clinical success of resin bonding procedures for indirect ceramic restorations and ceramic repairs depends on the quality and durability of the bond between the ceramic and the resin. The quality of this bond will depend upon the bonding mechanisms that are controlled in part by the surface treatment that promote micromechanical and/or chemical bonding to the substrate. The objective of this review is to correlate interfacial toughness (K A) with fracture surface morphological parameters of the dental ceramic-resin systems as a function of ceramic surface treatment. This analysis is designed to identify mechanisms that promote adhesion of these ceramic-resin systems and an appropriate bond test method to yield relevant adhesion performance data.

Composite pipe to metal joint

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

Leslie, James C.; Leslie, II, James C.; Heard, James

A method for making a metal to composite tube joint including selecting an elongated interior fitting constructed with an exterior barrel, reduced in exterior diameter to form a distally facing annular shoulder and then projecting still further distally to form an interior sleeve having a radially outwardly facing bonding surface. Selecting an elongated metal outer sleeve formed proximally with a collar constructed for receipt over the barrel and increased in interior diameter and projecting distally to form an exterior sleeve having a radially inwardly facing bonding surface cooperating with the first bonding surface to form an annulus receiving an extremitymore » of a composite tube and a bond bonding the extremity of the tube to the bonding surfaces.« less

pKa prediction from an ab initio bond length: part 3--benzoic acids and anilines.

PubMed

Harding, A P; Popelier, P L A

2011-06-21

The prediction of pK(a) from a single ab initio bond length has been extended to provide equations for benzoic acids and anilines. The HF/6-31G(d) level of theory is used for all geometry optimisations. Similarly to phenols (Part 2 of this series of publications), the meta-/para-substituted benzoic acids can be predicted from a single model constructed from one bond length. This model had an impressive RMSEP of 0.13 pK(a) units. The prediction of ortho-substituted benzoic acids required the identification of high-correlation subsets, where the compounds in the same subset have at least one of the same (e.g. halogens, hydroxy) ortho substituent. Two pK(a) equations are provided for o-halogen benzoic acids and o-hydroxybenzoic acids, where the RMSEP values are 0.19 and 0.15 pK(a) units, respectively. Interestingly, the bond length that provided the best model differed between these two high-correlation subsets. This demonstrates the importance of investigating the most predictive bond length, which is not necessarily the bond involving the acid hydrogen. Three high-correlation subsets were identified for the ortho-substituted anilines. These were o-halogen, o-nitro and o-alkyl-substituted aniline high-correlation subsets, where the RMSEP ranged from 0.23 to 0.44 pK(a) units. The RMSEP for the meta-/para-substituted aniline model was 0.54 pK(a) units. This value exceeded our threshold of 0.50 pK(a) units and was higher than both the m-/p-benzoic acids in this work and the m-/p-phenols (RMSEP = 0.43) of Part 2. Constructing two separate models for the meta- and para- substituted anilines, where RMSEP values of 0.63 and 0.33 pK(a) units were obtained respectively, revealed it was the meta-substituted anilines that caused the large RMSEP value. For unknown reasons the RMSEP value increased with the addition of a further twenty meta-substituted anilines to this model. The C-N bond always produced the best correlations with pK(a) for all the high-correlation subsets. A higher level of theory and an ammonia probe improved the statistics only marginally for the hydroxybenzoic acid high-correlation subsets.

Computations and estimates of rate coefficients for hydrocarbon reactions of interest to the atmospheres of outer solar system

NASA Technical Reports Server (NTRS)

Laufer, A. H.; Gardner, E. P.; Kwok, T. L.; Yung, Y. L.

1983-01-01

The rate coefficients, including Arrhenius parameters, have been computed for a number of chemical reactions involving hydrocarbon species for which experimental data are not available and which are important in planetary atmospheric models. The techniques used to calculate the kinetic parameters include the Troe and semiempirical bond energy-bond order (BEBO) or bond strength-bond length (BSBL) methods.

Bond breaking in epoxy systems: A combined QM/MM approach

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

Barr, Stephen A.; Ecker, Allison M.; Berry, Rajiv J., E-mail: Rajiv.Berry@us.af.mil

2016-06-28

A novel method to combine quantum mechanics (QM) and molecular mechanics has been developed to accurately and efficiently account for covalent bond breaking in polymer systems under high strain without the use of predetermined break locations. Use of this method will provide a better fundamental understanding of the mechano-chemical origins of fracture in thermosets. Since classical force fields cannot accurately account for bond breaking, and QM is too demanding to simulate large systems, a hybrid approach is required. In the method presented here, strain is applied to the system using a classical force field, and all bond lengths are monitored.more » When a bond is stretched past a threshold value, a zone surrounding the bond is used in a QM energy minimization to determine which, if any, bonds break. The QM results are then used to reconstitute the system to continue the classical simulation at progressively larger strain until another QM calculation is triggered. In this way, a QM calculation is only computed when and where needed, allowing for efficient simulations. A robust QM method for energy minimization has been determined, as well as appropriate values for the QM zone size and the threshold bond length. Compute times do not differ dramatically from classical molecular mechanical simulations.« less

Zn Coordination Chemistry:  Development of Benchmark Suites for Geometries, Dipole Moments, and Bond Dissociation Energies and Their Use To Test and Validate Density Functionals and Molecular Orbital Theory.

PubMed

Amin, Elizabeth A; Truhlar, Donald G

2008-01-01

We present nonrelativistic and relativistic benchmark databases (obtained by coupled cluster calculations) of 10 Zn-ligand bond distances, 8 dipole moments, and 12 bond dissociation energies in Zn coordination compounds with O, S, NH3, H2O, OH, SCH3, and H ligands. These are used to test the predictions of 39 density functionals, Hartree-Fock theory, and seven more approximate molecular orbital theories. In the nonrelativisitic case, the M05-2X, B97-2, and mPW1PW functionals emerge as the most accurate ones for this test data, with unitless balanced mean unsigned errors (BMUEs) of 0.33, 0.38, and 0.43, respectively. The best local functionals (i.e., functionals with no Hartree-Fock exchange) are M06-L and τ-HCTH with BMUEs of 0.54 and 0.60, respectively. The popular B3LYP functional has a BMUE of 0.51, only slightly better than the value of 0.54 for the best local functional, which is less expensive. Hartree-Fock theory itself has a BMUE of 1.22. The M05-2X functional has a mean unsigned error of 0.008 Å for bond lengths, 0.19 D for dipole moments, and 4.30 kcal/mol for bond energies. The X3LYP functional has a smaller mean unsigned error (0.007 Å) for bond lengths but has mean unsigned errors of 0.43 D for dipole moments and 5.6 kcal/mol for bond energies. The M06-2X functional has a smaller mean unsigned error (3.3 kcal/mol) for bond energies but has mean unsigned errors of 0.017 Å for bond lengths and 0.37 D for dipole moments. The best of the semiempirical molecular orbital theories are PM3 and PM6, with BMUEs of 1.96 and 2.02, respectively. The ten most accurate functionals from the nonrelativistic benchmark analysis are then tested in relativistic calculations against new benchmarks obtained with coupled-cluster calculations and a relativistic effective core potential, resulting in M05-2X (BMUE = 0.895), PW6B95 (BMUE = 0.90), and B97-2 (BMUE = 0.93) as the top three functionals. We find significant relativistic effects (∼0.01 Å in bond lengths, ∼0.2 D in dipole moments, and ∼4 kcal/mol in Zn-ligand bond energies) that cannot be neglected for accurate modeling, but the same density functionals that do well in all-electron nonrelativistic calculations do well with relativistic effective core potentials. Although most tests are carried out with augmented polarized triple-ζ basis sets, we also carried out some tests with an augmented polarized double-ζ basis set, and we found, on average, that with the smaller basis set DFT has no loss in accuracy for dipole moments and only ∼10% less accurate bond lengths.

Correlation of nonorthogonality of best hybrid bond orbitals with bond strength of orthogonal orbitals

PubMed Central

Pauling, Linus

1976-01-01

An expression is derived for the bond length of two spd orbitals with maximum values in two directions forming a given bond angle by consideration of the nonorthogonality integral of two best orbitals in these directions. This equation is equivalent to the expression derived by formulating the pair of orthogonal orbitals. Similar expressions are derived for spdf orbitals. Applications are made to icosahedral and cuboctahedral bonds and to the packing of nucleons in atomic nuclei. PMID:16578736

Correlation of nonorthogonality of best hybrid bond orbitals with bond strength of orthogonal orbitals.

PubMed

Pauling, L

1976-02-01

An expression is derived for the bond length of two spd orbitals with maximum values in two directions forming a given bond angle by consideration of the nonorthogonality integral of two best orbitals in these directions. This equation is equivalent to the expression derived by formulating the pair of orthogonal orbitals. Similar expressions are derived for spdf orbitals. Applications are made to icosahedral and cuboctahedral bonds and to the packing of nucleons in atomic nuclei.

Differential segregation in a cell-cell contact interface: the dynamics of the immunological synapse.

PubMed Central

Burroughs, Nigel John; Wülfing, Christoph

2002-01-01

Receptor-ligand couples in the cell-cell contact interface between a T cell and an antigen-presenting cell form distinct geometric patterns and undergo spatial rearrangement within the contact interface. Spatial segregation of the antigen and adhesion receptors occurs within seconds of contact, central aggregation of the antigen receptor then occurring over 1-5 min. This structure, called the immunological synapse, is becoming a paradigm for localized signaling. However, the mechanisms driving its formation, in particular spatial segregation, are currently not understood. With a reaction diffusion model incorporating thermodynamics, elasticity, and reaction kinetics, we examine the hypothesis that differing bond lengths (extracellular domain size) is the driving force behind molecular segregation. We derive two key conditions necessary for segregation: a thermodynamic criterion on the effective bond elasticity and a requirement for the seeding/nucleation of domains. Domains have a minimum length scale and will only spontaneously coalesce/aggregate if the contact area is small or the membrane relaxation distance large. Otherwise, differential attachment of receptors to the cytoskeleton is required for central aggregation. Our analysis indicates that differential bond lengths have a significant effect on synapse dynamics, i.e., there is a significant contribution to the free energy of the interaction, suggesting that segregation by differential bond length is important in cell-cell contact interfaces and the immunological synapse. PMID:12324401

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.

Lattice effects on ferromagnetism in perovskite ruthenates

PubMed Central

Cheng, J.-G.; Zhou, J.-S.; Goodenough, John B.

2013-01-01

Ferromagnetism and its evolution in the orthorhombic perovskite system Sr1–xCaxRuO3 have been widely believed to correlate with structural distortion. The recent development of high-pressure synthesis of the Ba-substituted Sr1–yBayRuO3 makes it possible to study ferromagnetism over a broader phase diagram, which includes the orthorhombic Imma and the cubic phases. However, the chemical substitutions introduce the A-site disorder effect on Tc, which complicates determination of the relationship between ferromagnetism and structural distortion. By clarifying the site disorder effect on Tc in several unique series of ruthenates in which the average bond length 〈A–O〉 remains the same but the bond-length variance varies, we are able to demonstrate a parabolic curve of Tc versus mean bond length 〈A–O〉. A much higher Tc ∼ 177 K than that found in orthorhombic SrRuO3 can be obtained from the curve at a bond length 〈A–O〉, which makes the geometric factor t = 〈A–O〉/(√2〈Ru–O〉) ∼ 1. This result reveals not only that the ferromagnetism in the ruthenates is extremely sensitive to the lattice strain, but also that it has an important implication for exploring the structure–property relationship in a broad range of oxides with perovskite or a perovskite-related structure. PMID:23904477

Caries-preventive effect of fissure sealant containing surface reaction-type pre-reacted glass ionomer filler and bonded by self-etching primer.

PubMed

Shimazu, Kisaki; Ogata, Kiyokazu; Karibe, Hiroyuki

2012-01-01

We aimed to evaluate the caries-preventive effect of a fissure sealant containing surface reaction-type pre-reacted glass ionomer (S-PRG) filler and bonded by self-etching primer versus those of 2 conventional resin-based sealants bonded by acid etching in terms of its impact on enamel demineralization and remineralization, enamel bond strength, and integrity of debonded enamel surfaces. Demineralization, remineralization, and bond strength on untreated enamel and enamel subsurface lesions of bovine incisors were assessed among the sealants by polarizing microscopy and microradiography; debonded enamel surfaces were examined by scanning electron microscopy. The conventional resin-based sealants bonded by acid etching caused surface defects on the enamel subsurface lesions and significantly increased the lesion depth (p = 0.014), indicative of enamel demineralization. However the S-PRG filler-containing sealant bonded by self-etching primer maintained the enamel surface integrity and inhibited enamel demineralization. No difference in bond strength on both untreated enamel and enamel subsurface lesions was noted among the sealants. An S-PRG filler-containing fissure sealant bonded by self-etching primer can prevent enamel demineralization, microleakage, and gaps without the tags created by acid etching regardless of the enamel condition. Such sealants are suitable for protecting the pits and fissures of immature permanent teeth.

(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

A comparison between the shear bond strength of brackets bonded to glazed and deglazed porcelain surfaces with resin-reinforced glass-ionomer cement and a bis-GMA resin adhesive.

PubMed

Lifshitz, Abraham B; Cárdenas, Marianela

2006-01-01

This study compared the shear bond strength of a light-cure resin-reinforced glass-ionomer cement with a bis-GMA light-cure resin system in the bonding of stainless steel brackets to glazed and deglazed porcelain surfaces. Porcelain surfaces were divided into 4 groups: group 1, deglazed porcelain surfaces with Transbond XT, group 2, glazed porcelain surfaces with Transbond XT; group 3, deglazed porcelain surfaces with Fuji Ortho LC; and group 4, porcelain surfaces with Fuji Ortho LC. Microetching with 50-microm aluminum oxide for 2 seconds at a distance of 5 mm deglazed the porcelain surfaces in groups 1 and 3. All brackets were bonded to the porcelain surfaces using the same procedure and light-cured for 40 seconds with a visible light. All samples were thermocycled between 5 degrees C and 55 degrees C for 300 cycles before testing for shear bond strength with a universal testing machine. The analysis of variance showed no significant difference (P < .05) among the 4 groups; ie, group 1, 10.12 MPa; group 2, 7.00 MPa; group 3, 6.78 MPa; and group 4, 11.15 MPa. The F test also failed to demonstrate any statistical difference among the groups. Conditioning the porcelain surfaces with 37% phosphoric acid immediately followed by a nonhydrolyzed silane coupling agent resulted in clinically adequate bond strength when using either a composite resin or a resin-reinforced glass-ionomer cement. Microetching of these porcelain surfaces apparently offers no bonding advantage.

Measurement of intercolumnar forces between parallel guanosine four-stranded helices.

PubMed Central

Mariani, P; Saturni, L

1996-01-01

The deoxyguanosine-5'-monophosphate in aqueous solution self-associates into stable structures, which include hexagonal and cholesteric columnar phases. The structural unit is a four-stranded helix, composed of a stacked array of Hoogsteen-bonded guanosine quartets. We have measured by osmotic stress method the force per unit length versus interaxial distance between helices in the hexagonal phase under various ionic conditions. Two contributions have been recognized: the first one is purely electrostatic, is effective at large distances, and shows a strong dependence on the salt concentration of the solution. The second contribution is short range, dominates at interaxial separations smaller than about 30-32 A, and rises steeply as the columns approach each other, preventing the coalescence of the helices. This repulsion has an exponential nature and shows a magnitude and a decay length insensitive to the ionic strength of the medium. Because these features are distinctive of the hydration force detected between phospholipid bilayers or between several linear macromolecules (DNA, polysaccharides, collagen), we conclude that the dominant force experienced by deoxyguanosine helices approaching contact is hydration repulsion. The observed decay length of about 0.7 A has been rationalized to emerge from the coupling between the 3-A decay length of water solvent and the helically ordered structure of the hydrophilic groups on the opposing surfaces. The present results agree with recent measurements, also showing the dependence of the hydration force decay on the structure of interacting surfaces and confirm the correlations between force and structure. Images FIGURE 1 PMID:8744324

Hydroxide-catalyzed bonding

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2003-01-01

A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

Cleanliness inspection tool for RSRM bond surfaces

NASA Technical Reports Server (NTRS)

Mattes, Robert A.

1995-01-01

Using optically stimulated electron emission (OSEE), Thiokol has monitored bond surfaces in process for contamination on the Redesigned Solid Rocket Motor (RSRM). This technique provides process control information to help assure bond surface quality and repeatability prior to bonding. This paper will describe OSEE theory of operation and the instrumentation implemented at Thiokol Corporation since 1987. Data from process hardware will be presented.

Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes

NASA Astrophysics Data System (ADS)

Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

2016-06-01

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

Pillared graphene on the basis of zigzag carbon nanotubes for adsorption in medicine: mechanical properties

NASA Astrophysics Data System (ADS)

Kolesnikova, Anna S.; Mazepa, Margarita M.

2018-02-01

In nowadays the nanoscale materials are actively used in medicine, based on the properties of adsorption. One of the main problems of this field of medicine is the increase in specific surface of sorbent. We proposed to use carbon composites consisting of an extended in its directions graphene sheet with attached to it by chemical bonds zigzag carbon nanotubes (CNT). This paper presents the results of a theoretical study of the mechanical properties of graphene based on the CNT zigzag depending on the geometric dimensions of the composite (length and diameter of CNTs).

Shear strengths of a gallium alloy bonded to human enamel following nine different surface treatments.

PubMed

Claire, J; Williams, P T

2001-03-01

Gallium and indium-containing alloys have demonstrated an ability to wet and bond to many types of materials including enamel. The purpose of this study was to evaluate and compare the bond strengths of a gallium-and-indium-containing alloy and a dental amalgam to human enamel surfaces. A flat enamel bonding surface was created by slicing recently extracted human molars with a 180-grit diamond wheel. Cylinders of amalgam or a gallium-indium alloy were bonded to the as-cut surfaces or to as-cut surfaces that had been pumiced, air-abraded or acid-etched for various times. Before testing, samples were stored under different conditions (100% humidity, immersed in water, thermocycled). The shear-bond strength was determined using a crosshead speed of 0.1 mm x min(-1). Sample size was 10. Data was subjected to ANOVA and a post-hoc Tukey's test. The bond strength of amalgam to enamel was zero. The bond strength of the gallium-indium alloy ranged between 6.5 MPa (10s etch with 10% phosphoric acid) and 4.2 MPa (pumiced enamel). Acid-etching significantly increased the bond strength (P>0.0001) The bond strength was not significantly affected by the type of mechanical surface preparation, storage conditions, thermocycling, etching times or acid concentrations. Bonding, particularly chemical bonding, suggests a greater potential for better wetting and therefore better sealing of a cavity. Since microleakage of restorations is one of the principal causes of restoration failure, materials that can bond may in turn posses enhanced resistance to microleakage and ultimately, resistance to restoration failure. The gallium-indium alloy evaluated in this study may be such an alloy.

Two-year water degradation of self-etching adhesives bonded to bur ground enamel.

PubMed

Abdalla, Ali I; Feilzer, Albert J

2009-01-01

To evaluate the effect of water storage on the microshear bond strength to ground enamel of three "all-in-one" self-etch adhesives: Futurabond DC, Clearfil S Tri Bond and Hybrid bond; a self-etching primer; Clearfil SE Bond and an etch-and-rinse adhesive system, Admira Bond. Sixty human molars were used. The root of each tooth was removed and the crown was sectioned into two halves. The convex enamel surfaces were reduced by polishing on silicon paper to prepare a flat surface that was roughened with a parallel-sided diamond bur with abundant water for five seconds. The bonding systems were applied on this surface. Prior to adhesive curing, a hollow cylinder (2.0 mm in height/0.75 mm in internal diameter) was placed on the treated surfaces and cured. A resin composite was then inserted into the tube and cured. For each adhesive, two procedures were carried out: A--the specimens were kept in water for 24 hours, then the tube was removed and the microshear bond strength was determined in a universal testing machine at a crosshead speed of 0.5 mm/minute; B--the specimens were stored in water for two-years before microshear testing. The fractured surface of the bonded specimens after each test procedure was examined by SEM. For the 24-hour control, there was no significant difference in bond strength between the tested adhesives. After two years of water storage, the bond strength of Admira Bond, Clearfil SE Bond and Futurabond DC decreased, but the reduction was not significantly different from that of 24 hours. For Clearfil S Tri Bond and Hybrid Bond, the bond strengths were significantly reduced compared to their 24-hour results.

Enamel Wetness Effects on Microshear Bond Strength of Different Bonding Agents (Adhesive Systems): An in vitro Comparative Evaluation Study.

PubMed

Kulkarni, Girish; Mishra, Vinay K

2016-05-01

The purpose of this study was to compare the effect of enamel wetness on microshear bond strength using different adhesive systems. To evaluate microshear bond strength of three bonding agents on dry enamel; to evaluate microshear bond strength of three bonding agents on wet enamel; and to compare microshear bond strength of three different bonding agents on dry and wet enamel. Sixty extracted noncarious human premolars were selected for this study. Flat enamel surfaces of approximately 3 mm were obtained by grinding the buccal surfaces of premolars with water-cooled diamond disks. This study evaluated one etch-and-rinse adhesive system (Single Bond 2) and two self-etching adhesive systems (Clearfil SE Bond and Xeno-V). The specimens were divided into two groups (n = 30). Group I (dry) was air-dried for 30 seconds and in group II (wet) surfaces were blotted with absorbent paper to remove excess water. These groups were further divided into six subgroups (n = 10) according to the adhesives used. The resin composite, Filtek Z 250, was bonded to flat enamel surfaces that had been treated with one of the adhesives, following the manufacturer's instructions. After being stored in water at 37°C for 24 hours, bonded specimens were stressed in universal testing machine (Fig. 3) at a crosshead speed of 1 mm/min. The data were evaluated with one-way and two-way analysis of variance (ANOVA), t-test, and Tukey's Multiple Post hoc tests (a = 0.05). The two-way ANOVA and Tukey's Multiple Post hoc tests showed significant differences among adhesive systems, but wetness did not influence microshear bond strength (p = 0.1762). The one-way ANOVA and t-test showed that the all-in-one adhesive (Xeno-V) was the only material influenced by the presence of water on the enamel surface. Xeno-V showed significantly higher microshear bond strength when the enamel was kept wet. Single Bond 2 adhesive showed significantly higher microshear bond strength as compared with Xeno-V adhesive but no significant difference when compared with Clearfil SE Bond adhesive in dry enamel. Single Bond 2 adhesive showed no significant difference in microshear bond strength as compared with self-etching adhesive systems (Clearfil SE Bond and Xeno-V), when the enamel was kept wet. From the findings of the results, it was concluded that self-etching adhesives were not negatively affected by the presence of water on the enamel surface. The all-in-one adhesive showed different behavior depending on whether the enamel surface was dry or wet. So the enamel surface should not be desiccated, when self-etching adhesives are used.

Synthesis, spectra and X-ray crystallography of dipyridin-2-ylmethanone oxime and its CuX2(oxime)2 complexes: Thermal, Hirshfeld surface and DFT analysis

NASA Astrophysics Data System (ADS)

Warad, Ismail; Abdoh, Muneer; Al Ali, Anas; Shivalingegowda, Naveen; Kumara, Karthik; Zarrouk, Abdelkader; Lokanath, Neartur Krishnappagowda

2018-02-01

Dipyridin-2-ylmethanone oxime (C11H9N3O), was prepared using di-2-pyridyl ketone. The oxime ligand and its neutral CuX2 (oxime)2 (X = Cl or Br) complexes have been identified with the aid of several spectroscopic techniques such as: IR, EI-MS, EA, UV-visible, TG, 1H-NMR and finally the structure of the free oxime ligand was confirmed by X-ray diffraction studies. The oxime crystallizes in the monoclinic space group P21/c, with cell parameters a = 8.8811 (8) Å, b = 10.6362 (8) Å, c = 11.2050 (8) Å, β = 109.085 (4) º, V = 1000.26 (14) Å3 and Z = 4. The molecular conformation is stabilized by a strong intramolecular Osbnd H⋯N hydrogen bonding between the hydroxyl group of the oxime moiety and the nitrogen of the pyridine ring. Since the oxime structure was solved by XRD, the ligand structure parameters like bond length and angles were compared to the DFT computed one, the UV-visible to TD-SCF and Hirshfeld surface to MEP analysis.

Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): characterizing the role of spacer groups.

PubMed

McNellis, Erik R; Bronner, Christopher; Meyer, Jörg; Weinelt, Martin; Tegeder, Petra; Reuter, Karsten

2010-06-28

We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface bonding. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N[double bond, length as m-dash]N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.

Supersonic Retropulsion Surface Preparation of Carbon Fiber Reinforced Epoxy Composites for Adhesive Bonding

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Belcher, Marcus A.; Wohl, Christopher J.; Blohowiak, Kay Y.; Connell, John W.

2013-01-01

Surface preparation is widely recognized as a key step to producing robust and predictable bonds in a precise and reproducible manner. Standard surface preparation techniques, including grit blasting, manual abrasion, and peel ply, can lack precision and reproducibility, which can lead to variation in surface properties and subsequent bonding performance. The use of a laser to ablate composite surface resin can provide an efficient, precise, and reproducible means of preparing composite surfaces for adhesive bonding. Advantages include elimination of physical waste (i.e., grit media and sacrificial peel ply layers that ultimately require disposal), reduction in process variability due to increased precision (e.g. increased reproducibility), and automation of surface preparation, all of which improve reliability and process control. This paper describes a Nd:YAG laser surface preparation technique for composite substrates and the mechanical performance and failure modes of bonded laminates thus prepared. Additionally, bonded specimens were aged in a hot, wet environment for approximately one year and subsequently mechanically tested. The results of a one year hygrothermal aging study will be presented.

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.

Temperature-controlled two-wavelength laser soldering of tissues.

PubMed

Gabay, Ilan; Abergel, Avraham; Vasilyev, Tamar; Rabi, Yaron; Fliss, Dan M; Katzir, Abraham

2011-11-01

Laser tissue soldering is a method for bonding of incisions in tissues. A biological solder is spread over the cut, laser radiation heats the solder and the underlying cut edges and the incision is bonded. This method offers many advantages over conventional techniques (e.g., sutures). Past researches have shown that laser soldering, using a single laser, does not provide sufficient strength for bonding of cuts in thick (>1 mm) tissues. This study introduces a novel method for laser soldering of thick tissues, under temperature control, using two lasers, emitting two different wavelengths. An experimental system was built, using two lasers: (i) a CO(2) laser, whose radiation heated the upper surface of the tissue and (ii) a GaAs laser that heated an albumin layer under the tissue. An infrared fiber-optic radiometer monitored the temperature of the tissue. All three devices were connected to a computer that controlled the process. A computer simulation was written to optimize the system parameters. The system was tested on tissue phantoms, to validate the simulation and ensure that both the upper and lower sides of the cut were heated, and that the temperature could be controlled on both sides. The system was then used ex vivo to bond longitudinal cuts of lengths ∼12 mm in the esophagi of large farm pigs. The theoretical simulations showed a good stabilization of the temperatures at the upper and lower tissue surfaces at the target values. Experiments on tissue phantom showed a good agreement with these simulations. Incisions in esophagi, removed from large farm pigs, were then successfully bonded. The mean burst pressure was ∼3.6 m of water. This study demonstrated the capability of soldering cuts in thick tissues, paving the way for new types of surgical applications. Copyright © 2010 Wiley Periodicals, Inc.

Optimized ultra-thin manganin alloy passivated fine-pitch damascene compatible bump-less Cu-Cu bonding at sub 200 °C for three-dimensional Integration applications

NASA Astrophysics Data System (ADS)

Panigrahi, Asisa Kumar; Hemanth Kumar, C.; Bonam, Satish; Ghosh, Tamal; Rama Krishna Vanjari, Siva; Govind Singh, Shiv

2018-02-01

Enhanced Cu diffusion, Cu surface passivation, and smooth surface at the bonding interface are the key essentials for high quality Cu-Cu bonding. Previously, we have demonstrated optimized 3 nm thin Manganin metal-alloy passivation from oxidation and also helps to reduce the surface roughness to about 0.8 nm which substantially led to high quality Cu-Cu bonding. In this paper, we demonstrated an ultra fine-pitch (<25 µm) Cu-Cu bonding using an optimized Manganin metal-alloy passivation. This engineered surface passivation approach led to high quality bonding at sub 200 °C temperature and 0.4 MPa. Very low specific contact resistance of 1.4 × 10-7 Ω cm2 and the defect free bonded interface is clear indication of high quality bonding for future multilayer integrations. Furthermore, electrical characterization of the bonded structure was performed under various robust conditions as per International Technology Roadmap for Semiconductors (ITRS Roadmap) in order to satisfy the stability of the bonded structure.

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection-absorption spectroscopy.

PubMed

Biswas, Somnath; Husek, Jakub; Baker, L Robert

2018-04-24

Here we review the recent development of extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy. This method combines the benefits of X-ray absorption spectroscopy, such as element, oxidation, and spin state specificity, with surface sensitivity and ultrafast time resolution, having a probe depth of only a few nm and an instrument response less than 100 fs. Using this technique we investigated the ultrafast electron dynamics at a hematite (α-Fe2O3) surface. Surface electron trapping and small polaron formation both occur in 660 fs following photoexcitation. These kinetics are independent of surface morphology indicating that electron trapping is not mediated by defects. Instead, small polaron formation is proposed as the likely driving force for surface electron trapping. We also show that in Fe2O3, Co3O4, and NiO, band gap excitation promotes electron transfer from O 2p valence band states to metal 3d conduction band states. In addition to detecting the photoexcited electron at the metal M2,3-edge, the valence band hole is directly observed as transient signal at the O L1-edge. The size of the resulting charge transfer exciton is on the order of a single metal-oxygen bond length. Spectral shifts at the O L1-edge correlate with metal-oxygen bond covalency, confirming the relationship between valence band hybridization and the overpotential for water oxidation. These examples demonstrate the unique ability to measure ultrafast electron dynamics with element and chemical state resolution using XUV-RA spectroscopy. Accordingly, this method is poised to play an important role to reveal chemical details of previously unseen surface electron dynamics.

Comparison of quaternary ammonium-containing with nano-silver-containing adhesive in antibacterial properties and cytotoxicity

PubMed Central

Li, Fang; Weir, Michael D.; Chen, Jihua; Xu, Hockin H. K.

2013-01-01

Objective Antibacterial primer and adhesive are promising to help combat biofilms and recurrent caries. The objectives of this study were to compare novel bonding agent containing quaternary ammonium dimethacrylate (QADM) with bonding agent containing nanoparticles of silver (NAg) in antibacterial activity, contact-inhibition vs. long-distance inhibition, glucosyltransferases (gtf) gene expressions, and cytotoxicity for the first time. Methods QADM and NAg were incorporated into Scotchbond Multi-Purpose adhesive and primer. Microtensile dentin bond strength was measured. Streptococcus mutans (S. mutans) biofilm on resin surface (contact-inhibition) as well as S. mutans in culture medium away from the resin surface (long-distance inhibition) were tested for metabolic activity, colony-forming units (CFU), lactic acid production, and gtf gene expressions. Eluents from cured primer/adhesive samples were used to examine cytotoxicity against human gingival fibroblasts. Results Bonding agent with QADM greatly reduced CFU and lactic acid of biofilms on the resin surface (p < 0.05), while having no effect on S. mutans in culture medium away from the resin surface. In contrast, bonding agent with NAg inhibited not only S. mutans on the resin surface, but also S. mutans in culture medium away from the resin surface. Bonding agent with QADM suppressed gtfB, gtfC and gtfD gene expressions of S. mutans on its surface, but not away from its surface. Bonding agent with NAg suppressed S. mutans gene expressions both on its surface and away from its surface. Bonding agents with QADM and NAg did not adversely affect microtensile bond strength or fibroblast cytotoxicity, compared to control (p > 0.1). Significance QADM-containing adhesive had contact-inhibition and inhibited bacteria on its surface, but not away from its surface. NAg-containing adhesive had long-distance killing capability and inhibited bacteria on its surface and away from its surface. The novel antibacterial adhesives are promising for caries-inhibition restorations, and QADM and NAg could be complimentary agents in inhibiting bacteria on resin surface as well as away from resin surface. PMID:23428077

Influence of enamel surface preparation on composite bond strength.

PubMed

Matos, Adriana Bona; Tate, William H; Powers, John M

2003-09-01

To evaluate the influence of air-particle abrasion and treatments on in vitro tensile bond strength of resin composite bonded to human enamel was evaluated using a single-bottle adhesive. Human teeth were divided into 12 groups of three treatments (none, 27-microm Al2O3 air-particle abrasion, 50-microm Al2O3 air-particle abrasion) and four conditioners [none, phosphoric acid (PA), NRC (no-rinse conditioner), and PA/NRC]. Bonding agent (Prime & Bond NT) and a resin composite (TPH Spectrum) were applied as inverted cones. Specimens were stored for 24 hours at 37 degrees C and debonded in tension using a testing machine at 0.5 mm/minute. Phosphoric acid treatment used with Prime & Bond NT produced the best bond strengths (24 MPa) to enamel for surfaces treated with 27-microm air-particle abrasion and for surfaces not treated with air-particle abrasion (control). With one exception, air-particle abraded surfaces resulted in bond strengths between 9 to 16 MPa. NRC with or without the use of phosphoric acid in general did not improve tensile bond strength to enamel when compared to surfaces not treated with NRC.

Crystallographic perturbations to valence charge density and hydrogen-surface interactions

NASA Astrophysics Data System (ADS)

Ciston, James W.

The subject of surfaces has been the epicenter of numerous studies in recent years, particularly with respect to applications in catalysis, thin films, and self-assembly of nanostructures where the surface-to-volume ratio is large. Understanding how the atomic structure of materials differs at surfaces where the atoms are far less constrained can yield fundamental insight into these interesting nanoscale phenomena. Quantum surface crystallography takes this one step further in an attempt to experimentally measure the structure of the electrons themselves, which is of greater importance than atomic positions in determining material properties. We report a procedure for obtaining a much better initial parameterization of the charge density than what is possible from a neutral atom model. This procedure involves the parameterization of a bulk charge density model in terms of simple variables such as bond lengths, which can then be transferred to the problem of interest, for instance a surface. Parameterization is accomplished through the fitting of Density Functional Theory calculations of a variety of crystal distortions to a bond-centered pseudoatom (BCPA) model. This parameterized model can then be applied to surfaces or for other problems where an initial higher-order model is needed without the addition of any extra fitted parameters. Through the use of the BCPA model, we report a three-dimensional charge density refinement from x-ray diffraction intensities of the Si (001) 2x1H surface. By properly accounting for the covalent bonding effects in the silicon structure, we were able to stably refine the positions of hydrogen atoms at this surface in three dimensions, which had never before been accomplished for any surface. In addition, we found experimentally an increased, slightly localized bond density of approximately 0.31 electrons between each Si atom pair at the surface. Both the atomic positions and the charge density were found to be in remarkably good agreement with density functional theory (DFT) calculations. The BCPA model was also applied to an experimental refinement of the local charge density at the Si (111) 7x7 surface utilizing a combination of x-ray and high energy electron diffraction. By perturbing about the bond-centered pseudoatom model, we found experimentally that the adatoms were in an anti-bonding state with the atoms directly below. We were also able to experimentally refine a charge transfer of 0.26+/-0.04 e- from each adatom site to the underlying layers. This was the first statistically significant refinement of site-specific bonding information at any surface utilizing x-ray diffraction data. Precession electron diffraction (PED) is a technique which is gaining increasing interest due to its ease of use and reduction of the dynamical scattering problem in electron diffraction. To further investigate the usefulness of this technique, we performed a systematic study of the effect of precession angle on the mineral andalusite where the semiangle was varied from 6.5 to 32 mrad in five discrete steps. We have shown that the intensities of kinematically forbidden reflections decayed exponentially as the precession semiangle (ϕ) was increased. Additionally, we have determined that charge density effects were best observed at moderately low angles (6.5-13 mrad) even though PED patterns became more kinematical in nature as the precession angle was increased further. We have also shown that the amount of interpretable information provided by direct methods phase inversion of the diffraction data increases monotonically but non-systematically as ϕ increases. We report an experimental and theoretical analysis of the ✓3x✓3-R30° and 2x2 reconstructions on the MgO (111) surface combining transmission electron microscopy, x-ray photoelectron spectroscopy, and reasonably accurate density functional calculations using the meta-GGA functional TPSS. We have not only conclusively solved the atomic structures of these reconstructions, but have developed a kinetic model for an evolutionary pathway between structures driven entirely by exchange of water molecules between the surface and the environment that does not require the cations to move when the structure transforms. This is the first time an experimentally and theoretically supported kinetic model has described not only all of the structures in a series on a single oxide surface, but also describes why none of the structures pass through the thermodynamically most stable configuration. Lastly, we have investigated the observability of valence bonding effects in aberration-corrected high resolution electron microscopy (HREM) images along the [010] projection of the mineral Forsterite (Mg2SiO 4). Direct observability of bonding effects would be both faster and less ambiguous than the refinement of similar features against diffraction data. Through analysis of simulated high resolution electron microscopy images, we have determined that bonding effects should be observable at levels approaching 20% of the total contrast. Initial experimental results for this material system have also been presented.

Method of making a composite tube to metal joint

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

Leslie, James C.; Leslie, II, James C.; Heard, James

A method for making a metal to composite tube joint including selecting an elongated interior fitting constructed with an exterior barrel, reduced in exterior diameter to form a distally facing annular shoulder and then projecting still further distally to form an interior sleeve having a radially outwardly facing bonding surface. Selecting an elongated metal outer sleeve formed proximally with a collar constructed for receipt over the barrel and increased in interior diameter and projecting distally to form an exterior sleeve having a radially inwardly facing bonding surface cooperating with the first bonding surface to form an annulus receiving an extremitymore » of a composite tube and a bond bonding the extremity of the tube to the bonding surfaces.« less

Effect of Reduced Phosphoric Acid Pre-etching Times 
on Enamel Surface Characteristics and Shear Fatigue Strength Using Universal Adhesives.

PubMed

Tsujimoto, Akimasa; Fischer, Nicholas; Barkmeier, Wayne; Baruth, Andrew; Takamizawa, Toshiki; Latta, Mark; Miyazaki, Masashi

2017-01-01

To examine the effect of reduced phosphoric acid pre-etching times on enamel fatigue bond strength of universal adhesives and surface characteristics by using atomic force microscopy (AFM). Three universal adhesives were used in this study (Clearfil Universal Bond [C], G-Premio Bond [GP], Scotchbond Universal Adhesive [SU]). Four pre-etching groups were employed: enamel pre-etched with phosphoric acid and immediately rinsed with an air-water spray, and enamel pre-etched with phosphoric acid for 5, 10, or 15 s. Ground enamel was used as the control group. For the initial bond strength test, 15 specimens per etching group for each adhesive were used. For the shear fatigue test, 20 specimens per etching group for each adhesive were loaded using a sine wave at a frequency of 20 Hz for 50,000 cycles or until failure occurred. Initial shear bond strengths and fatigue shear strengths of composite adhesively bonded to ground and pre-etched enamel were determined. AFM observations of ground and pre-etched enamel were also conducted, and surface roughness as well as surface area were evaluated. The initial shear bond strengths and fatigue shear strengths of the universal adhesives in the pre-etched groups were significantly higher than those of the control group, and were not influenced by the pre-etching time. Significantly higher surface roughness and surface area of enamel surfaces in pre-etched groups were observed compared with those in the control group. While the surface area was not significantly influenced by etching time, surface roughness of the enamel surfaces in the pre-etched groups significantly increased with pre-etching time. The results of this in vitro study suggest that reduced phosphoric acid pre-etching times do not impair the fatigue bond strength of universal adhesives. Although fatigue bond strength and surface area were not influenced by phosphoric-acid etching times, surface roughness increased with increasing etching time.

Anisotropy of the monomer random walk in a polymer melt: local-order and connectivity effects

NASA Astrophysics Data System (ADS)

Bernini, S.; Leporini, D.

2016-05-01

The random walk of a bonded monomer in a polymer melt is anisotropic due to local order and bond connectivity. We investigate both effects by molecular-dynamics simulations on melts of fully-flexible linear chains ranging from dimers (M  =  2) up to entangled polymers (M  =  200). The corresponding atomic liquid is also considered a reference system. To disentangle the influence of the local geometry and the bond arrangements, and to reveal their interplay, we define suitable measures of the anisotropy emphasising either the former or the latter aspect. Connectivity anisotropy, as measured by the correlation between the initial bond orientation and the direction of the subsequent monomer displacement, shows a slight enhancement due to the local order at times shorter than the structural relaxation time. At intermediate times—when the monomer displacement is comparable to the bond length—a pronounced peak and then decays slowly as t -1/2, becoming negligible when the displacement is as large as about five bond lengths, i.e. about four monomer diameters or three Kuhn lengths. Local-geometry anisotropy, as measured by the correlation between the initial orientation of a characteristic axis of the Voronoi cell and the subsequent monomer dynamics, is affected at shorter times than the structural relaxation time by the cage shape with antagonistic disturbance by the connectivity. Differently, at longer times, the connectivity favours the persistence of the local-geometry anisotropy, which vanishes when the monomer displacement exceeds the bond length. Our results strongly suggest that the sole consideration of the local order is not enough to understand the microscopic origin of the rattling amplitude of the trapped monomer in the cage of the neighbours.

77 FR 5728 - Airworthiness Directives; Airbus Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-06

... between bonding lead and the harness, due to over length of the bonding lead. As the affected wire is not... chafing of the wires, and corrective actions, if necessary. We are proposing this AD to detect and correct contact or chafing of wires and bonding leads which, if not detected could be a source of sparks in the...

30 CFR 800.14 - Determination of bond amount.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 800.14 Mineral Resources OFFICE OF SURFACE MINING RECLAMATION AND ENFORCEMENT, DEPARTMENT OF THE INTERIOR BONDING AND INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS UNDER REGULATORY PROGRAMS § 800.14...

Dentin surface treatment using a non-thermal argon plasma brush for interfacial bonding improvement in composite restoration

PubMed Central

Ritts, Andy Charles; Li, Hao; Yu, Qingsong; Xu, Changqi; Yao, Xiaomei; Hong, Liang; Wang, Yong

2010-01-01

The objective of this study is to investigate the treatment effects of non-thermal atmospheric gas plasmas on dentin surfaces for composite restoration. Extracted unerupted human third molars were used by removing the crowns and etching the exposed dentin surfaces with 35% phosphoric acid gel. The dentin surfaces were treated by using a non-thermal atmospheric argon plasma brush for various durations. The molecular changes of the dentin surfaces were analyzed using FTIR/ATR and an increase in carbonyl groups on dentin surfaces was detected with plasma treated dentin. Adper Single Bond Plus adhesive and Filtek Z250 dental composite were applied as directed. To evaluate the dentin/composite interfacial bonding, the teeth thus prepared were sectioned into micro-bars as the specimens for tensile test. Student Newman Keuls tests showed that the bonding strength of the composite restoration to peripheral dentin was significantly increased (by 64%) after 30 s plasma treatment. However, the bonding strength to plasma treated inner dentin did not show any improvement. It was found that plasma treatment of peripheral dentin surface up to 100 s gave an increase in interfacial bonding strength, while a prolong plasma treatment of dentin surfaces, e.g., 5 min treatments, showed a decrease in interfacial bonding strength. PMID:20831586

Effect of Nd: YAG laser irradiation on surface properties and bond strength of zirconia ceramics.

PubMed

Liu, Li; Liu, Suogang; Song, Xiaomeng; Zhu, Qingping; Zhang, Wei

2015-02-01

This study investigated the effect of neodymium-doped yttrium aluminum garnet (Nd: YAG) laser irradiation on surface properties and bond strength of zirconia ceramics. Specimens of zirconia ceramic pieces were divided into 11 groups according to surface treatments as follows: one control group (no treatment), one air abrasion group, and nine laser groups (Nd: YAG irradiation). The laser groups were divided by applying with different output power (1, 2, or 3 W) and irradiation time (30, 60, or 90 s). Following surface treatments, the morphological characteristics of ceramic pieces was observed, and the surface roughness was measured. All specimens were bonded to resin cement. After, stored in water for 24 h and additionally aged by thermocycling, the shear bond strength was measured. Dunnett's t test and one-way ANOVA were performed as the statistical analyses for the surface roughness and the shear bond strength, respectively, with α = .05. Rougher surface of the ceramics could be obtained by laser irradiation with higher output power (2 and 3 W). However, cracks and defects were also found on material surface. The shear bond strength of laser groups was not obviously increased, and it was significantly lower than that of air abrasion group. No significant differences of the shear bond strength were found among laser groups treated with different output power or irradiation time. Nd: YAG laser irradiation cannot improve the surface properties of zirconia ceramics and cannot increase the bond strength of the ceramics. Enhancing irradiation power and extending irradiation time cannot induce higher bond strength of the ceramics and may cause material defect.

Analytical energy gradient for the two-component normalized elimination of the small component method

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

Zou, Wenli; Filatov, Michael; Cremer, Dieter, E-mail: dcremer@smu.edu

2015-06-07

The analytical gradient for the two-component Normalized Elimination of the Small Component (2c-NESC) method is presented. The 2c-NESC is a Dirac-exact method that employs the exact two-component one-electron Hamiltonian and thus leads to exact Dirac spin-orbit (SO) splittings for one-electron atoms. For many-electron atoms and molecules, the effect of the two-electron SO interaction is modeled by a screened nucleus potential using effective nuclear charges as proposed by Boettger [Phys. Rev. B 62, 7809 (2000)]. The effect of spin-orbit coupling (SOC) on molecular geometries is analyzed utilizing the properties of the frontier orbitals and calculated SO couplings. It is shown thatmore » bond lengths can either be lengthened or shortened under the impact of SOC where in the first case the influence of low lying excited states with occupied antibonding orbitals plays a role and in the second case the jj-coupling between occupied antibonding and unoccupied bonding orbitals dominates. In general, the effect of SOC on bond lengths is relatively small (≤5% of the scalar relativistic changes in the bond length). However, large effects are found for van der Waals complexes Hg{sub 2} and Cn{sub 2}, which are due to the admixture of more bonding character to the highest occupied spinors.« less

Effect of electronic structure of the diamond surface on the strength of the diamond-metal interface

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1981-01-01

A diamond surface undergoes a transformation in its electronic structure by a vacuum anneal at approximately 900 C. The polished surface has no electronic states in the band gap, whereas the annealed surface has both occupied and unoccupied states in the and gap and exhibits some electrical conductivity. The effect of this transformation on the strength of the diamond metal interface was investigated by measuring the static friction force of an atomically clean meta sphere on a diamond flat in ultrahigh vacuum. It was found that low friction (weak bonding) is associated with the diamond surface devoid of gap states whereas high friction (strong bonding) is associated with the diamond surface with gap states. Exposure of the annealed surface to excited hydrogen also leads to weak bonding. The interfacial bond is discussed in terms of interaction of the metal conduction band electrons with the band gap states on the diamond surface. Effects of surface electrical conductivity on the interfacial bond are also be considered.

Laser Surface Preparation of Epoxy Composites for Secondary Bonding: Optimization of Ablation Depth

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Hopkins, John; Wohl, Christopher J.; Lin, Yi; Connell, John W.; Belcher, Marcus A.; Blohowiak, Kay Y.

2015-01-01

Surface preparation has been identified as one of the most critical aspects of attaining predictable and reliable adhesive bonds. Energetic processes such as laser ablation or plasma treatment are amenable to automation and are easily monitored and adjusted for controlled surface preparation. A laser ablation process was developed to accurately remove a targeted depth of resin, approximately 0.1 to 20 micrometers, from a carbon fiber reinforced epoxy composite surface while simultaneously changing surface chemistry and creating micro-roughness. This work demonstrates the application of this process to prepare composite surfaces for bonding without exposing or damaging fibers on the surface. Composite panels were prepared in an autoclave and had a resin layer approximately 10 micrometers thick above the fiber reinforcement. These composite panels were laser surface treated using several conditions, fabricated into bonded panels and hygrothermally aged. Bond performance of aged, experimental specimens was compared with grit blast surface treated specimens using a modified double cantilever beam test that enabled accelerated saturation of the specimen with water. Comparison of bonded specimens will be used to determine how ablation depth may affect average fracture energies and failure modes.

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.

Influence of aluminum oxide film on thermocompression bonding of gold wire to evaporated aluminum film

NASA Technical Reports Server (NTRS)

Iwata, S.; Ishizaka, A.; Yamamoto, H.

1984-01-01

The influence of Al surface condition on the thermocompression bonding of Au wires to Al electrodes for integrated electric circuits was studied. Au wires were connected to Al electrodes by nail-head bonding after various Al surface treatments. Bonding was evaluated by measuring the wire pull strength and fraction of the number of failures at Au-Al bonds to the total number of failures. Dependence of the fraction on applied load was derived theoretically with a parameter named critical load to take into consideration the differences in Al surface condition. The relation also held explicately for various surface treatments. Characterization of the Al surface was carried out by electron microscopy for chemical analysis.

NEXAFS and XPS characterization of molecular oxygen adsorbed on Ni(100) at 80 K

NASA Astrophysics Data System (ADS)

Kim, C. M.; Jeong, H. S.; Kim, E. H.

2000-07-01

X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and near edge extended X-ray absorption fine structure (NEXAFS) have been combined to investigate the adsorption of oxygen on Ni(100) at 80 K. Three O(1s) XPS features were observed at 530.0, 531.1 and 534.7 eV when the Ni(100) surface was exposed to 600 L of oxygen at 80 K. They are assigned as O 2-, O 1- and molecular oxygen species, respectively. The presence of molecular oxygen has been confirmed by TDS and NEXAFS. Molecular O 2 on Ni(100) is oriented perpendicular to the surface, and the OO bond length is estimated to be 1.24 Å, based on the NEXAFS σ ∗ resonance energy.

Magnesium isotope fractionation between brucite [Mg(OH)2] and Mg aqueous species: Implications for silicate weathering and biogeochemical processes

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Beard, Brian L.; Li, Chengxiang; Johnson, Clark M.

2014-05-01

Brucite, with its octahedral structure, has a lattice configuration that is similar to the Mg-bearing octahedral layers in phyllosilicates. Understanding stable Mg isotope fractionation between brucite and aqueous solution therefore bears on interpretation of Mg isotope data in natural weathering systems. In this study, we experimentally determined Mg isotope fractionation between brucite and two Mg aqueous species, the free Mg aquo ion ([Mg(OH2)6]2+) and EDTA-bonded Mg (Mg-EDTA2-). Results from recrystallization and brucite synthesis experiments suggest mild preferential partitioning of light Mg isotopes into brucite compared to Mg aquo ions at low temperatures, where measured ΔMgbrucite-Mg26 fractionation increased from ca. -0.3‰ at 7 °C, to ca. -0.2‰ at 22 °C, to ca. 0‰ at 40 °C. MgO hydrolysis experiments in EDTA-bearing solutions suggest that the ΔMgbrucite-Mg-EDTA26 fractionation is ⩾+2.0‰ at 22 °C, indicating that light Mg isotopes strongly partition into Mg-EDTA complex relative to brucite, as well as relative to Mg aquo ions. Magnesium atoms in brucite, Mg aquo ions, and Mg-EDTA complexes are all octahedrally coordinated, and the measured Mg isotope fractionations correlate with average bond lengths for Mg. Aqueous Mg ions have the shortest bond length among the three phases, and enrich heavy Mg isotopes relative to brucite and Mg-EDTA. In contrast, Mg-EDTA has the longest average bond length for Mg, and enriches light Mg isotopes relative to Mg aquo ions and brucite; the relatively long Mg-EDTA bond suggests that organically bound Mg may commonly have low 26Mg/24Mg ratios, which may explain proposed "vital" effects for stable Mg isotopes. Such relations between bond length and Mg isotope fractionation could be extended to other phyllosilicates such as serpentine- and clay-group minerals where Mg is also octahedrally coordinated.

Charging and geometric effects on conduction through Anthracene molecular junctions

NASA Astrophysics Data System (ADS)

Kaur, Rupan Preet; Sawhney, Ravinder Singh; Engles, Derick

We studied the geometric effects on the charge transfer through the anthracenedithiol (ADT) molecular junction using density functional theory combined with the non-equilibrium Green’s function approach. Two major geometric aspects, bond length and bond angle, were moderated to optimize the electrical conduction. From the results established in this paper, we found that the electrical conduction can be tuned from 0.2 G0 to 0.9 G0 by varying the Au-S bond length, whereas the moderation of bonding angle assayed a minor change from 0.37 G0 to 0.47 G0. We attributed this escalating zero bias conductance to the increasing charge on the terminal sulfur atom of the ADT molecule, which increased the energy of the HOMO orbital towards Fermi level and exhibited a semi-metallic behaviour. Therefore, geometry plays a critical role in deciding the charge transport through the metal/molecule interface.

Nanoscopic length scale dependence of hydrogen bonded molecular associates’ dynamics in methanol

PubMed Central

Bertrand, C. E.; Self, J. L.; Copley, J. R. D.; Faraone, A.

2017-01-01

In a recent paper [C. E. Bertrand et al., J. Chem. Phys. 145, 014502 (2016)], we have shown that the collective dynamics of methanol shows a fast relaxation process related to the standard density-fluctuation heat mode and a slow non-Fickian mode originating from the hydrogen bonded molecular associates. Here we report on the length scale dependence of this slow relaxation process. Using quasielastic neutron scattering and molecular dynamics simulations, we show that the dynamics of the slow process is affected by the structuring of the associates, which is accessible through polarized neutron diffraction experiments. Using a series of partially deuterated samples, the dynamics of the associates is investigated and is found to have a similar time scale to the lifetime of hydrogen bonding in the system. Both the structural relaxation and the dynamics of the associates are thermally activated by the breaking of hydrogen bonding. PMID:28527447

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

Relationship between enamel bond fatigue durability and surface free-energy characteristics with universal adhesives.

PubMed

Nagura, Yuko; Tsujimoto, Akimasa; Barkmeier, Wayne W; Watanabe, Hidehiko; Johnson, William W; Takamizawa, Toshiki; Latta, Mark A; Miyazaki, Masashi

2018-04-01

The relationship between enamel bond fatigue durability and surface free-energy characteristics with universal adhesives was investigated. The initial shear bond strengths and shear fatigue strengths of five universal adhesives to enamel were determined with and without phosphoric acid pre-etching. The surface free-energy characteristics of adhesive-treated enamel with and without pre-etching were also determined. The initial shear bond strength and shear fatigue strength of universal adhesive to pre-etched enamel were higher than those to ground enamel. The initial shear bond strength and shear fatigue strength of universal adhesive to pre-etched enamel were material dependent, unlike those to ground enamel. The surface free-energy of the solid (γ S ) and the hydrogen-bonding force (γSh) of universal adhesive-treated enamel were different depending on the adhesive, regardless of the presence or absence of pre-etching. The bond fatigue durability of universal adhesives was higher to pre-etched enamel than to ground enamel. In addition, the bond fatigue durability to pre-etched enamel was material dependent, unlike that to ground enamel. The surface free-energy characteristics of universal adhesive-treated enamel were influenced by the adhesive type, regardless of the presence or absence of pre-etching. The surface free-energy characteristics of universal adhesive-treated enamel were related to the results of the bond fatigue durability. © 2018 Eur J Oral Sci.

Ligand-to-ligand charge-transfer transitions of platinum(II) complexes with arylacetylide ligands with different chain lengths: spectroscopic characterization, effect of molecular conformations, and density functional theory calculations.

PubMed

Tong, Glenna So Ming; Law, Yuen-Chi; Kui, Steven C F; Zhu, Nianyong; Leung, King Hong; Phillips, David Lee; Che, Chi-Ming

2010-06-11

The complexes [Pt(tBu(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)R}](+) (n = 1: R = alkyl and aryl (Ar); n = 1-3: R = phenyl (Ph) or Ph-N(CH(3))(2)-4; n = 1 and 2, R = Ph-NH(2)-4; tBu(3)tpy = 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine) and [Pt(Cl(3)tpy)(C[triple bond]CR)](+) (R = tert-butyl (tBu), Ph, 9,9'-dibutylfluorene, 9,9'-dibutyl-7-dimethyl-amine-fluorene; Cl(3)tpy = 4,4',4''-trichloro-2,2':6',2''-terpyridine) were prepared. The effects of substituent(s) on the terpyridine (tpy) and acetylide ligands and chain length of arylacetylide ligands on the absorption and emission spectra were examined. Resonance Raman (RR) spectra of [Pt(tBu(3)tpy)(C[triple bond]CR)](+) (R = n-butyl, Ph, and C(6)H(4)-OCH(3)-4) obtained in acetonitrile at 298 K reveal that the structural distortion of the C[triple bond]C bond in the electronic excited state obtained by 502.9 nm excitation is substantially larger than that obtained by 416 nm excitation. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on [Pt(H(3)tpy)(C[triple bond]CR)](+) (R = n-propyl (nPr), 2-pyridyl (Py)), [Pt(H(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)Ph}](+) (n = 1-3), and [Pt(H(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)C(6)H(4)-N(CH(3))(2)-4}](+)/+H(+) (n = 1-3; H(3)tpy = nonsubstituted terpyridine) at two different conformations were performed, namely, with the phenyl rings of the arylacetylide ligands coplanar ("cop") with and perpendicular ("per") to the H(3)tpy ligand. Combining the experimental data and calculated results, the two lowest energy absorption peak maxima, lambda(1) and lambda(2), of [Pt(Y(3)tpy)(C[triple bond]CR)](+) (Y = tBu or Cl, R = aryl) are attributed to (1)[pi(C[triple bond]CR)-->pi*(Y(3)tpy)] in the "cop" conformation and mixed (1)[d(pi)(Pt)-->pi*(Y(3)tpy)]/(1)[pi(C[triple bond]CR)-->pi*(Y(3)tpy)] transitions in the "per" conformation. The lowest energy absorption peak lambda(1) for [Pt(tBu(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)C(6)H(4)-H-4}](+) (n = 1-3) shows a redshift with increasing chain length. However, for [Pt(tBu(3)tpy){C[triple bond]C(C6H4C[triple bond]C)(n-1)C(6)H(4)-N(CH(3))(2)-4}](+) (n = 1-3), lambda(1) shows a blueshift with increasing chain length n, but shows a redshift after the addition of acid. The emissions of [Pt(Y(3)tpy)(C[triple bond]CR)](+) (Y = tBu or Cl) at 524-642 nm measured in dichloromethane at 298 K are assigned to the (3)[pi(C[triple bond]CAr)-->pi*(Y(3)tpy)] excited states and mixed (3)[d(pi)(Pt)-->pi*(Y(3)tpy)]/(3)[pi(C[triple bond]C)-->pi*(Y(3)tpy)] excited states for R = aryl and alkyl groups, respectively. [Pt(tBu(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)C(6)H(4)-N(CH(3))(2)-4}](+) (n = 1 and 2) are nonemissive, and this is attributed to the small energy gap between the singlet ground state (S(0)) and the lowest triplet excited state (T(1)).

Redox properties of undoped 5 nm diamond nanoparticles.

PubMed

Holt, Katherine B; Ziegler, Christoph; Caruana, Daren J; Zang, Jianbing; Millán-Barrios, Enrique J; Hu, Jingping; Foord, John S

2008-01-14

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp(3) diamond core with a surface that has significant delocalised pi character due to unsatisfied surface atoms and C[double bond, length as m-dash]O bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.

Cohesion and coordination effects on transition metal surface energies

NASA Astrophysics Data System (ADS)

Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

2017-10-01

Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

A theoretical investigation of the structural and electronic properties of 55-atom nanoclusters: The examples of Y-Tc and Pt.

PubMed

Batista, Krys E A; Piotrowski, Maurício J; Chaves, Anderson S; Da Silva, Juarez L F

2016-02-07

Several studies have found that the Pt55 nanocluster adopts a distorted reduced core structure, DRC55, in which there are 8-11 atoms in the core and 47-44 atoms in the surface, instead of the compact and high-symmetry icosahedron structure, ICO55, with 13 and 42 atoms in the core and surface, respectively. The DRC structure has also been obtained as the putative global minimum configuration (GMC) for the Zn55 (3d), Cd55 (4d), and Au55 (5d) systems. Thus, the DRC55 structure has been reported only for systems with a large occupation of the d-states, where the effects of the occupation of the valence anti-bonding d-states might play an important role. Can we observe the DRC structure for 55-atom transition-metal systems with non-occupation of the anti-bonding d-states? To address this question, we performed a theoretical investigation of the Y 55, Zr55, Nb55, Mo55, Tc55, and Pt55 nanoclusters, employing density functional theory calculations. For the putative GMCs, we found that the Y 55 adopts the ICO55 structure, while Nb55 and Mo55 adopt a bulk-like fragment based on the hexagonal close-packed structure and Tc55 adopts a face-centered cubic fragment; however, Zr55 adopts a DRC55 structure, like Zn55, Cd55, Pt55, and Au55. Thus we can conclude that the preference for DRC55 structure is not related to the occupation of the anti-bonding d-states, but to a different effect, in fact, a combination of structural and electronic effects. Furthermore, we obtained that the binding energy per atom follows the occupation of the bonding and anti-bonding model, i.e., the stability of the studied systems increases from Y to Tc with a small oscillation for Mo, which also explains the equilibrium bond lengths. We obtained a larger magnetic moment for Y 55 (31 μB) which can be explained by the localization of the d-states in Y at nanoscale, which is not observed for the remaining systems (0-1 μB).

Shear bond strength of resin composite bonded with two adhesives: Influence of Er: YAG laser irradiation distance

PubMed Central

Shirani, Farzaneh; Birang, Reza; Malekipour, Mohammad Reza; Hourmehr, Zahra; Kazemi, Shantia

2014-01-01

Background: Dental surfaces prepared with different Er:YAG laser distance may have different characteristics compared with those prepared with conventional instruments. The aim of this study was to investigate the effect of Er:YAG laser irradiation distance from enamel and dentin surfaces on the shear bond strength of composite with self-etch and etch and rinse bonding systems compared with conventional preparation method. Materials and Methods: Two hundred caries-free human third molars were randomly divided into twenty groups (n = 10). Ten groups were designated for enamel surface (E1-E10) and ten for dentin surface (D1-D10). Er: YAG laser (2940 nm) was used on the E1-E8 (240 mJ, 25 Hz) and D1-D8 (140 mJ, 30 Hz) groups at four different distances of 0.5 (standard), 2, 4 and 11 mm. Control groups (E9, E10, D9 and D10) were ground with medium grit diamond bur. The enamel and dentin specimens were divided into two subgroups that were bonded with either Single Bond or Clearfil SE Bond. Resin composite (Z100) was dispensed on prepared dentin and enamel. The shear bond strengths were tested using a universal testing machine. Data were analyzed by SPSS12 statistical software using three way analysis of variance, Tukey and independent t-test. P < 0.05 was considered as significant. Results: There was a significant difference between enamel and dentin substrates (P < 0.001) and between lased and un-lased groups; the un-lased group had significantly higher bond strength (P < 0.001). Shear bond strength increased significantly with an increase in the laser irradiation distance (P < 0.05) on enamel surfaces (in both bonding agent subgroups) and on dentin surfaces (in the Single Bond subgroup). Conclusion: Laser irradiation decreases shear bond strength. Irradiation distance affects shear bond strength and increasing the distance would decrease the negative effects of laser irradiation. PMID:25540665

Effect of indirect composite treatment microtensile bond strength of self-adhesive resin cements

PubMed Central

Escribano, Nuria; Baracco, Bruno; Romero, Martin; Ceballos, Laura

2016-01-01

Background No specific indications about the pre-treatment of indirect composite restorations is provided by the manufacturers of most self-adhesive resin cements. The potential effect of silane treatment to the bond strength of the complete tooth/indirect restoration complex is not available.The aim of this study was to determine the contribution of different surface treatments on microtensile bond strength of composite overlays to dentin using several self-adhesive resin cements and a total-etch one. Material and Methods Composite overlays were fabricated and bonding surfaces were airborne-particle abraded and randomly assigned to two different surface treatments: no treatment or silane application (RelyX Ceramic Primer) followed by an adhesive (Adper Scotchbond 1 XT). Composite overlays were luted to flat dentin surfaces using the following self-adhesive resin cements: RelyX Unicem, G-Cem, Speedcem, Maxcem Elite or Smartcem2, and the total-etch resin cement RelyX ARC. After 24 h, bonded specimens were cut into sticks 1 mm thick and stressed in tension until failure. Two-way ANOVA and SNK tests were applied at α=0.05. Results Bond strength values were significantly influenced by the resin cement used (p<0.001). However, composite surface treatment and the interaction between the resin cement applied and surface treatment did not significantly affect dentin bond strength (p>0.05). All self-adhesive resin cements showed lower bond strength values than the total-etch RelyX ARC. Among self-adhesive resin cements, RelyX Unicem and G-Cem attained statistically higher bond strength values. Smartcem2 and Maxcem Elite exhibited 80-90% of pre-test failures. Conclusions The silane and adhesive application after indirect resin composite sandblasting did not improve the bond strength of dentin-composite overlay complex. Selection of the resin cement seems to be a more relevant factor when bonding indirect composites to dentin than its surface treatment. Key words:Bond strength, self-adhesive cement, silane, dentin, indirect composite. PMID:26855700

Bonding Effectiveness of Luting Composites to Different CAD/CAM Materials.

PubMed

Peumans, Marleen; Valjakova, Emilija Bajraktarova; De Munck, Jan; Mishevska, Cece Bajraktarova; Van Meerbeek, Bart

To evaluate the influence of different surface treatments of six novel CAD/CAM materials on the bonding effectiveness of two luting composites. Six different CAD/CAM materials were tested: four ceramics - Vita Mark II; IPS Empress CAD and IPS e.max CAD; Celtra Duo - one hybrid ceramic, Vita Enamic, and one composite CAD/CAM block, Lava Ultimate. A total of 60 blocks (10 per material) received various mechanical surface treatments: 1. 600-grit SiC paper; 2. sandblasting with 30-μm Al2O3; 3. tribochemical silica coating (CoJet). Subsequent chemical surface treatments involved either no further treatment (control), HF acid etching (HF), silanization (S, or HF acid etching followed by silanization (HF+S). Two specimens with the same surface treatment were bonded together using two dual-curing luting composites: Clearfil Esthetic Cement (self-etching) or Panavia SA Cement (self-adhesive). After 1 week of water storage, the microtensile bond strength of the sectioned microspecimens was measured and the failure mode was evaluated. The bonding performance of the six CAD/CAM materials was significantly influenced by surface treatment (linear mixed models, p < 0.05). The luting cement had a significant influence on bond strength for Celtra Duo and Lava Ultimate (linear mixed models, p < 0.05). Mechanical surface treatment significantly influenced the bond strength for Celtra Duo (p = 0.0117), IPS e.max CAD (p = 0.0115), and Lava Ultimate (p < 0.0001). Different chemical surface treatments resulted in the highest bond strengths for the six CAD/CAM materials: Vita Mark II and IPS Empress CAD: S, HF+S; Celtra Duo: HF, HF+S; IPS e.max CAD: HF+S; Vita Enamic: HF+S, S. For Lava Ultimate, the highest bond strengths were obtained with HF, S, HF+S. Failure analysis showed a relation between bond strength and failure type: more mixed failures were observed with higher bond strengths. Mainly adhesive failures were noticed if no further surface treatment was done. The percentage of adhesive failures was higher for CAD/CAM materials with higher flexural strength (Celtra Duo, IPS e.max CAD, and Lava Ultimate). The bond strength of luting composites to novel CAD/CAM materials is influenced by surface treatment. For each luting composite, an adhesive cementation protocol can be specified in order to obtain the highest bond to the individual CAD/CAM materials.

Hydrogen-assisted versus hydroxyl-assisted CO dissociation over Co-doped Cu(111): A DFT study

NASA Astrophysics Data System (ADS)

Zha, Hao; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2018-03-01

First principle based density functional theory (DFT) was used to calculate the step-by-step hydrogenation and dissociation reaction network of carbon monoxide (CO) over Co-doped Cu(111) surface as a model for understanding the lateral interaction of surface hydroxyl species (OH) on these reactions. We discussed the Csbnd O bond length and the adsorption energy changes of reaction intermediates under different adsorption circumstances for purpose of making out the effect of surface hydroxyl on the reaction selectivity. Reaction intermediates co-adsorbed with H atom and hydroxyl could undergo H-assisted or OH-assisted routes. The calculations show that the OH-assisted route prefers with the formation of COH, CHOH and CH2OH while general H-assisted route prefers with the formation of HCO, CH2O and CH3O. Considering the rather low activation barrier of COH, CHOH and CH2OH to form CHX, the existence of hydroxyl on the surface is in favor of boosting the CHX and suppressing the methanol.

Axial compression behaviour of reinforced wallettes fabricated using wood-wool cement panel

NASA Astrophysics Data System (ADS)

Noh, M. S. Md; Kamarudin, A. F.; Mokhatar, S. N.; Jaudin, A. R.; Ahmad, Z.; Ibrahim, A.; Muhamad, A. A.

2018-04-01

Wood-wool cement composite panel (WWCP) is one of wood based composite material that produced in a stable panel form and suitable to be used as building wall system to replace non-ecofriendly material such as brick and other masonry element. Heavy construction material such as brick requires more manpower and consume a lot of time to build the wall panel. WWCP is a lightweight material with a density range from 300 kg/m3 to 500 kg/m3 and also capable to support an imposed load from the building. This study reported on the axial compression behaviour of prefabricated reinforced wallettes constructed with wood-wool cement panel. A total of six specimens were fabricated using two layers of cross laminated WWCP bonded with normal mortar paste (Portland cement) at a mix ratio of 1:3 (cement : sand). As part of lifting mechanism, the wallettes were equipped with three steel reinforcement (T12) that embedded inside the core of wallettes. Three replicates of wallettes specimens with dimension 600 mm width and 600 mm length were fabricated without surface plaster and with 16 mm thickness of surface plaster. The wallettes were tested under axial compression load after 28 days of fabrication until failure. The result indicated that, the application of surface plaster significantly increases the loading capacity about 35 % and different orientation of the panels improve the bonding strength of the wall.

Utilization of Microwave Spectroscopy to Identify and Probe Reaction Dynamics of Hsno, a Crucial Biological Signaling Molecule

NASA Astrophysics Data System (ADS)

Nava, Matthew; Martin-Drumel, Marie-Aline; Stanton, John F.; Cummins, Christopher; McCarthy, Michael C.

2016-06-01

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries. Its existence and stability in vivo, however, remain controversial. By means of Fourier-transform microwave spectroscopy, we establish that HSNO is spontaneously formed in high concentration when NO and H2S gases are simply mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed with high efficiency by the reaction H2S and N2O3 to produce HSNO and HNO2, where N2O3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H2S may form HNO and HSSH. The length of the S--N bond has been derived to high precision from isotopic studies, and is found to be unusually long, 1.84 Å -- the longest S--N bond reported to date for an SNO compound. The present structural and reactivity investigations of this elusive molecule provide a firm fundation to better understand its physiological chemistry and propensity to undergo S--N bond homolysis in vivo.

Vertically aligned nanowires from boron-doped diamond.

PubMed

Yang, Nianjun; Uetsuka, Hiroshi; Osawa, Eiji; Nebel, Christoph E

2008-11-01

Vertically aligned diamond nanowires with controlled geometrical properties like length and distance between wires were fabricated by use of nanodiamond particles as a hard mask and by use of reactive ion etching. The surface structure, electronic properties, and electrochemical functionalization of diamond nanowires were characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) as well as electrochemical techniques. AFM and STM experiments show that diamond nanowire etched for 10 s have wire-typed structures with 3-10 nm in length and with typically 11 nm spacing in between. The electrode active area of diamond nanowires is enhanced by a factor of 2. The functionalization of nanowire tips with nitrophenyl molecules is characterized by STM on clean and on nitrophenyl molecule-modified diamond nanowires. Tip-modified diamond nanowires are promising with respect to biosensor applications where controlled biomolecule bonding is required to improve chemical stability and sensing significantly.

Linear and nonlinear susceptibilities from diffusion quantum Monte Carlo: application to periodic hydrogen chains.

PubMed

Umari, P; Marzari, Nicola

2009-09-07

We calculate the linear and nonlinear susceptibilities of periodic longitudinal chains of hydrogen dimers with different bond-length alternations using a diffusion quantum Monte Carlo approach. These quantities are derived from the changes in electronic polarization as a function of applied finite electric field--an approach we recently introduced and made possible by the use of a Berry-phase, many-body electric-enthalpy functional. Calculated susceptibilities and hypersusceptibilities are found to be in excellent agreement with the best estimates available from quantum chemistry--usually extrapolations to the infinite-chain limit of calculations for chains of finite length. It is found that while exchange effects dominate the proper description of the susceptibilities, second hypersusceptibilities are greatly affected by electronic correlations. We also assess how different approximations to the nodal surface of the many-body wave function affect the accuracy of the calculated susceptibilities.

Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001)

DOE PAGES

Steinrück, H. -G.; Magerl, A.; Deutsch, M.; ...

2014-10-06

The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ~1% – 3% to the sapphire’s and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in themore » crystalline coherence length of the SAM’s powderlike crystallites when rotationally aligned with the sapphire’s lattice. As a result, the increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.« less

Molecular dynamics simulations of AP/HMX composite with a modified force field.

PubMed

Zhu, Wei; Wang, Xijun; Xiao, Jijun; Zhu, Weihua; Sun, Huai; Xiao, Heming

2009-08-15

An all-atom force field for ammonium perchlorate (AP) is developed with the framework of pcff force field. The structural parameters of AP obtained with the modified force field are in good agreement with experimental values. Molecular dynamics (MD) simulations have been performed to investigate AP/HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) composite at different temperatures. The binding energies, thermal expansion coefficient, and the trigger bond lengths of HMX in the AP/HMX composite have been obtained. The binding energies of the system increase slightly with temperature increasing, peak at 245K, and then gradually decrease. The volume thermal expansion coefficient of the AP/HMX composite has been derived from the volume variation with temperature. As the temperature rises, the maximal lengths of the trigger bond N-NO(2) of HMX increase gradually. The simulated results indicate that the maximal length of trigger bond can be used as a criterion for judging the sensitivity of energetic composite.

Shear Bond Strength of Three Orthodontic Bonding Systems on Enamel and Restorative Materials.

PubMed

Hellak, Andreas; Ebeling, Jennifer; Schauseil, Michael; Stein, Steffen; Roggendorf, Matthias; Korbmacher-Steiner, Heike

2016-01-01

Objective. The aim of this in vitro study was to determine the shear bond strength (SBS) and adhesive remnant index (ARI) score of two self-etching no-mix adhesives (iBond ™ and Scotchbond ™ ) on different prosthetic surfaces and enamel, in comparison with the commonly used total etch system Transbond XT ™ . Materials and Methods . A total of 270 surfaces (1 enamel and 8 restorative surfaces, n = 30) were randomly divided into three adhesive groups. In group 1 (control) brackets were bonded with Transbond XT primer. In the experimental groups iBond adhesive (group 2) and Scotchbond Universal adhesive (group 3) were used. The SBS was measured using a Zwicki 1120 ™ testing machine. The ARI and SBS were compared statistically using the Kruskal-Wallis test ( P ≤ 0.05). Results . Significant differences in SBS and ARI were found between the control group and experimental groups. Conclusions . Transbond XT showed the highest SBS on human enamel. Scotchbond Universal on average provides the best bonding on all other types of surface (metal, composite, and porcelain), with no need for additional primers. It might therefore be helpful for simplifying bonding in orthodontic procedures on restorative materials in patients. If metal brackets have to be bonded to a metal surface, the use of a dual-curing resin is recommended.

Quantitative assessment of intermolecular interactions by atomic force microscopy imaging using copper oxide tips

NASA Astrophysics Data System (ADS)

Mönig, Harry; Amirjalayer, Saeed; Timmer, Alexander; Hu, Zhixin; Liu, Lacheng; Díaz Arado, Oscar; Cnudde, Marvin; Strassert, Cristian Alejandro; Ji, Wei; Rohlfing, Michael; Fuchs, Harald

2018-05-01

Atomic force microscopy is an impressive tool with which to directly resolve the bonding structure of organic compounds1-5. The methodology usually involves chemical passivation of the probe-tip termination by attaching single molecules or atoms such as CO or Xe (refs 1,6-9). However, these probe particles are only weakly connected to the metallic apex, which results in considerable dynamic deflection. This probe particle deflection leads to pronounced image distortions, systematic overestimation of bond lengths, and in some cases even spurious bond-like contrast features, thus inhibiting reliable data interpretation8-12. Recently, an alternative approach to tip passivation has been used in which slightly indenting a tip into oxidized copper substrates and subsequent contrast analysis allows for the verification of an oxygen-terminated Cu tip13-15. Here we show that, due to the covalently bound configuration of the terminal oxygen atom, this copper oxide tip (CuOx tip) has a high structural stability, allowing not only a quantitative determination of individual bond lengths and access to bond order effects, but also reliable intermolecular bond characterization. In particular, by removing the previous limitations of flexible probe particles, we are able to provide conclusive experimental evidence for an unusual intermolecular N-Au-N three-centre bond. Furthermore, we demonstrate that CuOx tips allow the characterization of the strength and configuration of individual hydrogen bonds within a molecular assembly.

Length-dependence of intramolecular electron transfer in σ-bonded rigid molecular rods: an ab initio molecular orbital study

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Karna, Shashi P.

2002-01-01

The dependence of electron transfer (ET) coupling element, VAB, on the length of rigid-rod-like systems consisting of bicyclo[1.1.1]pentane (BCP), cubane (CUB), and bicyclo[2.2.2]octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of VAB decreases exponentially with increase in the number of the cage units of the σ-bonded molecules. The calculated decay constant, β, shows good agreement with previously reported data. For molecular length⩾15 Å, the value of VAB becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

Room-temperature wafer bonding of LiNbO3 and SiO2 using a modified surface activated bonding method

NASA Astrophysics Data System (ADS)

Takigawa, Ryo; Higurashi, Eiji; Asano, Tanemasa

2018-06-01

In this paper, we report room-temperature bonding of LiNbO3 (LN) and SiO2/Si for the realization of a LN on insulator (LNOI)/Si hybrid wafer. We investigate the applicability of a modified surface activated bonding (SAB) method for the direct bonding of LN and a thermally grown SiO2 layer. The modified SAB method using ion beam bombardment demonstrates the room-temperature wafer bonding of LN and SiO2. The bonded wafer was successfully cut into 0.5 × 0.5 mm2 dies without interfacial debonding owing to the applied stress during dicing. In addition, the surface energy of the bonded wafer was estimated to be approximately 1.8 J/m2 using the crack opening method. These results indicate that a strong bond strength can be achieved, which may be sufficient for device applications.

Dimensional Stability of Hexoloy SA® Silicon Carbide and Zerodur™ Materials for the LISA Mission

NASA Astrophysics Data System (ADS)

Preston, Alix; Cruz, Rachel J.; Thorpe, J. Ira; Mueller, Guido; Boothe, G. Trask; Delgadillo, Rodrigo; Guntaka, Sridhar R.

2006-11-01

In the LISA mission, incoming gravitational waves will modulate the distance between proof masses while laser beams monitor the optical path length changes with 20 pm/√Hz accuracy. Optical path length changes between bench components or the relative motion between the primary and secondary mirrors of the telescope need to be well below this level to result in a successful operation of LISA. The reference cavity for frequency stabilization must have a dimensional stability of a few fm/√Hz. While the effects of temperature fluctuations are well characterized in most materials at the macroscopic level (i.e. coefficients of thermal expansion), microscopic material internal processes and long term processes in the bonds between different components can dominate the dimensional stability at the pm or fm levels. Zerodur and ULE have been well studied, but the ultimate stabilities of other materials like silicon carbide or CFRP are virtually unknown. Chemical bonding techniques, like hydroxide bonding, provide significantly stronger bonds than the standard optical contacts. However, the noise levels of these bonds are also unknown. In this paper we present our latest results on the stability of silicon carbide and hydroxide bonds on Zerodur.

Crystal structure of cis-aqua­chlorido­bis­(1,10-phenanthroline-κ2 N,N′)chromium(III) tetra­chlorido­zincate monohydrate from synchrotron data

PubMed Central

Moon, Dohyun; Choi, Jong-Ha

2015-01-01

The structure of the title compound, [CrCl(C12H8N2)2(H2O)][ZnCl4]·H2O, has been determined from synchrotron data. The CrIII ion is bonded to four N atoms from two 1,10-phenanthroline (phen) ligands, one water mol­ecule and a Cl atom in a cis arrangement, displaying an overall distorted octa­hedral coordination environment. The Cr—N(phen) bond lengths are in the range of 2.0495 (18) to 2.0831 (18) Å, while the Cr—Cl and Cr—(OH2) bond lengths are 2.2734 (7) and 1.9986 (17) Å, respectively. The tetra­hedral [ZnCl4]2− anion is slightly distorted owing to its involvement in O—H⋯Cl hydrogen bonding with coordinating and non-coordinating water mol­ecules. The two types of water mol­ecules also inter­act through O—H⋯O hydrogen bonds. The observed hydrogen-bonding pattern leads to the formation of a three-dimensional network structure. PMID:25844190

Evaluation of surface roughness of enamel after various bonding and clean-up procedures on enamel bonded with three different bonding agents: An in-vitro study

PubMed Central

Goel, Amit; Singh, Atul; Gupta, Tarun

2017-01-01

Background The purpose of this study was to analyze and compare the enamel surface roughness before bonding and after debonding, to find correlation between the adhesive remnant index and its effect on enamel surface roughness and to evaluate which clean-up method is most efficient to provide a smoother enamel surface. Material and Methods 135 premolars were divided into 3 groups containing 45 premolars in each group. Group I was bonded by using moisture insensitive primer, Group II by using conventional orthodontic adhesive and Group III by using self-etching primer. Each group was divided into 3 sub-groups on the basis of type of clean-up method applied i,e scaling followed by polishing, tungsten carbide bur and Sof-Lex disc. Enamel surface roughness was measured and compared before bonding and after clean-up. Results Evaluation of pre bonding and post clean-up enamel surface roughness (Ra value) with the t test showed that Post clean-up Ra values were greater than Pre bonding Ra values in all the groups except in teeth bonded with self-etching primer cleaned with Sof-Lex disc. Reliability of ARI score taken at different time interval tested with Kruskal Wallis test suggested that all the readings were reliable. Conclusions No clean-up procedure was able to restore the enamel to its original smoothness. Self-etching primer and Sof-Lex disc clean-up method combination restored the enamel surface roughness (Ra value) closest to its pre-treatment value. Key words:Enamel surface roughness, clean-up method, adhesive remnant index. PMID:28512535

Surface fluorination of zirconia: adhesive bond strength comparison to commercial primers.

PubMed

Piascik, Jeffrey R; Swift, Edward J; Braswell, Krista; Stoner, Brian R

2012-06-01

This study evaluated contact angle and shear bond strength of three commercial zirconia primers and compared them to a recently developed fluorination pre-treatment. Earlier investigations reported that plasma fluorinated zirconia modifies the chemical bonding structure creating a more reactive surface. Yttria-stabilized zirconia (LAVA, 3M ESPE) plates were highly polished using 3μm diamond paste (R(a) ∼200nm) prior to pretreatments. After primer and fluorination treatment, contact angles were measured to quantify surface hydrophobicity before and after ethanol clean. Additionally, simple shear bond tests were performed to measure the adhesion strength to a composite resin. Plasma fluorination produced the lowest contact angle (7.8°) and the highest shear bond strength (37.3MPa) suggesting this pretreatment facilitates a more "chemically" active surface for adhesive bonding. It is hypothesized that plasma fluorination increase hydroxylation at the surface, making it more reactive, thus allowing for covalent bonding between zirconia surface and resin cement. A strong correlation was observed between contact angle and adhesion strength for all specimens; a relationship which may help understand the frequency and modes of failures, clinically. It is also believed that this surface treatment can increase long-term viability of zirconia restorations over other adhesive techniques. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Method of bonding functional surface materials to substrates and applications in microtechnology and anti-fouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

2001-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer preferably, (N,N'-diethylamine) dithiocarbamoylpropyl-(trimethoxy) silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N, N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Method of bonding functional surface materials to substrates and applications in microtechnology and antifouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

1999-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer, preferably, (N,N'-diethylamine)dithiocarbamoylpropyl-(trimethoxy)silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N,N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Influence of de/remineralization of enamel on the tensile bond strength of etch-and-rinse and self-etching adhesives.

PubMed

Farias de Lacerda, Ana Julia; Ferreira Zanatta, Rayssa; Crispim, Bruna; Borges, Alessandra Bühler; Gomes Torres, Carlos Rocha; Tay, Franklin R; Pucci, Cesar Rogério

2016-10-01

To evaluate the bonding behavior of resin composite and different adhesives applied to demineralized or remineralized enamel. Bovine tooth crowns were polished to prepare a 5 mm2 enamel bonding area, and divided into five groups (n= 48) according to the surface treatment: CONT (sound enamel control), DEM (demineralized with acid to create white spot lesions), REMS (DEM remineralized with artificial saliva), REMF (DEM remineralized with sodium fluoride) and INF (DEM infiltrated with Icon resin infiltrant). The surface-treated teeth were divided into two subgroups (n= 24) according to adhesive type: ER (etch-and-rinse; Single Bond Universal) and SE (self-etching; Clearfill S3 Bond), and further subdivided into two categories (n= 12) according to aging process: Thermo (thermocycling) and NA (no aging). Composite blocks were made over bonded enamel and sectioned for microtensile bond strength (MTBS) testing. Data were analyzed with three-way ANOVA and post-hoc Tukey's test (α= 0.05). Significant differences were observed for enamel surface treatment (P< 0.0001), adhesive type (P< 0.0001) and aging (P< 0.0001). CONT and INF groups had higher MTBS than the other groups; Single Bond Universal had higher MTBS than Clearfil S3 Bond; thermo-aging resulted in lower MTBS irrespective of adhesive type and surface treatment condition. The predominant failure mode was mixed for all groups. Enamel surface infiltrated with Icon does not interfere with adhesive resin bonding procedures. Treatment of enamel surface containing white spot lesions or cavities with cavosurface margins in partially-demineralized enamel can benefit from infiltration with a low viscosity resin infiltrant prior to adhesive bonding of resin composites.

The effect of Er:YAG laser irradiation on the bond stability of self-etch adhesives at different dentin depths.

PubMed

Karadas, Muhammet; Çağlar, İpek

2017-07-01

The aim of this study was to evaluate the effect of Er:YAG laser irradiation on the micro-shear bond strength of self-etch adhesives to the superficial dentin and the deep dentin before and after thermocycling. Superficial dentin and deep dentin surfaces were prepared by flattening of the occlusal surfaces of extracted human third molars. The deep or superficial dentin specimens were randomized into three groups according to the following surface treatments: group I (control group), group II (Er:YAG laser; 1.2 W), and group III (Er:YAG laser; 0.5 W). Clearfil SE Bond or Clearfil S 3 Bond was applied to each group's dentin surfaces. After construction of the composite blocks on the dentin surface, the micro-shear bond testing of each adhesive was performed at 24 h or after 15,000 thermal cycles. The data were analyzed using a univariate analysis of variance and Tukey's test (p < 0.05). Laser irradiation in superficial dentin did not significantly affect bond strength after thermocycling (p > 0.05). However, deep-dentin specimens irradiated with laser showed significantly higher bond strengths than did control specimens after thermocycling (p < 0.05). Thermocycling led to significant deterioration in the bond strengths of all deep-dentin groups. The stable bond strength after thermocycling was measured for all of the superficial-dentin groups. No significant difference was found between the 0.5 and 1.2 W output power settings. In conclusion, the effect of laser irradiation on the bond strength of self-etch adhesives may be altered by the dentin depth. Regardless of the applied surface treatment, deep dentin showed significant bond degradation.

Sintered silver joints via controlled topography of electronic packaging subcomponents

DOEpatents

Wereszczak, Andrew A.

2014-09-02

Disclosed are sintered silver bonded electronic package subcomponents and methods for making the same. Embodiments of the sintered silver bonded EPSs include topography modification of one or more metal surfaces of semiconductor devices bonded together by the sintered silver joint. The sintered silver bonded EPSs include a first semiconductor device having a first metal surface, the first metal surface having a modified topography that has been chemically etched, grit blasted, uniaxial ground and/or grid sliced connected to a second semiconductor device which may also include a first metal surface with a modified topography, a silver plating layer on the first metal surface of the first semiconductor device and a silver plating layer on the first metal surface of the second semiconductor device and a sintered silver joint between the silver plating layers of the first and second semiconductor devices which bonds the first semiconductor device to the second semiconductor device.

Bonded ultrasonic transducer and method for making

DOEpatents

Dixon, Raymond D.; Roe, Lawrence H.; Migliori, Albert

1995-01-01

An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements.

Effect of blood and saliva contamination on bond strength of brackets bonded with a protective liquid polish and a light-cured adhesive.

PubMed

Sayinsu, Korkmaz; Isik, Fulya; Sezen, Serdar; Aydemir, Bulent

2007-03-01

The application of a polymer coating to the labial enamel tooth surface before bonding can help keep white spot lesions from forming. Previous studies evaluating the effects of blood and saliva contamination on the bond strengths of light-cured composites showed significant reductions in bond strength values. The purpose of this study was to investigate whether the bond strength of a light-cured system (Transbond XT, 3M Unitek, Puchheim, Germany) used with a liquid polish (BisCover, Bisco, Schaumburg, Ill) is affected by contamination with blood or saliva. One hundred twenty permanent human premolars were randomly divided into 6 groups of 20. Various enamel surface conditions were studied: dry, blood contaminated, and saliva contaminated. A light-cured bonding system (Transbond XT) was used in all groups. The teeth in group 1 were bonded with Transbond XT. In the second group, BisCover polymeric resin polish was applied on the etched tooth surfaces before the brackets were bonded with Transbond XT resin. Comparison of the first and second groups showed no statistically significant difference. Groups 3 through 6 were bonded without Transbond XT. For groups 3 and 5, a layer of blood or saliva, respectively, was applied to the etched enamel followed by BisCover. In groups 4 and 6, blood or saliva, respectively, was applied on the light-cured BisCover. Shear forces were applied to the samples with a universal testing machine, and bond strengths were measured in megapascals. The protective liquid polish (BisCover) layer did not affect bond strength. Blood contamination on acid-etched surfaces affects bond strength more than saliva contamination. When a protective liquid polish (BisCover) is applied to the tooth surface, the effect of contamination by blood or saliva is prevented.

Raman spectroscopy as a tool to investigate the structure and electronic properties of carbon-atom wires

PubMed Central

Milani, Alberto; Tommasini, Matteo; Russo, Valeria; Li Bassi, Andrea; Lucotti, Andrea; Cataldo, Franco

2015-01-01

Summary Graphene, nanotubes and other carbon nanostructures have shown potential as candidates for advanced technological applications due to the different coordination of carbon atoms and to the possibility of π-conjugation. In this context, atomic-scale wires comprised of sp-hybridized carbon atoms represent ideal 1D systems to potentially downscale devices to the atomic level. Carbon-atom wires (CAWs) can be arranged in two possible structures: a sequence of double bonds (cumulenes), resulting in a 1D metal, or an alternating sequence of single–triple bonds (polyynes), expected to show semiconducting properties. The electronic and optical properties of CAWs can be finely tuned by controlling the wire length (i.e., the number of carbon atoms) and the type of termination (e.g., atom, molecular group or nanostructure). Although linear, sp-hybridized carbon systems are still considered elusive and unstable materials, a number of nanostructures consisting of sp-carbon wires have been produced and characterized to date. In this short review, we present the main CAW synthesis techniques and stabilization strategies and we discuss the current status of the understanding of their structural, electronic and vibrational properties with particular attention to how these properties are related to one another. We focus on the use of vibrational spectroscopy to provide information on the structural and electronic properties of the system (e.g., determination of wire length). Moreover, by employing Raman spectroscopy and surface enhanced Raman scattering in combination with the support of first principles calculations, we show that a detailed understanding of the charge transfer between CAWs and metal nanoparticles may open the possibility to tune the electronic structure from alternating to equalized bonds. PMID:25821689

Characterisation of CFRP surface contamination by laser induced fluorescence

NASA Astrophysics Data System (ADS)

Malinowski, Pawel H.; Sawczak, Miroslaw; Wandowski, Tomasz; Ostachowicz, Wieslaw M.; Cenian, Adam

2014-03-01

The application of Carbon Fibre Reinforced Polymers (CFRP) in aeronautics has been increasing. The CFRP elements are joint using rivets and adhesive bonding. The reliability of the bonding limits the use of adhesive bonding for primary aircraft structures, therefore it is important to assess the bond quality. The performance of adhesive bonds depends on the physico-chemical properties of the adhered surfaces. This research is focused on characterization of surfaces before bonding. In-situ examination of large surface materials, determine the group of methods that are preferred. The analytical methods should be non-destructive, enabling large surface analysis in relatively short time. In this work a spectroscopic method was tested that can be potentially applied for surface analysis. Four cases of surface condition were investigated that can be encountered either in the manufacturing process or during aircraft service. The first case is related to contamination of CFRP surface with hydraulic fluid. This fluid reacts with water forming a phosphoric acid that can etch the CFRP. Second considered case was related to silicone-based release agent contamination. These agents are used during the moulding process of composite panels. Third case involved moisture content in CFRP. Moisture content lowers the adhesion quality and leads to reduced performance of CFRP resulting in reduced performance of the adhesive bond. The last case concentrated on heat damage of CFRP. It was shown that laser induced fluorescence method can be useful for non-destructive evaluation of CFRP surface and some of the investigated contaminants can be easily detected.

Tadpole-like Conformations of Huntingtin Exon 1 Are Characterized by Conformational Heterogeneity that Persists regardless of Polyglutamine Length.

PubMed

Newcombe, Estella A; Ruff, Kiersten M; Sethi, Ashish; Ormsby, Angelique R; Ramdzan, Yasmin M; Fox, Archa; Purcell, Anthony W; Gooley, Paul R; Pappu, Rohit V; Hatters, Danny M

2018-05-11

Soluble huntingtin exon 1 (Httex1) with expanded polyglutamine (polyQ) engenders neurotoxicity in Huntington's disease. To uncover the physical basis of this toxicity, we performed structural studies of soluble Httex1 for wild-type and mutant polyQ lengths. Nuclear magnetic resonance experiments show evidence for conformational rigidity across the polyQ region. In contrast, hydrogen-deuterium exchange shows absence of backbone amide protection, suggesting negligible persistence of hydrogen bonds. The seemingly conflicting results are explained by all-atom simulations, which show that Httex1 adopts tadpole-like structures with a globular head encompassing the N-terminal amphipathic and polyQ regions and the tail encompassing the C-terminal proline-rich region. The surface area of the globular domain increases monotonically with polyQ length. This stimulates sharp increases in gain-of-function interactions in cells for expanded polyQ, and one of these interactions is with the stress-granule protein Fus. Our results highlight plausible connections between Httex1 structure and routes to neurotoxicity. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Crystalline Structure and Surface Reactivity: Atomistic models are unique tools for dealing with the chemical and physical properties of surfaces.

PubMed

Gatos, H C

1962-08-03

The role of crystalline structure in the surface reactivity of predominantly covalent materials has been examined in terms of chemical bonding concepts. In this context a solid surface can be viewed as a giant lattice defect characterized by dangling bonds. Although it is difficult, at the present stage of development of the quantum mechanical approach to surfaces, to define precisely the perturbations resulting from the abrupt termination of the lattice at the surface, a host of experimental observations can be understood by assuming displacements of surface atoms and distortions of bonding configurations in accordance with simple chemical bonding principles. A purely atomistic approach has been shown to account not only for the chemical behavior but also for certain structural and electrical characteristics of the surfaces considered. A number of phenomena, such as crystal growth and the behavior of certain lattice defects (for example, dislocations), are intimately related to the presence of dangling bonds and the associated distortions of the lattice at the surface (32).

[The influence of surface conditioning on the shear bond strength of La-Porcelain and titanium].

PubMed

Mo, Anchun; Cen, Yuankun; Liao, Yunmao

2003-04-20

To determine the influence of different surface conditioning methods on bonding strength of low fusing porcelain (La-Porcelain) and titanium. The surface of the samples were sandblasted for 2 min with 80-250 microns Al2O3 or coated for two times with Si-couple agent or conditioned by pre-oxidation. The shear bond strength was examined by push-type shear test with a speed of 0.5 mm/min in a universal testing machine. Scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA) were employed to explore the relationship between bonding strength and microstructures, as well as the element diffusion at the interface between porcelain coating and titanium when heated at 800 degrees C. Bonding strength was not statistically different (P > 0.05) after sandblasting with Al2O3 in particle size ranged from 80 microns to 250 microns. When a Si-couple agent was used, bond of porcelain to titanium was significantly lower (P < 0.05). The shear bond strength of the porcelain to the pre-oxidized titanium surface remained unchanged after heating (P > 0.05). The SEM results revealed integrity of porcelain and titanium. La-Porcelain showed a small effect of surface coarseness. Sandblasting the titanium surface with 150-180 microns Al2O3 can be recommended as a method for better bonding between La-Porcelain and titanium. The Si-couple agent coating and pre-oxidation of titanium surface is unnecessary.

Laser Ablation Surface Preparation of Ti-6A1-4V for Adhesive Bonding

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Watson, Kent A.; Morales, Guillermo; Williams, Thomas; Hicks, Robert; Wohl, Christopher J.; Hopkins, John W.; Connell, John W.

2012-01-01

Adhesive bonding offers many advantages over mechanical fastening, but requires certification before it can be incorporated in primary structures for commercial aviation without disbond-arrestment features or redundant load paths. Surface preparation is widely recognized as the key step to producing robust and predictable bonds. Laser ablation imparts both topographical and chemical changes to a surface which can lead to increased bond durability. A laser based process provides an alternative to chemical-dip, manual abrasion and grit blast treatments which are expensive, hazardous, polluting, and less precise. This report documents preliminary testing of a surface preparation technique using laser ablation as a replacement for the chemical etch and abrasive processes currently applied to Ti-6Al-4V alloy adherends. Failure mode, surface roughness, and chemical makeup were analyzed using fluorescence enhanced visualization, microscopy, and X-ray photoelectron spectroscopy, respectively. Single lap shear tests were conducted on bonded and aged specimens to observe bond strength retention and failure mode. Some promising results showed increasing strength and durability of lap shear specimens as laser ablation coverage area and beam intensity increased. Chemical analyses showed trends for surface chemical species which correlated with improved bond strength and durability. Combined, these results suggest that laser ablation is a viable process for inclusion with or/and replacement of one or more currently used titanium surface treatments. On-going work will focus on additional mechanical tests to further demonstrate improved bond durability.

Effect of Atmospheric Pressure Plasma Treatment on Surface Characteristics and Adhesive Bond Quality of Peel Ply Prepared Composites

NASA Astrophysics Data System (ADS)

Tracey, Ashley C.

The purpose of this research was to investigate if atmospheric pressure plasma treatment could modify peel ply prepared composite surfaces to create strong adhesive bonds. Two peel ply surface preparation composite systems previously shown to create weak bonds (low fracture energy and adhesion failure) that were potential candidates for plasma treatment were Toray T800/3900-2 carbon fiber reinforced polymer (CFRP) prepared with Precision Fabrics Group, Inc. (PFG) 52006 nylon peel ply and Hexcel T300/F155 CFRP prepared with PFG 60001 polyester peel ply. It was hypothesized that atmospheric pressure plasma treatment could functionalize and/or remove peel ply remnants left on the CFRP surfaces upon peel ply removal. Surface characterization measurements and double cantilever beam (DCB) testing were used to determine the effects of atmospheric pressure plasma treatment on surface characteristics and bond quality of peel ply prepared CFRP composites. Previous research showed that Toray T800/3900-2 carbon fiber reinforced epoxy composites prepared with PFG 52006 peel ply and bonded with Cytec MetlBond 1515-3M structural film adhesive failed in adhesion at low fracture energies when tested in the DCB configuration. Previous research also showed that DCB samples made of Hexcel T300/F155 carbon fiber reinforced epoxy composites prepared with PFG 60001 peel ply and bonded with Henkel Hysol EA 9696 structural film adhesive failed in adhesion at low fracture energies. Recent research suggested that plasma treatment could be able to activate these "un-bondable" surfaces and result in good adhesive bonds. Nylon peel ply prepared 177 °C cure and polyester peel ply prepared 127 °C cure CFRP laminates were treated with atmospheric pressure plasma after peel ply removal prior to bonding. Atmospheric pressure plasma treatment was capable of significantly increasing fracture energies and changing failure modes. For Toray T800/3900-2 laminates prepared with PFG 52006 and bonded with MetlBond 1515-3M, plasma treatment increased fracture energies from 460 J/m 2. Atmospheric pressure plasma treatment also increased fracture energies of Hexcel T300/F155 laminates prepared with PFG 60001 and bonded with EA 9696 from 1500 J/m2. It was demonstrated that atmospheric pressure plasma treatment was able to transform poor bonding surfaces into acceptable ones by reversing the negative effects of incorrect peel ply usage. To determine if the primary reason for adhesion was functionalization or removal, a number of experiments were performed. Surface characteristics of peel ply only and plasma treated samples were determined using contact angle (CA) measurements, FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). CA was used to assess solid surface energy that was useful to determine wetting of the adhesive on the adherend, one requirement of adhesion. FTIR and XPS were used to analyze composite surface chemistry, including the identification of functional groups that were a product of atmospheric pressure plasma treatment, as well as contaminants that can inhibit adhesive bonding. SEM was used to capture surface morphology to identify peel ply remnants and whether these remnants were physically removed or modified due to plasma treatment. This research supported that atmospheric pressure plasma treatment resulted in adhesion primarily due to functionalization of peel ply remnants, though a removal mechanism was not disproven. It was also shown that surface energy exhibited potential for predicting adhesion. Lastly, this research indicated that plasma treatment is a robust surface preparation, as strong bonds were observed up to 30 days after treatment.

Bonding durability of dual-curing composite core material with different self-etching adhesive systems in a model complete vertical root fracture reconstruction.

PubMed

Waidyasekera, Kanchana; Nikaido, Toru; Weerasinghe, Dinesh; Nurrohman, Hamid; Tagami, Junji

2012-04-01

This study evaluated a dual-curing composite along with different dentin adhesive systems for 1 year under water storage, as a new bonding method of root fragments in complete vertical root fracture. Bovine root fragments were bonded with the dual-curing resin composite Clearfil DC Core Automix (DCA) and one of three adhesive systems: two-step self-etching adhesive Clearfil SE Bond (SE), one-step self-etching adhesive Tokuyama Bond Force (BF), one-step dual-curing self-etching adhesive Clearfil DC Bond (DC). Microtensile bond strength (µTBS)/ultimate tensile bond strength (UTS), FE-SEM ultramorphology of fracture modes, and adhesive dentin interface were observed after water storage for periods of up to one year. The data were analyzed with two-way ANOVA. µTBS was influenced by "dentin adhesive system" (F = 324.455, p < 0.001) and "length of water storage" (F = 8.470, p < 0.001). SE yielded significantly higher µTBS, regardless of storage period (p < 0.05) and maintained the initial µTBS without a significant change after 1 year of water storage (p > 0.05). From 24 h to 1 month, BF showed significantly higher bond strength than DC. UTS of DCA was influenced only by the curing mode of the material (F = 5.051, p = 0.027), but not by the length of water storage (F = 0.053, p > 0.05). Two-step self-etching adhesive systems and dual-curing composite core material can be considered as a suitable bonding method for complete root fractures.

Application of the bond valence method in the non-isovalent semiconductor alloy (GaN) 1–x (ZnO) x

DOE PAGES

Liu, Jian

2016-09-29

This paper studies the bond valence method (BVM) and its application in the non-isovalent semiconductor alloy (GaN) 1-x(ZnO) x. Particular attention is paid to the role of short-range order (SRO). A physical interpretation based on atomic orbital interaction is proposed and examined by density-functional theory (DFT) calculations. Combining BVM with Monte-Carlo simulations and a DFT-based cluster expansion model, bond-length distributions and bond-angle variations are predicted. The correlation between bond valence and bond stiffness is also revealed. Lastly the concept of bond valence is extended into the modelling of an atomistic potential.

The effect of water storage, elapsed time and contaminants on the bond strength and interfacial polymerization of a nanohybrid composite.

PubMed

Perriard, Jean; Lorente, Maria Cattani; Scherrer, Susanne; Belser, Urs C; Wiskott, H W Anselm

2009-12-01

To systematically characterize the effect of time lapse, water storage, and selected contaminants on the bond strength of a nanofilled dental composite. Half-dumbbell-shaped samples were fabricated out of light-polymerizing composite resin. To function as substrates they were aged for 30 days in water. Prior to bonding, the substrates' surfaces were subjected to the following treatments: 1) Removing a 0.2- to 0.4-mm layer using a fluted carbide bur; 2) grit blasting with 50 microm alumina particles; 3) etching with phosphoric acid gel; 4) grit blasting followed by etching; 5) blasting with tribochemical particles followed by silane application; 6) sanding with 400-grit paper, air aging of the adherent half-sample before bonding; 7) surface contamination with saliva; 8) surface contamination with blood. In each group (n = 30), freshly polymerized (except in group 6) adherent half-samples were bonded to the substrate half-samples by a layer of unfilled adhesive resin. Fifteen full dumbbell-shaped specimens were subjected to tensile testing after 1 h and 15 after 7 days water storage. In a positive control group, freshly cured half-samples were bonded shortly after fabrication. The tensile strength was analyzed using Weibull statistics and presented in terms of the material's characteristic strength and shape parameter. Fractographs of the two weakest and strongest samples of each group were produced. The surfaces were searched to locate hackle, wake hackle and the origin of the fracture. Surface roughness and time lapse increased the bond strength of the repaired specimens. All groups in which surface roughness was produced before bonding increased in repair strength. Post-bonding aging improved strength. Fractographs yielded interpretable data whenever larger surfaces of single phase bonding resin were present. 1) Roughening and etching an aged composite's surface prior to applying a coat of unfilled resin and the filled material increases repair bond strength by up to 100%. 2) The repair bond strength of a roughened aged composite is 25% to 30% inferior to the tensile strength of solid specimens. 3) After 7 days' storage in water, no detrimental effect could be seen from saliva or blood contamination if the surfaces were properly rinsed.

Hydrogen bonding between nitriles and hydrogen halides and the topological properties of molecular charge distributions

NASA Astrophysics Data System (ADS)

Boyd, Russell J.; Choi, Sai Cheng

1986-08-01

The topological properties of the charge density of the hydrogen-bonded complexes between nitrites and hydrogen chloride correlate linearly with theoretical estimates of the hydrogen-bond energy. At the 6-31G ** level, the hydrogenbond energies range from a low of 10 kJ/mol m NCCN—HC1 to a high of 38 kJ/mol in LiCN—HCl. A linear relationship between the charge density at the hydrogen-bond critical point and the NH internuclear distance of the RCN—HC1 complexes indicates that the generalization of the bond-length-bond-order relationship of CC bonds due to Bader, Tang, Tal and Biegler-König can be extended to intermolecular hydrogen bonding.

Method for maintaining precise suction strip porosities

NASA Technical Reports Server (NTRS)

Gallimore, Frank H. (Inventor)

1989-01-01

This invention relates to a masking method generally and, more particularly to a method of masking perforated titanium sheets having laminar control suction strips. As illustrated in the drawings, a nonaerodynamic surface of a perforated sheet has alternating suction strip areas and bonding land areas. Suction strip tapes overlie the bonding land areas during application of a masking material to an upper surface of the suction strip tapes. Prior to bonding the perforated sheet to a composite structure, the bonding land tapes are removed. The entire opposite aerodynamic surface is masked with tape before bonding. This invention provides a precise control of suction strip porosities by ensuring that no chemicals penetrate the suction strip areas during bonding.

Picosecond Pulsed Laser Ablation for the Surface Preparation of Epoxy Composites

NASA Technical Reports Server (NTRS)

Palmieri, Frank; Ledesma, Rodolfo; Fulton, Tayler; Arthur, Alexandria; Eldridge, Keishara; Thibeault, Sheila; Lin, Yi; Wohl, Chris; Connell, John

2017-01-01

As part of a technical challenge under the Advanced Composites Program, methods for improving pre-bond process control for aerospace composite surface treatments and inspections, in conjunction with Federal Aviation Administration guidelines, are under investigation. The overall goal is to demonstrate high fidelity, rapid and reproducible surface treatment and surface characterization methods to reduce uncertainty associated with the bonding process. The desired outcomes are reliable bonded airframe structure, and reduced timeline to certification. In this work, laser ablation was conducted using a q-switched Nd:YVO4 laser capable of nominal pulse durations of 8 picoseconds (ps). Aerospace structural carbon fiber reinforced composites with an epoxy resin matrix were laser treated, characterized, processed into bonded assemblies and mechanically tested. The characterization of ablated surfaces were conducted using scanning electron microscopy (SEM), water contact angle (WCA) goniometry, micro laser induced breakdown spectroscopy (uLIBS), and electron spin resonance (ESR). The bond performance was assessed using a double cantilever beam (DCB) test with an epoxy adhesive. The surface characteristics and bond performance obtained from picosecond ablated carbon fiber reinforced plastics (CFRPs) are presented herein.

A slow-forming isopeptide bond in the structure of the major pilin SpaD from Corynebacterium diphtheriae has implications for pilus assembly

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

Kang, Hae Joo; Paterson, Neil G.; Kim, Chae Un

2014-05-01

Two crystal structures of the major pilin SpaD from C. diphtheriae have been determined at 1.87 and 2.5 Å resolution. The N-terminal domain is found to contain an isopeptide bond that forms slowly over time in the recombinant protein. Given its structural context, this provides insight into the relationship between internal isopeptide-bond formation and pilus assembly. The Gram-positive organism Corynebacterium diphtheriae, the cause of diphtheria in humans, expresses pili on its surface which it uses for adhesion and colonization of its host. These pili are covalent protein polymers composed of three types of pilin subunit that are assembled by specificmore » sortase enzymes. A structural analysis of the major pilin SpaD, which forms the polymeric backbone of one of the three types of pilus expressed by C. diphtheriae, is reported. Mass-spectral and crystallographic analysis shows that SpaD contains three internal Lys–Asn isopeptide bonds. One of these, shown by mass spectrometry to be located in the N-terminal D1 domain of the protein, only forms slowly, implying an energy barrier to bond formation. Two crystal structures, of the full-length three-domain protein at 2.5 Å resolution and of a two-domain (D2-D3) construct at 1.87 Å resolution, show that each of the three Ig-like domains contains a single Lys–Asn isopeptide-bond cross-link, assumed to give mechanical stability as in other such pili. Additional stabilizing features include a disulfide bond in the D3 domain and a calcium-binding loop in D2. The N-terminal D1 domain is more flexible than the others and, by analogy with other major pilins of this type, the slow formation of its isopeptide bond can be attributed to its location adjacent to the lysine used in sortase-mediated polymerization during pilus assembly.« less

Electronic structure studies of Ni( 1 0 0 ) surface reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2003-01-01

Solid-state Fenske-Hall band structure calculations have been used to study the different surface structures which result from adsorption of a half monolayer of C, N, or O atoms on the Ni(1 0 0) surface. C or N atoms sit nearly coplanar with the surface Ni atoms and induce the "clock" reconstruction of the surface. In contrast, adsorbed O atoms sit slightly above the Ni(1 0 0) surface plane and have little effect on the overall surface structure. The local environments of the C, N, and O atoms on these surfaces are similar to their environments in a series of late transition metal carbonyl clusters, suggesting that some of the same electronic factors may play a role in favoring the different structures. Results of the calculations indicate that when adsorbates occupy coplanar sites on Ni(1 0 0), much of the Ni-Ni bonding within the surface layer and between the surface- and second-layers is disrupted. On the C- and N-covered surfaces the disruption is more than compensated for by the formation of strong adsorbate-Ni bonds and by new Ni-Ni surface bonds resulting from the clock reconstruction. When O is forced into a coplanar site, however, both the higher electron count and increased electronegativity of the O atoms lead to severe disruption of the surface bonding and weak Ni-O bonds. When O atoms sit above the surface, they form more polar Ni-O bonds, contribute less electron density to the Ni surface bands, and cause less disruption to Ni-Ni surface bonds. These results suggest that, similar to the organometallic clusters, the site preferences of C, N, and O atoms are directly related to their electron count, and in turn to the relative occupation of both Ni-Ni and X-Ni (X=C, N, O) antibonding bands.

Quasi-Monolithic Structures for Spaceflight Using Hydroxide-Catalysis Bonding

NASA Technical Reports Server (NTRS)

Preston, Alix; Thorpe, J. Ira; Miner, Linda

2012-01-01

Future space-based missions will take measurements of the universe with unprecedented results. To do this, these missions will require materials and bonding techniques with ever-increasing stability in order to make their measurements. As an example, the Laser Interferometer Space Antenna (LISA) will detect and observe gravitational waves in the 0.1 mHz to 1 Hz frequency range with strain sensitivities on the order of 10(exp -21) at its most sensitive frequency. To make these measurements, critical components such as the optical bench or telescope support structure, will need to have path-length stabilities of better than 1 pm/(square root)Hz. The baseline construction method for the LISA optical bench is to affix fused silica optical components to a Zerodur baseplate using hydroxide-catalysis bonding (HCB). HCB is a recently developed technique that allows the bonding of glasses, some metals, and silicon carbide with significant strength and stability with a bond thickness of less than a few micrometers. In addition, a wide range of surface profiles can be bonded using only a small amount of hydroxide solution. These characteristics make HCB ideal for adhering optical components in complex optical systems. In addition to being used to construct the LISA optical bench, the HCB technique shows great promise for constructing other structures such as hollow retroreflectors to be used for lunar laser ranging, or a visible nulling coronograph to be used for exo-planet detection. Here we present construction techniques that could be used to make an optical bench, hollow retroreflector, nulling coronograph, or other quasi-monolithic structures using HCB. In addition, we present dimensional stability results of an optical bench that was made using HCB, as well as HCB strength measurements.

Orbital Exponent Optimization in Elementary VB Calculations of the Chemical Bond in the Ground State of Simple Molecular Systems

ERIC Educational Resources Information Center

Magnasco, Valerio

2008-01-01

Orbital exponent optimization in the elementary ab-initio VB calculation of the ground states of H[subscript 2][superscript +], H[subscript 2], He[subscript 2][superscript +], He[subscript 2] gives a fair description of the exchange-overlap component of the interatomic interaction that is important in the bond region. Correct bond lengths and…

Combined surface activated bonding using H-containing HCOOH vapor treatment for Cu/Adhesive hybrid bonding at below 200 °C

NASA Astrophysics Data System (ADS)

He, Ran; Fujino, Masahisa; Akaike, Masatake; Sakai, Taiji; Sakuyama, Seiki; Suga, Tadatomo

2017-08-01

Cu/adhesive hybrid bonding is an attractive approach to three-dimensional (3D) integration because it provides direct Cusbnd Cu vertical interconnects and high mechanical stability. However, Cu/adhesive hybrid bonding at below 200 °C is still challenging because of bonding temperature mismatch between Cusbnd Cu and polymer adhesives and lacking of effective adhesive-compatible Cu surface activation methods. In this paper, we investigate and demonstrate a ;Cu-first; hybrid bonding technique by using hydrogen(H)-containing formic acid (HCOOH) vapor prebonding surface treatment for the first time. In this technique, high-quality Cusbnd Cu bonding is obtained at 180-200 °C that is close to or even lower than the temperature of subsequent adhesive curing. We experimentally investigate the effects of the H-containing HCOOH vapor treatment for Cusbnd Cu bonding and cyclo-olefin polymer adhesive-adhesive bonding. This technique enables Cu/adhesive hybrid bonding at below 200 °C, promising smaller thermal stress, higher throughput, and lower cost comparing to the existing ;adhesive-first; hybrid bonding method.

The effects of chain length, embedded polar groups, pressure, and pore shape on structure and retention in reversed-phase liquid chromatography: molecular-level insights from Monte Carlo simulations.

PubMed

Rafferty, Jake L; Siepmann, J Ilja; Schure, Mark R

2009-03-20

Particle-based simulations using the configurational-bias and Gibbs ensemble Monte Carlo techniques are carried out to probe the effects of various chromatographic parameters on bonded-phase chain conformation, solvent penetration, and retention in reversed-phase liquid chromatography (RPLC). Specifically, we investigate the effects due to the length of the bonded-phase chains (C(18), C(8), and C(1)), the inclusion of embedded polar groups (amide and ether) near the base of the bonded-phase chains, the column pressure (1, 400, and 1000 atm), and the pore shape (planar slit pore versus cylindrical pore with a 60A diameter). These simulations utilize a bonded-phase coverage of 2.9 micromol/m(2)and a mobile phase containing methanol at a molfraction of 33% (about 50% by volume). The simulations show that chain length, embedded polar groups, and pore shape significantly alter structural and retentive properties of the model RPLC system, whereas the column pressure has a relatively small effect. The simulation results are extensively compared to retention measurements. A molecular view of the RPLC retention mechanism emerges that is more complex than can be inferred from thermodynamic measurements.

Direct mounted photovoltaic device with improved adhesion and method thereof

DOEpatents

Boven, Michelle L; Keenihan, James R; Lickly, Stan; Brown, Jr., Claude; Cleereman, Robert J; Plum, Timothy C

2014-12-23

The present invention is premised upon a photovoltaic device suitable for directly mounting on a structure. The device includes an active portion including a photovoltaic cell assembly having a top surface portion that allows transmission of light energy to a photoactive portion of the photovoltaic device for conversion into electrical energy and a bottom surface having a bottom bonding zone; and an inactive portion immediately adjacent to and connected to the active portion, the inactive portion having a region for receiving a fastener to connect the device to the structure and having on a top surface, a top bonding zone; wherein one of the top and bottom bonding zones comprises a first bonding element and the other comprises a second bonding element, the second bonding element designed to interact with the first bonding element on a vertically overlapped adjacent photovoltaic device to bond the device to such adjacent device or to the structure.

Evaluation of an alternative technique to optimize direct bonding of orthodontic brackets to temporary crowns.

PubMed

Dias, Francilena Maria Campos Santos; Pinzan-Vercelino, Célia Regina Maio; Tavares, Rudys Rodolfo de Jesus; Gurgel, Júlio de Araújo; Bramante, Fausto Silva; Fialho, Melissa Nogueira Proença

2015-01-01

To compare shear bond strength of different direct bonding techniques of orthodontic brackets to acrylic resin surfaces. The sample comprised 64 discs of chemically activated acrylic resin (CAAR) randomly divided into four groups: discs in group 1 were bonded by means of light-cured composite resin (conventional adhesive); discs in group 2 had surfaces roughened with a diamond bur followed by conventional direct bonding by means of light-cured composite resin; discs in group 3 were bonded by means of CAAR (alternative adhesive); and discs in group 4 had surfaces roughened with a diamond bur followed by direct bonding by means of CAAR. Shear bond strength values were determined after 24 hours by means of a universal testing machine at a speed of 0.5 mm/min, and compared by analysis of variance followed by post-hoc Tukey test. Adhesive remnant index (ARI) was measured and compared among groups by means of Kruskal-Wallis and Dunn tests. Groups 3 and 4 had significantly greater shear bond strength values in comparison to groups 1 and 2. Groups 3 and 4 yielded similar results. Group 2 showed better results when compared to group 1. In ARI analyses, groups 1 and 2 predominantly exhibited a score equal to 0, whereas groups 3 and 4 predominantly exhibited a score equal to 3. Direct bonding of brackets to acrylic resin surfaces using CAAR yielded better results than light-cured composite resin. Surface preparation with diamond bur only increased shear bond strength in group 2.

Comparing the shear bond strength of direct and indirect composite inlays in relation to different surface conditioning and curing techniques

PubMed Central

Zorba, Yahya Orcun; Ilday, Nurcan Ozakar; Bayındır, Yusuf Ziya; Demirbuga, Sezer

2013-01-01

Objective: The aim of this study was to test the null hypothesis that different surface conditioning (etch and rinse and self-etch) and curing techniques (light cure/dual cure) had no effect on the shear bond strength of direct and indirect composite inlays. Materials and Methods: A total of 112 extracted human molar teeth were horizontally sectioned and randomly divided into two groups according to restoration technique (direct and indirect restorations). Each group was further subdivided into seven subgroups (n = 8) according to bonding agent (etch and rinse adhesives Scotchbond multi-purpose plus, All-Bond 3, Adper Single Bond and Prime Bond NT; and self-etch adhesives Clearfil Liner Bond, Futurabond DC and G bond). Indirect composites were cemented to dentin surfaces using dual-curing luting cement. Shear bond strength of specimens was tested using a Universal Testing Machine. Two samples from each subgroup were evaluated under Scanning electron microscopy to see the failing modes. Data was analyzed using independent sample t-tests and Tukey's tests. Results: Surface conditioning and curing of bonding agents were all found to have significant effects on shear bond strength (P < 0.05) of both direct and indirect composite inlays. With direct restoration, etch and rinse systems and dual-cured bonding agents yielded higher bond strengths than indirect restoration, self-etch systems and light-cured bonding agents. Conclusions: The results of the present study indicated that direct restoration to be a more reliable method than indirect restoration. Although etch and rinse bonding systems showed higher shear bond strength to dentin than self-etch systems, both systems can be safely used for the adhesion of direct as well as indirect restorations. PMID:24932118

Comparison of the tensile bond strength of high-noble, noble, and base metal alloys bonded to enamel.

PubMed

Sen, D; Nayir, E; Pamuk, S

2000-11-01

Although the bond strengths of various resin composite luting materials have been reported in the literature, the evaluation of these systems with various cast alloys of different compositions has not been completely clarified. To evaluate the tensile bond strength of sandblasted high-noble, noble, and base metal alloys bonded to etched enamel by 2 different bonding agents of different chemical composition: Panavia-Ex (BIS-GMA) and Super-Bond (4-META acrylic). Flat enamel surfaces were prepared on buccal surfaces of 60 extracted noncarious human incisors. Teeth were divided into 3 groups of 20 each. Twenty circular disks of 5 mm diameter were prepared for casting for each group. Group I was cast with a high-noble, group II with a noble, and group III with a base metal alloy. The surfaces of the disks were sandblasted with 250 microm Al(2)O(3). Ten disks of each group were bonded to exposed enamel surfaces with Super-Bond and 10 disks with Panavia-Ex as recommended by the manufacturer. The tensile bond strength was measured with an Instron universal testing machine with a crosshead speed of 0.5 mm/min until failure occurred. Two-way ANOVA was used to evaluate the results. The differences in bond strengths of Super-Bond and Panavia-Ex with different alloys were not significant. The highest bond strengths were obtained in base metal alloys, followed by noble and high-noble alloys. These results were significant. Panavia-Ex and Super-Bond exhibited comparable tensile bond strengths. For both luting agents, the highest bond strengths were achieved with base metal alloys and the lowest with high-noble alloys.

Comparing the shear bond strength of direct and indirect composite inlays in relation to different surface conditioning and curing techniques.

PubMed

Zorba, Yahya Orcun; Ilday, Nurcan Ozakar; Bayındır, Yusuf Ziya; Demirbuga, Sezer

2013-10-01

The aim of this study was to test the null hypothesis that different surface conditioning (etch and rinse and self-etch) and curing techniques (light cure/dual cure) had no effect on the shear bond strength of direct and indirect composite inlays. A total of 112 extracted human molar teeth were horizontally sectioned and randomly divided into two groups according to restoration technique (direct and indirect restorations). Each group was further subdivided into seven subgroups (n = 8) according to bonding agent (etch and rinse adhesives Scotchbond multi-purpose plus, All-Bond 3, Adper Single Bond and Prime Bond NT; and self-etch adhesives Clearfil Liner Bond, Futurabond DC and G bond). Indirect composites were cemented to dentin surfaces using dual-curing luting cement. Shear bond strength of specimens was tested using a Universal Testing Machine. Two samples from each subgroup were evaluated under Scanning electron microscopy to see the failing modes. Data was analyzed using independent sample t-tests and Tukey's tests. Surface conditioning and curing of bonding agents were all found to have significant effects on shear bond strength (P < 0.05) of both direct and indirect composite inlays. With direct restoration, etch and rinse systems and dual-cured bonding agents yielded higher bond strengths than indirect restoration, self-etch systems and light-cured bonding agents. The results of the present study indicated that direct restoration to be a more reliable method than indirect restoration. Although etch and rinse bonding systems showed higher shear bond strength to dentin than self-etch systems, both systems can be safely used for the adhesion of direct as well as indirect restorations.

Identification of hydrophilic group formation on polymer surface during Ar{sup +} ion irradiation in O{sub 2} environment

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

Cho, J.S.; Choi, W.K.; Jung, H.J.

1997-12-01

Ar{sup +} ion irradiation on low density polyethylene (LDPE), and polystyrene (PS) was performed in an O{sub 2} environment in order to improve wettability of polymers to water and to identify the formation of hydrophilic groups originated from chemical reactions on the surface of polymers. Doses of a broad Ar{sup +} ion beam of 1 keV energy were changed from 5 {times} 10{sup 15} to 1 {times} 10{sup 17}/cm{sup 2} and the rate of oxygen gas flowing near the sample surface was varied from 0 to 7 ml/min. The contact angle of polymers was not reduced much by Ar{sup +}more » ion irradiation without oxygen gas. However, it dropped largely to a minimum of 35{degree} and 26{degree} for Ar{sup +} ion irradiation in the presence of flowing oxygen gas on LDPE and PS, respectively. From x-ray photoelectron spectroscopy analysis, it was observed that hydrophilic groups were formed on the surface of polymers through an ion-assisted chemical reaction between the ion-induced unstable chains and oxygen. The newly formed hydrophilic group was identified as {single_bond}(C{double_bond}){single_bond} bond and {single_bond}(C{double_bond}O){single_bond}O{single_bond} bond. The contact angle of polymer was greatly dependent on the hydrophilic group formed on the surface.« less

Influence of surface treatments on the shear bond strength of orthodontic brackets to porcelain

NASA Astrophysics Data System (ADS)

Wang, Cong; Zeng, Jishan; Wang, Shaoan; Yang, Zheng; Huang, Qian; Chen, Pixiu; Zhou, Shujuan; Liu, Xiaoqing

2008-11-01

The purpose of this study was to investigate the effect of various surface treatments after different storage time and thermocycling on the shear bond strength of orthodontic brackets to the feldspathic porcelain surfaces. 128 disc-shaped porcelain specimens were randomly assigned to the following surface treatments: 9.6% HFA, 9.6% HFA combined with silane, 50 μ aluminum trioxide sandblasting followed by silane and application of silane after 37% phosphoric acid. Metal or ceramic brackets were bonded onto each treated porcelain facet with light cured resin. The samples were stored in 37 °C water 1 day or 7 days, thermocycled 500 times from 5 to 55 °C. The shear bond strengths were measured (1 mm/min), and statistically analyzed. The bond failure sites were classified according to ARI system. The surface of the glazed, sandblasted, hydrofluoric and phosphoric acid etched porcelain were examined with SEM. All groups achieved reasonable bond strengths to withstand the application of orthodontic forces. Water storage for 7 days caused lower shear bond strength than that of 1 day. But there is no statistically significant difference between the two groups. The mean shear bond strength provided by ceramic bracket with mechanical retention had no statistical difference with that of metal bracket. Therefore, the optimal treatment for orthodontic brackets bonding to feldspathic porcelain was to apply phosphoric acid combined with silane.

Spectroscopic and electric properties of the LiCs molecule: a coupled cluster study including higher excitations

NASA Astrophysics Data System (ADS)

Sørensen, L. K.; Fleig, T.; Olsen, J.

2009-08-01

Aimed at obtaining complete and highly accurate potential energy surfaces for molecules containing heavy elements, we present a new general-order coupled cluster method which can be applied in the framework of the spin-free Dirac formalism. As an initial application we present a systematic study of electron correlation and relativistic effects on the spectroscopic and electric properties of the LiCs molecule in its electronic ground state. In particular, we closely investigate the importance of excitations higher than coupled cluster doubles, spin-free and spin-dependent relativistic effects and the correlation of outer-core electrons on the equilibrium bond length, the harmonic vibrational frequency, the dissociation energy, the dipole moment and the static electric dipole polarizability. We demonstrate that our new implementation allows for highly accurate calculations not only in the bonding region but also along the complete potential curve. The quality of our results is demonstrated by a vibrational analysis where an almost complete set of vibrational levels has been calculated accurately.

Laser rods with undoped, flanged end-caps for end-pumped laser applications

DOEpatents

Meissner, H.E.; Beach, R.J.; Bibeau, C.; Sutton, S.B.; Mitchell, S.; Bass, I.; Honea, E.

1999-08-10

A method and apparatus for achieving improved performance in a solid state laser is provided. A flanged, at least partially undoped end-cap is attached to at least one end of a laserable medium. Preferably flanged, undoped end-caps are attached to both ends of the laserable medium. Due to the low scatter requirements for the interface between the end-caps and the laser rod, a non-adhesive method of bonding is utilized such as optical contacting combined with a subsequent heat treatment of the optically contacted composite. The non-bonded end surfaces of the flanged end-caps are coated with laser cavity coatings appropriate for the lasing wavelength of the laser rod. A cooling jacket, sealably coupled to the flanged end-caps, surrounds the entire length of the laserable medium. Radiation from a pump source is focused by a lens duct and passed through at least one flanged end-cap into the laser rod. 14 figs.

Evaluation of Internal Brushing on Pinch Weld Quality

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

Korinko, P

2005-12-01

Post machining operations such as borescope inspection can cause linear indications down the length of the bore of fill stems. Often these indications are removed or obscured using rotary wire brushing. This study evaluated the effect this mechanical operation may have on pinch weld quality when relatively cold welds were made. A total of four stems with two levels of brushing of both Type 304L and 21-6-9 stainless steels were tested. In addition, two each of the Type 304L stems were Nitradd cleaned and the other two were aqueously cleaned; all four 21-6-9 stems were aqueously cleaned. All of themore » brushed stem areas exhibited more surface anomalies based on borescope evaluation. On average, the bond rating was a higher value (worse) for the brushed areas than the unadulterated areas for both Type 304L and 21-6-9 stems. The test method used may have biased the results towards a lesser quality bond for the brushed areas so additional testing is recommended.« less

Bonding between oxide ceramics and adhesive cement systems: a systematic review.

PubMed

Papia, Evaggelia; Larsson, Christel; du Toit, Madeleine; Vult von Steyern, Per

2014-02-01

The following aims were set for this systematic literature review: (a) to make an inventory of existing methods to achieve bondable surfaces on oxide ceramics and (b) to evaluate which methods might provide sufficient bond strength. Current literature of in vitro studies regarding bond strength achieved using different surface treatments on oxide ceramics in combination with adhesive cement systems was selected from PubMed and systematically analyzed and completed with reference tracking. The total number of publications included for aim a was 127 studies, 23 of which were used for aim b. The surface treatments are divided into seven main groups: as-produced, grinding/polishing, airborne particle abrasion, surface coating, laser treatment, acid treatment, and primer treatment. There are large variations, making comparison of the studies difficult. An as-produced surface of oxide ceramic needs to be surface treated to achieve durable bond strength. Abrasive surface treatment and/or silica-coating treatment with the use of primer treatment can provide sufficient bond strength for bonding oxide ceramics. This conclusion, however, needs to be confirmed by clinical studies. There is no universal surface treatment. Consideration should be given to the specific materials to be cemented and to the adhesive cement system to be used. Copyright © 2013 Wiley Periodicals, Inc.

Influence of dentinal regions on bond strengths of different adhesive systems.

PubMed

Ozer, F; Unlü, N; Sengun, A

2003-06-01

This in vitro study assessed comparatively the shear bond strengths of three composite resins, 3M Valux Plus (3MVP), Herculite (H), Clearfil AP-X (CAP-X), a polyacid modified composite resin Dyract (D), and a resin modified glass-ionomer materials Vitremer (V), to cervical and buccal dentine regions of extracted human molar teeth. Four different bonding systems, 3M ScotchBond Multipurpose (SB), Clearfil Liner Bond 2 (LB2), Opti Bond (OB), and Prime & Bond 2.1 (PB 2.1) were used with the manufacturer's respective composite and compomer materials. One hundred freshly extracted mandibular molar teeth were selected for this study. Flat buccal dentine surfaces were created on 50 teeth and cylindrical rods of the five materials were bonded to the dentine surfaces. For assessment of cervical bond strengths, the materials were bonded to mesial and distal enamel bordered occlusal dentinal surfaces of the remaining 50 teeth. The five groups of restorative procedures were applied as follows; Group 1: SB + 3MVP, Group 2: LB2 + CAP-X, Group 3: OB + H, Group 4: PB2.1 + D, Group 5: Vitremer primer (VP) VP + V. Each restorative procedure thus had 20 specimens (10 buccal + 10 cervical). After 24 h of water storage (37 degrees C), the specimens were tested on a Universal Testing machine in shear with a cross head speed of 0.5 mm min-1. The bond strength values were calculated in MPa and the results were evaluated statistically using Kruskal-Wallis one-way/anova and Mann-Whitney U-tests. It was found that the bond strengths of SB + 3MVP, LB2 + CAP-X and VP + V to buccal dentine surfaces were significantly stronger (P < 0.05) than those to the occluso-cervical dentine floors. When the bond strengths to the occluso-cervical dentine and buccal dentine surface were compared, there was no significant difference between the materials (P > 0.05). Vitremer was found the least successful adhesive material in terms of shear bond strength on both buccal and occluso-cervical dentine surfaces.

Role of Defects on Regioselectivity of Nano Pristine Graphene.

PubMed

Kudur Jayaprakash, Gururaj; Casillas, Norberto; Astudillo-Sánchez, Pablo D; Flores-Moreno, Roberto

2016-11-17

Here analytical Fukui functions based on density functional theory are applied to investigate the redox reactivity of pristine and defected graphene lattices. A carbon H-terminated graphene structure (with 96 carbon atoms) and a graphene defected surface with Stone-Wales rearrangement and double vacancy defects are used as models. Pristine sp 2 -hybridized, hexagonal arranged carbon atoms exhibit a symmetric reactivity. In contrast, common carbon atoms at reconstructed polygons in Stone-Wales and double vacancy graphene display large reactivity variations. The improved reactivity and the regioselectivity at defected graphene is correlated to structural changes that caused carbon-carbon bond length variations at defected zones.

Porcelain surface conditioning protocols and shear bond strength of orthodontic brackets.

PubMed

Lestrade, Ashley M; Ballard, Richard W; Xu, Xiaoming; Yu, Qingzhao; Kee, Edwin L; Armbruster, Paul C

2016-05-01

The objective of the present study was to determine which of six bonding protocols yielded a clinically acceptable shear bond strength (SBS) of metal orthodontic brackets to CAD/CAM lithium disilicate porcelain restorations. A secondary aim was to determine which bonding protocol produced the least surface damage at debond. Sixty lithium disilicate samples were fabricated to replicate the facial surface of a mandibular first molar using a CEREC CAD/CAM machine. The samples were split into six test groups, each of which received different mechanical/chemical pretreatment protocols to roughen the porcelain surface prior to bonding a molar orthodontic attachment. Shear bond strength testing was conducted using an Instron machine. The mean, maximum, minimal, and standard deviation SBS values for each sample group including an enamel control were calculated. A t-test was used to evaluate the statistical significance between the groups. No significant differences were found in SBS values, with the exception of surface roughening with a green stone prior to HFA and silane treatment. This protocol yielded slightly higher bond strength which was statistically significant. Chemical treatment alone with HFA/silane yielded SBS values within an acceptable clinical range to withstand forces applied by orthodontic treatment and potentially eliminates the need to mechanically roughen the ceramic surface.

Effect of Dentin Wetness on the Bond Strength of Universal Adhesives.

PubMed

Choi, An-Na; Lee, Ji-Hye; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong Hoon; Park, Jeong-Kil

2017-10-25

The effects of dentin wetness on the bond strength and adhesive interface morphology of universal adhesives have been investigated using micro-tensile bond strength (μTBS) testing and confocal laser scanning microscopy (CLSM). Seventy-two human third molars were wet ground to expose flat dentin surfaces. They were divided into three groups according to the air-drying time of the dentin surfaces: 0 (without air drying), 5, and 10 s. The dentin surfaces were then treated with three universal adhesives: G-Premio Bond, Single Bond Universal, and All-Bond Universal in self-etch or etch-and-rinse mode. After composite build up, a μTBS test was performed. One additional tooth was prepared for each group by staining the adhesives with 0.01 wt % of Rhodamine B fluorescent dye for CLSM analysis. The data were analyzed statistically using ANOVA and Tukey's post hoc tests (α = 0.05). Two-way ANOVA showed significant differences among the adhesive systems and dentin moisture conditions. An interaction effect was also observed ( p < 0.05). One-way ANOVA showed that All-Bond Universal was the only material influenced by the wetness of the dentin surfaces. Wetness of the dentin surface is a factor influencing the micro-tensile bond strength of universal adhesives.

Effect of Dentin Wetness on the Bond Strength of Universal Adhesives

PubMed Central

Lee, Ji-Hye; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong Hoon

2017-01-01

The effects of dentin wetness on the bond strength and adhesive interface morphology of universal adhesives have been investigated using micro-tensile bond strength (μTBS) testing and confocal laser scanning microscopy (CLSM). Seventy-two human third molars were wet ground to expose flat dentin surfaces. They were divided into three groups according to the air-drying time of the dentin surfaces: 0 (without air drying), 5, and 10 s. The dentin surfaces were then treated with three universal adhesives: G-Premio Bond, Single Bond Universal, and All-Bond Universal in self-etch or etch-and-rinse mode. After composite build up, a μTBS test was performed. One additional tooth was prepared for each group by staining the adhesives with 0.01 wt % of Rhodamine B fluorescent dye for CLSM analysis. The data were analyzed statistically using ANOVA and Tukey’s post hoc tests (α = 0.05). Two-way ANOVA showed significant differences among the adhesive systems and dentin moisture conditions. An interaction effect was also observed (p < 0.05). One-way ANOVA showed that All-Bond Universal was the only material influenced by the wetness of the dentin surfaces. Wetness of the dentin surface is a factor influencing the micro-tensile bond strength of universal adhesives. PMID:29068404

The effect of grinding and/or airborne-particle abrasion on the bond strength between zirconia and veneering porcelain: a systematic review

PubMed Central

Lundberg, Karin; Wu, Lindsey; Papia, Evaggelia

2017-01-01

Abstract Objective: The aim of the study was to make an inventory of current literature on the bond strength between zirconia and veneering porcelain after surface treatment of zirconia by grinding with diamond bur and/or with airborne-particle abrasion. Material and methods: The literature search for the present review was made following recommended guidelines using acknowledged methodology on how to do a systematic review. The electronic databases PubMed, Cochrane Library, and Science Direct were used in the present study. Results: Twelve studies were selected. Test methods used in the original studies included shear bond strength (SBS) test, tensile bond strength test, and micro-tensile bond strength test. The majority of studies used SBS. Results showed a large variation within each surface treatment of zirconia, using different grain size, blasting time, and pressure. Conclusions: Airborne-particle abrasion might improve the bond strength and can therefore be considered a feasible surface treatment for zirconia that is to be bonded. Grinding has been recommended as a surface treatment for zirconia to improve the bond strength; however, this recommendation cannot be verified. A standardized test method and surface treatment are required to be able to compare the results from different studies and draw further conclusions. PMID:28642927

Shear Bond Strength of Three Orthodontic Bonding Systems on Enamel and Restorative Materials

PubMed Central

Ebeling, Jennifer; Schauseil, Michael; Stein, Steffen; Roggendorf, Matthias; Korbmacher-Steiner, Heike

2016-01-01

Objective. The aim of this in vitro study was to determine the shear bond strength (SBS) and adhesive remnant index (ARI) score of two self-etching no-mix adhesives (iBond™ and Scotchbond™) on different prosthetic surfaces and enamel, in comparison with the commonly used total etch system Transbond XT™. Materials and Methods. A total of 270 surfaces (1 enamel and 8 restorative surfaces, n = 30) were randomly divided into three adhesive groups. In group 1 (control) brackets were bonded with Transbond XT primer. In the experimental groups iBond adhesive (group 2) and Scotchbond Universal adhesive (group 3) were used. The SBS was measured using a Zwicki 1120™ testing machine. The ARI and SBS were compared statistically using the Kruskal–Wallis test (P ≤ 0.05). Results. Significant differences in SBS and ARI were found between the control group and experimental groups. Conclusions. Transbond XT showed the highest SBS on human enamel. Scotchbond Universal on average provides the best bonding on all other types of surface (metal, composite, and porcelain), with no need for additional primers. It might therefore be helpful for simplifying bonding in orthodontic procedures on restorative materials in patients. If metal brackets have to be bonded to a metal surface, the use of a dual-curing resin is recommended. PMID:27738633

Bonded ultrasonic transducer and method for making

DOEpatents

Dixon, R.D.; Roe, L.H.; Migliori, A.

1995-11-14

An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements. 12 figs.

Interfacial adhesion of dental ceramic-resin systems

NASA Astrophysics Data System (ADS)

Della Bona, Alvaro

The clinical success of resin bonding procedures for indirect ceramic restorations and ceramic repairs depends on the quality and durability of the bond between the ceramic and the resin. The quality of this bond will depend upon the bonding mechanisms that are controlled in part by the surface treatment that promotes micromechanical and/or chemical bonding to the substrate. The objective of this study is to correlate interfacial toughness (K A) with fracture surface morphological parameters of the dental ceramic-resin systems as a function of ceramic surface treatment. The analytical procedures focused on characterizing the microstructure and fracture properties of EmpressRTM ceramics (a leucite-based core ceramic, two lithia disilicate-based core ceramics, and a glass veneer) and determining the ceramic-resin adhesion zone bond strength characteristics. Microstructure and composition are controlling factors in the development of micromechanical retention produced by etching. Silane treated ceramics negated the effect of surface roughening produced by etching, inducing lower surface energy of the ceramic and, reduced bonding effectiveness. There was a positive correlation between WA, tensile bond strength (a), and KA, i.e., higher mean WA value, and higher mean sigma and KA values. This study suggests that (1) the sigma and KA values for ceramic bonded to resin are affected by the ceramic microstructure and the ceramic surface treatments; (2) the definition of the adhesion zone is essential to classify the modes of failure, which should be an integral component of all failure analyses; (3) the microtensile test may be preferable to conventional shear or flexural tests as an indicator of composite-ceramic bond quality; and (4) careful microscopic analysis of fracture surfaces and an x-ray dot map can produce a more consistent and complete description of the fracture process and interpretation of the modes of failure. The mode of failure and fractographic analyses provide important a more comprehensive assessment of mechanisms that control the survival times of dental adhesive systems. Thus, the quality of the bond should not be assessed based on bond strength data alone.

Fracture surface analysis in composite and titanium bonding: Part 1: Titanium bonding

NASA Technical Reports Server (NTRS)

Sanderson, K. A.; Wightman, J. P.

1985-01-01

Fractured lap shear Ti 6-4 adherends bonded with polyphenyquinoxaline (PPQ) and polysulfone were analyzed. The effects of adherend pretreatment, stress level, thermal aging, anodizing voltage, and modified adhesive of Ti 6-4 adherend bonded with PPQ on lap shear strength were studied. The effect of adherend pretreatment on lap shear strength was investigated for PS samples. Results of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) used to study the surface topography and surface composition are also discussed.

The ZnSe(110) puzzle - Comparison with GaAs(110)

NASA Technical Reports Server (NTRS)

Duke, C. B.; Paton, A.; Kahn, A.; Tu, D.-W.

1984-01-01

The surface structure of monocrystalline ZnSe(110) and of 4-5-nm-thick ZnSe(110) layers epitaxially grown on GaAs(110) is investigated by means of elastic LEED and AES; the results are analyzed using the computer programs and R-factor methods of Duke et al. (1981 and 1983), presented in graphs and tables, and compared to those for GaAs(110). Significant differences are attributed to bond-length-conserving outward rotation of Se and inward rotation of Zn in the top layer, with an angle of 4 deg between the actual plane of the cation-anion chain and the truncated bulk surface. The R intensities measured for ZnSe(110) and GaAs(110) are given as Rx = 0.22 and RI = 0.21 and Rx = 0.24 and RI = 0.16, respectively.

Nanoleakage of dentin adhesive systems bonded to Carisolv-treated dentin.

PubMed

Kubo, Shisei; Li, Heping; Burrow, Michael F; Tyas, Martin J

2002-01-01

The hybrid layer created in caries-affected dentin has not been fully elucidated and may influence bond durability. This study investigated the nanoleakage patterns of caries-affected dentin after excavation with Carisolv or conventional instruments treated with one of three adhesive systems. Flat occlusal dentin surfaces, including carious lesions, were prepared from extracted human molars and finished with wet 600-grit silicon carbide paper. Carious dentin was removed with Carisolv or round steel burs in conjunction with Caries Detector. PermaQuik, Single Bond or One-Up Bond F was bonded to the excavated dentin surfaces and adjacent flat occlusal surfaces and it was covered with Silux Plus resin-based composite. After 24-hour storage in 37 degrees C water, the bonded interfaces were polished to remove flash, and the surrounding tooth surfaces were coated with nail varnish. Specimens were immersed in 50% (w/v) silver nitrate solution for 24 hours, exposed to photo developing solution for eight hours, then sectioned longitudinally through the bonded, excavated dentin or "normal" dentin surfaces. The sectioned surfaces were polished, carbon coated and observed in a Field Emission-SEM using back scattered electrons. Silver deposition occurred along the base of the hybrid layer for all specimens. However, Single Bond showed a greater density of silver deposition in the caries-affected dentin compared with normal dentin. PermaQuik had a thicker hybrid layer in caries-affected dentin than normal dentin. One-Up Bond F exhibited a thin hybrid layer in normal dentin, but the hybrid layer was often difficult to detect in caries-affected dentin.

Controlling Internal Organization of Multilayer Poly(methacrylic acid) Hydrogels with Polymer Molecular Weight

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

Kozlovskaya, Veronika; Zavgorodnya, Oleksandra; Ankner, John F.

Here, we report on tailoring the internal architecture of multilayer-derived poly(methacrylic acid) (PMAA) hydrogels by controlling the molecular weight of poly(N-vinylpyrrolidone) (PVPON) in hydrogen-bonded (PMAA/PVPON) layer-by-layer precursor films. The hydrogels are produced by cross-linking PMAA in the spin-assisted multilayers followed by PVPON release. We found that the thickness, morphology, and architecture of hydrogen-bonded films and the corresponding hydrogels are significantly affected by PVPON chain length. For all systems, an increase in PVPON molecular weight from M w = 2.5 to 1300 kDa resulted in increased total film thickness. We also show that increasing polymer M w smooths the hydrogen-bonded filmmore » surfaces but roughens those of the hydrogels. Using deuterated dPMAA marker layers in neutron reflectometry measurements, we found that hydrogen-bonded films reveal a high degree of stratification which is preserved in the cross-linked films. We observed dPMAA to be distributed more widely in the hydrogen-bonded films prepared with small M w PVPON due to the greater mobility of short-chain PVPON. Furthermore, these variations in the distribution of PMAA are erased after cross-linking, resulting in a distribution of dPMAA over about two bilayers for all M w but being somewhat more widely distributed in the films templated with higher M w PVPON. Finally, our results yield new insights into controlling the organization of nanostructured polymer networks using polymer molecular weight and open opportunities for fabrication of thin films with well-organized architecture and controllable function.« less

High resolution crystal structure of the methylcobalamin analogues ethylcobalamin and butylcobalamin by X-ray synchrotron diffraction.

PubMed

Hannibal, Luciana; Smith, Clyde A; Smith, Jessica A; Axhemi, Armend; Miller, Abby; Wang, Sihe; Brasch, Nicola E; Jacobsen, Donald W

2009-07-20

The X-ray crystal structures of the methylcobalamin (MeCbl) analogues ethylcobalamin (EtCbl) and butylcobalamin (BuCbl) are reported. The X-ray crystal structures of EtCbl and BuCbl were obtained with some of the lowest crystallographic residuals ever achieved for cobalamins (R = 0.0468 and 0.0438, respectively). The Co-C bond distances for EtCbl and BuCbl are 2.023(2) and 2.028(4) A, whereas the Co-alpha-5,6-dimethylbenzimidazole (Co-N3B) bond distances were 2.232(1) and 2.244(1) A, respectively. Although EtCbl and BuCbl displayed a longer Co-N3B bond than that observed in the naturally occurring methylcobalamin, the orientation of the alpha-5,6-dimethylbenzimidazole moiety with respect to the corrin ring did not vary substantially among the structures. The lengthening of both Co-C and Co-N3B bonds in EtCbl and BuCbl can be attributed to the "inverse" trans influence exerted by the sigma-donating alkyl groups, typically observed in alkylcobalamins. Analysis of the molecular surface maps showed that the alkyl ligands in EtCbl and BuCbl are directed toward the hydrophobic side of the corrin ring. The corrin fold angles in EtCbl and BuCbl were determined to be 14.7 degrees and 13.1 degrees, respectively. A rough correlation exists between the corrin fold angle and the length of the Co-N3B bond, and both alkylcobalamins follow the same trend.

High Resolution Crystal Structure of the Methylcobalamin Analogs Ethylcobalamin and Butylcobalamin by X-ray Synchrotron Diffraction

PubMed Central

Hannibal, Luciana; Smith, Clyde A; Smith, Jessica A.; Axhemi, Armend; Miller, Abby; Wang, Sihe; Brasch, Nicola E.; Jacobsen, Donald W.

2009-01-01

The X-ray crystal structures of the methylcobalamin (MeCbl) analogs ethylcobalamin (EtCbl) and butylcobalamin (BuCbl) are reported. The X-ray crystal structures of EtCbl and BuCbl were obtained with some of the lowest crystallographic residuals ever achieved for cobalamins (R = 0.0468 and 0.0438, respectively). The Co-C bond distances for EtCbl and BuCbl are 2.023(2) and 2.028(4) Å, whereas the Co-α-5,6-dimethylbenzimidazole (Co-N3B) bond distances were 2.232(1) and 2.244(1) Å, respectively. Although EtCbl and BuCbl displayed a longer Co-N3B bond than that observed in the naturally occurring methylcobalamin, the orientation of the α-5,6-dimethylbenzimidazole moiety with respect to the corrin ring did not vary substantially amongst the structures. The lengthening of both Co-C and Co-N3B bonds in EtCbl and BuCbl can be attributed to the “inverse” trans influence exerted by the σ-donating alkyl groups, typically observed in alkylcobalamins. Analysis of the molecular surface maps showed that the alkyl ligands in EtCbl and BuCbl are directed towards the hydrophobic side of the corrin ring. The corrin fold angles in EtCbl and BuCbl were determined to be 14.7° and 13.1°, respectively. A rough correlation exists between the corrin fold angle and the length of the Co-N3B bond, and both alkylcobalamins follow the same trend. PMID:19545130

Controlling Internal Organization of Multilayer Poly(methacrylic acid) Hydrogels with Polymer Molecular Weight

DOE PAGES

Kozlovskaya, Veronika; Zavgorodnya, Oleksandra; Ankner, John F.; ...

2015-11-16

Here, we report on tailoring the internal architecture of multilayer-derived poly(methacrylic acid) (PMAA) hydrogels by controlling the molecular weight of poly(N-vinylpyrrolidone) (PVPON) in hydrogen-bonded (PMAA/PVPON) layer-by-layer precursor films. The hydrogels are produced by cross-linking PMAA in the spin-assisted multilayers followed by PVPON release. We found that the thickness, morphology, and architecture of hydrogen-bonded films and the corresponding hydrogels are significantly affected by PVPON chain length. For all systems, an increase in PVPON molecular weight from M w = 2.5 to 1300 kDa resulted in increased total film thickness. We also show that increasing polymer M w smooths the hydrogen-bonded filmmore » surfaces but roughens those of the hydrogels. Using deuterated dPMAA marker layers in neutron reflectometry measurements, we found that hydrogen-bonded films reveal a high degree of stratification which is preserved in the cross-linked films. We observed dPMAA to be distributed more widely in the hydrogen-bonded films prepared with small M w PVPON due to the greater mobility of short-chain PVPON. Furthermore, these variations in the distribution of PMAA are erased after cross-linking, resulting in a distribution of dPMAA over about two bilayers for all M w but being somewhat more widely distributed in the films templated with higher M w PVPON. Finally, our results yield new insights into controlling the organization of nanostructured polymer networks using polymer molecular weight and open opportunities for fabrication of thin films with well-organized architecture and controllable function.« less

Method of making reflecting film reflector

DOEpatents

Cottingham, James G.

1980-01-01

A reflector of the reflecting film type is disclosed and which may be used in a heliostatic system for concentrating solar energy and comprising a reflecting film bonded to an appropriate rigid substrate in such a way that specularity of a very high order is achieved. A method of bonding the reflecting film to the substrate is also disclosed and comprises the steps of initially adhering the film to a smooth, clean flat rigid surface with a non-bonding liquid between the rigid surface and film, and then bonding the substrate and film. The non-bonding liquid has a molecular adhesion greater than any stresses due to handling or curing of the bonding agent which is applied between the film and the opposing surface of the rigid substrate.

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

PubMed

Chen, Ying; Bylaska, Eric J; Weare, John H

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe-OH 2 distances in the DFT calculations it was proposed that the surface Fe 3+ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination. Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe 3+ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe 3+ is coordinated with only 5 neighbors.

Effect of sandblasting on surface roughness of zirconia-based ceramics and shear bond strength of veneering porcelain.

PubMed

He, Min; Zhang, Zutai; Zheng, Dongxiang; Ding, Ning; Liu, Yan

2014-01-01

This study aims to investigate the effect of sandblasting on the surface roughness of zirconia and the shear bond strength of the veneering porcelain. Pre-sintered zirconia plates were prepared and divided into four groups. Group A were not treated at all; group B were first sandblasted under 0.2 MPa pressure and then densely sintered; group C and D were sintered first, and then sandblasted under 0.2 MPa and 0.4 MPa pressures respectively. Surface roughness was measured and 3D roughness was reconstructed for the specimens, which were also analyzed with X-ray diffractometry. Finally after veneering porcelain sintering, shear bond tests were conducted. Sandblasting zirconia before sintering significantly increased surface roughness and the shear bond strength between zirconia and veneering porcelain (p<0.05). Sandblasting zirconia before sintering is a useful method to increase surface roughness and could successfully improve the bonding strength of veneering porcelain.

Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu

PubMed Central

Liu, Chien-Min; Lin, Han-Wen; Huang, Yi-Sa; Chu, Yi-Cheng; Chen, Chih; Lyu, Dian-Rong; Chen, Kuan-Neng; Tu, King-Ning

2015-01-01

Direct Cu-to-Cu bonding was achieved at temperatures of 150–250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10–60 min at 10−3 torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement. PMID:25962757

Reprogrammable Assembly of Molecular Motor on Solid Surfaces via Dynamic Bonds.

PubMed

Yu, Li; Sun, Jian; Wang, Qian; Guan, Yan; Zhou, Le; Zhang, Jingxuan; Zhang, Lanying; Yang, Huai

2017-06-01

Controllable assembly of molecular motors on solid surfaces is a fundamental issue for providing them to perform physical tasks. However, it can hardly be achieved by most previous methods due to their inherent limitations. Here, a general strategy is designed for the reprogrammable assembly of molecular motors on solid surfaces based on dynamic bonds. In this method, molecular motors with disulfide bonds can be remotely, reversibly, and precisely attached to solid surfaces with disulfide bonds, regardless of their chemical composition and microstructure. More importantly, it not only allows encoding geometric information referring to a pattern of molecular motors, but also enables erasing and re-encoding of geometric information via hemolytic photocleavage and recombination of disulfide bonds. Thus, solid surfaces can be regarded as "computer hardware", where molecular motors can be reformatted and reprogramed as geometric information. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Contact and Length Dependent Effects in Single-Molecule Electronics

NASA Astrophysics Data System (ADS)

Hines, Thomas

Understanding charge transport in single molecules covalently bonded to electrodes is a fundamental goal in the field of molecular electronics. In the past decade, it has become possible to measure charge transport on the single-molecule level using the STM break junction method. Measurements on the single-molecule level shed light on charge transport phenomena which would otherwise be obfuscated by ensemble measurements of groups of molecules. This thesis will discuss three projects carried out using STM break junction. In the first project, the transition between two different charge transport mechanisms is reported in a set of molecular wires. The shortest wires show highly length dependent and temperature invariant conductance behavior, whereas the longer wires show weakly length dependent and temperature dependent behavior. This trend is consistent with a model whereby conduction occurs by coherent tunneling in the shortest wires and by incoherent hopping in the longer wires. Measurements are supported with calculations and the evolution of the molecular junction during the pulling process is investigated. The second project reports controlling the formation of single-molecule junctions by means of electrochemically reducing two axial-diazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in-situ between the molecule and gold electrodes. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond. Finally, the third project investigates the role that molecular conformation plays in the conductance of oligothiophene single-molecule junctions. Ethyl substituted oligothiophenes were measured and found to exhibit temperature dependent conductance and transition voltage for molecules with between two and six repeat units. While the molecule with only one repeat unit shows temperature invariant behavior. Density functional theory calculations show that at higher temperatures the oligomers with multiple repeat units assume a more planar conformation, which increases the conjugation length and decreases the effective energy barrier of the junction.

Programmable Assembly of Peptide Amphiphile via Noncovalent-to-Covalent Bond Conversion

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

Sato, Kohei; Ji, Wei; Palmer, Liam C.

Controlling the number of monomers in a supramolecular polymer has been a great challenge in programmable self-assembly of organic molecules. One approach has been to make use of frustrated growth of the supramolecular assembly by tuning the balance of attractive and repulsive intermolecular forces. We report here on the use of covalent bond formation among monomers, compensating for intermolecular electrostatic repulsion, as a mechanism to control the length of a supramolecular nanofiber formed by self-assembly of peptide amphiphiles. Circular dichroism spectroscopy in combination with dynamic light scattering, size-exclusion chromatography, and transmittance electron microscope analyses revealed that hydrogen bonds between peptidesmore » were reinforced by covalent bond formation, enabling the fiber elongation. To examine these materials for their potential biomedical applications, cytotoxicity of nanofibers against C2C12 premyoblast cells was tested. We demonstrated that cell viability increased with an increase in fiber length, presumably because of the suppressed disruption of cell membranes by the fiber end-caps.« less

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

First principles study of the electronic properties and band gap modulation of two-dimensional phosphorene monolayer: Effect of strain engineering

NASA Astrophysics Data System (ADS)

Phuc, Huynh V.; Hieu, Nguyen N.; Ilyasov, Victor V.; Phuong, Le T. T.; Nguyen, Chuong V.

2018-06-01

The effect of strain on the structural and electronic properties of monolayer phosphorene is studied by using first-principle calculations based on the density functional theory. The intra- and inter-bond length and bond angle for monolayer phosphorene is also evaluated. The intra- and inter-bond length and the bond angle for phosphorene show an opposite tendency under different directions of the applied strain. At the equilibrium state, monolayer phosphorene is a semiconductor with a direct band gap at the Γ-point of 0.91 eV. A direct-indirect band gap transition is found in monolayer phosphorene when both the compression and tensile strain are simultaneously applied along both zigzag and armchair directions. Under the applied compression strain, a semiconductor-metal transition for monolayer phosphorene is observed at -13% and -10% along armchair and zigzag direction, respectively. The direct-indirect and phase transition will largely constrain application of monolayer phosphorene to electronic and optical devices.

Programmable Assembly of Peptide Amphiphile via Noncovalent-to-Covalent Bond Conversion

DOE PAGES

Sato, Kohei; Ji, Wei; Palmer, Liam C.; ...

2017-06-22

Controlling the number of monomers in a supramolecular polymer has been a great challenge in programmable self-assembly of organic molecules. One approach has been to make use of frustrated growth of the supramolecular assembly by tuning the balance of attractive and repulsive intermolecular forces. We report here on the use of covalent bond formation among monomers, compensating for intermolecular electrostatic repulsion, as a mechanism to control the length of a supramolecular nanofiber formed by self-assembly of peptide amphiphiles. Circular dichroism spectroscopy in combination with dynamic light scattering, size-exclusion chromatography, and transmittance electron microscope analyses revealed that hydrogen bonds between peptidesmore » were reinforced by covalent bond formation, enabling the fiber elongation. To examine these materials for their potential biomedical applications, cytotoxicity of nanofibers against C2C12 premyoblast cells was tested. We demonstrated that cell viability increased with an increase in fiber length, presumably because of the suppressed disruption of cell membranes by the fiber end-caps.« less

Spectroscopic and theoretical investigations of alkali metal linoleates and oleinates

NASA Astrophysics Data System (ADS)

Świsłocka, Renata; Regulska, Ewa; Jarońko, Paweł; Lewandowski, Włodzimierz

2017-11-01

The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the linoleic (cis-9,cis-12-octadecadienoic) and oleic (cis-9-octadecenoic) acids was investigated. The complementary analytical methods: vibrational (IR, Raman) and electronic (UV) molecular absorption spectroscopy as well as DFT quantum mechanical calculations (charge distribution, angles between bonds, bond lengths, theoretical IR and NMR spectra) were carried out. The regular shifts of bands connected with carboxylate anion in the spectra of studied salts were observed. Some bonds and angles reduced or elongated in the series: acid→Li→Na→K linoleates/oleinates. The highest changes were noted for bond lengths and angles concerning COO- ion. The electronic charge distribution in studied molecules was also discussed. Total atomic charges of carboxylate anion decrease as a result of the replacement of hydrogen atom with alkali metal cation. The increasing values of dipole moment and decreasing values of total energy in the order: linoleic/oleic acid→lithium→sodium→potassium linoleates/oleinates indicate an increase in stability of the compounds.

Mach-like capillary-gravity wakes.

PubMed

Moisy, Frédéric; Rabaud, Marc

2014-08-01

We determine experimentally the angle α of maximum wave amplitude in the far-field wake behind a vertical surface-piercing cylinder translated at constant velocity U for Bond numbers Bo(D)=D/λ(c) ranging between 0.1 and 4.2, where D is the cylinder diameter and λ(c) the capillary length. In all cases the wake angle is found to follow a Mach-like law at large velocity, α∼U(-1), but with different prefactors depending on the value of Bo(D). For small Bo(D) (large capillary effects), the wake angle approximately follows the law α≃c(g,min)/U, where c(g,min) is the minimum group velocity of capillary-gravity waves. For larger Bo(D) (weak capillary effects), we recover a law α∼√[gD]/U similar to that found for ship wakes at large velocity [Rabaud and Moisy, Phys. Rev. Lett. 110, 214503 (2013)]. Using the general property of dispersive waves that the characteristic wavelength of the wave packet emitted by a disturbance is of order of the disturbance size, we propose a simple model that describes the transition between these two Mach-like regimes as the Bond number is varied. We show that the new capillary law α≃c(g,min)/U originates from the presence of a capillary cusp angle (distinct from the usual gravity cusp angle), along which the energy radiated by the disturbance accumulates for Bond numbers of order of unity. This model, complemented by numerical simulations of the surface elevation induced by a moving Gaussian pressure disturbance, is in qualitative agreement with experimental measurements.

Programming the Assembly of Unnatural Materials with Nucleic Acids

NASA Astrophysics Data System (ADS)

Mirkin, Chad

Nature directs the assembly of enormously complex and highly functional materials through an encoded class of biomolecules, nucleic acids. The establishment of a similarly programmable code for the construction of synthetic, unnatural materials would allow researchers to impart functionality by precisely positioning all material components. Although it is exceedingly difficult to control the complex interactions between atomic and molecular species in such a manner, interactions between nanoscale components can be directed through the ligands attached to their surface. Our group has shown that nucleic acids can be used as highly programmable surface ligands to control the spacing and symmetry of nanoparticle building blocks in structurally sophisticated and functional materials. These nucleic acids function as programmable ``bonds'' between nanoparticle ``atoms,'' analogous to a nanoscale genetic code for assembling materials. The sequence and length tunability of nucleic acid bonds has allowed us to define a powerful set of design rules for the construction of nanoparticle superlattices with more than 30 unique lattice symmetries, tunable defect structures and interparticle spacings, and several well-defined crystal habits. Further, the nature of the nucleic acid bond enables an additional level of structural control: temporal regulation of dynamic material response to external biomolecular and chemical stimuli. This control allows for the reversible transformation between thermodynamic states with different crystal symmetries, particle stoichiometries, thermal stabilities, and interparticle spacings on demand. Notably, our unique genetic approach affords functional nanoparticle architectures that, among many other applications, can be used to systematically explore and manipulate optoelectronic material properties, such as tunable interparticle plasmonic interactions, microstructure-directed energy emission, and coupled plasmonic and photonic modes.

The Effect of Phosphoric Acid Pre-etching Times on Bonding Performance and Surface Free Energy with Single-step Self-etch Adhesives.

PubMed

Tsujimoto, A; Barkmeier, W W; Takamizawa, T; Latta, M A; Miyazaki, M

2016-01-01

The purpose of this study was to evaluate the effect of phosphoric acid pre-etching times on shear bond strength (SBS) and surface free energy (SFE) with single-step self-etch adhesives. The three single-step self-etch adhesives used were: 1) Scotchbond Universal Adhesive (3M ESPE), 2) Clearfil tri-S Bond (Kuraray Noritake Dental), and 3) G-Bond Plus (GC). Two no pre-etching groups, 1) untreated enamel and 2) enamel surfaces after ultrasonic cleaning with distilled water for 30 seconds to remove the smear layer, were prepared. There were four pre-etching groups: 1) enamel surfaces were pre-etched with phosphoric acid (Etchant, 3M ESPE) for 3 seconds, 2) enamel surfaces were pre-etched for 5 seconds, 3) enamel surfaces were pre-etched for 10 seconds, and 4) enamel surfaces were pre-etched for 15 seconds. Resin composite was bonded to the treated enamel surface to determine SBS. The SFEs of treated enamel surfaces were determined by measuring the contact angles of three test liquids. Scanning electron microscopy was used to examine the enamel surfaces and enamel-adhesive interface. The specimens with phosphoric acid pre-etching showed significantly higher SBS and SFEs than the specimens without phosphoric acid pre-etching regardless of the adhesive system used. SBS and SFEs did not increase for phosphoric acid pre-etching times over 3 seconds. There were no significant differences in SBS and SFEs between the specimens with and without a smear layer. The data suggest that phosphoric acid pre-etching of ground enamel improves the bonding performance of single-step self-etch adhesives, but these bonding properties do not increase for phosphoric acid pre-etching times over 3 seconds.

Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.

Real-space identification of intermolecular bonding with atomic force microscopy.

PubMed

Zhang, Jun; Chen, Pengcheng; Yuan, Bingkai; Ji, Wei; Cheng, Zhihai; Qiu, Xiaohui

2013-11-01

We report a real-space visualization of the formation of hydrogen bonding in 8-hydroxyquinoline (8-hq) molecular assemblies on a Cu(111) substrate, using noncontact atomic force microscopy (NC-AFM). The atomically resolved molecular structures enable a precise determination of the characteristics of hydrogen bonding networks, including the bonding sites, orientations, and lengths. The observation of bond contrast was interpreted by ab initio density functional calculations, which indicated the electron density contribution from the hybridized electronic state of the hydrogen bond. Intermolecular coordination between the dehydrogenated 8-hq and Cu adatoms was also revealed by the submolecular resolution AFM characterization. The direct identification of local bonding configurations by NC-AFM would facilitate detailed investigations of intermolecular interactions in complex molecules with multiple active sites.

Effect of surface treatments on the bond strengths of facing composite resins to zirconia copings.

PubMed

Tsumita, M; Kokubo, Y; Kano, T

2012-09-01

The present study evaluated and compared the bond strength between zirconia and facing composite resin using different surface conditioning methods before and after thermocycling. Four primers, three opaque resins, and two facing composite resins were used, and 10 surface treatment procedures were conducted. The bond strength was measured before and after 4,000 cycles of thermocycling. The mean values of each group were statistically analyzed using one-way analysis of variance (ANOVA). The bond strengths of facing composite resins to zirconia after various treatments varied depending on the primers, opaque resins, body resins, and thermocycling. The application of primers and opaque resins to the zirconia surface after sandblasting is expected to yield strong bond strength of the facing composite resin (Estenia CG&B) even after thermocycling.

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).

[Influence of carbodiimide-ethanol solution surface treatment on dentin microtensile bond strength].

PubMed

Zhang, Yi; Liu, Yu-hua; Zhou, Yong-sheng; Chung, Kwok-hung

2015-10-18

To evaluate the microtensile bond strength changes and patterns of fractures of the bonding interface after dentine surface treatment with carbodiimide-ethanol solution. 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) dissolved in ethanol was diluted into different concentrations of 2, 1, 0.3, 0.1 and 0.01 mol/L EDC-ethanol solutions. Twenty-eight caries-free extracted human third molars were ground metallurgically to prepare flat occlusal mid-coronal dentin surfaces and etched with 35% (mass fraction) phosphoric acid gel. Then they were treated with EDC-ethanol solution for 60 s before the bonding procedure and randomly divided into five experimental groups corresponding to the tested EDC-ethanol concentrations. The ethanol treated and no pre-treated surfaces were used as controls. Single Bond 2 adhesive was applied and resin composite disk was stacked on the treated dentine surface. The teeth with resin composite disks were stored in water at room temperature for 24 h and then sectioned longitudinally to produce stick specimens for microtensile bond strength test. Fracture patterns were observed with a stereomicroscope. The dentin surfaces pre-treated with 2 mol/L [(22.17±13.31) MPa] and 1 mol/L [(45.31±17.80) MPa] EDC-ethanol solutions resulted in statistically significant lower bond strength value (P<0.05). Increasing numbers of fracture pattern at the resin-dentin interface were also found in this two groups with percentages of 81.2% and 41.3% respectively. No significant difference was observed in the groups with 0.3, 0.1, 0.01 mol/L EDC surface treatment (P>0.05). No significant difference of immediate bond strengths was found in the 0.3, 0.1, 0.01 mol/L groups compared with the control group. EDC-ethanol solution surface treatment with concentrations of 2 mol/L and 1 mol/L resulted in decreasing of the bonding strength.

In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

PubMed

Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

2017-05-01

Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

Glycine Polymerization on Oxide Minerals.

PubMed

Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Bond efficacy and interface morphology of self-etching adhesives to ground enamel.

PubMed

Abdalla, Ali I; El Zohairy, Ahmed A; Abdel Mohsen, Mohamed M; Feilzer, Albert J

2010-02-01

This study compared the microshear bond strengths to ground enamel of three one-step self-etching adhesive systems, a self-etching primer system and an etch-and-rinse adhesive system. Three self-etching adhesives, Futurabond DC (Voco), Clearfil S Tri Bond (Kuraray) and Hybrid bond (Sun-Medical), a self-etching primer, Clearfil SE Bond (Kuraray), and an etch-and-rinse system, Admira Bond (Voco), were selected. Thirty human molars were used. The root of each tooth was removed and the crown was sectioned into halves. The convex enamel surfaces were reduced by polishing on silicone paper to prepare a flat surface. The bonding systems were applied on this surface. Prior to adhesive curing, a hollow cylinder (2.0 mm height/0.75 mm internal diameter) was placed on the treated surfaces. A resin composite was then inserted into the tube and cured. After water storage for 24 h, the tube was removed and shear bond strength was determined in a universal testing machine at a crosshead speed of 0.5 mm/min. The results were analyzed with ANOVA and the Tukey.-Kramer test at a 59 degrees confidence level. The enamel of five additional teeth was ground, and the etching component of each adhesive was applied and removed with absolute ethanol instead of being light cured. These teeth and selected fractured surfaces were examined by SEM. Adhesion to ground enamel of the Futurabond DC (25 +/- 3.5 MPa) and Clearfil SE Bond (23 +/- 2.9 MPa) self-etching systems was not significantly different from the etch-and-rinse system Admira Bond (27 +/- 2.3 MPa). The two self-etching adhesives Clearfil S Tri bond and Hybrid Bond demonstrated significantly lower bond strengths (14 +/- 1.4 MPa; 11 +/- 1.9 MPa) with no significant differences between them (p < 0.05). Bond strengths to ground enamel of self-etching adhesive systems are dependent on the type of adhesive system. Some of the new adhesive systems showed bond strength values comparable to that of etch-and-rinse systems. There was no correlation between bond strength and morphological changes in enamel.

Self-healable interfaces based on thermo-reversible Diels-Alder reactions in carbon fiber reinforced composites.

PubMed

Zhang, W; Duchet, J; Gérard, J F

2014-09-15

Thermo-reversible Diels-Alder (DA) bonds formed between maleimide and furan groups have been used to generate an interphase between carbon fiber surface and an epoxy matrix leading to the ability of interfacial self-healing in carbon:epoxy composite materials. The maleimide groups were grafted on an untreated T700 carbon fiber from a three step surface treatment: (i) nitric acid oxidization, (ii) tetraethylenepentamine amination, and (iii) bismaleimide grafting. The furan groups were introduced in the reactive epoxy system from furfuryl glycidyl ether. The interface between untreated carbon fiber and epoxy matrix was considered as a reference. The interfacial shear strength (IFSS) was evaluated by single fiber micro-debonding test. The debonding force was shown to have a linear dependence with embedded length. The highest healing efficiency calculated from the debonding force was found to be about 82% more compared to the value for the reference interface. All the interphases designed with reversible DA bonds have a repeatable self-healing ability. As after the fourth healing, they can recover a relatively high healing efficiency (58% for the interphase formed by T700-BMI which is oxidized for 60 min during the first treatment step). Copyright © 2014 Elsevier Inc. All rights reserved.

Halogen-Adatom Mediated Phase Transition of Two-Dimensional Molecular Self-Assembly on a Metal Surface.

PubMed

Niu, Tianchao; Wu, Jinge; Ling, Faling; Jin, Shuo; Lu, Guanghong; Zhou, Miao

2018-01-09

Construction of tunable and robust two-dimensional (2D) molecular arrays with desirable lattices and functionalities over a macroscopic scale relies on spontaneous and reversible noncovalent interactions between suitable molecules as building blocks. Halogen bonding, with active tunability of direction, strength, and length, is ideal for tailoring supramolecular structures. Herein, by combining low-temperature scanning tunneling microscopy and systematic first-principles calculations, we demonstrate novel halogen bonding involving single halogen atoms and phase engineering in 2D molecular self-assembly. On the Au(111) surface, we observed catalyzed dehalogenation of hexabromobenzene (HBB) molecules, during which negatively charged bromine adatoms (Br δ- ) were generated and participated in assembly via unique C-Br δ+ ···Br δ- interaction, drastically different from HBB assembly on a chemically inert graphene substrate. We successfully mapped out different phases of the assembled superstructure, including densely packed hexagonal, tetragonal, dimer chain, and expanded hexagonal lattices at room temperature, 60 °C, 90 °C, and 110 °C, respectively, and the critical role of Br δ- in regulating lattice characteristics was highlighted. Our results show promise for manipulating the interplay between noncovalent interactions and catalytic reactions for future development of molecular nanoelectronics and 2D crystal engineering.

Density Functional Theory Calculations Revealing Metal-like Band Structures for Ultrathin Ge {111} and {211} Surface Layers.

PubMed

Tan, Chih-Shan; Huang, Michael Hsuan-Yi

2018-05-21

To find out if germanium should also possess facet-dependent electrical conductivity properties, surface state density functional theory (DFT) calculations were performed on 1-6 layers of Ge (100), (110), (111), and (211) planes. Tunable Ge (100) and (110) planes always present the same semiconducting band structure with a band gap of 0.67 eV expected of bulk germanium. In contrast, 1, 2, 4, and 5 layers of Ge (111) and (211) plane models show metal-like band structures with continuous density of states (DOS) throughout the entire band. For 3 and 6 layers of Ge (111) and (211) plane models, the normal semiconducting band structure was obtained. The plane layers with metal-like band structures also show Ge-Ge bond length deviations and bond distortions, as well as significantly different 4s and 4p frontier orbital electron count and their relative percentages integrated over the valence and conduction bands from those of the semiconducting state. These differences should contribute to strikingly dissimilar band structures. The calculation results suggest observation of facet-dependent electrical conductivity properties of germanium materials, and transistors made of germanium may also need to consider the facet effects with shrinking dimensions approaching 3 nm. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Origin of anisotropic negative Poisson's ratio in graphene.

PubMed

Qin, Zhenzhen; Qin, Guangzhao; Hu, Ming

2018-06-07

Negative Poisson's ratio (NPR) in auxetic materials is of great interest due to the typically enhanced toughness, shear resistance, and sound and vibration absorption, which enables plenty of novel applications such as aerospace and defense. Insight into the mechanism underlying NPR is significant to the design of auxetic nanomaterials and nanostructures. However, the analysis of NPR in previous studies mainly remains on the level of the evolution of geometry parameters, such as bond length and bond angle, while a thorough and fundamental understanding is lacking. In this paper, we report anisotropic differential NPR in graphene for uniaxial strains applied along both zigzag and armchair directions based on first-principles calculations. The mechanism underlying the emergence of NPR in graphene (evolution of bond length and bond angle) is found to be different from the conclusions from previous classical molecular dynamics simulations with empirical potential. We propose that the decentralized electron localization function (ELF) driven by strain leads to ELF coupling between different types of bonds, which results in the counter-intuitive anomalous increase of the bond angle and thus the emergence of NPR in graphene. Moreover, the NPR phenomenon can be anticipated to emerge in other nanomaterials or nanostructures with a similar honeycomb structure as that of graphene, where the ELF coupling would also be possible.

Monte Carlo simulations of lattice models for single polymer systems

NASA Astrophysics Data System (ADS)

Hsu, Hsiao-Ping

2014-10-01

Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N ˜ O(10^4). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and sqrt{10}, we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior.

Controlling factors of oligomerization at the water surface: why is isoprene such a unique VOC?

PubMed

Ishizuka, Shinnosuke; Fujii, Tomihide; Matsugi, Akira; Sakamoto, Yosuke; Hama, Tetsuya; Enami, Shinichi

2018-06-06

Recent studies have shown that atmospheric particles are sufficiently acidic to enhance the uptake of unsaturated volatile organic compounds (VOCs) by triggering acid-catalyzed oligomerization. Controlling factors of oligomerization at the aqueous surfaces, however, remain to be elucidated. Herein, isoprene (2-methyl-1,3-butadiene, ISO), 1,3-butadiene (1,3-b), 1,4-pentadiene (1,4-p), 1-pentene (1-p), and 2-pentene (2-p) vapors are exposed to an acidic water microjet (1 ≤ pH ≤ 5), where cationic products are generated on its surface within ∼10 μs and directly detected using surface-sensitive mass spectrometry. We found that carbocations form at the air-water interface in all the cases, whereas the extent of oligomerization largely depends on the structure in the following order: ISO ≫ 1,3-b > 1,4-p ≫ 1-p ≈ 2-p. Importantly, the cationic oligomerization of ISO yields a protonated decamer ((ISO)10H+, a C50 species of m/z 681.6), while the pentenes 1-p/2-p remain as protonated monomers. We suggest that ISO oligomerization is uniquely facilitated by (1) the resonance stabilization of (ISO)H+ through the formation of a tertiary carbocation with a conjugated C[double bond, length as m-dash]C bond pair, and (2) π-electron enrichment induced by the neighboring methyl group. Experiments in D2O and D2O : H2O mixtures revealed that ISO oligomerization on the acidic water surface proceeds via two competitive mechanisms: chain-propagation and proton-exchange reactions. Furthermore, we found that ISO carbocations undergo addition to relatively inert 1-p, generating hitherto uncharacterized co-oligomers.

30 CFR 800.21 - Collateral bonds.

Code of Federal Regulations, 2010 CFR

2010-07-01

... INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS UNDER REGULATORY PROGRAMS § 800.21 Collateral bonds... subject to the following conditions: (1) The regulatory authority shall keep custody of collateral...

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

Effect of Er,Cr:YSGG laser, air abrasion, and silane application on repaired shear bond strength of composites.

PubMed

Cho, S D; Rajitrangson, P; Matis, B A; Platt, J A

2013-01-01

Aged resin composites have a limited number of carbon-carbon double bonds to adhere to a new layer of resin. Study objectives were to 1) evaluate various surface treatments on repaired shear bond strength between aged and new resin composites and 2) to assess the influence of a silane coupling agent after surface treatments. Eighty disk-shape resin composite specimens were fabricated and thermocycled 5000 times prior to surface treatment. Specimens were randomly assigned to one of the three surface treatment groups (n=20): 1) air abrasion with 50-μm aluminum oxide, 2) tribochemical silica coating (CoJet), or 3) Er,Cr:YSGG (erbium, chromium: yttrium-scandium-gallium-garnet) laser or to a no-treatment control group (n=20). Specimens were etched with 35% phosphoric acid, rinsed, and dried. Each group was divided into two subgroups (n=10): A) no silanization and B) with silanization. The adhesive agent was applied and new resin composite was bonded to each conditioned surface. Shear bond strength was evaluated and data analyzed using two-way analysis of variance (ANOVA). Air abrasion with 50-μm aluminum oxide showed significantly higher repair bond strength than the Er,Cr:YSGG laser and control groups. Air abrasion with 50-μm aluminum oxide was not significantly different from tribochemical silica coating. Tribochemical silica coating had significantly higher repair bond strength than Er,Cr:YSGG laser and the control. Er,Cr:YSGG laser and the control did not have significantly different repair bond strengths. Silanization had no influence on repair bond strength for any of the surface treatment methods. Air abrasion with 50-μm aluminum oxide and tribochemical silica followed by the application of bonding agent provided the highest repair shear bond strength values, suggesting that they might be adequate methods to improve the quality of repairs of resin composites.

Variables related to materials and preparing for bond strength testing irrespective of the test protocol.

PubMed

Mair, Lawrence; Padipatvuthikul, P

2010-02-01

Resin bonding can be compared to making a sandwich with the tooth on one side and the restoration on the other, a layer of bonding resin is applied to either side and a filled resin (composite) placed in between. This presentation considers factors that influence the restoration side of the sandwich and various ways that the assembled testpieces may be "aged" prior to testing. The materials to be bonded may be either ceramic, metal or composite formed by methods such as casting, pressing, sintering or machining. The fabrication method determines the susceptibility of the bonding surface to physical or chemical modification. The treatment of the surface prior to bonding can be physical (e.g. sandblasting) or chemical (e.g. metal primer); but is more likely to be a combination (e.g. silica deposition+silane). Successful bonding depends on establishing a surface with a high population of unreacted vinyl groups (-CC) that can then be cross-polymerized to the resin in the bonding composite. The physical approach has involved etching or sandblasting the surfaces; but the ability to form a microretentive surface in this way depends on a heterogeneous surface. Noble metals and modern high strength ceramics have a more homogeneous surface and are not easily etched. To overcome this problem a number of ways to deposit a silica layer on the bonding surface have been developed: the Silicoater that involves baking on a silica layer, the Rocatec technique (CoJet) that involves air blasting silica onto the surface in conjunction with an abrasive; and two more modern approaches: sol-gel evaporation and molecular vapor deposition (MVD). All these techniques require the subsequent application of a silane layer to provide the -CC moieties. The use of primers without an intervening silica layer has been tested and found to be successful with some specialized bonding systems that contain agents such as methacryloyloxydecyldihydrogen-phosphate (MDP) (PanaviaEX). AGING OF TESTPIECES PRIOR TO BONDING: The most common type of aging is storage in water at temperatures from ambient to 100 degrees Celsius. This generally decreases bond strengths; but not to catastrophic values. A more exacting pre-test regime is thermal cycling. In some studies this caused a slightly greater reduction in bond strength than storage in water; but in other tests it resulted in total failure. As some testpieces have spontaneously debonded during thermal cycling, it seems sensible to include TC in any screening test of new materials. Mechanical cycling (fatigue) prior to testing has a very significant effect and the bond strength that can withstand 1,000,000 cycles can be one sixth of the bond strength in a simple monotonic test (tensile, shear or compression). Whereas simple monotonic tests provide a blunt instrument for eliminating poorly performing techniques their use for discriminating between established techniques is open to discussion. Copyright 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Density functional theory and chromium: Insights from the dimers

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

Würdemann, Rolf; Kristoffersen, Henrik H.; Moseler, Michael

2015-03-28

The binding in small Cr clusters is re-investigated, where the correct description of the dimer in three charge states is used as criterion to assign the most suitable density functional theory approximation. The difficulty in chromium arises from the subtle interplay between energy gain from hybridization and energetic cost due to exchange between s and d based molecular orbitals. Variations in published bond lengths and binding energies are shown to arise from insufficient numerical representation of electron density and Kohn-Sham wave-functions. The best functional performance is found for gradient corrected (GGA) functionals and meta-GGAs, where we find severe differences betweenmore » functionals from the same family due to the importance of exchange. Only the “best fit” from Bayesian error estimation is able to predict the correct energetics for all three charge states unambiguously. With this knowledge, we predict small bond-lengths to be exclusively present in Cr{sub 2} and Cr{sub 2}{sup −}. Already for the dimer cation, solely long bond-lengths appear, similar to what is found in the trimer and in chromium bulk.« less

40 CFR 63.3092 - How must I control emissions from my electrodeposition primer system if I want to comply with the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... electrodeposition primer system if I want to comply with the combined primer-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? 63.3092 Section 63.3092 Protection of...-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? If your...

40 CFR 63.3092 - How must I control emissions from my electrodeposition primer system if I want to comply with the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... electrodeposition primer system if I want to comply with the combined primer-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? 63.3092 Section 63.3092 Protection of...-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? If your...

Thermally robust and biomolecule-friendly room-temperature bonding for the fabrication of elastomer-plastic hybrid microdevices.

PubMed

Nguyen, T P O; Tran, B M; Lee, N Y

2016-08-16

Here, we introduce a simple and fast method for bonding a poly(dimethylsiloxane) (PDMS) silicone elastomer to different plastics. In this technique, surface modification and subsequent bonding processes are performed at room temperature. Furthermore, only one chemical is needed, and no surface oxidation step is necessary prior to bonding. This bonding method is particularly suitable for encapsulating biomolecules that are sensitive to external stimuli, such as heat or plasma treatment, and for embedding fracturable materials prior to the bonding step. Microchannel-fabricated PDMS was first oxidized by plasma treatment and reacted with aminosilane by forming strong siloxane bonds (Si-O-Si) at room temperature. Without the surface oxidation of the amine-terminated PDMS and plastic, the two heterogeneous substrates were brought into intimate physical contact and left at room temperature. Subsequently, aminolysis occurred, leading to the generation of a permanent seal via the formation of robust urethane bonds after only 5 min of assembling. Using this method, large-area (10 × 10 cm) bonding was successfully realized. The surface was characterized by contact angle measurements and X-ray photoelectron spectroscopy (XPS) analyses, and the bonding strength was analyzed by performing peel, delamination, leak, and burst tests. The bond strength of the PDMS-polycarbonate (PC) assembly was approximately 409 ± 6.6 kPa, and the assembly withstood the injection of a tremendous amount of liquid with the per-minute injection volume exceeding 2000 times its total internal volume. The thermal stability of the bonded microdevice was confirmed by performing a chamber-type multiplex polymerase chain reaction (PCR) of two major foodborne pathogens - Escherichia coli O157:H7 and Salmonella typhimurium - and assessing the possibility for on-site direct detection of PCR amplicons. This bonding method demonstrated high potential for the stable construction of closed microfluidic systems socketed with biomolecule-immobilized surfaces such as DNA, antibody, enzyme, peptide, and protein microarrays.

Evaluation of surface topography of zirconia ceramic after Er:YAG laser etching.

PubMed

Turp, Volkan; Akgungor, Gokhan; Sen, Deniz; Tuncelli, Betul

2014-10-01

The aim of this study is to evaluate the effect of Erbium: yttrium-aluminum-garnet (Er:YAG) laser with different pulse lengths on the surface roughness of zirconia ceramic and airborne particle abrasion. Er:YAG laser treatment is expected to be an alternative surface treatment method for zirconia ceramics; however, the parameters and success of the application are not clear. One hundred and forty zirconia discs (diameter, 10 mm; thickness, 1.2 mm) were prepared by a computer-aided design and computer-aided manufacturing (CAD/CAM) system according to the manufacturer's instructions. Specimens were divided into 14 groups (n=10). One group was left as polished control, one group was air-particle abraded with Al2O3 particles. For the laser treatment groups, laser irradiation was applied at three different pulse energy levels (100, 200, and 300 mJ) and for each energy level at four different pulse lengths; 50, 100, 300, and 600 μs. Surface roughness was evaluated with an optical profilometer and specimens were evaluated with scanning electron microscopy (SEM). Data was analyzed with one way ANOVA and Tukey multiple comparison tests (α=0.05). For the 100 and 200 mJ laser etching groups, 50 and 100 μs laser duration resulted in significantly higher surface roughness compared with air-particle abrasion (p<0.05). The difference among Ra values of 300 μs, 600 μs, and air-particle abrasion groups were not statistically significant (p>0.05). For the 300 mJ laser etching groups; there was no statistically significant difference among the Ra values of 50 μs, 100 μs, 300 μs, 600 μs, and air-particle abrasion groups (p>0.05). In order to increase surface roughness and promote better bonding to resin luting agents, Er:YAG laser etching may be an alternative to air-particle abrasion for zirconia ceramics. However, high levels of pulse energy and longer pulse length may have an adverse effect on micromechanical locking properties, because of a decrease in surface roughness.

Influence of hydrophilic pre-treatment on resin bonding to zirconia ceramics.

PubMed

Noro, Akio; Kameyama, Atsushi; Haruyama, Akiko; Takahashi, Toshiyuki

2015-01-01

Atmospheric plasma or ultraviolet (UV) treatment alters the surface characteristics of tetragonal zirconia polycrystal (TZP), increasing its hydrophilicity by reducing the contact angle against water to zero. This suggests that such treatment would increase the wettability of bonding resin. The purpose of this study was to determine how increasing the hydrophilicity of TZP through plasma irradiation, UV treatment, or application of ceramic primer affected initial bonding with resin composites. Here, the effect of each pre-treatment on the hydrophilicity of TZP surfaces was determined by evaluating change in shear bond strength. Plasma irradiation, UV, or ceramic primer pre-treatment showed no significant effect on bonding strength between TZP surfaces and resin composites. In addition, alumina blasting yielded no significant increase in bond strength. Plasma irradiation, UV treatment, or ceramic primer pre-treatment did not lead to significant increase in bond strength between TZP and resin composites.